Photoresist composition and the polymer

 

(57) Abstract:

The invention relates to radiation-sensitive photoresists composition. Describes photoresist composition comprising generating acid photoinitiator, solvent, optionally, a dissolution inhibitor and a polymer containing polycyclic repeating units containing acid-labile groups, with a molecular weight of from about 500 to about 1,000,000, which is the product of polymerization of polycyclic monomers substituted with at least one acid-labile group, and optionally in combination with a monomer selected from the group comprising maleic anhydride, carbon monoxide, polycyclic monomer, substituted carboxyl group, alkyl substituted polycyclic monomer, and mixtures thereof. When exposed to the imaging radiation source acid photoinitiator generates acid that breaks down the side acid labile group, which leads to a change of polarity of the polymer. The polymer becomes soluble in an aqueous solution of the base in places exposure to the imaging radiation source. Proposed photoresist composition provides compatibility with the General chemical scheme is C.p. f-crystals, table 2.

The invention relates to polymers containing polycyclic monomer units, and methods for their use as photoresists in the manufacture of integrated circuits. More specifically, the invention relates to photoresist compositions containing the polymer containing polycyclic monomer units, and, for example, cationic photoinitiator. The polymer contains recurring side of the acid-labile group, linked to the main chain of the polymer. The acid-labile groups can be selectively cleaved with the formation of the recurring polar groups in the main polymer chain. The polymers are transparent relative to the wavelength to the imaging radiation, and are resistant to reactive ion etching.

Integrated circuits (IC) are important in the production of matrices of electronic devices. They are made by the sequential formation of alternating and interlocking strips of conductive, semiconductive and conductive layers on a suitable substrate (e.g. silicon wafer), which selectively modeled for the formation of circuits and interconnections in order to perform specific electrical functions. Education to the practical method in the fabrication of IC devices is photolithography using ultraviolet (UV) radiation and radiation deep penetrating UV-light or other radiation. On the plate surface is applied photosensitive polymer layer (photoresist) and dried. Then close to photoresistors the film put photomask containing a picture of the desired information. The photoresist is irradiated through the layer photomasks one or more types of image forming radiation, including UV radiation, electron radiation, x-rays or ion radiation. Under irradiation, the photoresist undergoes chemical changes leading to change its solubility. After exposure, the plate is dipped into the solution, exhibiting a pattern on a photosensitive polymeric film (i.e., selectively removes either the exposed or unexposed areas). Depending on the type of polymer or the polarity of the developing solvent in the development process removes either the exposed or unexposed areas of the film with the disclosure below of the substrate, after which the open or unwanted substrate material with the applied configuration is deleted or changed in the process of pickling, preserving the desired pattern in the functional layer of the plate. Applied plasma etching, etching by sputtering and reactively. Remove the remaining photoresistive material results in circuits with printed pattern.

In the manufacture of devices containing the figure of IP, the most critical step is the etching of the different layers on the wafer. One method is immersing the substrate and the resist coated pattern in a chemical bath, which is the impact on an exposed surface of the substrate while maintaining intact the resist. The disadvantage of this "wet" chemical process is the difficulty of achieving a well defined edges on the etched surfaces. This is due to the chemical protravlivanija material of the resist and education isotropic image. In other words, the conventional chemical process does not provide selectivity directions (anisotropy) that is necessary to achieve optimal functional of a given size, the relevant existing technological requirements. In addition, the wet process leads to undesirable consequences for the environment and safety.

To overcome the drawbacks of wet chemical processes have been proposed various "dry" processes. Such dry processes is ectrode in the presence of gas. Plasma containing ionized matter generated by creating a voltage, used for etching is placed in the chamber of the substrate. Generated in the plasma ionized matter is directed to an open substrate, where it interacts with the surface of the material with the formation of volatile products, which are removed from the surface. Typical examples of the dry etching is a plasma etching, etching by sputtering and reactive ion etching.

Reactive ion etching provides education on the substrate profiles with well-marked vertical side walls, and the uniformity of etching from the substrate to the substrate. Such advantages reactive ion etching has become a standard in the production of IP.

The industry uses two types of photoresists: negative and positive photoresists. Negative resists after exposure to the imaging radiation polymerized, are sewn or change the solubility so that the exposed areas become insoluble in relation to showing the solution. No exposed areas remain soluble and are washed away. Positive formiruem image radiation.

The basis of one type of positive ratestogo of material is a Novolac phenol-formaldehyde polymers. A specific example is used in industry material Shipley AZ 1350 containing Novolac m-crazyforbargains polymer composition and diazoketone (ether 2-diazo-1-naphthol-5-sulfonic acids). When exposed to the imaging radiation diazoketone turns into carbonic acid, which in turn transforms the phenolic polymer is easily soluble in manifesting aqueous solution of the weak base polymer.

In the patent US 4491628 issued to Ito et al., described positive and negative photoresist composition comprising generating acid photoinitiator and polymers with side acid-labile groups. Since each generated acid removes protection from a variety of acid-labile groups, such approach is known as chemical amplification is used to increase the quantitative output of the overall photochemical process. Described polymers include vinyl polymers, such as polystyrenes, polyvinylacetate and polyacrylates, substituted repetitive side groups, subject to acidosis with obtaining products with a R is e esters of carboxylic acid and tert-butyl carbonates of phenols. Depending on the nature of the used developing solution can be obtained a positive or negative photoresists.

Trends in the development of the electronics industry continually require an IP, which is faster and consumes less energy. To meet these requirements shall be made IP the smaller sizes. Conductive lines (i.e. lines) should be more thin and placed closer to each other. A significant decrease in the size of transistors and lines increases the efficiency of IP, for example, increase the amount of stored information and performance chips. To achieve a more subtle line item IP need a higher resolution image. Higher resolution images are possible with a shorter wavelength of the source used for irradiation photoresistive material. However, the previously known technique photoresists, such as Novolac phenol-formaldehyde polymers and substituted styrene polymers contain aromatic groups, which by their nature are more optically dense at the wavelength of light less than approximately 300 nm. (ACS Symposium Series 537, Polymers for Microelc Press, p. 67-118). Sources with shorter wavelength is usually less bright than traditional sources, requiring chemical amplification using photocolor. The opacity of the aromatic polymers with respect to light with a short wavelength is a disadvantage, because under the surface of the polymer motociclete unevenly irradiated by the light source and, as a consequence, the polymer does not occur. To overcome the lack of transparency of these polymers, the content of aromatics in photoresist polymers should be reduced. If you want transparency in relation to deep UV radiation (i.e. radiation with a wavelength of 248 nm and, particularly 193 nm), the content of aromatics in the polymer should be minimal.

Patent US 5372912 refers to photoresists compositions containing acrylate copolymer, a phenolic binder and a photosensitive acid generator. Acrylate copolymer is the product of copolymerization of acrylic acid, alkylacrylate or methacrylate and a monomer containing side of the acid-labile group.

At that time, as the composition is sufficiently transparent with respect to UV radiation at a wavelength of about 240 nm, using an aromatic binder OHV, the improvement of one property is usually achieved at the expense of other properties. When using acrylate polymers increase transparency in relation to UV radiation with a shorter wavelength is achieved by reducing the resistance of the resist with respect to reactive ion etching.

In many cases, improving transparency in relation to forming the image shortwave radiation leads to erosion ratestogo material in a subsequent process of dry etching. Because photoresistive materials usually are, by nature, organic, and substrates used in the manufacture of IP are usually inorganic, photoresistive material inherently has a higher etching rate than the material of the substrate when using the technique of reactive ion etching (RIT). This raises the need for photoresist material of greater thickness than below the substrate. Otherwise photoresist material is removed by erosion before the complete etching of the underlying substrate. From this it follows that resisty material with a lesser rate of erosion can be used as more than the tone of the misfit, a higher resolution, which ultimately allows to achieve a more narrow conductive lines and the transistors smaller.

J. V. Crivello et al. (Chemically Amplified Electron-Beam Photoresists, Chem. Mater., 1996, 8, p. 376-381) describe a polymer blend containing 20 wt.% obtained in the process of free-radical polymerization of homopolymer norbornene containing acid labile group, and 80 wt.% homopolymer 4-hydroxy-methylstyrene containing acid labile group, intended for use in electron-beam photoresists. As stated by the authors, the increased optical density of aromatic groups (especially at high concentrations) gives these compositions opacity and makes them impossible to use in the radiation forming the image shortwave radiation with a wavelength less than 200 nm.

The described compositions are suitable only for electron-beam photoresists, and may not be used for formation of images by deep UV radiation (especially for resists with a wavelength of 193 nm).

Crivello et al. used a mix compositions, because they found that oxygen plasma has an etching rate that is unacceptably high for the Poluy acid groups.

Therefore, there is a need to photoresist compositions that are compatible with the General scheme of the chemical amplification and ensuring transparency in relation to short-wave form.

The main technical problem of the invention is to provide photoresists composition containing the polymer, the main chain of which contains a side of the acid-labile group, generating acid photoinitiator.

Another technical object of the invention is a polymer having recurring side of the acid-labile groups that can be split with the formation of polar groups.

Another objective of the invention is to provide polymer compositions that are transparent with respect to forming the image shortwave radiation.

Following the technical task of the invention is to provide polymer compositions that are resistant to dry etching.

Another objective of the invention is to provide polymer compositions that are transparent with respect to forming the image shortwave radiation and resistant to dry etching.

Another object of the invention is the creation of povanim polymers, measurable manifestation in aqueous base.

These and other technical problems of the invention are achieved by a polymerization reaction mixture containing polycyclic monomer with functional acid-labile groups, a solvent, a single or multicomponent catalyst system containing a source of metal ions of group VIII of the Periodic system. In multi-component catalytic systems according to the invention, the source of metal ions of group VIII is used in conjunction with one or two ORGANOMETALLIC socialization and the third component. Single and multi-component catalytic system can be used with optimal agent chain transfer announcing the library, selected from compounds having a terminal olefinic double bond between adjacent carbon atoms, where at least one of the above-mentioned adjacent carbon atoms contains associated with two hydrogen atoms. Announcing the library are selected from unsaturated compounds, which are usually not capable of cationic polymerization, and therefore exclude styrene, vinyl ethers, and related dieny.

The resulting polymers are used photoresist compositions comprising generating acid foteini istna composition, containing generating acid photoinitiator, the solvent, the polymer containing polycyclic repeating units containing an acid-labile group, and, optionally, a dissolution inhibitor. Another object of the invention is the polymer is a polymerization product of a Monomeric composition containing polycyclic monomer and the solvent, in the presence of a single component catalyst of the formula

EnNi(C6F5)2,

where E denotes the neutral ligand donor 2 electrons and n = 1 or 2, as specified polycyclic monomer selected from monomers having the formula

< / BR>
where the substituents R1-R4independently from each other selected from the group comprising hydrogen, normal and branched alkyl WITH1-C10and the group -(CH2)nC(O)OR*, -(CH2)n-C(O)OR, -(CH2)n-OR, -(CH2)n-OC(O)R, -(CH2)n-OC(O)OR, or -(CH2)n-C(O)R, -(CH2)nC(R)2CH(R)(C(O)OR**and -(CH2)nC(R)2CH(C(O)OR**)2provided that at least one of the substituents R1-R4selected from the group comprising an acid-labile group -(CH2)n-C(O)OR*R means bodoro is to split the generating acid by photoinitiation and selected from the group of radicals including- (CH3)3, -Si(CH3)3isobornyl, 2-methyl-2-substituted, tetrahydrofuranyl, tetrahydropyranyl, 3-oxo-cyclohexanyl, lactones avalonbay acid, dicyclopropyl and dimethylpropylene, R**independent means R and R*.

The present invention relates to radiation-sensitive resistol composition comprising generating acid photoinitiator and a polymer containing a repeating side of the acid-labile groups along the main polymer chain. The composition containing the polymer and generating acid photoinitiator, is applied on a substrate in a thin film, dried in controlled conditions, irradiated by simulated configuration of the picture and, if necessary, further dried under controlled conditions to further remove protection. In places the film, which was subjected to irradiation, repetitive side of the acid-labile groups in the polymer chain are split with the formation of the recurring polar groups. Thus treated irradiated region is selectively removed showing an alkaline solution. Alternative, non-irradiated designated polymer remain non-polar and can be selectionstate can be easily achieved by proper selection of the developing solution due to differences in the solubility of the irradiated and non-irradiated parts of the polymer.

The polymers of the present invention contain the repeating polycyclic units, some of which are replaced by acid-labile groups. These polymers are produced by polymerization of polycyclic monomers according to the invention. The term "polycyclic" (type norbornene or functional norbornene) include a monomer containing at least one part norbornene as shown below

< / BR>
The simplest polycyclic monomer of the invention is bicyclic monomer bicyclo[2.2.1]hept-2-ene, commonly known as norbornene. Functional acid-labile groups introduced into the polymer chain polymerization reaction mixture containing one or more polycyclic monomers with acid-labile substituents listed below in formula I, if necessary, in combination with one or more polycyclic monomer represented below in formula II, III, IV and V, in the presence of a catalytic system of the metal of group VIII of the Periodic system.

The monomers

Polycyclic monomers with acid-labile groups used in the invention are selected from monomers having the following formula

< / BR>
where R1, R2, R3, R410, -(CH2)n-C(O)OR*, -(CH2)n-C(O)R, -(CH2)n-OR, -(CH2)n-OC(O)R, -(CH2)n-C(O)R and -(CH2)n-OC(O)OR,

-(CH2)nC(R)2CH(R)(C(O)OR**and -(CH2)nC(R)2CH(C(O)OR**)2provided

that at least one of the substituents from R1to R4represents an acid-labile group -(CH2)nC(O)OR*where R denotes hydrogen, a linear or branched alkyl WITH1-C10and m = 0 to 5, and n = 0 to 10, preferably 0; R*mean group (i.e., blocking or protective group, which can be split under the action of generating an acid photoinitiator selected from the groups- (CH3)3, -Si(CH3)3isobornyl, 2-methyl-2-substituted, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexyl, lactones avalonbay acid (3,5-dioxy-3-methylvaleramide acid), dicyclopropyl (Dcpm) and dimethylcyclopropene (Dmcp). R**independently from each other, means R and R*the meaning of which is indicated above. Dcpm and DMSP groups have respectively the following structure

< / BR>
Polycyclic monomers of the above formula, containing substituents selected from the t to be represented by the following formulas

< / BR>
< / BR>
In the above formulas, m preferably has a value of 0 or 1, more preferably 0. If m = 0, then the preferred structure can be represented by the following formula

< / BR>
where the substituents from R1to R4have the above meaning.

Specialist in the art it is obvious that for carrying out the invention any suitable capable motocicleta splitting groups, provided that they do not inhibit the polymerization reaction.

The preferred acid labile groups are organic ester group, a splitting in the presence of acid. The preferred acid labile groups include ester groups and carbonate groups. Particularly preferred groups of the tert-butyl esters of carboxylic acids.

In the polymerization of monomers of the formula I get the polymer main chain of which contains a side of acid-sensitive groups, which are then cleaved to give the polymer polarity or solubility.

Possible, but an optional second monomer may be represented by formula II

< / BR>
where neutral substituents R5-R8independently /SUB>-OC(O)OR", -(CH2)n-C(O)R", -(CH2)nC(R*)2CH(R*)(C(O)OR*), and -(CH2)nC(R*)2CH(C(O)OR*)2where p = 0 to 5, preferably 0 or 1 and more preferably 0, and n = 0 to 10, preferably 0. The substituents from R5to R8can, independently of one another, mean a hydrogen, a normal or branched alkyl WITH1-C10provided that at least one of the remaining substituents R5to R8selected from one of the neutral groups presented above. The substituents R, independently of each other denote hydrogen, a normal or branched alkyl WITH1-C10, R" denotes hydrogen, straight or branched alkyl WITH1-C10mono - and politicalization group4-C20, cyclic ethers, cyclic ketones, and cyclic esters (lactones). Examples monociliated groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Examples policyqualifierid groups are norbornyl, substituted, tetrahydroisoquinolines (tricyclo[5.2.1.02,6]decenyl) and the like. Some simple examples of cyclic ethers include tetrahydrofuranyl and tetrahydropyranyl. Example collector avalonbay acid.

The preferred monomers of formula II are1-C5alkalemia esters of carboxylic acids, preferably methyl and ethyl esters. Ester functional groups impart hydrophilicity, providing good wetting developing solution and improving the mechanical properties of the film. An optional third Monomeric component is represented by a structure of formula III

< / BR>
where the substituents R9- R12independently of one another, mean a carboxyl group of the formula -(CH2)n(O)HE, where q = 0 to 5, preferably 0 or 1 and more preferably 0, and n = 0 to 10, preferably 0. The substituents from R9- R12independently of one another can denote hydrogen, a normal or branched alkyl WITH1-C10provided that at least one of the remaining substituents R9-R12means the above-mentioned carboxyl group.

Monomers containing carboxyl functional group attached to the polymer hydrophilicity, which, consequently, contributes to the high speed manifestations of the polymer in an aqueous solution of the base.

Possible monomer of formula IV is represented by the following formula

< / BR>
where the substituents R13preferably 0 or 1, particularly preferably 0. Any Deputy from R13to R16can mean hydrogen, provided that at least one of the remaining substituents R13to R16selected from the above alkyl groups. Especially preferred alkyl Deputy is decyl.

Polymerization of alkyl substituted monomers in the polymer chain is a method of regulating the glass transition temperature (TD) of the polymer, as described in patent US 5468819 issued by Goodall et al.

Economical scheme for polycyclic monomers with functional and hydrocarbon substituents according to the invention is the reaction of the Diels-alder reaction, according to which the cyclopentadiene (CPD) or substituted cyclopentadiene interacts with the appropriately substituted diene at elevated temperatures with the formation of substituted polycyclic adduct according to the following reaction scheme:

< / BR>
Other polycyclic adducts receive thermal pyrolysis of Dicyclopentadiene in the presence of a suitable diene. The reaction proceeds by the initial pyrolysis of Dicyclopentadiene (DCPD) in the JRS with the subsequent interaction between the JRC and the diene in the Diels-alder reaction with the formation of addounia above for substituents on R1to R16in formulas I, II, III and IV.

For example, 2-norbornene-5-carboxylic acid (bicyclo[2.2.1]hept-5-ene-2-carboxylic acid) can be obtained by Diels-alder reaction interaction of cyclopentadiene with acrylic acid by the following reaction scheme:

< / BR>
The corresponding tert-butyl ether carboxylic acids can be obtained by the interaction of the carboxyl functional group with isobutylene in the presence of a small amount of acid at low temperature (i.e., from (-30)oWith up to (-20)oC) according to the following scheme:

< / BR>
Another preferred method of obtaining tert-butyl ester of norbornene carboxylic acid is the interaction of cyclopentadiene with tert-butyl acrylate by the reaction of the Diels-alder reaction.

Another method of synthesis of substituted acid and ester groups of the monomers of the present invention is to obtain polycyclic monomers, substituted in the ortho-position of the ester groups, followed by hydrolysis them with the formation of carboxyl functional groups, or a partial hydrolysis with the formation of ester functional groups. Carboxyl functional groups can be esterified is obreteniyu have the formula V

< / BR>
where the substituents R17, R18and R19independently from each other presents normal or branched C1-C5alkyl group or any of R17, R18and R19together with the oxygen atom to which it is attached, forms a substituted or unsubstituted 5 - to 10-membered cyclic or bicyclic ring, containing from 3 to 8 atoms (excluding the replacement group), s = 0 to 5, preferably 0, and t = 1 to 5, preferably 1. Examples of structures in which s = 0, t = 1 and the substituents R17, R18and R19together with the oxygen atoms to which they are attached, form a cyclic or bicyclic ring below in the form of formulas Va, Vb, Vc

< / BR>
< / BR>
< / BR>
where the substituents R17', R18' and R19' independently of one another denote hydrogen or normal, branched C1-C5alkyl. Monomers, substituted in the ortho-position of the ester group according to the invention can be obtained according to the so-called synthesis of Silver (A. Pinner, Chem. Ber., 1883, 16, 1643) and the method proposed by S. M. McElvain, J. T. Venerable (J. Am. Chem. Soc. , 1950, 72, p. 1661); SM. McElvain, C. L. Aldridge (J. Am. Chem. Soc., 1953, 75, R. 3987). A typical example of the synthesis is represented reaction scheme I (see the end of the description). the borate salt followed by treatment of the salt of an alkali metal (sodium alcoholate) to obtain the ortho-triakontameron of ester. (H. Meerwein, P. Borner, A. Fuchs, H. J. Sasse, H. Schrodt and J. Spille, Chem. Ber., 1956, 89, p. 2060).

As mentioned above, the ortho ester group can be subjected to hydrolysis in the presence as catalyst of a weak acid, such as Hydrobromic, uudistoodetena and acetic acid with the formation of carboxylic acids. In turn, the carboxylic acid may be etherification in the presence of an aliphatic alcohol and an acid catalyst with the formation of the corresponding ether complex. It should be clear that in the case of polycyclic monomers, substituted in ortho-position on two or more ester groups, the latter can be partially hydrolyzed in acidic group with the formation of acid and the usual complex ester of the same monomer (see scheme II).

Other, more preferred method of obtaining a bifunctional polycyclic monomers, is the hydrolysis or partial hydrolysis of the anhydride, endo-5-norbornene-2,3-dicarboxylic acid (nadiawala anhydride). Nedieval anhydride can be fully obtained dicarboxylic acid, or partially hydrolyzed to the acid and ether complex or diapir, as shown in scheme III,

where R17independent means the sludge. Preferably in the synthesis nadiawala anhydride as starting substances are used Exo-isomer. Exo-isomer is easily obtained by heating the endo-isomer in 190oWith followed by recrystallization from the appropriate solvent (toluene). To obtain the dicarboxylic acid in the reaction scheme 1 simply hydrolyzing nedieval anhydride in boiling water to obtain a nearly quantitative yield of the target product. To obtain a mixture of monomers with carboxyl and alkylamine groups according to the scheme 3 nedieval anhydride is heated under reflux for 3 to 4 hours in the presence of an appropriate aliphatic alcohol (R17IT). Alternative the same product can be obtained by the interaction of the first nadiawala anhydride with aliphatic alcohol and trialkylamines followed by treatment with diluted hydrochloric acid. Fluids, replaced with identical alkyl groups (R17) can be obtained from a dicarboxylic acid by its interaction with triallylisocyanurate, for example, R173[F4] in methylene chloride at room temperature in the presence of diisopropylethylamine. To obtain esters with different alkyl groups of the th scheme 3. In this case, the acid group atrificial as shown in reaction scheme 2. However, use triallylisocyanurate with other alkyl groups other than alkyl groups already present in the ester functional groups.

It should be noted that the monomers of the preceding stage containing a functional group corresponding to the preceding stage can be converted into monomers with the desired functional groups before polymerization, or these monomers can be polymerized, and then the corresponding polymers containing as substituents of the same functional group as at the previous stage can be subjected to the subsequent reaction to produce the desired functional groups.

In the scope of the present invention, it is assumed that the monomers of formulas I to V, where m, p, q, r and s = 0, a methylene bridge may be replaced by oxygen with obtaining derivatives of 7-oxo-norbornene.

It is also assumed that for use at a wavelength of 248 nm, the substituents from R5to R16and R11in formulas II, III and IV can be aromatic, such as phenyl.

Polymers

One or more policy or in a mixture with one or more polycyclic monomers of the formula II, III, IV and V. it is also Assumed that the polycyclic monomers of formulas I-V may be copolymerizable with carbon monoxide to obtain copolymers of polycyclic monomers and carbon monoxide. Copolymers of norbornene with lateral carboxyl group, and the carbon monoxide is described in the patent US 4960857 provided here as a reference. The monomers of formulas I-V and the carbon monoxide will copolymerized in the presence of catalytic systems containing palladium as described in Chem. Rev., 1996, 96, R. 663-681. Expert it is clear that the copolymers of alternating links of polycyclic monomers and carbon monoxide can exist in the keto - or spirochaetales isomeric form. Accordingly, the present invention involves the use of homopolymers and copolymers containing randomly recurring units derived (polymerized from a monomer or monomers of the formula I, copolymers containing random repeating units derived (polymerized from monomer(s) of formula I, possibly in a mixture with any monomer(s) of formulas II-V. in Addition, the present invention involves the use of copolymers containing recurring units obtained (polymerized) from carbon monoxide and monomer(s), preseli. The polymer typically contains from 5 to 100 mol.% monomer (repeating group) containing acid labile groups. Preferably, the polymer contains about 20 to 90 mol.% monomer containing acid labile groups. More preferably, the polymer contains about 30-70 mol.% monomer containing labile functional acid groups. The remainder of the polymer consists of repeating units polymerized from possible monomers of formulas II-V. the Choice and number of specific monomers used in the polymer may vary in accordance with the desired properties. For example, changing the number of carboxyl functional groups in the polymer chain can be achieved desired solubility of the polymer manifesting in different solvents. To improve the mechanical properties of the polymer and the radiation sensitivity of the system can be varied monomers containing ester functional groups. Finally, it is possible to adjust the glass transition temperature of the polymer included in the polymer chain recurring cyclic units containing long-chain alkyl groups such as decyl.

There are several ways polymerization of cyclic olefin monomelic: (1) metathesis polymerization disclosure cycle (ERC); (2) NRC with subsequent hydrogenation and (3) additive polymerization. Each of these methods yields a polymer with a specific structure as shown in figure 1.

NRC-polymer has a structure different from the additive polymer. NRC-polymer contains repeating units containing one circular element compared with the original monomer. Duplicate links are interconnected in unsaturated polymer chain, as shown in figure 1. Due to the unsaturation of the polymer, preferably, should be subjected to further hydrogenation to give a polymer chain oxidation stability. In contrast, the additive polymers have no C=C unsaturation in the polymer chain, although they are derived from the same monomer.

The monomers according to the invention can be polymerized additive polymerization and metathetical polymerization with ring opening (MPRC), preferably with subsequent hydrogenation. Cyclic polymers of the present invention have the following structure:

< / BR>
< / BR>
where the substituents R' to R"", independently of one another, are radicals from R1to R19

NRC-polymers of the present invention is produced by polymerization in the presence of the specific catalyst for the polymerization in an appropriate solvent. How MPRC polymerization and subsequent hydrogenation of the thus obtained polymers are described in US patents 5053471 and 5202388, shown here as a reference.

According to one variant NRC polycyclic monomers according to the invention can be polymerized in the presence of a single component ruthenium complex or osmanaga karbonovogo catalyst, such as described in WO 95-US 9655. The ratio of monomer and catalyst should be from about 100:1 to about 2000:1, mainly about 500:1. The reaction can be carried out in a halogenated hydrocarbon solvent such as dichloroethane, dichloromethane, chlorobenzene and the like, or in a hydrocarbon solvent such as toluene. The quantitative content of the solvent in the reaction medium should be sufficient to achieve concentrations of solids from about 5 wt.% to about 40 wt.%, preferably from 6 wt.% up to 25 wt.%. The reaction can be conducted at a temperature of about from 0oWith up to 60oWith, preferably logicalhost)benzylideneamino. It has been unexpectedly found that this catalyst can be used as a catalyst initial MRZ reaction and as an effective catalyst for hydrogenation to obtain a practically saturated NRC-polymer. Use of any additional catalyst for hydrogenation is not required. After the initial reaction NRC for the hydrogenation of a polymer chain is only required to maintain the hydrogen pressure above the reaction medium at a temperature above about 100oBut below about 220oC, preferably from about 150oWith up to 200oC.

The additive polymers of the present invention can be obtained by standard free-radical polymerization in solution, is well known to specialists. The monomer of formula I-V may be subjected Homo - or copolymerization in the presence of maleic anhydride. Methods of free-radical polymerization are described in Encyclopedia of Polymer Science, John Wiley & Sons, 1988, 13, R. 708.

Alternatively and preferably, the monomers of the present invention will polimerizuet in the presence of a single or multicomponent catalyst system containing a source of metal ions of group VIII, preferably palladium, ILU in relation to deep UV light (193 nm) and exhibit excellent resistance to reactive ion etching.

Preferred polymers of the present invention will polimerizuet from the reaction mixture, containing at least one polycyclic monomer of the formula I, a solvent, a catalytic system containing a source of metal ions of group VIII and, if necessary, the agent of the transfer chain. The catalytic system may contain a single component catalyst based on a metal of group VIII or multicomponent catalyst based on a metal of group VIII.

One-component system

According to one variant of the one-component catalytic system of the present invention contains a cationic complex of a metal of group VIII and weakly associated with donor-acceptor bond protivoiadie as represented by the following formula

[LyMXz][CA]a< / BR>
cationic complex protivoiadie

where L denotes a ligand containing 1, 2 or 3-communication; M stands for a transition metal of group VIII; X is a ligand containing one-bond and between 0 to 3 links; y = 0, 1, or 2, and z = 0 or 1, and y and z cannot simultaneously both mean 0 and if = 0, then a = 2, and if y = 1 then a = 1; SA means weakly bound anion.

The phrase "weakly coupled donor-acceptor bond the counterion" Osnach substitution of a neutral Lewis base. More specific this expression means an anion which, when performing the function of a stabilizing anion in the catalyst system of the present invention does not transfer an anionic substituent or part of the cation. Protivoiadie is not oxidizing, not recovering, not nucleophilic and relatively inert.

L is a neutral ligand, weakly coordinated to the cation complex of a metal of group VIII. In other words, the ligand is relatively inert and easily replaced in the cationic complex metal penetrating monomer into the growing polymer chain. Suitable non-bonding ligands include monoolefinic C2-C12(for example, 2,3-dimethyl-2-butene), diolefine4-C12(for example, norbornadiene) and aromatic compounds (C6-C20. The preferred ligand L is a chelating bidentate cyclo(C6-C12)diolefin, for example, cyclooctadiene (DPC) or dibenzocycloheptadiene, or an aromatic compound such as benzene, toluene or mesitylene.

The metal of group VIII selected from metals of group VIII of the Periodic system. Preferably M is selected from the group comprising Nickel, palladium, cobalt, platinum, iron and rutin is forming in the cationic complex single-valence metal-carbon (with no links) with metal or (ii) the group, in forming the cationic complex single-valence metal-carbon and 1-3-bonds with the metal. According to (i) the group is associated with a metal of group VIII of the single-bond metal-carbon in the absence of ties. Examples of ligands include:1-C10alkyl such as methyl, ethyl, normal or branched alkyl, such as propyl, butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl and C7-C15aralkyl, such as benzyl. In the case of option (ii) above, the cation contains a hydrocarbon group directly related to the metal single - link metal-carbon and at least one, but no more than three links. Under hydrocarbon group mean group capable of stabilizing cationic complex of a metal of group VIII through education-carbon-metal and from one to three links, which can be conjugated and unconjugated. Representatives of the hydrocarbon groups is3-C20alkenyl, which may be acyclic, monocyclic or polycyclic and may be substituted normal or branched C1-C20alkoxy group, a C6-C15aryloxy group or halogen (ApriI, forming connection and connection or connection of forming at least one olefin-bond with the metal and the contact with the metal from a remote distance from the center carbon atom separated from the olefinic carbon atom, at least two simple carbon-carbon bonds (option iii).

The specialist should be clear that in the absence of ligand L or X (i.e. y -, or z = 0) metal cationic complex is weakly associated with the solvent in which the reaction was carried out. Examples of solvents can be (but are not limited to, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and aromatic solvents such as benzene, toluene, methicillin, chlorobenzene and nitrobenzene and the like. A more detailed discussion of suitable solvents will be conducted below.

Some choices cationic complexes of metals of group VIII of the one-component catalytic systems according to the invention is shown below.

Structure VII illustrates the variant (i), in which the ligand X is a methyl group associated with a single metal-bonding metal-carbon, and the ligand L is cyclooctadiene (DPC), weakly coordinatesin is a palladium or Nickel.

< / BR>
Structure VIII, IX and X illustrate various examples of option (ii), where X is an allyl group, associated with the metal (palladium is shown solely for the purpose of illustration) single-link metal-carbon and at least one but not more than three links.

In structure VIII, L is absent, but aromatic group, creating a three-link, poorly coordinated in relation to palladium metal; X is allyl group, providing single-valence metal-carbon olefinic connection with palladium.

In the structure of IX L means cyclooctadiene (DPC), and X is an allyl group, providing connection of the metal-carbon olefinic connection with palladium.

Structure X illustrates a variation in which the ligand X is an unsaturated hydrocarbon group, providing connection of the metal-carbon conjugate connection and two additional communication with palladium; L is absent.

< / BR>
< / BR>
< / BR>
The substituents R20, R21, R22will be described in detail below.

Patterns XI and XII illustrate examples of option (iii), where L means cyclooctadiene and X is a ligand, providing at least one olefin-bond with the metal of group VIII, at least, two simple bonds of carbon-carbon.

< / BR>
< / BR>
The above-described cationic complexes of a metal of group VIII is associated with weakly coordinating or not coordinating counterion CA-that is relatively inert, subnuclear and provides cationic complex, substantially soluble in the solvent of the reaction mixture. The anion is selected to meet the requirements lability, stability and inertness with respect to the cationic complex of a metal of group VIII in the final sample of the catalyst and give a one-component catalyst according to the invention the solubility in the solvents used in the present invention. Anions, stable in contact with water or acids of Bronsted and without proton acids located on the outer side of the anion (i.e., anionic complexes, not interacting with strong acids or bases), have the necessary stability to qualify them as a stable anion for the catalytic system. The properties of the anion, which is important for maximum lability, include the overall size and shape (i.e., a large radius of curvature) and nucleophiles.

In General a suitable anion may avli the following requirements: (1) the anion should form stable salts with the above-mentioned Lewis acids, acids of Branstad, recovering Lewis acids, protonated Lewis bases, cations of thallium and silver; (2) the negative charge of the anion should be delocalized over the structure of the anion or localized in the nucleus of the anion; (3) the anion should be relatively weakly nucleophilic and (4) the anion should not be a strong reducing agent or oxidizing agent.

Anions that meet these criteria are anions selected from the group comprising Tetra Ga, Al or In; hexafloride P, Sb or As; perforated, propionate and butyrate, hydrogenated perchlorate, toluensulfonate, triftormetilfullerenov and substituted tetraphenylborate substituted in the phenyl ring by fluorine or trifluoromethyl. Selected examples of protivoionov include F4-PF6-, lF3ABOUT3SF3-, SbF6-, SbF5SO3F-AsF6-triptorelin (CF3CO2-), pentafluoropropionate (C2F5CO2-), heptafluorobutyrate (CF3CF2CF2CO2-), perchlorate (lO4-H2O), p-toluensulfonate (p-CH3WITH6H4SO3-and tetraphenylborate having the formula

< / BR>
The catalyst contains-allyl complex of a metal of group VIII with subcoordinator protivoiona. Allyl groups of the cationic complex of the metal are created using compounds containing allyl functional groups associated with the metal atom single carbon-metal bond and olefinic connection. The metal M of group VIII, preferably selected from Nickel and palladium. The most preferred metal is palladium. It was unexpectedly found that such single-component catalysts, in which M is palladium and the cationic complex does not contain other ligands in addition to the allyl functional groups (i.e., Ly=0), show excellent activity in the polymerization of functional polycyclic monomers, such as monomers containing silyl functional group, according to the invention. As discussed above, it should be clear that the catalysts solvated by the solvent in the reaction medium, which may be regarded as a very weak ligand towards the metal of group VIII in the cationic complex.

The substituents R20, R21and R22in allyl group, presented above in structures VIII, IX and XIII, independently of one another, denote VI tert-butyl, C6-C14aryl such as phenyl and naphthyl, WITH7-C10aralkyl such as benzyl, -COOR16, -(CH2)nOR16, Cl and cycloaliphatic radical C5-C6where R16means alkyl WITH1-C5such as methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, and n = 1 - 5.

Any two substituent of R20, R21and R22can be connected to each other to form a cyclic or polycyclic ring structures, but not necessarily. Cyclic ring structure may be carbocyclic or heterocyclic. Preferably any two of the substituent R20, R21and R22together with the carbon atoms to which they are linked, form a ring containing from 5 to 20 atoms. Representatives of the heteroatoms are nitrogen, sulfur, and carbonyl. Examples of cyclic groups with allyl functionality are the following patterns:

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
where R23means hydrogen, a normal or branched alkyl WITH1-C5such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and pentyl, R24means methylcarbamyl and R25means normal or branched alkyl WITH1-C20

One-component catalyst of the above options can be obtained by attaching very halide component metal of group VIII salt, which creates a counterion for subsequently formed cationic complex of the metal. Legirovannoi connection halide of a metal of group VIII, salt, creating protivoiadie and possibly compound containing connection, for example, cyclooctadiene, are combined in a solvent capable of solutionat educated one-component catalyst. When this is used, preferably the same solvent that is introduced into the reaction environment. The catalyst may be pre-formed in the solvent or directly (in situ) in the reaction medium.

Suitable salts that create protivoanemi are any salt capable of anions described above. For example, salts of sodium, lithium, potassium, silver, thallium, and ammonium, in which the anion is selected from PR is 6
, AgPF6, AgSbF6, LiF4, NH4PF6, KAsF6, AgC2F5CO2, AgBF4, gF3CO2, glO4H2Oh, AgAsF6, gF3CF2CF2CO2, AgC2F5CO2, (C4H9)4N(C6F5)4and

< / BR>
The specific catalyst [allyl-PD-cyclooctadiene]+F6-get advanced education very compounds of palladium halide, for example, bis(allyl Pd bromide), which is then subjected to cleavage agent chip off the halogen in the form of salt, creating protivoiadie, i.e., TIPF6in the presence of cyclooctadiene. The reaction scheme, see the end of the description.

After splitting there is only one cyclooctadiene ligand associated two-links with palladium. Allyl functional group is associated with palladium one connection metal-carbon and one connection.

To obtain the preferred one-component catalysts containing compound is allyl metal of group VIII/protivoiadie corresponding structure XIII above, in which M stands for palladium, allylpalladium chloride is combined with the desired counterion forming salt, preferred is ladiesare complex in the form of precipitated silver chloride (AgCl), which can be filtered from the solution. One-component catalyst containing allylpalladium cationic complex/protivoiadie, remains in solution. Palladium is devoid of any ligand, in addition to the allyl functional groups.

Alternative one-component catalyst used in the invention can be represented by the following formula:

Pd[R27CN]4[CA-]2,

where R27independently means a normal or branched alkyl WITH1-C10and CA-means described above protivoiadie.

Another one-component catalytic system for polymers used in the invention corresponds to the formula

EnNi(C6F5)2,

where n = 1 or 2 and E represents a neutral ligand donor 2 electrons. When n=1, E is preferably-Aranova ligand, such as toluene, benzene and mesitylene. When n=2, E means preferably diethyl ether, tetrahydrofuran (THF) and dioxane. The ratio of monomer and catalyst in the reaction medium can vary from about 2000:1 to about 100:1. The reaction can be carried out in a hydrocarbon solvent such as cyclohexane, toluene and podobn the o
With and, more preferably from about 20oWith up to approximately 40oC. Preferred catalysts of the above formula are: toluole(perftoralkil)Nickel, mesitylene(perftoralkil)Nickel, besovic(perftoralkil)Nickel, bis(tetrahydrofuran)bis(perftoralkil) Nickel and bis(dioxane)bis(perftoralkil)Nickel.

Multicomponent systems

Multi-component catalytic system according to the invention contain a source of metal ions of group VIII in combination with one or more ORGANOMETALLIC catalyst and the third component. Socialization choose from organoaluminium compounds, hydrides dialkylamino, dialkylzinc compounds, dialkylamines compounds and alkyllithium connections.

The source of metal ions of group VIII, preferably selected from compounds containing Nickel, palladium, cobalt, iron and ruthenium, most preferably Nickel and palladium. There are no restrictions on the connection of the metal of group VIII, provided that it is a source of catalytically active metal ions of group VIII. Preferably, the compound of the metal of group VIII is soluble or can be soluble in the reaction medium.

Representatives of the ionic ligands, which may be associated with the metal with the formation of the compound of metal of group VIII, are anionic ligands selected from halogen ions such as chlorine, bromine, iodine and fluorine; such halogenated compounds, such as cyanide, cyanate, thiocyanates, hydrides; hydrocarbon anions, such as branched or unbranched1-C40alkyl anions, phenyl anions; cyclopentadienide anions, -allyl groupings; enolate-dicarbonyl compounds such as acetylacetonate, 4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedionato and halogenated acetylacetonates, such as 1,1,1,5,5,5-hexaplar-2,4-pentanedionate, 1,1,1-Cryptor-2,4-pentanedionate; anions of acidic derivatives of oxides of carbon such as carboxylates and halogenated carboxylates (e.g. acetates, 2-ethylhexanoate, neodecanoate,triptoreline and so on) and oxides of nitrogen (e.g., nitrates, nitrites, and so on), bismuth (e.g., bismuthate and so on), oxides of aluminum (e.g., aluminates, etc.), silicon (for example, silicates, and so on), phosphorus (for example, fosfato so on); the ylides; amides; imides oxides; phosphides; sulfides; C6-C24aryloxides,1-C20alkoxides; hydroxides, hydroxyalkyl1-C20; category; oxalates; chelating alkoxides and aryloxides. Palladium compounds can also contain anions such as PF6-, lF3ABOUT3SF3-, SbF6-and compounds corresponding to the formula

Al(R"')-4; (X)-4,

where R"' and X, independently of one another denote halogen atom selected from the group of Cl, F, J and Sh, or a substituted or unsubstituted hydrocarbon group. Representatives of the hydrocarbon groups are alkyl WITH1-C25such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, monodecyl, eicosyl, genacote, docosyl, tricosal, tetracosyl, pentasil and their isomers; C2-C25alkenyl, such as vinyl, allyl, crotyl, butenyl, pentenyl, hexenyl, octenyl, nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecane, Pentecostal and their isomers; C6-C25aryl, such as finitenesses, Neftochim and the like; (C3-C8cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbornyl, 2-norbornyl and the like. In addition to the above-mentioned values x is the radical

< / BR>
The term "substituted hydrocarbon" means a hydrocarbon group, defined above, in which one or more atoms are replaced by halogen atom such as Cl, F, Br and J (for example, as in performanceline radical; hydroxyl; amino; alkyl; nitro; mercapto and the like. Compound of metal of group VIII can also contain cations such as, for example, organoammonium, ORGANOARSENIC, organophosphonate and pyridine compounds corresponding to the formula

< / BR>
where a represents nitrogen, arsenic and phosphorus, and the radicals R28can be independently selected from hydrogen, razvetvlennogo or unbranched alkyl WITH1-C20branched or unbranched, alkenyl C2-C20and cycloalkyl C5-C16for example, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. R29and R30independently from each other selected from hydrogen, branched or unbranched alkyl WITH1-C50 is as defined above; n = 1 to 5, preferably 1, 2 or 3, most preferably n = 1. The radicals R30preferably attached in positions 3, 4 and 5 of the pyridine ring.

It should be noted that the increase in the total number of carbon atoms in the radical R28promotes better solubility of transition metal compounds in organic medium, such as organic solvents and polycyclic monomers. Preferably the radicals R28selected from alkyl groups WITH1-C18and the total number of carbon atoms in all of the radicals R2815 - 72, preferably 25 to 48, more preferably 21 - 42. The radical R21preferably selected from normal or branched alkyl WITH1-C50more preferably, alkyl WITH10-C40. The radical R30preferably selected from normal or branched alkyl WITH1-C40more preferably the alkyl WITH2-C30.

Specific examples organoammonium cations include: tridodetsilamin, methyltryptamine, Tris(tridecyl)ammonium and trioctylamine. Specific examples ORGANOARSENIC and organophosphonic cations include tridodetsilamin and phosphonium, m the e pyridinium cations include eicosyl-4-(1-butylpentyl)pyridine, docosyl-4-(13-pentasil)pyridine and eicosyl-4-(1-butylpentyl)pyridine.

Suitable neutral ligands, which may be associated with the transition metal is palladium, are olefins; acetylene; carbon monoxide; nitric oxide; nitrogen-containing compounds such as ammonia, alkalization, alkilizotsyanat, allylisothiocyanate; pyridine and derivatives of pyridine (for example, 1,10-phenanthroline, 2,2'-(dipyridyl), 1,4-dialkyl-1,3-Diisobutylene, 1,4-diaryl-1,3-Diisobutylene and amines, such as represented by formulas

N(R31)3,

< / BR>
< / BR>
where the radicals R31independently denote a hydrocarbon or substituted hydrocarbon radical, as defined above, and n = 2 - 10. Urea, NITRILES, such as acetonitrile, benzonitrile and their halogenated derivatives; organic ethers such as dimethyl ether of diethylene glycol, dioxane, tetrahydrofuran, prandially ether, diethyl ether, cyclic ethers, such as cyclic oligomers of diethylene glycol; organic sulfides such as simple thioethers (diethylsulfide); arsine; STIBINE; phosphines, such as triarylphosphine (e.g., triphenylphosphine), trialkylphosphine (for example, trimethylphosphine, triethylphosphine, tripropyltin, trypan the but)propane, bis(diphenylphosphino)butane, (S)-(-)2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and bis(2-diphenylphosphinoethyl)phenylphosphine; phosphine oxides, halides of phosphorus; phosphites of the formula

P(OR31)3,

where R31independently means a hydrocarbon or substituted hydrocarbon radical, such as described above; oxychloride phosphorus; phosphonates; phosphonites; posterity; ketones; sulfoxidov, such as alkylsulfonic1-C20; arylsulfatase C6-C20; alkarylsulphonate7-C40and similar. It should be clear that the above-mentioned neutral ligands can be used as a possible third component, as described below.

Examples of transition metal compounds of group VIII, suitable as a source of metal ions of group VIII are: ethylhexanoate, palladium, TRANS-dl2(h3)2, bis(triptorelin) palladium (II) bis(acetylacetonate) palladium (II) 2-ethylhexanoate, palladium (II), Pd(acetate)2(h3)2, bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, palladium (II), monoacetylated(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palla is benzonitrile) palladium (II), the palladium acetylacetonate, bis(acetonitrile)dichloride, palladium bis(dimethylsulfoxide)dichloride, palladium; Nickel acetylacetonates, Nickel carboxylates, Nickel dimethylglyoxime, Nickel ethylhexanoate, NiCl2(PPh3)2, NiCl2(PPh2CH2)2(P(cyclohexyl)3)H-Ni(Ph2P(C6H4)CO2), (h3)(C6H5)Ni(PH2RSN= C(O)PH), bis(2,2,6,6-tetramethyl-3,5-heptanedionato) Nickel (II) tetrahydrate hexafluoroacetylacetonate Nickel (II) dihydrate triftoratsetilatsetonom Nickel (II) acetylacetonate tetrahydrate Nickel (II), nickelocene, acetate Nickel (II), Nickel bromide, Nickel chloride, dichlorophenylisocyanate, Nickel lactate, Nickel oxide, tetracarbonyl Nickel, bis(allyl)Nickel, bis(cyclopentadienyl)Nickel, neodecanoate cobalt acetate cobalt (II) acetylacetonate, cobalt (II), acetylacetonate cobalt (III) benzoate, cobalt (II), cobalt chloride, cobalt bromide, dichloracetate cobalt stearate, cobalt (II), tetrafluoroborate cobalt (II), iron naphthenate, iron chloride (II) chloride iron (III) bromide, iron (II) bromide iron (III) acetate, iron (II) acetylacetonate Fe (III), ferrocene; ruthenium Tris(triphenylphosphine) dichloride, ruthenium Tris(triphenylphosphine) hydridable the rhodium chloride, rhodium Tris(triphenylphosphine) trichloride.

Organoaluminium connection multi-component catalytic systems according to the present invention can be represented by the formula

AIR323-xQx,

where R32independently mean a normal or branched alkyl WITH1-C20, aryl (C6-C24aralkyl7-C20cycloalkyl3-C10; Q means halide lamp or pseudohalide a compound selected from chlorine, Florina, bromine, iodine, normal or branched C1-C20alkoxy, C6-C24aryloxy, and x = 0 to 2.5, preferably 0 to 2.

Representatives organoaluminium compounds include trialkylamine, such as trimethylaluminum, triethylaluminum, Tripropylamine, triisopropanolamine, triisobutylaluminum, three 2-methylbutylamine, three-3-methyl-butylamine, three 2-methylpentylamine, three 3-methylpentylamine, three 4-methylpentylamine, three 2-methylhexanamine, three 3-methylhexanamine, trioctylamine, Tris-2-norbornanamine and the like; dialkylamino halides, such as dimethylaluminum chloride, diethylaluminum chloride, Diisopropylamine chloride, diisobutylaluminium holdem is Alumini diode, propylene dichloride, Isopropylamine dichloride, bucillamine dichloride, isobutylamine dichloride and the like; alkylamines protragonist halides, such as methylamine polutoraglazy, ethylaluminum polutoraglazy, Propylamine polutoraglazy, isobutylamine polutoraglazy and the like.

Hydrides dialkylamide choose from normal and branched hydrides (C1-C10) dialkylamide. It is preferable hydride diisobutylaluminum.

Connection dialkylzinc choose from normal and branched compounds (C1-C10)dialkylzinc. Preferred is diethylzinc. Connection dialkylamide choose from normal and branched (C1-C10)-dialkylamide. Most preferred is dibutylamine. Connection alkylate choose from normal and branched compounds (C1-C10)-alkylate. It is preferable utility.

Hydrides dialkylamide choose from normal or branched hydrides (C1-C10)-dialkylamide. It is preferable hydride diisobutylaluminum.

Dialkylzincs connection choose tilting. Dialkylamino compounds are selected from normal or branched (C1-C10)dialkylamide. It is preferable dibutylamine. Alkylate choose from normal or branched compounds (C1-C10)-alkylate. Preferred is utility.

According to the present invention, the catalytic system obtained from a source of metal ions of group VIII, use with one or two components selected from the group comprising compounds - socializaton and connection of the third component.

Examples of the third component is a Lewis acid such as F3apirat, TiCl4, SbF5, Tris(perftoralkil)boron, l3IN(OCH2CH3)3; strong acid Bronsted, such as geksaftorpropena acid (HSbF6), hydrate HPF6, triperoxonane acid (CF3CO2H) and FSO3HSbF5N2C(SO2CF3)2CF3SO3N and paratoluenesulfonyl acid; halogenated compounds such as hexachloroacetone, HEXAFLUOROACETONE, 2,2,3,4,4-pentachlorobutane ether 3-butenova acid, hexapetala acid, hexafluoroisopropanol and chloranil, i.e. the compound of the formula

WITH12and cycloaliphatic diolefins C6-C12such as butadiene, cyclooctadiene and norbornadiene.

The acidity of strong acids Branstad, can be assessed by determining their functions Hammett acidity of Howhose definition can be found in Advanced Inorganic Chemistry, F. A. Cotton and G. Wilkinson, Wiley-lnterscience, 1988, p. 107.

As noted above, the neutral ligands can be used as an optional third component with an electron-donor properties.

According to one variant embodiment of the invention the multicomponent catalyst system may be prepared jointly by mixing the catalyst components, i.e., compounds of a metal of group VIII, connection - socializaton and a third component, in the case of the latter, in a hydrocarbon or halogenated hydrocarbon solvent, followed by mixing the catalytic system obtained in the process of pre-mixing, with the components of the reaction medium containing at least one polycyclic monomer with a strong functional group. Alternatively, (in the case of a possible third component) any two components of the catalytic system can bitou environment. The remaining component of the catalyst can be introduced into the reaction medium before or after adding the pre-mixed components.

According to another variant of the multi-component catalyst system can be prepared in situ by the joint mixture of all catalyst components in the reaction medium. The order of mixing is not important.

According to one variant of multi-component catalytic system of the present invention a typical catalytic system contains a salt of a transition metal of group VIII, for example, Nickel ethylhexanoate, organoaluminium connection, for example, triethylamine, and the third mixture components, for example, F3epirate and hexaferrites acid (HSbF6in the preferred molar ratio of Al/F3apirat/Ni/acid 10:9:1:0,5-2. The reaction scheme is as follows:

1. Ethylhexanoate, Nickel + HSbF6+ 9F3apirat + 10 triethylaluminium -->Active catalyst

According to another variant of the multi-component catalytic system according to the invention a typical catalytic system contains a salt of Nickel, for example, ethylhexanoates, organoaluminium connection, for example, triethylaluminium, the BR>
2. Ethylhexanoate, Nickel + Tris(perftoralkil)boron + triethylaluminium -->Active catalyst

In the next version of multi-component catalytic system according to the invention the third component is a halogenated compound selected from various halogenated activators. Typical catalytic system contains a salt of a transition metal of group VIII, organoaluminium and as a third component of halogenated compound, as shown below

3. Ethylhexanoate, Nickel + triethylamine + chloranil -->Active catalyst

In yet another embodiment, multi-component catalytic system according to the invention socialization missing. The catalytic system contains a salt of metal of group VIII (e.g., dimer 3-allylacetamide and a Lewis acid (for example, Tris(PERFLUORO-phenyl)boron) as shown below:

4.3-Allergically + Tris(perftoralkil)Bor --> Active catalyst

We found that the choice of metal of the group VIII metal-containing cationic complex both single-and multi-component catalytic systems according to the invention affects the microstructure and physical properties of the obtained polymers. For example, we have found that palladium categotry degree of regularity. The polymers obtained in the presence of catalytic systems and type 2 in the presence of one-component catalytic systems of equationsnNi(C6F5)2as described above, contain, as we hope, only the repeating unit attached to the polymer chain in position to 2.7. These polymers also contain performanceline group at least at one end of the polymer chain. In other words, performanceline group can be located at one end or at both ends of the polymer. In any case, performanceline groups are connected by covalent bonds and are lateral relative to the end of polycyclic repeating parts of the main polymer chain. Reactions using single and multi-component catalysts according to this invention is carried out in an organic solvent which has no adverse effect on the catalytic system and which is a solvent for the monomer. Examples for organic monomers are aliphatic non-polar hydrocarbons such as pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, chlorobenzene, o-dichlorobenz the Republic of Moldova, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane and 1-chloropentane.

The choice of solvent for the reaction is performed with the consideration of several factors, including the type of the selected catalyst and the type of polymerization (suspension polymerization or polymerization in solution). For most of the catalysts according to the invention, the preferred solvents are chlorinated hydrocarbons such as methylene chloride and 1,2-dichloroethane, and aromatic hydrocarbons such as chlorobenzene and nitrobenzene. Simple hydrocarbons are less preferred due to less conversion of monomers with functional groups NB-type. Unexpectedly, we have discovered that some catalytic systems, most notably, multicomponent catalysts based on compounds of a metal of group VIII halide and alkylamine, especially diploidy monoalkylamines (for example, dichloroethylene) and catalysts of type 2, above, also give excellent results (high degree of conversion of monomer) when conducting the reaction in heptane, cyclohexane and toluene.

t 20:1 - 100 000:1, preferably 50:1 to 20,000:1, and most preferably 100:1 to 10000:1.

In multi-component catalytic systems, the molar ratio of metal socializaton (for example, aluminum, zinc, magnesium and lithium) and a metal of group VIII is less than or equal to 100:1, preferably less than or equal to 30:1 and most preferably less than or equal to 20:1.

The third component is used in a molar ratio of metal of group VIII of 0.25:1 to 20:1. In the case of using the acid as a third component, the molar ratio of the acid and a metal of group VIII is less than or equal to 4:1, preferably less than or equal to 2:1.

The polymerization reaction of the present invention is usually carried out at temperatures from (-100)oWith up to 120oC, preferably from (-60)oWith up to 90oS, most preferably, from (-10)oWith up to 80oC.

The optimum temperature of the present invention depends on a number of changing factors, primarily on the choice of catalyst and diluent of the reaction mixture. Therefore, for any particular polymerization process, the optimum temperature is determined experimentally, taking into account the mentioned variables.

dinusha palladium catalyst with a growing polymer chain, particularly sustainable. This is the main advantage in the polymerization of polycyclic monomers containing acid labile groups, ester and carboxyl functional groups as palladium catalysts are particularly resistant to such functional groups. However, this stability, on the other hand, significantly complicates the removal of the palladium catalyst from the resulting polymer. When developing such new components we have found that the relationship palladium-carbon is conveniently cleaved (by deposition of palladium, which can be removed by filtration or centrifugation) when using carbon monoxide, preferably in the presence of a protonic solvent, such as alcohol, moisture, or carboxylic acid.

The polymers obtained by the method in accordance with the invention have a molecular mass (Mnfrom about 1000 to about 1,000,000, preferably from about 2000 to about 700000, and more preferably from about 5,000 to 500,000 and most preferably from about 10,000 to about 50,000.

The molecular weight of the polymer can be adjusted by changing the quantitative ratio of the catalyst to the monomer, i.e., by changing the ratio of the initiator to monogenoidea polymerization process in the presence of a transfer agent in the chain. Macromonomer and oligomers containing from 4 to 50 repeating units can be obtained in the presence of the agent chain transfer announcing the library, selected from compounds containing terminal olefinic double bond between adjacent carbon atoms in which at least one of the adjacent carbon atoms has two related hydrogen atom. Agent chain transfer are connections excluding styrene (not styrene), simple vinyl esters (not vinyl ethers, and conjugated diene. Under connections, non-styrene and simple vinyl esters (not styrene and not simple vinyl ethers), mean compounds having the following structures, which are excluded from transfer agents circuit according to the invention

< / BR>
< / BR>
where a represents aromatic substituent and R is a hydrocarbon radical.

The preferred agents of the transmission circuit according to the invention are compounds corresponding to the formula below,

< / BR>
where R1and R2independently from each other denote hydrogen, a branched or unbranched alkyl WITH1-C40branched or unbranched of alkenyl2-C40, halogen or a group.

From predstave, ethylene, propylene, 4-methyl-1-penten, 1-hexene, 1-mission, 1,7-octadien and 1,6-octadien or isobutylene.

Although the optimal conditions to achieve any predetermined result should be determined experimentally by the specialist, taking into account all the above factors, there are some General guidelines that can be used in appropriate cases. We found that, in General, olefins (e.g. ethylene, propylene, 1-hexene, 1-mission 4-methyl-1-penten) are the most effective agents of chain transfer, compared to 1.1-diamesinae olefins, which is less efficient. In other words, ceteris paribus, to achieve the desired molecular weight will require a much higher concentration of isobutylene than using ethylene. Styrene olefins, conjugated diene and simple vinyl ethers are not effective agents of chain transfer due to their tendency to polymerization with the catalyst described above.

The transfer agent of the circuit can be used in an amount of from about 0.10 to say. % to more than 50 mol.% the number of moles of all monomers NB-type. Preferably the agent chain transfer is used in the amount of 0.10 to 10.0 mol.% the tees, the efficiency of the transfer agent of the circuit and the desired end groups, the concentration of transfer agent of the circuit can be more than 50 mol. % (calculated on the total number of monomers present with NB-functionality), for example, 60 to 80 mol.%. To obtain low molecular weight products according to the invention, such as oligomers and macromonomers, you may need a higher concentration of the agent chain transfer (for example, greater than 100 mol. %). It is important to note that, surprisingly, even such high concentrations of agents, chain transfer (except isobutylene) not copolymerized in the main chain of the polymer, and are included in the form of end groups of each polymer chain. The method according to the invention provides that in addition to the transfer agents of the chain ends of the polymer chain can be enabled end-olefinic group.

The polymers of the present invention, obtained in the presence of a transfer agent chains have a molecular mass (Mnfrom about 1,000 to about 500,000, preferably from about 2,000 to about 300,000, and most preferably from about 5,000 to about 200,000.

Photoresist compositions of the present invention described contain polycyclic compositions, the solvent and generating acid photo is composition. A suitable dissolution inhibitor is tert - bootyhole (J. V. Crivello et al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater., 1996, 8, p. 376-381).

Upon irradiation of the photosensitive acid generator generates a strong acid. Suitable generating acid photoinitiator include triflate (for example, triphenylsulfonium triflate), pyragollole (for example, trimethylol pyragollole); onieva layers, such as triarylsulfonium and dearylation hexafluoroantimonate, hexafluoroarsenate, triftoratsetata; esters of hydroxyimino,, bis-sulfonyl-diazomethane, sulphonate esters nitrosamines benzyl alcohol and naphthoquinone-4-diazide. Other suitable generating acid photoinitiator described Reichmanis et al., Chem. Mater., 1991, 3, p. 395. Compositions containing triarylsulfonium or dialylsulphide salts are preferred because of their sensitivity to deep UV (193 nm to 300 nm) and very high resolution images. Most preferred are unsubstituted and symmetrical or unsymmetrical substituted diarylethene or triarylsulfonium salt. The content of generating acid photoinitiator component is about 1 to 100 wt.% polymerase invention does not necessarily contain a sensitizer, able to sensitize generating acid photoinitiator in relation to the longer-wavelength radiation in the region from mid-wave UV radiation to visible light. Depending on the purpose of such sensitizers include polycyclic aromatic compounds such as Perini and Perlane. Sensitization of generating acid photoinitiator well known and described in patents US 4250053, 4371605 and 4491628, shown here as a reference. The invention is not limited to a specific class of sensitizers and generating acid photoinitiator.

The present invention relates also to a method of producing on a substrate a positive resistin images, comprising the stage of: a) coating the substrate with a film containing resistol composition positive tone according to the invention, b) irradiation of the film by the radiation forming the image, and C) the manifestation of the image.

The first stage comprises coating the substrate with a film obtained from

positive resistol composition dissolved in a suitable solvent. A suitable substrate is made of silicone, ceramic, polymer, etc., Suitable solvents include methyl acetate ester of propylenglycol the methods of coating, such as centrifugation or sputtering, or doctor blade. Preferably, before the irradiation of the film is heated at an elevated temperature from about 90oWith up to 150oWith in a short period of time of about 1 min In the second stage of the process the film is irradiated by the radiation forming the image, for example, electron beams or, preferably, electromagnetic radiation, such as UV or x-ray radiation, preferably UV radiation, for example, with a wavelength of about 193 nm to 514 nm, preferably, from about 193 nm to 248 nm. Suitable radiation sources are: mercury, mercury/xenon, and xenon lamps, x-ray and electron beam. Generating acid photoinitiator absorbs radiation for education in the irradiated areas of the free acid. The free acid breaks down the side of the acid-labile groups of the copolymer, resulting copolymer becomes of the inhibitor dissolved in the power of dissolution, increasing, thus, the solubility of the irradiated resistol composition in an aqueous solution of the base. It was unexpectedly found that irradiated resista composition readily soluble in an aqueous solution of the base. This solubility ( mass parts of norbornene monomer, containing functional carboxyl group. Preferably, after irradiation, the film is again heated at a high temperature of approximately 90oWith up to 150oWith in a short period of time of about 1 min

The third stage consists in obtaining a positive tone image using a suitable solvent. Suitable solvents include, preferably, an aqueous solution of the base, nestorgames metal ions, such as hydroxide of Tetramethylammonium or choline. The composition according to the invention creates a high contrast positive image with smooth walls. Uniquely, the solubility of the composition according to the present invention can be varied by simply changing the composition of the copolymer.

The present invention also relates to blocks of integrated circuits, such as an integrated chip, multichip module integrated circuit, or a circuit Board manufactured by the method according to the present invention. The unit integrated circuits contains a diagram obtained on the substrate in the steps: a) coating the substrate with a film obtained from a positive resistol compositions according to the invention; b) exposure of the film by the radiation forming the image; C) the manifestation, known methods.

After disclosure of the substrate at locations of the disclosure can be obtained, the image schema coating of conductive material, such as conductive metals, using known techniques, such as deposition from the gas phase, sputtering, covering the metal, chemical deposition from the gas phase or laser deposition. The surface of the film may be subjected to milling to remove excess conductive material. In the manufacturing process diagrams in a similar manner to the substrate can be printed dielectric materials. In the process of getting a p or n doped circuit transistors in the substrate can be implanted inorganic ions, such as ions of boron, phosphorus and arsenic. Other methods of obtaining schemes well known to the specialist.

The following examples are described methods for the preparation and use of certain compositions according to the invention. Detailed description serves as an example of the invention, at the time, as a more General methods of preparation described above. Examples are provided only to illustrate and not limit the scope of the invention.

As noted above, the photoresists used for is determined by the wavelength of the imaging radiation, the sensitivity of the photoresist and the ability to withstand the etching conditions in which the liberated areas of the substrate creates an image. Photoresists are most often used in consumer form, when the photoresists is etched in the areas not exposed to radiation (for positive photoresists), and the substrate is etched in the areas of exposure. Because the photoresist is an organic material, and the substrate is a typical inorganic material, the photoresist is inherently has a higher etching rate in the process of reactive ion etching, which requires increasing the thickness of the photoresist in comparison with the substrate material. The lower the etching rate of the substance of the photoresist, the thinner should be photoresist layer. The result can be achieved with high resolution images. Therefore, the smaller the rate reactive ion etching of the photoresist, so it is more attractive from a technological point of view. The etching rate is primarily determined by the main polymer chain, as shown below for process chlorine plasma etching, which represents a commonly used method of reactive ion is of the monomer to the catalyst (see table. A).

Polymers 1 and 2 are initially aromatic, whereas the polymer 3 obtained by copolymerization with a small amount of acrylate, which increases the etching rate of the polymer. Polymer 4 is completely based on the acrylate to ensure transparency at 193 nm (aromatic rings give the material opacity in this area, so there is no practically acceptable resistin materials for 193 nm based on traditional novolaks or p-hydroxystyrene). These polymers etching rate almost doubled. Polymer 5 is the etching rate even lower than the standard photoresist materials (1 and 2), in addition to transparency at 193 nm. Consequently, the main chain of the polymer 5 (additive cyclic olefin), obtained in the presence of multicomponent Nickel catalyst according to the invention, is an achievement compared to all previous attempts described in the technical literature, to obtain a resist operating at 193 nm at the characteristics of reactive ion etching, comparable with commercial materials irradiated at longer wavelengths. Indeed, the additive cyclic olefinic. It is known from literature (N. Gokan, S. Esho and Y. Ohnishi, J. Electrochem. Soc., 1983, 130 (1), R. 143) that higher values of s/N reduces the rate of etching of polymeric materials. Under this assumption, the etching rate of the polymer 5 was supposed to be between the etching rate of the systems on the aromatic based and acrylate systems. It is amazing that the additive cyclic olefin exhibits a super-resistant to etching even in comparison with aromatic systems.

Example 1. In a glass tube, with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add tert-butyl ester of 5-norbornene-carboxylic acid (Carbo-tert-butoxycarbonyl) (2.0 g, 10,3 mmol, Exo, endo 44/56). To this mix the monomer at room temperature is added dropwise within 30 min a solution of the catalyst obtained by the addition of dimer3-allylpalladium chloride (38 mg, 103 μmol) in chlorobenzene (5 ml) to hexafluoroantimonate silver (99 mg, 290 μmol) in chlorobenzene (5 ml), the mixture is then filtered through a Millipore filter (to remove the precipitated silver chloride). The reaction is performed within 36 hours By this time, the reaction mixture gelatinized, becoming transparent W is with excess methanol and dried. The polymer yield 1.5 g (75%). The presence of the monomer with aromatic groups in the polymer is confirmed by infrared analysis shows a strong band at 1728 cm-1(C=0 band), 1251 cm-1(C-O-C band) and 1369 cm-1and 1392 cm-1(characteristics of the tert-butyl groups), and the absence of unconverted monomer - proton NMR. Found the molecular weight of the polymer (Mw) 22 500. Thermogravimetric analysis (TGA) in nitrogen atmosphere (heating rate of 10oC/min) indicates thermal stability of the polymer up to about 210oAnd then the loss of approximately 28% by weight at 260oWith (manifested in the loss of the tert-butyl groups in the form of isobutene with getting homopolymer 5-norbornanamine acid) and degradation of the polymer (a loss of 90% of total mass) at about 400oC.

Example 2. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add norbornene (0.8 g, 8.6 mmol), 1,2-dichloroethane (8 ml) and tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (0.2 g, 1 mmol, Exo, endo 44/56). To this stirred solution at ambient temperature was added Nickel ethylhexanoate (3 Microm), tripartition (23 m is the iMER less than 10 C. After 60 min the reaction the contents of the reactor dissolved in cyclohexane, and poured into excess methanol. The polymer was washed with excess methanol and dried overnight in a vacuum oven at 80oC. the polymer Yield was 0.9 g (90%). Found by the method of gel chromatography the molecular weight of the polymer is equal to 535000 (Mwdegree from polydispersity 4,7.

Example 3. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (2.2 g, 11.3 mmol, Exo, endo 44/56). To this mix the monomer at room temperature was added a catalyst solution obtained by adding dimer 3-allylpalladium chloride (29 mg, 74 μmol) in dichloroethane (6 ml) to tetrafluoroborate silver (61 mg, 311 μmol) in dichloroethane (6 ml) for 30 min followed by filtration through a Millipore filter (to remove the precipitated silver chloride). After the reaction for 36 h, the mixture gelatinase, the formation of clear yellow gel. After adding the gel to the excess of methanol, the polymer precipitates as a white powder. The polymer was washed with excess methanol and is confirmed by infrared analysis, showing strong bands at 1728 cm-1(C=0 band), 1251 cm-1(C-O-C band) and 1369 cm-1and 1392 cm-1(characteristics of the tert-butyl groups), and the absence of unconverted monomer or carboxyl functional groups (proton NMR and IR). Found molecular weight polymer (MW) equal 54100. Thermogravimetric analysis (TGA) in nitrogen atmosphere (heating rate of 10oC/min) shows thermal stability of the polymer up to about 210oAnd then a loss of about 29% by weight at 250o(Which indicates the loss of the tert-butyl groups in the form of isobutene education homopolymer 5-norbornanamine acid) with subsequent degradation of the polymer (80% loss of weight) at about 400oC.

Example 4. In a glass tube with a capacity of 100 ml, equipped with a covered Teflona mixing rod, add norbornene (1,16 g, 12.3 mmol), 1,2-dichloroethane (50 ml) and tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (0.6 g, 3.1 mmol, Exo, endo 44/56). To this stirred solution at ambient temperature was added palladium bis(2,2,6,6-tetramethyl-3,5-pentadione) (31 mmol), tripartition (279 mmol). After 16 h the reaction the contents of the reactor pouring is SUP>C. the polymer Yield was 0.54 g (31%).

Example 5. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (4.4 g, 22.7 mmol, Exo, endo 44/56). To this mix the monomer at room temperature, add a solution of the catalyst obtained by adding dimer 3-allylpalladium chloride at 41.5 mg, 113 μmol) in dichloroethane (7 ml) to tetrafluoroborate silver (42 mg, 215 μmol) in dichloroethane (7 ml) for 30 min followed by filtration through a Millipore filter (to remove the precipitated silver chloride). Then the reaction mixture is heated on an oil bath at 75oC. After 90 min is found that the mixture hardened into a gray polymer mass. The mass is dissolved in acetone to obtain temnookrashennaya solution. Through the solution for 30 min bubbled gaseous carbon monoxide, resulting in a richly deposited finely ground black precipitate of metallic palladium and possibly other residues of catalyst). The precipitate is removed by centrifugation, and this process is repeated two more times. In conclusion, the obtained colorless solution is filtered che is collected by centrifuge and dried overnight to obtain a copolymer in the form of a white powder (2,21 g, 50%). Thermogravimetric analysis under nitrogen (heating rate 10oC/min) shows thermal stability of the polymer up to about 210oAnd then the loss of mass of about 28% at 260o(Pointing to the loss of the tert-butyl groups in the form of isobutene with getting homopolymer 5-norbornanamine acid) with subsequent degradation of the polymer (a loss of 90% of total mass) at approximately 400oC. Molecular mass Mn= 3300 g/mol and Mw=6 900 g/mol (obtained by the method of gel chromatography in tetrahydrofuran (THF, polystyrene standards).

Example 6. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add pure Exo-isomer of tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (0.6 g). To this mix the monomer at room temperature, add a solution of the catalyst obtained by adding dimer3-allylpalladium chloride (30 mg) in dichloroethane (10 ml) to hexafluoroantimonate silver (50 mg) in dichloroethane (20 ml) for 30 min followed by filtration through a Millipore filter (to remove the precipitated silver chloride). After 15 h the reaction mixture to the dry, the polymer yield 0.5 g (85%). Found molecular weight polymerw= 46900 and a polydispersity of 2.4.

Example 7. In a glass tube with a capacity of 100 ml, equipped with a covered Teflona mixing rod, add norbornene (4,01 g of 42.6 mmol), 1,2-dichloroethane (50 ml) and tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (2 g, or 10.3 mmol, Exo, endo mixture). To this stirred solution at room temperature, add a solution of the catalyst obtained by the interaction of the dimer3-allylpalladium chloride (10 mg, 27,3 µmol) hexafluoroantimonate silver (19.6 mg, 57 μmol) in 1,2-dichloroethane (3 ml) for 30 min followed by filtration through a microporous filter. After 20 h the reaction the contents of the reactor was poured into excess methanol. The polymer was washed with excess methanol and dried. The polymer yield 4,15, Found the value of the molecular weight of the copolymer, determined by means of gel chromatography, Mw= 618000 with polydispersity 7,1.

Example 8. In a glass tube with a capacity of 100 ml, equipped with a covered Teflona mixing rod, add norbornene (3.75 g, 39.8 mmol), 1,2-dichloroethane (50 ml) and tert-butyl methyl ether is the reception to the solution at room temperature is added palladium ethylhexanoate (12 μmol), Tris(perftoralkil)boron (108 mmol) and triethylamine (120 μmol). After 72 h of reaction the reactor is poured into an excess of methanol. The polymer was washed with excess methanol and dried, re-dissolved in chlorobenzene and precipitated with excess methanol, filtered and washed with methanol before the final drying in a vacuum oven overnight at 80oC. the Yield of copolymer of 1.66, the Molecular weight of the copolymer, determined by means of gel chromatography Mw = 194000 with a polydispersity of 2.3. The presence in the copolymer of the monomer with ether groups is confirmed by infrared analysis showed the bands at 1730 cm-1(C=0 band) and 1154 cm-1(C-O-C band) in the absence of unconverted monomer (proton NMR).

Example 9. In a glass tube with a capacity of 100 ml, equipped with a covered Teflona mixing rod, add 1,2-dichloroethane (25 ml) and tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (10 g, 51,5 mmol, Exo, endo mixture). To this stirred solution at room temperature, add a solution of the catalyst obtained by the interaction of the dimer 3-allylpalladium chloride (82 mg, 223 μmol) hexafluoroantimonate silver (200 mg, 581 μmol) tion of the reaction the contents of the reactor was poured into excess methanol. The polymer was washed with excess methanol and dried. The output of homopolymer 4,5,

Example 10. In a glass tube with a capacity of 100 ml, equipped with a covered Teflona mixing rod, add 1,2-dichloroethane (50 ml), tert-butyl ester 5-norbornanamine acid (Carbo-tert-butoxycarbonyl) (5 g, from 25.8 mmol, Exo, endo mixture) norbornene (0,82 g, 8,7 mmol) and 5-triethoxysilane (of 0.47 g, 1.8 mmol). To this stirred solution at room temperature, add a solution of the catalyst obtained by the interaction of the dimer3-allylpalladium chloride (to 47.2 mg, 128 μmol) tetrafluoroborate silver (138 mg, 700 μmol) in 1,2-dichloroethane (10 ml) for 30 min followed by filtration through a microporous filter. After 48 h of reaction the reactor is poured into an excess of methanol. The polymer was washed with excess methanol and dried. The output of thermopolymer of 5.3, the Value of molecular weight, obtained by the method of the gel chromatography, 39900 (Mw) if polydispersity 3,2.

Example 11. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, type of 7.25 g (37.5 mmol) of tert-butyl methyl ether norbornene, and 1.9 g (12.5 mmol) of methyl evennou tube supplied coated with Teflonmixing rod load 0,0365 g (0.1 mmol) of the dimer3-allylpalladium chloride (resulting in a ratio of monomer to catalyst 500:1) and 2 ml of dichloroethane. In another 10 ml glass test tube download 0,0344 g (0.1 mmol) hexafluoroantimonate silver and 2 ml of dichloroethane. The catalyst solution is prepared by mixing dimer allylpalladium chloride solution hexafluoroantimonate silver inside of the box with a dry atmosphere. There is immediate precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The active solvent yellow catalyst are added to a solution of the monomer syringe, and the reaction mixture stirred for 20 h at 60oC. any significant increase in viscosity is not observed, but from the resulting solution is precipitated solid. The solution is cooled, concentrated in a rotary evaporator and precipitated in hexane to obtain a white polymer. Output 2.3 g, 26%. The polymer is dried in vacuum at room temperature and determine its molecular weight by the method of gel chromatography in tetrahydrofuran with polystyrene standards. The found value of molecular mass Mn= 1950 g/mol, and a small amount of acid - the product of hydrolysis of tert-butyl methyl ether.

Example 12. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add 2,42 g (12.5 mmol) of tert-butyl methyl ether norbornene, 5.7 g (37.5 mmol) of methyl ether norbornene, 50 ml of freshly distilled dichloromethane, and the solution Tegaserod in argon atmosphere. A 10 ml glass tube, equipped with a covered Teflona mixing rod, load 0,0365 g (0.1 mmol) of the dimer allylpalladium chloride, when the ratio of monomer to catalyst 500:1, and 2 ml of dichloroethane. In another 10 ml glass test tube download 0,0344 (0.1 mmol) of hexafluoroaluminate silver and 2 ml of dichloroethane. The catalyst solution is prepared by mixing a solution of the dimer allylpalladium chloride solution hexafluoroantimonate silver inside of the box with a dry atmosphere. There is immediate precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The active solvent yellow catalyst are added to a solution of the monomer syringe, and the reaction mixture stirred for 20 h at 60oC. any significant increase in viscosity is not observed, but from the solution is deposited solids. Ihad 2,05 g, 25%. The polymer is dried in vacuum at room temperature and determine its molecular weight by the method of gel chromatography in tetrahydrofuran with polystyrene standards. The found value of molecular mass Mn=1440 g/mol and Mw=2000 g/mol.1H-NMR indicates the presence of both methyl and tert-butyl methyl ether norbornene, and a small amount of acid - hydrolysis product tert-butyl ether.

Example 13. In a glass tube with a capacity of 25 ml, is supplied coated with Teflona mixing rod, add 2 g (7,94 mmol) of pure bicyclo[2.2.1]hept-5-ene-Exo-2-tert-butyl-Exo-3-methyl ether dicarboxylic acid, and then 15 ml of freshly distilled methylene chloride and 10 ml of methanol, and the solution Tegaserod in argon atmosphere. A 10 ml glass tube, equipped with a covered Teflona mixing rod, load 0,00588 g (0,0158 mmol) of the dimer 3-allylpalladium chloride at a ratio of monomer to catalyst 500:1, and 2 ml of methylene chloride. In another 10 ml glass test tube download 0,0108 g (0,0312 mmol) hexafluoroantimonate silver and 2 ml of methylene chloride. The catalyst solution is prepared by mixing a solution of the dimer3-allyl is medlenno the precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The active solvent yellow catalyst are added to a solution of the monomer syringe at 50oC, and the reaction mixture stirred for 16 h at room temperature. Any significant increase in viscosity is not observed, and the solution is filtered through a 0.5 micron filter, and then concentrated in a rotary evaporator. A viscous solution is dissolved in methanol and precipitated in a mixture of methanol with water to obtain a white solid. Yield 65%. Found the value of the molecular weight (determined by means of gel chromatography in tetrahydrofuran with polystyrene standards) Mn=10250 g/mol and Mw= 19700 g/mol.1H-NMR indicates the presence of both methyl and tert-butyl methyl ether norbornene.

Example 14. In a glass tube with a capacity of 25 ml, is supplied coated with Teflona mixing rod, add a 3.06 g (12.8 mmol) of pure diethyl ether bicyclo[2.2.1]hept-5-ene-Exo, Exo-2,3-dicarboxylic acid, 2.5 g (12.8 mmol) of tert-butyl methyl ether norbornene, and then 15 ml of freshly distilled methylene chloride and 10 ml of methanol, and the solution Tegaserod in argon atmosphere. A 10 ml glass is the iMER allylpalladium chloride (when the ratio of monomer to catalyst 500:1) and 2 ml of methylene chloride. In another 10 ml glass test tube download 0,0357 g (0.104 g mmol) hexafluoroantimonate silver and 2 ml of methylene chloride. The catalyst solution is prepared by mixing a solution of the dimer allylpalladium chloride solution hexafluoroantimonate silver inside of the box with a dry atmosphere. There is immediate precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The active solvent yellow catalyst are added to a solution of the monomer syringe at 50oC, and the reaction mixture stirred for 16 h at room temperature. Any significant increase in solution viscosity is not observed, and the solution is filtered through a 0.5 micron filter, and then concentrated in a rotary evaporator. The obtained viscous solution was dissolved in methanol and precipitated in a mixture of methanol with water to obtain a white solid. Yield 23%. Found the value of the molecular weight (determined by means of gel chromatography in tetrahydrofuran with polystyrene standards) Mn= 15 700 g/mol and Mw=32 100 g/mol. Thermogravimetric analysis (TGA) under nitrogen (heating rate 10oC/min) shows thermal stability of the polymer up to about 155oWith subsequent sweat the reattaching of homopolymer 5-norbornanamine acid) with subsequent degradation of the polymer at about 450oC.

Example 15. Synthesis of diethyl ester of bicyclo[2.2.1]hept-5-ene-Exo, Exo-2,3-dicarboxylic acid.

Exo, Exo-diethyl ether norbornene synthesized from Exo-5-norbornene-2,3-dicarboxylic acid. Exo-isomer receive thermal conversion of the anhydride, endo-5-norbornene-2,3-dicarboxylic acid at 190oWith subsequent recrystallization from toluene several times, as in reference 1 for the pure anhydride, Exo-5-norbornene-2,3-dicarboxylic acid. Part of the Exo-anhydride hydrolyzing in boiling water, and the solution is cooled to obtain pure dicarboxylic acid with almost quantitative yield. Dicarboxylic acid turn in diethyl ether using triethyloxonium salt, as set forth below.

In a 250 ml three-neck flask equipped with a magnetic stirring rod, load 16.0 g (0,0824 mol) of pure Exo-norbornene dicarboxylic acid and 35 g (0,1846 mol) triethyloxonium of tetrafluoroborate. The flask cork and add 300 ml of dichloroethane in an argon atmosphere. Replace the cap on the capacitor in an atmosphere of nitrogen, and at other neck insert an additional funnel. Through this funnel dropwise slowly add 35 ml of ethyldiethanolamine. Watching what I Amin the solution incubated at room temperature for 15 hours Then the reaction mixture was extracted with three portions of 50 ml each of a solution of hydrochloric acid with subsequent three-fold extraction with 50 ml of sodium bicarbonate and finally washed twice with water. The organic solution is dried over magnesium sulfate, treated with charcoal, filtered and concentrated on a rotary evaporator. After purification of the residue by distillation at 110oTo obtain 15 g (75%) of pure Exo-diethyl ether norbornene in the form of a colorless viscous liquid with a fruity odor.

1H-NMR (Dl3): d= 1,22 (3H, t, CH3), d=1,47 (1H), d=2,15 (1H), d=2,58 (2H; s,

), d=3,07 (2H; s, bridge head), d=4,10 (2H, m, CH2), d=to 6.19 (2H; s, C=C), FI-MS (DIP)=M+(238).

Example 16. Synthesis of bicyclo[2.2.1]hept-5-ene-Exo-2-tert-butyl ester, Exo-3-carboxylic acid.

In a 50 ml round bottom flask with one neck, supplied coated with Teflona mixing rod, add 1.5 g (to 9.15 mmol) of pure Exo-radicalized, 10 ml of freshly distilled methylene chloride, 20 ml of tert-butanol (0,209 mol). To the solution was added 7.5 g (0.061 mol) of dimethylaminopyridine and the solution heated under reflux at 75oC for 8 hours Initially, the anhydride is dissolved, but after some period of art on a rotary evaporator to remove the methylene chloride, and a viscous solution is added slowly in acidified with hydrochloric acid water. The precipitated solid is filtered off, washed with water and re-dissolved in simple ether, treated with magnesium sulfate, followed by treatment with soot. The solution is filtered on zeolite (Celite). Remove simple ether on a rotary evaporator to obtain a solid substance. Yield 8.5 g, 60%.

1H-NMR (Dl3): d=1,47 (N; s, tert-butyl), d=1,60 (1H), d=2,15 (1H), d= 2,58 (2H; m ), d=3,07 (2H; s, bridge head), d=to 6.19 (2H; s, C=C), d= 10,31 (1H; broad, COOH).

Example 17. Synthesis of bicyclo[2.2.1]hept-5-ene-Exo-2-tert-butyl, Exo-3-methyl ether dicarboxylic acid.

In a round-bottom three-neck flask with a capacity of 100 ml, equipped with a magnetic stirring rod, load 9.7 g (0,0408 mol) of pure Exo-tert-butyl Palmyra norbornanamine acid and 6,05 g (0,0408 mol) trimethyloxonium of tetrafluoroborate. The flask cork and add 100 ml of dichloromethane through the funnel in an argon atmosphere. Replace the rubber stopper on the capacitor in an atmosphere of argon, and other throat insert an additional funnel. Through this funnel dropwise added slowly 7.3 ml of ethyldiethanolamine. There is an exothermic reaction and the solution allow condense PM Then the reaction mixture was extracted with three portions of 50 ml each of a solution of hydrochloric acid with subsequent three-fold extraction with 50 ml of sodium bicarbonate and finally washed twice with water. The organic solution is dried over magnesium sulfate, treated with charcoal, filtered and concentrated on a rotary evaporator. Receive a colourless liquid, which begins to crystallize. The solid is washed with cold pentane, and the pentane solution was concentrated on a rotary evaporator to obtain a colorless liquid, crystallized by cooling. The output of 5.1 g

1H-NMR (Dl3): d=1,45 (N; s, tert-butyl), d=1,47 (1H), d=2,15 (1H), d= 2,54 (2H; m ), d=3,07 (2H; s, bridge head), d=the 3.65 (3H, s, CH3), d= to 6.19 (2H; s, C=C).

Example 18. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add 5-norbornanamine acid (2.0 g, 14.5 mmol, Exo, endo mixture) and dichloromethane (20 ml). To this stirred mixture at room temperature, add a solution of the catalyst obtained by adding dimer3-allylpalladium chloride (6 mg, 16 μmol) in dichloroethane (5 ml) to hexafluoroantimonate silver (50 mg, 146 μmol) for 30 min followed Ccii mixture gelatinizes the formation of clear yellow gel. After adding the gel to the excess of hexane, the polymer precipitates as a white powder. The polymer was washed with excess hexane and dried. The polymer yield 1.2 g (60%). Found the molecular weight of the polymer Mw= 22 000 and a polydispersity of 2.3.

After you add this polymer (0.5 g) 0.1 N aqueous solution of KOH (10 ml) under stirring, the polymer is immediately dissolved with the formation of colorless non-viscous solution. This demonstrates the ability to display these materials in an aqueous solution of the base, because no other homopolymers tert-butyl ester 5-norbornanamine acid does not show the tendency to dissolve under the same conditions.

Example 19. Synthesis of Silver (The Pinner syntesis) complex of ortho-esters consists of two stages.

Stage 1. Synthesis of hydrochloride medovuha ether.

The reaction is carried out in a two-neck round-bottom flask with a capacity of 1 l equipped with a stirrer, an oil bubbler, and a tube with anhydrous calcium chloride. In the flask is charged with the following reagents: 100 g (0.84 mol) of norbinaltorphimine (NB-CN), 37 ml of 0.91 mol) of anhydrous methanol and 200 ml of anhydrous diethyl ether. The flask was placed in an ice bath and bubbled through a mixture of 61 g (1,67 mol) of dry hydrogen chloride is t "cake". His break into pieces and add 200 ml of diethyl ether. The flask is kept in the refrigerator for another 10 days, with periodic stirring. At the end of this process, the precipitated hydrochloride mediavolo ether is filtered by suction and washed five times approximately 300 ml of diethyl ether. From the filtrate allocate approximately 20 g of unreacted NB-CN.

Output hydrochloride mediavolo ether - 76% (120 g, 0.64 mol).

Product structure confirmed1H-NMR spectroscopy.

Stage 2. Synthesis of ortho-esters.

In a flask with a capacity of 0.5 l load 56.7 g (0.30 mol) of the hydrochloride mediavolo ether, 37 ml of 0.91 mol) of anhydrous methanol and 250 ml of anhydrous petroleum ether. The reaction is carried out at room temperature for 5 days with occasional stirring. Besieged ammoniacal filtered and washed three times with petroleum ether. The filtrate and the washing water is collected, petroleum ether is distilled off and the product is separated into fractions by distillation in vacuum. The fraction with a boiling point of 68oWITH-69oC/3 mm Od cool. The output is 50%, 30 g, 0.15 mol). According to1H-NMR spectrum of the product contains 97% of 5-norbornene-2-trimethoxymethane (ortho-ester).

Example 20 the Tana add a solution of the reaction product, obtained by mixing 1 mole of dimer allylpalladium chloride with 2 mol hexafluoroantimonate silver dichloroethane, and filtering the obtained precipitate of silver chloride. The number of added catalyst corresponds to 0.08 mmol of palladium dissolved in 2 ml of dichloroethane. Stir the reaction mixture was placed in an oil bath at 70oWith and carry out the reaction for 20 hours

Upon completion of the reaction, add 2 ml of methanol, removing the solvent on a rotary evaporator and the polymer was dried in vacuum until constant weight. Yield 1.28 g (60%).

Example 21. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add bicyclo[2.2.1]hept-5-ene-2-acetate (18,44 g, 0,1109 mol) and tert-butyl methyl ether norbornene (21,55 g, 0,1109 mol) and 75 ml of toluene. The solution of Nickel catalyst [toluene complex of bis(perftoralkil)Nickel, (Tol)Ni(C6F5)2] prepared in a box with dry atmosphere by dissolving 0,5367 g (1,109 mmol (Tol)Ni(C6F5)2) in 15 ml of toluene. The solution of the active catalyst is added to the monomer solution via a syringe at room temperature. The reaction mixture is stirred for 6 hours at room temperature the acetone and dried overnight under vacuum. The output of the selected polymer 24,9 g (63%). The molecular weight determined gel chromatography. Found: Mn=21 000 and Mw=52 000. NMR analysis of the copolymer shows the presence of 51 mol.% tert-butyl groups. IR analysis of the copolymer indicates the absence of acid groups.

Example 22. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add bicyclo[2.2.1]hept-5-ene-2-methyl-ethylcarbonate (a 4.03 g, 0,0205 mol) and tert-butyl methyl ether norbornene (3.98 g, 0,0205 mol) and 50 ml of toluene. The solution of Nickel catalyst [toluene complex of bis(perftoralkil)Nickel, (Tol)Ni(C6F5)2] prepared in a box with dry atmosphere by dissolving 0,0991 g (0,2049 mmol (Tol)Ni(C6F5)2in 15 ml of toluene. The solution of the active catalyst are added to a solution of the monomer through the funnel at room temperature. The reaction is carried out at room temperature. The solution was diluted with toluene and the polymer precipitated with excess methanol. The precipitated polymer is filtered, washed with acetone and dried overnight under vacuum. The output of the selected polymer of 4.16 g (52%). The molecular weight of the polymer determine gel chromatography. Found: Mn=22 000 and Mis found in the absence of acid groups.

Example 23. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add bicyclo[2.2.1]hept-5-ene-2-methyl-BUTYLCARBAMATE (17,15 g, 0,0764 mol) and tert-butyl methyl ether norbornene (14,85 g, 0,0764 mol) and 72 ml of toluene. The solution of Nickel catalyst [toluene complex of bis(perftoralkil)Nickel, (Tol)Ni(C6F5)2] prepared in Boxing with dried and purified atmosphere by dissolving 0,3699 g (0,7644 mmol (Tol)Ni(C6F5)2in 15 ml of toluene. The solution of the active catalyst are added to a solution of the monomer through the funnel at room temperature. The reaction is carried out at peremeshivanii for 6 h with compote temperature. The solution was diluted with toluene, and the polymer precipitated with excess methanol. The precipitated polymer is filtered, washed with acetone and dried overnight under vacuum. The output of the selected polymer 17,53 g (54%). The molecular weight of the polymer determine gel chromatography. Found: Mn=22 000 and Mw=58 000. NMR analysis of the copolymer shows the presence of 54 mol.% tert-butyl groups. IR analysis of the copolymer indicates the absence of acid groups.

Example 24. In a glass tube with a capacity of 50 ml, equipped with a covered TeflonoC. To the reaction mixture using a dry syringe add degassed solution of benzoyl peroxide as free-radical polymerization initiator containing 0,9948 g (0.04 mol) of benzoyl peroxide in 10 ml of chlorobenzene. After completion of the reaction, the polymer solution was poured directly into hexane to precipitate the polymer. Precipitated white precipitate. The precipitated polymer is separated from the unreacted maleic anhydride, which may be present in the mixture. The polymer was then dried overnight in a vacuum oven at room temperature. The mass of the obtained dried polymer equal vs. 20.62 g, yield of 45.8%. The molecular weight of the polymer determine gel chromatography. Found: Mn= 4 200 and Mw=8 800. NMR analysis of the copolymer indicates the presence of tert-Budilnik groups, and groups of maleic anhydride.

Example 25. In a glass tube with a capacity of 50 ml, equipped with a covered Teflona mixing rod, add bicyclo[2.2.1]hept-5-ene-2-acetate (13.3 g, 0,0799 mol), tert-butyl methyl ether norbornene (15,70 g, 0,0808 mol) followed the removal of traces of oxygen. Then the reaction mixture is heated to 80oC. In the reaction mixture is dry syringe add degassed solution of benzoyl peroxide as free-radical polymerization initiator containing 1,0438 g level (0.041 mol) of benzoyl peroxide in 10 ml of chlorobenzene. The reaction is carried out under stirring for 19 hours. After completion of the reaction, the polymer solution was poured directly into hexane to precipitate the polymer. Precipitated white precipitate. The precipitated polymer is separated from the unreacted maleic anhydride, which may be available. The polymer was then dried overnight in a vacuum oven at room temperature. The mass of the obtained dried polymer equal 21,89 g, yield of 48.7%. The molecular weight of the polymer determine gel chromatography. Found: Mn=3 000 and Mw=6 600. NMR analysis of the copolymer indicates the presence of acetate and tert-butyl groups. IR analysis of the copolymer indicates the presence of acetate, tert-butyl groups of maleic anhydride.

Example 26. Copolymer of tert-butyl ester of norbornene norbornene carboxylic acid, 50:50.

In a glass tube with a capacity of 50 ml, equipped with a magnetic stirring rod in utmost acid (1,38 g, 10 mmol). To this stirred mixture is added initiator (peroxide tert-butyl) (2.9 g) and the resulting mixture is heated to 130oC. Stirring is continued for 16 hours, the polymer (soluble in tetrahydrofuran, and toluene) visidot in hexane and filtered to obtain the product. The mass of the dried product is equal to 2.91 in g (86% conversion). The obtained solid polymer has a molecular mass Mn=3 000 and Mw=20 000. IR, NMR and TGA analyses of the copolymers confirm that the resulting additive is a copolymer of two monomers having an irregular structure.

Example 27. Copolymer of tert-butyl methyl ether norbornene carboxylic acid methyl ester of norbornene carboxylic acid, 50:50. In a glass tube with a capacity of 50 ml, equipped with a magnetic stirring rod in a nitrogen atmosphere, add tert-butyl ether norbornanamine acid (2 g, 10 mmol) and methyl ester of norbornene carboxylic acid (1.5 g, 10 mmol). To this stirred mixture at room temperature add the initiator (peroxide tert-butyl) (2.9 g) and the resulting mixture is heated to 130oC. Stirring is continued for 16 hours. The obtained polymer (soluble in toluene) visidot in methanol is erdy polymer has a molecular mass Mn=6 000 and Mw=35 000. IR, NMR and TGA analyses confirm that the resulting additive is a copolymer of two monomers having an irregular structure.

Example 28. Copolymer of tert-butyl methyl ether norbornene carboxylic acid ethyl ester, tetracyclinebuy carboxylic acid, 50:50.

In a glass tube with a capacity of 100 ml, equipped with a magnetic stirring rod in a nitrogen atmosphere, add toluene (40 ml), tert-butyl methyl ether norbornanamine acid (1,94 g, 10 mmol) and ethyl ester of tetracyclinebuy carboxylic acid (2,32 g, 10 mmol). To this stirred solution at room temperature, add a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (34 mg, 0,042 mmol) in 5 ml of toluene. After 1 h, add ethylenically ether (0,015 ml, 0,156 mmol) and stirred for 1 h Polymer solution is precipitated by adding an excess of methanol, collected by filtration and dried in vacuum. Stands out of 3.46 g (yield 81%) of the copolymer. Found: Mn=133 000 and Mw=221 000.

The copolymer is re-dissolved in toluene and passed through a column of silica gel. Disappears noticeable color (ruthenium). The polymer was again precipitated in excess methanol to obtain the net Blagodatnoe carboxylic acid, 50:50.

In a glass tube with a capacity of 100 ml, equipped with a magnetic stirring rod in a nitrogen atmosphere, add toluene (80 ml), tert-butyl methyl ether norbornanamine acid (3.9 g, 20 mmol) and ethyl ether tetracyclinebuy acid (with 4.64 g, 20 mmol). To this stirred solution at room temperature, add a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (68 mg, 0,083 mmol) in 5 ml of toluene. After 2 hours add ethylenically ether (0,030 ml, 0.31 mmol) and stirred for 2 h

Organic-resin solution is passed through silicagel column to obtain a clear colorless solution. The solution is then precipitated by adding an excess of methanol, collected by filtration and dried under vacuum. Allocate 6,54 g (yield 77%) of the copolymer. Found: Mn=182 000 and Mw=244 000. Measured using DSC, the glass transition temperature equal to 220oC.

Example 30. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In the reactor of stainless steel with a capacity of 300 ml, equipped with a mechanical stirrer and containing nitrogen, add toluene (90 ml), tert-butyl methyl ether norbornanamine sour is the PTO to the solution at room temperature add a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (68 mg, 0,083 mmol) in 5 ml of toluene. After 2 hours add ethylenically ether (0,030 ml, 0.31 mmol) and stirred for 16 hours In the reactor serves hydrogen (pressure 2410 kPa (350 psig)) and keep the temperature at 175oWith over 7 hours At the end of the reaction the solution is passed through silicagel column and produce hydrogenated copolymer. The NMR method determines that the degree of hydrogenation of the copolymer is 95%. Found: Mn=163 000 and Mw=237 000.

Example 31. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In a steel reactor of stainless steel with a capacity of 300 ml, equipped with a mechanical stirrer and containing nitrogen, add toluene (90 ml), tert-butyl methyl ether norbornanamine acid (2.9 g, 15 mmol) and ethyl ether tetracyclinebuy acid (3.5 g, 15 mmol). To this stirred solution at ambient temperature is added a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (50 mg, to 0.060 mmol) in 5 ml of toluene. After 2 h in the reactor is injected hydrogen (pressure 5510 kPa (800 psig) and keep the temperature at 175oWith over 7 hours At the end of the reaction the solution is passed through silicagel Nr. ideno: Mn=172 000 and Mw=278 000.

Example 32. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In a glass tube with a capacity of 100 ml, equipped with a magnetic stirring rod and a nitrogen-containing, add toluene (40 ml), tert-butyl methyl ether norbornanamine acid (1,94 g, 10 mmol), ethyl ester tetracyclinebuy acid (2,32 g, 10 mmol) and 1-hexene (0,050 ml, 0.4 mmol). To this stirred solution at ambient temperature is added a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (34 mg, 0,042 mmol) in 5 ml of toluene. After 2 h the solution of polymer is added in an excess of methanol, collected by filtration and dried under vacuum. Obtain 3.1 g (yield 73%) of the polymer. Found:n=22 000 and Mw=35 000.

Example 33. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In a glass tube with a capacity of 100 ml, equipped with a magnetic stirring rod and a nitrogen-containing, add toluene (40 ml), tert-butyl methyl ether norbornanamine acid (1,94 g, 10 mmol), ethyl ester of tetratziklicescie the overall environment add a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (34 mg, 0,042 mmol) in 5 ml of toluene. After 2 h the solution of polymer is added in an excess of methanol, collected by filtration and dried under vacuum. Allot of 3.45 g (yield 81%) of the polymer. Found: Mn=6 000 and Mw=8 000.

Example 34. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In a glass test tube with a capacity of 100 ml, equipped with a magnetic stirring rod and a nitrogen-containing, add toluene (40 ml), tert-butyl methyl ether norbornanamine acid (1,94 g, 10 mmol), ethyl ester tetracyclinebuy acid (2,32 g, 10 mmol) and 1-hexene (of 0.62 ml, 5.0 mmol). To this stirred solution at ambient temperature is added a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (34 mg, 0,042 mmol) in 5 ml of toluene. After 2 h the solution of polymer is added in an excess of methanol, collected by filtration and dried under vacuum. Allot of 2.75 g (yield 65%) of the polymer.

Example 35. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In a glass tube with a capacity of 100 ml, equipped with a magnetic stirring rod and a nitrogen-containing, add the carboxylic acid (with 4.64 g, 20 mmol) and 1-hexene (0,088 ml, 0.7 mmol). To this stirred solution at ambient temperature is added a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (68 mg, 0,083 mmol) in 5 ml of toluene. After 2 hours add ethylenically ether (0,030 ml, 0.31 mmol) and stirred for 2 h

Amber-orange polymer solution is passed through silicagel column that resolves a dark color (ruthenium). The solution is then precipitated by adding an excess of methanol, collected by filtration and dried overnight at 80oWith under vacuum.

Allocation of 2.6 g (30% yield) of polymer. Found: Mn=3 000 and Mw=4 000.

Example 36. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In the reactor of stainless steel with a capacity of 300 ml, equipped with a mechanical stirrer and containing nitrogen, add toluene (80 ml), tert-butyl methyl ether norbornanamine acid (3.9 g, 20 mmol), ethyl ester tetracyclinebuy acid (with 4.64 g, 20 mmol) and 1-hexene (0,088 ml, 0.7 mmol). To this stirred solution at ambient temperature is added a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (68 mg, 0,042 175oWith over 20 am

The solution is then precipitated by adding an excess of methanol, collected by filtration and dried overnight at 80oWith under vacuum. Allocate approximately 5 g (yield 59%) of the polymer. Found: Mn=20 000 and Mw=30 000. The NMR method determines that the degree of hydrogenation of the copolymer is more than 99%.

Example 37. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 65:35.

In a round bottom flask with a capacity of 250 ml, equipped with a magnetic stirring rod and a nitrogen-containing, add toluene (160 ml), tert-butyl methyl ether norbornanamine acid (10.1 g, 52 mmol), ethyl ester tetracyclinebuy acid (6.5 g, 28 mmol) and 1-hexene (0,176 ml, 1.4 mmol). To this stirred solution at room temperature, add a solution of dichloride bis(tricyclohexylphosphine)benzyladenine (131 mg, 0,160 mmol) in 5 ml of toluene. After 16 h add ethylenically ether (to 0.060 ml, of 0.62 mmol) and stirred for 1.5 hours, the polymer Solution is passed through silicagel column to remove ruthenium. The solution is added to excess methanol, collected by filtration and dried under vacuum. Allocate RS 9.69 g (yield 58%) of the polymer.< methods DSC. Found the value of glass transition temperature is 110oC.

Example 38. A glass beaker with a capacity of 100 ml, containing nitrogen, dissolved 5.0 g of polymer from example 37 in tetrahydrofuran (80 ml). The solution is transferred into a steel reactor with a capacity of 300 ml reactor added 2.25 g of 5 wt. % palladium catalyst on aluminum (purchased from Aldrich). Then the reactor is heated to 175oWith and serves the hydrogen pressure 5510 kPa (800 psig)). The temperature and pressure support during the 9.5 hours, the Obtained polymer solution centrifuged, separated colourless solution and precipitate the polymer in an excess of methanol. NMR discovered that the resulting copolymer has a degree of hydrogenation of over 99%.

Example 39. Copolymer of tert-butyl methyl ether norbornanamine acid ethyl ester tetracyclinebuy acid, 50:50.

In a glass tube with a capacity of 100 ml, equipped with a magnetic stirring rod and a nitrogen-containing, add toluene (80 ml), tert-butyl methyl ether norbornanamine acid (3.9 g, 20 mmol), ethyl ester tetracyclinebuy acid (with 4.64 g, 20 mmol) and 1-hexene (0,088 ml, 0.7 mmol). To this stirred solution at ambient temperature type R is t ethylenically ether (30 ml) to suspend further reaction, and the mixture is stirred for 1.5 hours, the polymer Solution is passed through silicagel column to remove residual ruthenium, and precipitation in methanol produce a polymer in the form of a pure white solid. Found the value of the molecular weight of the polymer is equal to Mn=33 700 and Mw=46 000. The polymer is fully characterized by IR, NMR and TGA.

Example 40. In a stainless steel autoclave with an inner volume of 300 ml add ethyl-2-methyl-4-pentenoate (99 g, 0.7 mol) and swieciany cyclopentadiene (46.4 g, 0.7 mol). Stir the mixture heated to 200oWith and leave overnight. Then the reactor is cooled and the contents removed. The resulting norbornene functional groups (norbornene-CH2CH(CH3)S(O)OS2H5) purified by vacuum distillation and determine the boiling temperature of about 46-47oC at a pressure of 0.02 mm RT.article By gas chromatography determined that the product has a degree of purity to 98.4 99.3 percent (various factions). Output selected highly pure product about 33 g

Example 41. Copolymer of tert-butyl methyl ether norbornanamine acid ester of the formula (norbornene-CH2CH(CH3)S(O)OS2H5), 40:60.

In the glass the wading is t-butyl ether norbornanamine acid (2.7 g, 14 mmol), and ether from example 40 (norbornene-CH2CH(CH3)S(O)OS2H5) (4.4 g, 21 mmol). To this stirred solution at ambient temperature is added a solution of (toluene)Ni(C6F6)2in toluene (1 ml) and the resulting solution was heated to 50oC. Stirring is continued for 3 hours, the Polymer is precipitated in methanol and filtered. The obtained solid substance pererastayut in tetrahydrofuran, filtered and precipitated again with methanol and filtered. The obtained white solid polymer is dried. The mass of the obtained polymer 2,66, Found the value of the molecular weight of the polymer is equal to Mn=39 800 and Mw=70 000. The upper layer of the solution is evaporated until dry to obtain additional quantities of white polymer by weight in the dry state of 1.52, Found: Mn=31 000 and Mw=60 650. The overall yield of the polymer indicates the degree of conversion of monomers 59%. IR, NMR and TGA analysis of the copolymer confirm receipt of the additive copolymer of the two monomers with an irregular structure.

Example 42. Copolymer of tert-butyl ester of norbornene-ester of the formula (norbornene-CH2CH(CH3)S(O)OS2H5), 40:60.

In a glass tube with a capacity of 250 ml, equipped with magnanimous acid (7,76 g, 40 mmol), and ether from example 40 (norbornene-CH2CH(CH3)S(O)OS2H5) (12.5 g, 60 mmol) and 2,6-di-tert-butylpyrazine (28.8 mg, 0.26 mmol). To this stirred solution at ambient temperature is added a solution of catalyst obtained by mixing dimer chloride allylpalladium (0,183 g, 0.5 mmol) with hexafluoroantimonate silver (equivalent amount) in dichloroethane (3 ml) and filtered to remove the precipitated silver chloride. The resulting solution was heated to 50oWith the Stirring is continued for 16 hours, the polymer Solution is treated with carbon monoxide (pressure of 28 kPa (4 psig) for 48 h to precipitate precipitate of palladium is filtered through a filter with a mesh size of 0.45 μm, reduced in volume and precipitated with excess methanol to obtain 7.9 g of the copolymer (degree of conversion of 39%). The found value of molecular weight equal to Mn=7 000 and Mw= 11 600. The copolymer is fully characterized by IR, NMR and TGA analysis.

Example 43. The copolymerization of carbon monoxide with the norbornene-5-tert-butyl ether.

Non-oxygenated solution bipyridine (0.025 g, 0.16 mmol) in methanol is added to the palladium (II) acetate (0,012 g, 0,053 mmol) dissolved in deoxygenating methanol. This military brown solution was added to a solution of benzoquinone (1,72 g, to 1.59 mmol) in deoxygenating methanol. This solution is injected into the reactor of stainless steel, pre-heated to 50oC. Then, the reactor type norbornene-5-tert-butyl ether (5,14 g, or 0.027 mol) in 100 ml of methanol, deoxygenating in argon. The pressure in the reactor increases carbon monoxide to 4130 kPa (600 psig) and heated to 65oC. After 4.5 h is removed from the reactor, the carbon monoxide, and the reactor is cooled. Filtered pink solution to remove residual palladium and the solution evaporated. The resulting mixture was dissolved in a minimum amount of tetrahydrofuran and slowly poured into a mixture of water with methanol 25: 75 to precipitate the polymer. This procedure is repeated twice. The obtained white polymer was filtered and dried at room temperature under vacuum. The yield of 2.9 g

Example 43A. Non-oxygenated and dried tetrahydrofuran/methanol (35 ml/15 ml) solution of benzoquinone (0,43 g, 0.40 mmol), bipyridine (0,0062 g, 0,0040 mmol) and PD(MN)2(p-toluensulfonate)2(0,0070 g, 0,0013 mmol) is placed in a dry reactor made of stainless steel, 500 ml, heated to 50oC. In the reactor type norbornene-5-tert-butyl ether (5,14 g, or 0.027 mol) in 100 ml of tetrahydrofuran (deoxygenating and dried). Reactor h is UP>o
With 1.5 hours Then removed from the reactor, the carbon monoxide, and the reactor is cooled. The solution from the reactor Magenta filter to remove residual palladium and evaporated. The resulting mixture was dissolved in a minimum amount of tetrahydrofuran and slowly poured into a mixture of water with methanol, 25: 75 to precipitate the polymer. This procedure is repeated twice. The obtained white polymer was filtered and dried under vacuum. The yield of 2.9 g

Examples 44-50. Measure the optical density of the cyclic olefin Homo - and copolymers at 193 nm.

Optical density is a critical characteristic of effective photoresists, because it determines the uniformity of penetration of energy through the film thickness. The polymer chain is usually used in lithography polymer has an optical density of less than 0.2 od units/micron before adding generating acid photoinitiator. (T. Neenan, E. Chandross, J. Kometani and O. Nalamasu, "Styrylmethylsulfonamides: Versatile Base-Solubilizing Components of Photoresist Resins", pg. 199 in Microelectronics Technology, Polymers for Advanced Imaging and Packaging, ACS Symposium Series 614, Eds: E. Reichmanis, C. Ober, S. MacDonald, T. Iwayanagai and T. Nishikubo, 1995, April). Polyhydroxystearic, the original part of the normal wavelength of 248 nm UV photoresists, has an optical density of 2.8 the Optina waves.

Preparation of sample solution

Samples of various polymers described in the examples described above (0,0160,001 g polymer), weighed and dissolved in 4 ml of chloroform. The polymer solutions pipetted and molded of them on the net identical quartz slides thin film by the method of irrigation. The film is dried during the night. Obtained on quartz slides round film is further dried at 70oWith in an oven purged with nitrogen for 10 minutes

On Perkin-Elmer-Lambda 9UV/VIS/IR spectrophotometer at a scan rate of 120 nm/min receive UV spectra of the films. The range is set from 300 nm to 180 nm. By measuring the optical density of the film at 193 nm and bringing it to the normal thickness of the films measured the optical density of the film at 193 nm. The results are given in table 1.

Preparation of a solution of a resist, exposure and manifestation.

Obtained in the above examples, the polymers are dissolved in the acetate nanometrology ether of propylene glycol (IMEPG) at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add oneway salt according to sample at a concentration of 5% by weight of polymer or 10% by weight of polymers.

oC for 1 min and Then the film is irradiated through the quartz template UV radiation on the device Karl Suss MJB3 UV 250 at a wavelength of 230 to 250 nm. The irradiated film is heated to 125 to 150oC for 1 min and Then irradiated and heat treated films show in aqueous solution base with images of positive tone with high resolution without reducing the film thickness in the unexposed areas.

When expression in a non-polar solvent can be easily obtained negative working system. Such materials are easily sensibiliser for more long wave (365 nm) by adding small amounts of sensitizers, such as pyrene, perylene or thioxanthone, or for shorter wavelengths (193 nm), since these materials, as shown above have a very low optical density at 193 nm.

Example 51. Copolymer of bicyclo[2.2.1]hept-5-EN-2-acetate with tert-butyl methyl ether norbornene (polymer according to example 2) with srednetsenovoj molecular weight of 21 000 dissolved in acetate nanometrology ether of propylene glycol at a concentration of 10 wt.% in the calculation of t the solution through a Teflonthe filter of 0.2 μm, and after filtration of the solution formed by centrifuging a resist film on the surface of the precoated with hexamethyldisilazane, the silicon wafer at 500 rpm for 30 s, and then at 2000 rpm for 25 C. a layer thickness of 0.7 μm. The film is dried at 95oC for 1 min over the surface of the hot plate, and then irradiated through the quartz template UV (240 nm) dose of 50 MJ/cm2. After post-heat treatment at 125oC for 1 min, in the development process in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 52. Copolymer of bicyclo[2.2.1]hept-5-EN-2-acetate with tert-butyl methyl ether norbornene (polymer according to example 21) with srednetsenovoj molecular weight of 21 000 dissolved in acetate nanometrology ether of propylene glycol at a concentration of 10 wt.% in the calculation of the solid. Add diarylethene hexafluoroantimonate (Sartomer 1012) in the amount of 10% by weight of the polymer. The solution is filtered through a Teflonthe filter of 0.2 μm and after filtration of the solution formed by centrifuging a resist film on the surface of the precoated with hexamethyldisilazane, forces the coating of 0.7 μm. The film is dried at 95oC for 1 min over the surface of the hot plate, and then irradiated through the quartz template UV (240 nm) dose of 50 MJ/cm2. After post-heat treatment at 125oC for 1 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 53. Copolymer of bicyclo[2.2.1]hept-5-EN-2-acetate with tert-butyl methyl ether norbornene (polymer according to example 21) with srednetsenovoj molecular weight of 21 000 dissolved in acetate nanometrology ether of propylene glycol at a concentration of 10 wt.% in the calculation of the solid. Add to the solution diarylethene hexafluoroantimonate (Sartomer 1012) in the amount of 10% by weight of the polymer. The solution is filtered through a Teflonthe filter of 0.2 μm and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 0.7 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through a quartz mask to UV radiation is aStore reason for 60 to get a positive image with high resolution.

Example 54. Copolymer of bicyclo[2.2.1]hept-5-EN-2-acetate with tert-butyl methyl ether norbornene (polymer according to example 21) with srednetsenovoj molecular weight of 21 000 dissolved in acetate nanometrology ether of propylene glycol at a concentration of 10 wt.% in the calculation of the solid. To the solution add triphenylsulfonium hexafluoroarsenate in the amount of 10% (based on solid substance. The solution is filtered through a Teflonthe filter of 0.2 μm and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 0.7 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through a quartz photomask UV (240 nm) dose of 10 MJ/cm2. After post-heat treatment at 125oC for 1 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 55. Copolymer of bicyclo[2.2.1]hept-5-EN-2-acetate with tert-butyl methyl ether norbornene (polymer according to example 21) with srednei is 0 wt.% in the calculation of the solid. To the solution add triphenylsulfonium hexafluoroarsenate in the amount of 10% by weight of the polymer. Resulting solution is filtered through a Teflonthe filter of 0.2 μm, and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 0.7 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 30 MJ/cm2. After post-heat treatment at 125oC for 1 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 56. The copolymer of maleic anhydride with tert-butyl methyl ether norbornene obtained by the method of free-radical polymerization (polymer from example 24) with srednetsenovoj molecular weight of 4,000 was dissolved in acetate nanometrology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Srtmr is SUP>the filter of 0.2 μm and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 0.6 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 30 MJ/cm2. After post-heat treatment at 125oC for 1 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 57. The copolymer of maleic anhydride with tert-butyl methyl ether norbornene obtained by the method of free-radical polymerization (polymer from example 24) with srednetsenovoj molecular weight of 4,000 was dissolved in acetate nanometrology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a Teflona 0.2 μm filter and after filter is required by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 0.6 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 30 MJ/cm2. After post-heat treatment at 95oC for 1 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 58. Terpolymer maleic anhydride and bicyclo[2.2.1]hept-5-EN-2-acetate and tert-butyl ester of norbornene obtained by the method of free-radical polymerization (polymer according to example 25) with srednetsenovoj molecular weight of 3,000, is dissolved in the acetate nanometrology ether of propylene glycol at a concentration of 10 wt.% in the calculation of the solid. To the resulting solution add diarylethene hexafluoroantimonate (Sartomer 1012) in the amount of 10% by weight of the polymer. The solution is filtered through a Teflonthe filter of 0.2 μm and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 sec. At etourneau plate, and then irradiated through the quartz template UV (240 nm) dose of 50 MJ/cm2. After post-heat treatment at 125oC for 1 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 59. Copolymer of bicyclo[2.2.1] hept-5-EN-2-methylethylketone with tert-butyl methyl ether norbornene (polymer according to example 22) with srednetsenovoj molecular weight of 22,000 was dissolved in acetate nanometrology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a Teflonthe filter of 0.2 μm, and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 1.1 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 30 MJ/cmIe 60 to get a positive image with high resolution.

Example 60. Copolymer of bicyclo[2.2.1]hept-5-EN-2-methylethylketone with tert-butyl methyl ether norbornene (polymer according to example 22) with srednetsenovoj molecular weight of 22,000 was dissolved in acetate nanometrology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a Teflonthe filter of 0.2 μm, and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 1.1 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) at doses of 15 MJ/cm2. After post-heat treatment at 95oC for 1 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 61. Copolymer of bicyclo[2.2.1] hept-5-EN-2-methylbutanoate with tert-butile onomatology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a Teflonthe filter of 0.2 μm and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 1 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 30 MJ/cm2. After post-heat treatment at 125oC for 0.5 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 62. Copolymer of bicyclo[2.2.1] hept-5-EN-2-methylbutanoate with tert-butyl methyl ether norbornene (polymer according to example 23) with srednetsenovoj molecular weight of 22,000 was dissolved in acetate nanometrology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1>/SUP>the filter of 0.2 μm and after filtration of the solution is formed into a film of resist on the surface of the precoated with hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 1.0 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 30 MJ/cm2. After post-heat treatment at 150oC for 0.5 min and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

Example 63. Hydrogenated copolymer of 35 mol.% ethyl ester of tetracyclkne with 65 mol.% tert-butyl methyl ether norbornene (polymer according to example 37) with srednetsenovoj molecular weight of 23 000, obtained by the method of polymerization with permutation and disclosure of the rings, dissolved in acetate nanometrology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Srtmr CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered cher the STI, grounded hexamethyldisilazane, silicon wafers by centrifuging at 500 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 1.1 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 30 MJ/cm2. After post-heat treatment at 125oC for 1 min and manifestations in an aqueous solution of the base 30 to get a positive image with high resolution.

Example 64. Negitively copolymer of 50 mol.% ethyl ester of tetracyclkne with 50 mol.% tert-butyl methyl ether norbornene (polymer according to example 39) with srednetsenovoj molecular mass of 34 000, obtained by the method of polymerization with permutation and disclosure of the rings, dissolved in acetate nanometrology ether of propylene glycol at a concentration of 15 wt.% in the calculation of the solid. To the resulting solution add triarylsulfonium hexafluoroantimonate (Srtmr CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a Teflonthe filter of 0.2 μm and after filtration of the solution is formed into a film resis is 00 rpm for 30 s, and then at 2000 rpm for 25 C. by coating with a layer thickness of 1.25 μm. The film is dried at 95oC for 1 min on a hot plate surface, and then irradiated through the quartz template UV (240 nm) dose of 50 MJ/cm2. After post-heat treatment at 150oC for 30 s and manifestations in an aqueous solution of the base in 60 seconds get a positive image with high resolution.

1. Photoresist composition comprising generating acid photoinitiator, the solvent, the optional dissolution inhibitor, and a polymer containing polycyclic repeating units containing acid-labile groups, characterized in that the said polymer has a molecular weight of from about 500 to about 1,000,000 and is the product of polymerization of polycyclic monomers substituted with at least one acid-labile group, and optionally in combination with a monomer selected from the group comprising maleic anhydride, carbon monoxide, polycyclic monomer, substituted neutral group, polycyclic monomer, substituted carboxyl group, alkyl substituted polycyclic monomer, and mixtures thereof, moreover, the specified MES is awesime from each other selected from the group comprising hydrogen, a normal or branched alkyl WITH1-C10and the group -(CH2)n-C(O)OR SIG*, -(CH2)n-C(O)OR, -(CH2)n-OR, -(CH2)n-OC(O)R, -(CH2)n-OC(O)or, or -(CH2)n-C(O)R, -(CH2)nC(R)2CH(R)(C(O)OR**), and -(CH2)n-C(R)2CH(C(O)OR**)2provided that at least one of the substituents R1-R4selected from the group comprising an acid-labile group, -(CH2)n-C(O)OR*, where R is hydrogen or a normal or branched alkyl WITH1-C10m = 0 to 5, and n = 0 to 10, R* means the group is able to disintegrate under the action of generating an acid photoinitiator and selected from the group of radicals, including- (CH3)3, -Si(CH3)3isobornyl, 2-methyl-2-substituted, tetrahydrofuranyl, tetrahydropyranyl, 3-oxo-cyclohexanyl, lactones avalonbay acid, dicyclopropyl and dimethylpropylene, R** independently denotes an R and R*,

while specified monomer, substituted neutral group has the formula II

< / BR>
where R5-R8independently from each other - neutral Deputy selected from the group comprising -(CH2)n-C(O)OR", -(CH2)n-OR", -(CH2)n-OC(O)R", C(R)2CH(C(O)OR")2where R is hydrogen or a normal or branched alkyl WITH1-C10, R" is hydrogen or a normal or branched alkyl WITH1-C10mono - or politicalinfluence radicals C4-C20, cyclic esters, cyclic ketones, and cyclic ethers, provided that if the group R" is hydrogen, then at least one of the remaining R5-R8contains a Deputy, in which R" is alkyl WITH1-C10p = 0 to 5, and n = 0 to 10,

while specified monomer, substituted carboxyl group has the formula III

< / BR>
where the substituents R9-R12independently from each other hydrogen, a normal or branched alkyl WITH1-C10and replacing the carboxyl group has the formula -(CH2)n(O)IT is provided that at least one of the substituents R9-R12represents a carboxyl group, q = 0 to 5, and n = 0 to 10,

moreover, the specified alkyl substituted monomer has the formula IV

< / BR>
where the substituents R13-R16independently of one another is hydrogen or a normal or branched alkyl WITH1-C10provided that at least one of the substituents R13-R16is alkyl WITH1See erection cycle with the formation of polymer with open loops.

3. The composition according to p. 2, characterized in that the polymer is gidrirovanny polymer with open loops.

4. The composition according to p. 1, characterized in that the monomers are polymerized by free-radical polymerization.

5. The composition according to p. 1, characterized in that the monomers are polymerized in the presence of a catalyst comprising a single or multicomponent catalyst system, each of which includes a source of ions of a metal of group VIII and one-component catalyst has the formula

< / BR>
where E is a neutral ligand donor 2 electrons;

n = 1 or 2;

L is a ligand containing 1, 2 or 3-connection;

M is palladium or Nickel;

X is a ligand containing one-bond and between 0 to 3 ties;

y = 0, 1, or 2;

z = 0 or 1, and y and z both cannot mean 0 and if z = 0, a = 2, and if z = 1 then a = 1;

R27independently is a normal or branched alkyl WITH1-C10;

SA - protivoiadie selected from the group consisting of BF4-PF6-, lF3O3SF3-, SbF6-, SbF5SO3F-AsF6-perforated (CF3SOO-), performative>H2O) p-toluolsulfonic (R-CH3WITH6H4SO3-and tetraphenylborate formula

< / BR>
where R" independently is hydrogen, fluorine, trifluoromethyl and n = 1 to 5

and the said multi-component catalytic system contains (a) a source of metal ions of group VIII in combination with one or both of the components b) and C), b) the ORGANOMETALLIC socialization, C) a third component selected from the group comprising a Lewis acid is a strong acid Bronsted, halogenated compounds, electron-donor compounds selected from aliphatic or cycloaliphatic of diolefins and mixtures thereof, with the molar ratio of component b), ORGANOMETALLIC socializaton and component (a), the source of metal ions of group VIII is not more than 100:1, and the molar ratio of component a), source of metal ions of group VIII and component b), Lewis acids and strong acids Branstad is not more than 4: 1.

6. The composition according to p. 5, characterized in that the Lewis acid is selected from the group comprising F3apirat, TiCl4, SbF5, l3IN(OCH2CH3)3and Tris(perftoralkil)boron, indicated a strong acid of Bronsted selected from the group comprising HSbF6that is toluensulfonate, these halogenated compounds selected from the group comprising hexachloroacetone, HEXAFLUOROACETONE, 2,2,3,4,4-pentachlorobutane ether 3-butenova acid, hexafluoro acid, hexafluoroisopropanol and chloranil, and these electron-donor compound selected from the group including aliphatic and cycloaliphatic diolefine, phosphines and phosphites, and mixtures thereof.

7. The composition according to p. 5, characterized in that the ORGANOMETALLIC socialization is a compound selected from the group comprising alyuminiiorganicheskikh connection dialkylzincs connection dialkylamino, alkyllithium compounds and mixtures thereof.

8. The composition according to p. 5, wherein E is selected from the group comprising toluene, benzene, mesitylene, tetrahydrofuran and dioxane.

9. The composition according to p. 8, characterized in that the said catalyst is selected from the group comprising (toluene)bis(perftoralkil)Nickel, (benzene)bis(perftoralkil)Nickel, (mesitylene)bis(perftoralkil)Nickel, bis(tetrahydrofuran) bis(perftoralkil)Nickel and bis(dioxane) bis(perftoralkil)Nickel.

10. The composition according to p. 5, characterized in that the catalyst has the formula

EnNi(C6F5)2,
EnNi(C6F5)2,

in which n=2;

ligand E is selected from the group comprising tetrahydrofuran, dioxane and diethyl ether.

12. The composition according to p. 1, characterized in that the polymer contains the repeating unit of the formula I

< / BR>
where the substituents R1-R4independently from each other selected from the group comprising hydrogen, a normal or branched alkyl WITH1-C10and the group -(CH2)n-C(O)OR*, -(CH2)n-C(O)OR, -(CH2)n-OR, -(CH2)n-OC(O)R, -(CH2)n-OC(O)OR, -(CH2)n-C(O)R, -(CH2)nC(R)2CH(R)(C(O)OR**), and -(CH2)nC(R)2CH(C(O)OR**)2provided that at least one of the substituents R1-R4represents an acid-labile group, -(CH2)n-C(O)OR*, where R is hydrogen or a normal or branched alkyl WITH1-C10m = 0 to 5, and n = 0 to 10, R* is a group that can split under the action of generating an acid photoinitiator selected from the group of radicals, including- (CH3)3, -Si(CH3)3isobornyl, 2-methyl-2-substituted, tetrahydrofuranyl, tetrahydrothieno - R and R*.

13. The composition according to p. 12, characterized in that the said polymer further contains at least one repeating element selected from groups having the formula

< / BR>
< / BR>
< / BR>
where R5-R8independently from each other represent a neutral Deputy selected from the group comprising -(CH2)n-C(O)OR", -(CH2)n-OR", -(CH2)n-OC(O)R", -(CH2)n-OC(O)OR", -(CH2)n-C(O)R", -(CH2)n-C(R)2CH(R)(C(O)OR") and -(CH2)nC(R)2CH(C(O)OR")2where R is hydrogen or a normal or branched alkyl WITH1-C10; R" is hydrogen, a normal or branched alkyl WITH1-C10mono - or politicalinfluence radical WITH4-C20, cyclic esters, cyclic ketones, and cyclic ethers, provided that if the group R" is hydrogen, then at least one of the remaining R5-R8contains a Deputy, in which R" is alkyl WITH1-C10p = 0 to 5, and n = 0 to 10; R9-R12independently from each other hydrogen, a normal or branched alkyl WITH1-C10and carboxyl group -(CH2)n(O)IT is provided that at least one Deputy is 6
independently of one another is hydrogen or a normal or branched alkyl WITH1-C10provided that at least one of the substituents R13-R16- alkyl WITH1-C10and r = 0 to 5.

14. The composition according to p. 8, characterized in that the monomers are polymerized in the presence of a catalyst selected from the group comprising (toluene)bis(perftoralkil)Nickel, (mesitylene)bis(perftoralkil)Nickel, (benzene)bis(perftoralkil)Nickel, bis(tetrahydrofuran)bis(perftoralkil)Nickel and bis(dioxane)bis(perftoralkil)Nickel.

15. The composition according to p. 1, characterized in that the polymer contains the repeating unit of the formula

< / BR>
where the substituents R1-R4independently from each other selected from the group comprising hydrogen, a normal or branched alkyl WITH1-C10and the group -(CH2)n-C(O)OR SIG*, -(CH2)n-C(O)OR, -(CH2)n-OR, -(CH2)n-OC(O)R, -(CH2)n-OC(O)OR,

-(CH2)n-C(O)R, -(CH2)nC(R)2CH(R)(C(O)OR**), and -(CH2)nC(R)2CH(C(O)OR**)2provided that at least one of the substituents R1-R4represents an acid-labile group, -(CH2)n-C(O)OR*, where the ing to disintegrate under the action of generating an acid photoinitiator and selected from the group of radicals including- (CH3)3, -Si(CH3)3isobornyl, 2-methyl-2-substituted, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexyl, lactones avalonbay acid, dicyclopropyl and dimethylpropylene, R** is independently - R and R*.

16. The composition according to p. 15, characterized in that the said polymer further contains at least one repeating element selected from groups having the formula

< / BR>
< / BR>
< / BR>
where R5-R8independently from each other - neutral Deputy selected from the group comprising -(CH2)n-C(O)OR", -(CH2)n-OR", -(CH2)n-OC(O)R", -(CH2)n-OC(O)OR", -(CH2)n-C(O)R", -(CH2)n-C(R)2CH(R)(C(O)OR") and -(CH2)nC(R)2CH(C(O)OR")2where R is hydrogen or normal and branched alkyl WITH1-C10; R" is hydrogen or normal and branched alkyl WITH1-C10mono - or politicalinfluence radical WITH4-C20, cyclic esters, cyclic ketones, and cyclic ethers, provided that if the group R" is hydrogen, then at least one of the remaining R5-R8contains a Deputy, in which R" is alkyl WITH1-C10p = 0 to 5 and n =C10and carboxyl Deputy represented by the formula -(CH2)n(O)IT is provided that at least one of the substituents R9-R12is the specified carboxylic Deputy, q = 0 to 5, and n = 0 to 10;

the substituents R13-R16independently of one another is hydrogen or a normal or branched alkyl WITH1-C10provided that at least one of the substituents R13-R16is alkyl WITH1-C10and r = 0 to 5.

17. Composition according to any one of paragraphs.1, 12, 13, 15 or 16, characterized in that the polymer contains at least one end of the polymer chain side performancenow group.

18. The composition according to p. 1, characterized in that the polymer contains the repeating unit of the formula

< / BR>
where the substituents R1-R4independently from each other selected from the group comprising hydrogen, normal and branched alkyl WITH1-C10and the group -(CH2)n-C(O)OR*, -(CH2)n-C(O)OR, -(CH2)n-OR, -(CH2)n-OC(O)R, -(CH2)n-OC(O)or, or -(CH2)n-C(O)R, -(CH2)nC(R)2CH(R)(C(O)OR**), and -(CH2)nC(R)2CH(C(O)OR**)2provided that at least one of semesters and branched alkyl WITH1-C10m = 0 to 5, and n = 0 to 10, and R* is represented by the group, able to disintegrate under the action of generating an acid photoinitiator and selected from the group of radicals, including- (CH3)3, -Si(CH3)3isobornyl, 2-methyl-2-substituted, tetrahydrofuranyl, tetrahydropyranyl, 3-oxo-cyclohexanyl, lactones avalonbay acid, dicyclopropyl and dimethylpropylene, R** independently denotes an R and R*.

19. The composition according to p. 18, characterized in that the said polymer additionally contains at least one repeating element selected from groups having the formula

< / BR>
< / BR>
< / BR>
where R5-R8independently from each other represent a neutral Deputy selected from the group comprising -(CH2)n-C(O)OR SIG", -(CH2)n-OR", -(CH2)n-OC(O)R", -(CH2)n-OC(O)OR", -(CH2)n-C(O)R", -(CH2)nC(R)2-CH(R)(C(O)OR") and -(CH2)nC(R)2CH(C(O)OR")2where R is hydrogen or normal and branched alkyl WITH1-C10, R" is hydrogen or normal and branched alkyl WITH1-C10mono - or politicalinfluence radical WITH4-C20, cyclic esters, cyclic ketones, and cyclic simple is it Deputy, in which R" is alkyl WITH1-C10p = 0 to 5, and n = 0 to 10;

R9-R12independently from each other hydrogen, normal and branched alkyl WITH1-C10and carboxyl Deputy represented by the formula -(CH2)n(O)IT is provided that at least one of the substituents R9-R12is the specified carboxylic Deputy, q = 0 to 5, and n = 0 to 10;

the substituents R13-R16independently of one another is hydrogen or a normal or branched alkyl WITH1-C10provided that at least one of the substituents R13-R16is alkyl WITH1-C10,

r = 0 - 5.

20. The composition according to p. 19, characterized in that the polymer contains the repeating unit of the formula

< / BR>
< / BR>
where R is hydrogen or normal and branched alkyl WITH1-C10;

m and m' = 0 to 5 independently from each other;

n = 0 to 10;

R* means the group is able to disintegrate under the action of generating an acid photoinitiator and selected from the group of radicals, including- (CH3)3, -Si(CH3)3isobornyl, 2-methyl-2-substituted, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexyl, lactones avalonbay acid, d is, CLASS="ptx2">

22. The composition according to p. 21, characterized in that the polymer contains the repeating unit of the formula

< / BR>
< / BR>
23. Composition according to any one of paragraphs.18-20 or 22, characterized in that the bonds in the main polymer chain gidrirovanny more than 90%.

24. The composition according to p. 23, characterized in that the bonds in the main polymer chain of the specified polymer gidrirovanny more than 95%.

25. The composition according to p. 23, characterized in that the bonds in the main polymer chain gidrirovanny almost 100%.

26. Composition according to any one of paragraphs.1-4, 12-22, characterized in that the polymer contains 5 to 100 mol.% repeating polycyclic units that contain the specified side of the acid-labile group.

27. The composition according to p. 26, characterized in that the polymer contains 20 to 90 mol.% repeating polycyclic units that contain the specified side of the acid-labile group.

28. The composition according to p. 27, characterized in that the polymer contains 30 to 70 mol.% repeating polycyclic units that contain the specified side of the acid-labile group.

29. The composition according to p. 25, characterized in that the polymer contains 5SS="ptx2">

30. The polymer is a polymerization product of a Monomeric composition containing polycyclic monomer and the solvent, in the presence of a single component catalyst of the formula

EnNi(C6F5)2,

where E is a neutral ligand donor 2 electrons;

n = 1 or 2

moreover, the specified polycyclic monomer selected from monomers having the formula

< / BR>
where the substituents R1-R4independently from each other selected from the group comprising hydrogen, normal and branched alkyl WITH1-C10and the group -(CH2)nC(O)OR*, -(CH2)n-C(O)OR, -(CH2)n-OR, -(CH2)n-OC(O)R, -(CH2)n-OC(O)or SIG, or -(CH2)n-C(O)R, -(CH2)nC(R)2CH(R)(C(O)OR**), and -(CH2)nC(R)2CH(C(O)OR**)2provided that at least one of the substituents R1-R4selected from the group comprising an acid-labile group -(CH2)n-C(O)OR*, R is hydrogen or normal and branched alkyl WITH1-C10m = 0 to 5, and n = 0 to 10, and R* denotes the group is able to disintegrate under the action of generating an acid photoinitiator and selected from the group of radicals, including- (CH3)3, -Si(CH3)3Sorority, dicyclopropyl and dimethyl-propylether, R** is independently - R and R*.

31. The polymer p. 30, characterized in that the monomer composition further comprises a polycyclic monomer of the formula

< / BR>
where R5-R8independently from each other mean a neutral Deputy selected from the group comprising -(CH2)n-C(O)OR", -(CH2)n-OR", -(CH2)n-OC(O)R", -(CH2)n-OC(O)OR", -(CH2)n-C(O)R", -(CH2)nC(R)2-CH(R)(C(O)OR") and -(CH2)nC(R)2CH(C(O)OR")2where R is hydrogen or normal and branched alkyl WITH1-C10, R" denotes hydrogen or normal and branched alkyl1-C10mono - or politicalinfluence radicals containing 4 to 20 atoms, cyclic esters, cyclic ketones, and cyclic ethers, provided that in the case when the group R ' means hydrogen, then at least one of the remaining R5-R8contains a Deputy, in which R denotes alkyl WITH1-C10p = 0 to 5, and n = 0 to 10.

32. The polymer p. 31, characterized in that the monomer composition comprises a monomer of the formula:

< / BR>
and

< / BR>
where R8means a group -(CH1-C10.

33. The polymer according to any one of paragraphs.30 to 32, characterized in that it contains at least one end of the polymer chain side performancenow group.

34. The polymer p. 33, characterized in that the catalyst has the above formula in which n = 1, and the ligand, E is selected from the group comprising benzene, mesitylene and toluene.

35. The polymer p. 30, characterized in that the catalyst has the above formula in which n = 2 and the ligand, E is selected from the group comprising tetrahydrofuran, dioxane and diethyl ether.

 

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where X N3CH2C6H4N3,

YN,N,NO

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< / BR>
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FIELD: catalysts, chemical technology.

SUBSTANCE: invention relates to a method for preparing a catalyst used in additive polymerization of norbornene to polynorbornenes. Invention describes a method for preparing a catalyst for additive polymerization of norbornene involving interaction of palladium (II) compound with boron trifluoride etherate in toluene medium as a solvent. Components are mixed in the following order: palladium compound solution is added to norbornene solution in organic solvent followed by addition of boron trifluoride etherate. Optimal conditions for the process are the following: the molar ratio boron to palladium, B : Pd = (5-1):(60-1), temperature 15-60°C. Invention provides enhancing effectiveness of the polymerization process. Synthesized compounds are used in producing cover in electronics, television-communication materials, optical lens, substrates for plastic displays, photoresistors for producing chips and displays, dielectrics for semiconductors.

EFFECT: improved method of synthesis.

1 cl, 6 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, specifically to a method of producing ruthenium carbene complex and a method of metathesis polymerisation of dicyclopentadiene. The catalyst for metathesis polymerisation of dicyclopentadiene is(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-N,N-dimethylamino-methylphenylmethylene)ruthenium of formula The method of producing the said catalyst involves reacting a second generation Grubbs catalyst with 2-(N,N-dimethylaminomethyl)styrene in toluene while heating in an inert atmosphere. In another version of the said method, a first generation Grubbs catalyst is successively reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dimethylaminomethyl)styrene in a single reactor in toluene while heating in an inert atmosphere. The method of metathesis polymerisation of dicyclopentadiene is characterised by that, polymerisation is carried out using the proposed catalyst with ratio monomer: catalyst ranging from 75000:1 to 100000:1.

EFFECT: invention allows for obtaining a polymer with good mechanical properties at low expenses due to reduced catalyst consumption.

4 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: described is a method of producing norbornene addition polymers (bicycle[2.2.1]heptene-2)through polymerisation of norbornene in the presence of a catalyst system obtained by reacting a palladium cationic complex in an organic solvent and etharate of boron trifluoride of formula BF3OEt2, distinguished by that the palladium complex used is tetrafluoroborate acetylacetonatobis(triarylphosphine) palladium with general formula [(Acac)Pd(PR3)2]BF4, where Acac is acetylacetonate, where R=o-tolyl, n - tolyl, phenyl. The process is carried out in molar ratio of boron to palladium B:Pd=5:1-40:1 and temperature 15-70°C.

EFFECT: increased efficiency of norbornene polymerisation process through increased catalyst activity.

4 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: disclosed method relates to preparing a catalyst for addition polymerisation of norbornene to polynorbornene. Described is a method of preparing a catalyst for addition polymerisation of norbornene based on complexes of zero-valent nickel and BF3OEt2 involving use of catalyst systems of the composition (L)nNi(PR3)2/BF3OEt2, where n=1, 2; L=PR3 or ethylene; R=Ph, OC6H4CH3-o combined with a controlled amount of water as a modifying component, and the process is carried out in a medium of organic solvent, e.g. toluene in molar ratio of boron to nickel B: Ni=50:1-600:1, ratio H2O/Ni=2-104 and temperature 10-80°C.

EFFECT: high efficiency of the norbornene polymerisation process.

3 tbl, 8 ex

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