Metallation and functionalization of polymers and copolymers
(57) Abstract:In the invention described by way of introduction of the functional group in the copolymer isoolefine and alkylthiol place alkylbenzenes carbon atom, comprising preparing a solution of this copolymer in a hydrocarbon solvent, an introduction to polymer solution of the alkoxide of an alkali metal (Cs, K, or Na) and sociallising connection with obtaining coronoary in combination with a polymer solution and an introduction to such basic polymer solution electrophilic compounds. There are also metilirovannye copolymers and their functionalized derivatives. The technical objective is to develop ways functionalization of copolymers without modification in an inert hydrocarbon structure of the main copolymer chain. 4 C. and 19 C.p. f-crystals, 2 tab. This application is a partial continuation of patent application U.S. 08/447131 entitled "Metallation and functionalization of polymers and copolymers" and filed may 22, 1995 in the name of the authors Jean M. J. Frechet, Haque Shah, Joachim Steinke and Hsien Wang, which is a partial continuation of patent application U.S. 08/444951, filed may 19, 1995The invention relates to copolymers containing units alkylthiols is that can be functionalized accession to the electrophilic reagent.Background of the invention
Up to the present time as elastomers in the preparation of mixed compositions with thermoplastic compounds and other elastomeric compounds intended for use in the manufacture of automobile tyres, etc, used butylketone, i.e., copolymers of isobutylene and small amounts of isoprene as co monomer, and/or halogenated rubbers, i.e., halogenated derivatives of butyl rubber. Butyl and/or the halogenated butylketone give these mixtures, the number of target properties, such as low permeability, relatively low glass transition temperature (Tc), broad peaks damping, resistance to aging under the influence of the environment and so on, which is important in the manufacture of tyres with superior performance properties. However, the use of butyl - and/or halogenated butyl rubber is associated with various problems of a technological nature, the chief of which is their high incompatibility with most other polymers, including unsaturated elastomeric compounds to which they are weak adhesion. Therefore, the feature of butyl rubber, giving the lnyh tires namely chemical "inertia", which is the result of the lack of reactivity of the main hydrocarbon chain molecules of the butyl rubber polymer, is also the cause of its low reactivity and incompatibility with most other materials, which limits the possibility of its application in many engineering fields.In U.S. patent 5162445 been described a unique copolymer of isobutylene and a method of introducing functional groups into the main chain of such a copolymer, so that it becomes acceptable for use as a blend component, which has all the advantages of the properties of butyl - and/or halogenated butyl rubber, but which does not, however, an inherent disadvantage of incompatibility butyl and/or halogenated butyl rubber. In a broader aspect of this new copolymer isone direct product of the interaction of isoolefine containing 4-7 carbon atoms, with parallellism, and preferred monomers are isobutylene and parameterstyle, and such copolymers are characterized by an essentially homogeneous compositional distribution. Derivatives of such IB-PAS-copolymer containing functional is Mimi materials, with both thermoplastic and elastomeric polymers obtained by a halogenated intermediate product, which is prepared by gorodilova IB-PAS-copolymer, initiated by free radicals.Preferred for U.S. patent 5162445 copolymer is a copolymer of isobutylene and parameterstyle, and this copolymer bromilow with obtaining a copolymer, the part parameterstyle links which bromirovanii place Parametering groups. Commercially available brominated copolymer is a essentially high molecular weight isobutylene-parameterstyle-pararammelsbergite polymer with a narrow molecular weight distribution. In the presence of a nucleophilic reagent benzyl bromine atoms are highly reactive under mild conditions. It was found that at the place of brominated Parametering carbon atoms of the side phenyl groups, you can enter a variety of functional groups, replacing at least a portion of the bromine atoms, without compromising the structure of the main chain and not changing the molecular weight and/or characteristics of the molecular mass distribution of the main circuit of such a copolymer.According to various publications to present the N, N, N',N'-tetramethylethylenediamine (TMEDA), and then metallizovannoe derived by interaction with the electro-faceted reagent transform in various functionalized derivatives. In Harris and others in the U.S. patent 4145490 and in Macromolecules, 19, 2903-08 (1986) described the metallation lithium copolymers of isobutylene with styrene and/or etilirovannym styrene as a means of introducing functional groups in the copolymer to prepare for the polymerization evalulation. It is obvious that the result of this method, described by Harris and others, is the introduction of functional groups at the place of both primary and tertiary benzyl carbon atoms methylated styrene comonomers link, as well as its aromatic ring carbon atoms. Some of the disadvantages associated with the way Harris and others, are the necessity of using a large excess of reagent (alkyl-Li/TMEDA), the incompleteness of metallation p-methyl styrene group-level and long duration of the reaction. Therefore, we can assume that the possible advantage of the method of Harris and others as a means of introducing functional groups into the new IB-PAS-copolymers described in U.S. patent 5162445, it would probably only be achieved if combined the with the introduction of lithium also at the place of tertiary benzyl carbon atoms in the main copolymer chain.In the literature, there are also message concerning the combination sociallising connection with the alkoxide heavier alkali metal with the formation of the reagent, which was called "coronoary" and which has a very high reactivity when conducting metallation reactions in organic synthesis and polymer chemistry. The use of coronaves reagent prepared from litiialkilov and potassium alkoxide, for metallation of aromatic hydrocarbons like benzene, toluene, ethylbenzene and cumene to get metilirovannye materials, in which the counterion is not lithium, and the heavier alkali metal, described in such literature as J. Organometallic Chemistry, 28, 153-158 (1971); J. Organometallic Chemistry, 326, 1-7 (1987); Tetrahedron Letters, 32 (11), 1483-86 (1991).In various publications there are even reports of such simple aromatic molecules on a variety of intermediate metallizovannyh products that are derived products resulting from interactions metallizovannogo intermediate product with methyliodide. In addition to the products, the structure of which has not been specified, other products metallation reactions using alkyl-Li/K-alkoxide carbon atoms of the aromatic ring.At Lochmann and others in Polym. Mat. Sci. Eng., 69, 426-7 (1993), Polymer Preprints, 34(2), 588-9 (1993) described metallation of geopolitical and dendritic polyester alkyl-Li/potassium-tert-pentoxide Verhoeven reagent as a means of introducing functional groups, resulting in further functionalized polymeric materials can be turned into a grafted copolymers or polyfunctionality dendrimers with a significantly modified properties. In this publication reiterated that the metallation of the main circuit (i.e., the metallation tertiary benzyl carbon atoms in the main polymer chain) when using litearcy/potassium-tert-pentoxide of coronaves reagent flows to an even greater extent in comparison with that which is achieved using litearcy/TMEDA-reagent similar to that previously was used by Harris and others metallation of such carbon atoms of the main chain breaks, probably the hydrocarbon nature of the polymer main chain of these new copolymer materials described in U.S. patent 5162445, with possible undesirable effect on their chemical inertness. In addition, also reported a significant degree of metallation of aromatic ring carbon atoms, which is about the way, the objective of the invention is to develop a method of converting new copolymer materials functionalized derivatives without modification in an inert hydrocarbon structure of the main copolymer chain.According to the present invention proposes a method, which provides the functionalization is described in U.S. patent 5162445 isobutylene-paralleltimeline copolymer in place of the benzyl carbon paralelno group styrene comonomers link without noticeable changes of the microstructure of the main chain of the copolymer, the molecular weight or molecular mass distribution, and the nature of the aromatic ring carbon atoms of the aromatic group is suspended on the main copolymer chain. This method includes processing the isobutylene-paralleltimeline copolymer in the form of a solution in a hydrocarbon solvent exposure coronoary, i.e. coronoary obtained by the interaction sociallising connection with the alkoxide of an alkali metal higher atomic mass, with the formation of metallizovannogo material, the counterion of which is an atom of an alkali metal higher atomic mass (Na, K, Cs) and which is localized at the place of prealc the polymer material is formed very quickly, within a few minutes, allowing you to get the target metallizovannyj polymeric material according to the method of continuous reaction in the piston flow. You can contact such metallizovannogo copolymer with an electrophilic reagent for the conversion of metallizovannogo copolymer in a derivative containing a functional group which bears an electrophilic reagent and which is covalently linked with the benzyl carbon atom paralelno group, an aromatic radical, suspended on the main copolymer chain.All reaction conditions, the metallation of the copolymer on a molar ratio between liteally compound and the molar content paralleltimeline units in the copolymer, the molar ratio of alkoxide heavier alkali metal and alkyllithium compound and the reaction temperature of the metallation is chosen in such a way as to minimize the possibility of reaction of metallation at the place of the aromatic ring carbon atoms with a maximum metallation at the place of primary benzyl carbon atoms.It was found that in the selected reaction conditions tertiary benzyl carbon atom Somalia main copolymer chain in his functionalizing derived as the product obtained in the practical implementation of this method, is preserved intact. Moreover, it was found that appropriate selection of the conditions listed above in combination with a selection of coronoary (Na, K or Cs) can reduce the metallation at the place of the aromatic ring carbon atoms to the extent that it is irrelevant, and/or to the almost complete elimination, thereby reducing the amount of functional groups in these areas in the final product or excluding them completely. In addition, it was found that the degree of metallation, and hence the functionalization, if you have in mind paralleltimeline component of the copolymer, can be reduced to any desired level up to almost one hundred percent, if necessary. It was further established that the metallation reaction can be performed up to its optimal level under which refers to the completeness and specificity of the reaction in the direction of metallation benzyl plots in comparison with the metallation of aromatic plots within a relatively short period, usually less than 10 minutes, and without the necessity to use a substantial excess soronovych reagents. In addition to osmotica to use reduced amounts of nucleophilic reagents for processing in situ metallizovannogo copolymer during its conversion in the functionalized copolymer product. In addition, since the functional group in the copolymer is injected through the intermediate metallizovannyj copolymer using electrophilic reagents, there is the possibility to enter in the isobutylene-paralleltimeline copolymer functional groups of certain types, the introduction of which by way of using the synthesized nucleophilic reagent is described in U.S. patent 5162445, impossible.Thus, we propose a method of metallation copolymer isoolefine and alkylthiol place alkylbenzenes carbon atom, and this method includes the preparation of a solution of the copolymer in a hydrocarbon solvent; adding to this polymer solution of alkali metal alkoxide and sociallising connection with the formation of coronoary in combination with the polymer solution and the selection metallizovannogo copolymer. In accordance with the present invention it is also proposed a method of introducing a functional group in the copolymer isoolefine and parallelsthe place alkylbenzenes carbon atom, and this method includes the preparation of a solution of the copolymer in a hydrocarbon solvent; adding to this polymer solution of alkali metal alkoxide and whether the ESD polymer solution electrophilic compounds and the selection metallizovannogo copolymer. There are also new statistical copolymers empirical formula
< / BR>where a = 1-70000, b = 1-7000 and C = 0-7000, R1and R2each independently from each other - C1-C5alkyl or hydrogen, provided that at least one of R1and R2- alkyl and R1+ R25 carbon atoms; R3and R4each independently of one another is hydrogen or C1-C4alkyl group, and M is an alkali metal other than lithium. In a preferred embodiment, the alkaline metal chosen from the group comprising sodium, potassium or cesium. Also preferred alkylthiol is parallellity. In another variant implementation of the present invention is provided by the engagement metallizovannogo copolymer with electrophilic connection with obtaining translated in electrophilic form of alkylthiol.There are also functionalized derivatives of products of formula I. Such functionalized polymer is a product resulting from the interaction of a copolymer of Monoporeia and alkylthiol with sverhsoznanie and electrophilic reagent. These copolymers correspond to the formula
< / BR>where a = 1-70000, b = 1-7000 and C = 0-7000, R1and R2 from R1and R2- alkyl and R1+R25 carbon atoms; R3and R4each independently of one another is hydrogen or a fragment WITH1-C4alkyl group, a F - electrophile.Monitoredin-paralleltimeline copolymers that can be applied in the process of metallation/functionalization by the proposed method are the products described in U.S. patent 5162445, which fully included in the present description by reference. These copolymers are of particular interest and, therefore, the preferred copolymers are copolymers of isobutylene (IB) and parallelsthe (PAS), in particular copolymers of isobutylene and parameterstyle (PMS), which are further designated as IB-PMS copolymers. Of these IB-PMS copolymers are most preferred are IB-PMS copolymers which exhibit elastomeric properties, i.e., those in which the mass percentage of IB-monomer unit typically ranges from approximately 99.5 to about 50, and the content of PMS-of monomer units is from about 0.5 to about 50 wt.%. Srednekislye molecular weight (MP) of these elastomeric IB-PMS copolymers typically 500 or more, predpochtitel the place less than 6.0, preferably less than 4.0, and most preferably less than 2.5.IB-PMS-elastomeric copolymers, when they are functionalized in accordance with the present invention, is particularly effective and suitable for use in the composition of the compounded rubber compounds, as well as blending components in the preparation of compositions in a mixture with other thermoplastic and/or elastomeric polymers used in the manufacture of the carcass, sidewall, tread and other components of a pneumatic tire with excellent performance properties.Coronally reagent for metallation
The reagent used for treatment of IB-PMS-copolymer with getting it metallizovannogo option, is a product formed by the interaction of sociallising connection (AkLi) with the alkoxide heavier alkali metal (ACOM), when both substances are neutral non-polar solvent such as a hydrocarbon solvent.Socialscience connection
In accordance with one of the selection criteria sociallising compounds used to obtain coronoary, you should choose this litelnogo carbon atom.The alkali metal alkoxide
Alkoxide reagent with a heavier alkali metal can be obtained by the interaction of metallic sodium (Na), potassium (K), rubidium (Rb) or cesium (Cs) with alkanols in nonpolar solvent. This alkoxystyrene (Ako) alkoxide of an alkali metal as the reagent corresponds to alkanol (Law), from which he received. Among the alkoxides of alkali metals, which can be used as reagents for the practical implementation of the present invention, are those who receive the interaction of the alkali metal with isopropanol, sec-butanol, tert-butanol, 2-pentanol, 3-pentanol, tert-pentenol, 3-methyl-3-pentanol, 2-hexanol, 3-hexanol, 2-methyl-2-hexanol, 2-heptanol, 3-heptanol, 4-1(-)mentalgate.com, 3-methyl-3-hexanol, 2-ethyl-2-hexanol, 3-ethyl-3-hexanol, 2-propyl-2-pentanol, 2-isopropyl-2-pentanol, 3-propyl-3-pentanol, 3-isopropyl-3-pentanol, methanol, etc., Usually in a preferred embodiment, for the convenience of the process and selection of side reaction products functionalization as reagent use alkoxide of an alkali metal, boiling point akinrinola predecessor which under daleste reagents are containing alkali metals products interactions involving 2-ethyl-2-hexanol (2EtHexOH), menthol (MapOn), tert-pentanol (tert-Reon).Getting coronoary
Solvents that can be used to obtain litiialkilov, alkoxide of an alkali metal and/or coronoary, which is formed as a result of their interaction, are neutral non-polar liquid, preferably such as hydrocarbon solvents boiling temperature which is from about 0 to about 200oC. When appropriate, the boiling temperature can be higher or lower. As the hydrocarbon solvent can be used aliphatic or cycloaliphatic hydrocarbon, preferably a hydrocarbon, in which IB-PMS copolymer is soluble at least to the extent of approximately 2 wt.%. Among the acceptable solvents, preferred solvents include pentane, n-hexane, heptane, octane, decane, cyclohexane, methylcyclohexane etc.Coronally reagent can be prepared separately from the polymer solution, in which it is introduced in the future, or it can be obtained in situ, i.e. in the polymer solution in the introduction to this solution sociallising compounds and alkali metal alkoxide. In the case of obtaining in situ in the polymer solution in ptininae. The molar amount of coronoary is usually equal to the molar quantity of litiialkilov used to obtain it.The reaction conditions metallation
Regarding the extent to which metallinou alkylbenzene carbon atoms in comparison to aromatic ring carbon atoms of the styrene units IB-PAS-copolymer, it should be noted that on the course and nature of the reaction according to the observations is significantly influenced by the following reaction parameters: (1) the molar ratio between Verhoeven compound and styrene comonomer component of the copolymer; (2) the molar ratio between liteally connection and alkoxide compound of an alkali metal, which is used to obtain coronoary; (3) the nature of the alkali metal atom (M), used to obtain coronoary; (4) the temperature of the polymer solution during the metallation reaction; (5) the nature of the alkyl residue sociallising compounds selected to receive coronoary, and (6) the conditions of mixing, in which the reaction takes place metallation. With proper choice of conditions, the metallation reaction may occur to the extent the almost complete metallization styrene comp polymer chain) or does not proceed, or proceeds in such a small degree that is undetectable by standard methods NMR analysis.The molar ratio of coronoary to paralleltimeline the copolymer may be in the range from about 1 to about 2, preferably is 2.0. Litearcy can be applied in number, in which the molar ratio of it to the styrene comonomers component exceeds 2.0. The content of coronoary, in which the ratio exceeds 2:1, it may be undesirable, since this would require increasing the amount of the nucleophilic reagent used for processing in situ metallizovannogo copolymer for its conversion in functionalized product. The amount of the alkali metal alkoxide used to obtain coronaves reagent may be in the range in which the molar ratio of it to the number of used litiialkilov is from about 1 to about 5, preferably from about 1.1 to about 3.0, and more preferably equal to or approaches to 3.0. It is preferable to use an excessive amount of alkali metal alkoxide on the number of litiialkilov, preferably modernistisen 3:1. In these intervals, the higher the degree of metallation with the greatest focus in relation to the metallation benzyl carbon atoms parallelnyh groups styrene comonomer component in comparison with the metallation at the place of the aromatic carbon atoms is achieved when the molar ratio AkLi/AkOM/styrene comonomeric component is approximately 2/6/1.Moreover, when socialscience compound and the alkali metal alkoxide is used in preferred amounts, the highest degree of metallation in place of the benzyl carbon atoms parallelnyh groups styrene comonomer component with the greatest degree of orientation in comparison with the metallation at the place of the aromatic carbon atoms is achieved in the case where the alkali metal alkoxide of alkali metal reagent is cesium (Cs), less preferred potassium (K), and the least preferred is sodium (Na). Further, in the case of the preferred alkoxides Cs and To the highest degree of orientation in relation to the metallation at the place of benzyl carbon atoms parallelnyh groups styrene comonomer Zverev achieved taggerty atom, and with a secondary carbon atom alkyl residue.Preferred sverhsoznanie systems for the metallation otoolefan-paralleltimeline copolymer are combinations of second-utility or tert-Reach or MenOCs. The most preferred MenOCs. In this system for the metallation reaction metallation occurs in a wide temperature range from a temperature just above the freezing point of the used solvent to a temperature just below the boiling point of the solvent. The degree and direction in which the reaction takes place metallation, the temperature at which it is conducted, significant influence, apparently, has not. In a preferred embodiment, the metallation reaction is carried out at a temperature in the range of 15-85oWith, mainly 20-70oC, more preferably at about room temperature, i.e. at about 20-25oC.The metallation reaction is relatively fast, and its duration, as a rule, is in the range of about several minutes, in particular ranges from about 2 to 30 minutes, preferably about 15 min, and it is the time, in Technoeconomic cases leads to a decrease in the quality of the product relative to the optimum, which otherwise reach within a shorter reaction time.Functionalization metallizovannogo product
For the conversion of metallizovannogo isobutylene-paralleltimeline copolymer in a derived product in a solution containing the copolymer, the electrophilic reagent can be introduced as such or in the form of a solution.Electrophilic reagent (FMo) is a molecule that contains an atom or group (F) with a deficit of electrons, usually interacting with atoms of nucleophilic compounds, in which there is an excess of electrons. The remainder of the electrophilic reagent may be any molecular structure (MIS), including any number of functional groups (F). Atoms with a deficit of electrons electrophilic reagent interact with metallizovannyj carbon atoms metallizovannogo copolymer, and these last are essentially metilirovannye benzyl carbon atoms parallelnyh groups styrene comonomer component, which have an excess of electrons and is able to give a pair of electrons. Thus, the reaction in which P represents a polymer chain can be represented as follows:
< / BR>Actionline group of the obtained composition (as in the case of carbon dioxide, which forms a carboxyl functional group, or dimethylcarbonate, which forms methylcarbonate functional group) or makes the resulting composition of an already existing functional groups (as in the case of 3-bromo-1-propene, which forms a 4-butylene side group).Acceptable electrophilic reagents include organic or inorganic compounds. Examples of Lewis acids organic classes that can be used as electrophilic reagents are compounds bearing a carbonyl carbon atoms, such as aldehydes, ketones, esters; compounds containing halogen atoms, such as organic halides, acylchlorides (gililland, methacrylicacid), trialkylsilyl (chlorides and bromides), trimethylsilane, sulphonylchloride, benzylchloride, aliphatic or silicalite; Tony, fluoroaromatic compounds, substituted electron-withdrawing groups, such as paratanytarsus and performancefrom; compounds containing epoxy functional groups, such as ethylene oxide, and CO2.The composition resulting from the reaction with participation of metallizovannogo Solimar depending on the degree of metallation of this copolymer Monoporeia and parallelsthe before its interaction with an electrophilic reagent. In the case where the copolymer metallicafan in extent, which is below the full metallization his paralleltimeline comonomer component, the product formed as a result of its interaction with the electrophilic reagent is a ternary copolymer of Monoporeia, parallelsthe and parafunctional of alkylthiol, where the term "perfunctionary alkylthiol" means comonomer composition, which is formed during the interaction metallizovannogo paralleltimeline of co monomer with an electrophilic reagent. Although the invention is described with reference to alkylthiol, representing p-alkylthiol, you can also use m-alkyl - o-alkylthiols.These polymers are used in the material of the tire, upon receipt of the polymer mixture in the preparation of structural plastic mixtures, in forming air membranes, in the preparation of adhesives and sealants, materials for coating and manufacture of products of mechanical presses.EXAMPLES
General procedure a
Metallation of the isobutylene-parameterstyle copolymer
Cleaned and dried the isobutylene-parameterically copolymer is dissolved is th solution is stirred. The concentration of polymer in the solution is 5% (weight/volume). Before the introduction of the alkali metal alkoxide (approximately 1 M solution of alkali metal alkoxide in hexane or cyclohexane), the solution is cooled or heated to the temperature indicated in tables 1 and 2. After the introduction of the alkali metal alkoxide to add liteally component that in all cases, unless otherwise stated, represents approximately 1.3 M solution of sec-BuLi in hexane. Almost instantly the colour of the solution changed from colorless to yellow, orange, red or dark red depending on the choice of the alkoxide and the molar quantities of reagents used (alkoxide of an alkali metal and litiialkilov). Usually the reaction of formation of coronoary () allow to proceed for 15 minutes Adding an excess of appropriately selected electrophilic compounds (as such or in the form of a solution) type trimethylsilylpropyne (Tmscl) leads to the formation of transparent and almost colorless solution. Before processing the stirring is continued for at least an hour.General method B
Processing functionalized isobutylene-parameterstyle copolymer
The HCl Er, double-1 N. aqueous NaOH solution, twice with saturated aqueous sodium bicarbonate solution and finally with water. The organic layer is separated from the water. Precipitation in acetone, isopropanol or methanol (depending on the characteristics of the solubility of the functionalized polymer) get the target polymer product. Organic liquid decanted, and the remaining polymer was washed several times using methanol. In conclusion, the polymer is dried in vacuum at room temperature or at slightly elevated temperature (60oC).General method IN
The study of the dependence of the metallation isobutylene-parameterstyle from time
Cleaned and dried the isobutylene-parameterstyle dissolved, preferably in a hydrocarbon solvent such as hexane or cyclohexane. While continuing the stirring, add the metal alkoxide. After that, the solution is cooled or heated, as indicated in tables 1 and 2. Quickly add socialscience connection, which leads to almost instantaneous formation of a solution, painted in dark red color. At set intervals of time selected aliquots of the solution metallizovannogo polymer and quickly injected into 4-8-fold excess Tmscl, kotoryy. The upper liquid layer is decanted, and the remaining polymer was washed several times using methanol, followed by drying at 60oC in vacuum for at least 24 hEXAMPLES OF METALLATION
Molar quantities are given for the isobutylene-parameterstyle copolymer, are among the p-methylstyrene units contained in the polymer. The reaction was carried out according to the method described in "General procedure a". Unless another time period between adding sociallising connection and Tmscl was 15 minutes Processing, described in General method B", conducted without extraction of the organic phase. The polymer products were dried at 60oC in vacuum for at least 24 hours of Reaction, the duration of which is specified as other than 15 min, were performed according to the section "General methods".The following tables 1 and 2 summarizes soronovych the reagents and reaction conditions metallation, the measure of which is the result of sililirovanie. In these tables, "EQ." refers to the molar equivalents of the used product relative to the number of p-methylstyrene links contained in the isobutylene-parasiteware provisions in p-methylstyrene link copolymer; "CT" means room temperature. The degree of sililirovanie in place of benzyl/ring positions were determined by1H-NMR spectrogram; this degree is similarobama in a molar percent of these areas in terms of the molar content of the p-methylstyrene comonomeric component of the copolymer.The experiments whose results are presented in table 2, were carried out in accordance with the General methods a and B, except that in some experiments, as indicated, Verhoeven complement TMEDA or proton sponge as an additive, 1,8-bis (dimethylamino) naphthalene (proton sponge), in which these quantities were introduced in the polymer solution during the addition of alkali metal alkoxide.Example. 0.32 g isobutylene-parameterstyle (0,139 mmole of parameterstyle per 1 g of polymer) dissolved in 3.5 ml of cyclohexane. Add to 8.3 ml (0,833 mmol) of freshly prepared 1-(-)pentoxide cesium or 1-(-)pentoxide potassium (0.10 M solution in cyclohexane), and then add 0,214 ml (0,278 mmol) of sec-BuLi (1.30 M solution in hexane). The solution of dense dark red is stirred for 15 min at room temperature, and then the reaction abruptly stop 4x is the establishment of a 10-fold volume of isopropanol. The solvent is decanted, the remaining polymer is washed several times with methanol and finally dried at 60oC in vacuum for 24 hours of the Degree of sililirovanie, as determined by1H-NMR spectrogram, more than 99% for benzyl position, and approximately 2% sililirovanie reach at the place of the aromatic ring of p-methylstyrene group.EXAMPLES OF FUNCTIONALIZATION
General method G
The reaction functionalization using electrophilic compounds other than Tmscl, carried out according to the section "General procedure A, substituting Tmscl, as indicated, reactive electrophilic compound. Taking into account the number of p-methylstyrene links, as a reagent for the metallation using 2 EQ. sec-BuLi and 6 EQ. tert-Reach. The metallation reaction after 15 min abruptly stop using an excess of the specified electrofishing connection. In the case of electrophilic compounds, prone to side reactions such as crosslinking, preferably a reverse addition, the introduction of the solution metallizovannogo polymer in a solution of a hydrocarbon and electrophilic compounds. The treatment is carried out in sootwetstwii obtain, to which they relate.Gaseous formaldehyde
The pyrolysis of the dried paraformaldehyde was carried out at approximately 130oWith in an inert atmosphere. The resulting gas was introduced into the solution metallizovannogo polymer. After the disappearance of the dark red color of the reaction mixture and its transition to the yellow reaction mixture was treated according to the described method. Yield: 70%.This reaction was also conducted at elevated temperatures (40-50oC). May reduce the number used WITH the [sec-BuLi (1.1 EQ. )/tert-Reach (1.5 EQ.)] with a weak influence on the output. Yield: 60%.Paraformaldehyde
Paraformaldehyde was dried under reduced pressure over P2ABOUT5. It was introduced into the solution metallizovannogo polymer at room temperature, the resulting dark-red solution slowly turned yellow. After 1 h the reaction mixture was processed. Yield: 40%.Metallopolymeric
Dried metallopolymeric was introduced into the solution metallizovannogo polymer. Within 10 min of dark-red color changed to yellow and after 1 h the reaction mixture was processed. Yield: 57%.The ethylene oxide
Gaseous ethylene oxide entering the red colour of the solution changed to yellow. Despite the use of an excess of ethylene oxide growth chains were not observed. Output: 50-70%.When replacing pentoxide potassium 1-(-)minoxidol cesium watched the chain growth. However, the yield did not increase.CROTONALDEHYDE
Fresh CROTONALDEHYDE dropwise introduced into the solution metallizovannogo polymer. After 1 h the reaction mixture was treated according to the described method. Yield: 45%.Citral
Fresh citral dropwise introduced into the solution metallizovannogo polymer. After 1 h the reaction mixture was treated according to the described method. Yield: 40%.2.2.2-Trimethyloxonium aldehyde
Fresh tert-butyl aldehyde was dropwise introduced into the solution metallizovannogo polymer. After 1 h the reaction mixture was treated according to the described method. During this reaction, with the aim to study the influence of the chiral alkoxide in the reaction mechanism of the pentoxide potassium was replaced with 1-(-)minoxidol cesium. When determining the optical rotation of the product received a small, but significant positive value. However, the value of the rotation of the plane of polarization of light in alkoxides the solution is negative. Thus, nablyudatelnaya was dissolved in a mixture of cyclohexane with THF in a volume ratio of 2:1. At room temperature was added dropwise a solution of metallizovannogo polymer. Dark red color immediately disappeared. At the end of the addition the solution has gained a reddish color. To obtain a clear solution was added a THF, and then added 10% aqueous Hcl solution and the reaction mixture was stirred over night. The rest of the processing described in General method B. Yield: 15%. The acid treatment resulted in the removal of water. Thus, the final product contained stilbene units, substituted carboxyl groups.Dimethylcarbonate
To clean, dried and distilled to dimethylcarbonate dropwise and with vigorous stirring solution was added metallizovannogo polymer. Immediately disappeared dark red color and formed a transparent yellow solution. After stirring, which was continued at room temperature overnight, the reaction mixture was treated according to the "method B". In this particular case, extraction of the grounds was dismissed. Yield: 23%.Carbon dioxide
The solution metallizovannogo polymer was transferred into a large excess of solid carbon dioxide. The resin has hardened. Before dobavlenii dark red coloration of the polymer disappeared with the same speed, with which the polymer was in solution. After using a 10% aqueous solution of Hcl to obtain the carboxylic groups in their protonated state and abrupt stopping the reaction, the reaction mixture was left to stir at room temperature overnight. The product was pure enough, making functionalized polymer can be dried without prior deposition (yield: 74%). The metallation was performed with a more significant excess coronoary ratio (MMR/sec-BuLi/TpeT-PeOK was 1/4/7,3). The metallation was essentially completed within 2 minutes as a result of interaction with carbon dioxide yield was high (94%) and without detectable carboxylation product around the ring.Allylbromide
In the solution metallizovannogo polymer dropwise introduced the fresh allylbromide. During this procedure, the solution with dark red color was yellow. Stirring was continued for 1 h Treatment included precipitation, washing and drying (see General method B). Yield: 40%.2-Khlorehtilaminami ether
In the solution metallizovannogo polymer dropwise introduced a fresh 2-khlorehtilaminami ether. While this was procedual deposition, washing and drying (see General method B). Yield: 50%.220.127.116.11-Tetramethyl-1-(3-chlorpropyl)-1-Aza-2.5-disilacyclobutane
Before applying protected by the silane amine was distilled. It was dissolved in cyclohexane (approximately 0.60 M solution) and at room temperature this solution was added metallizovannyj polymer. When you add a dark red polymer solution immediately disappeared. After this add the light yellow solution was stirred for 1 h was Added acetic acid (concentration of 50 vol.%) in the amount of one-fifth volume of this solution and the reaction mixture is boiled under reflux for 1 h the Solution is the color of milk was cooled to room temperature, and then were extracted with isopropanol/water solution of KOH (approximately 1 N.; isopropanol/N2O in a volume ratio of 1:10). It additionally was extracted 6 times with isopropanol/N2About in a volume ratio of 1:1. The organic layer was concentrated and finally the polymer from solution besieged in the 5-fold volume of isopropanol. The polymer was repeatedly washed with isopropanol. Functionalized with primary amino groups, the polymer was dried in vacuum at 65oC for at least 1 day. Vyhodnogo polymer. The reaction proceeded instantly, as it was shown by the disappearance of dark-red colour and the formation of a clear solution with a yellow tint. After 1 h the reaction abruptly stopped using 10-fold excess under the conditions. Stirring is continued initially at room temperature, and then boiling the solution under reflux for 3 hours This reaction mixture was treated according to the section "General procedure B, except that in the implementation stage of drying at room temperature in vacuum was cross-linked polymer.N. N-Dimethylformamide (DMF)
Stir in the emulsion of fresh DMF) in n-hexane at -78oWith a slow flow solution was added metallizovannogo polymer (-78oC). During this add a dark red color, characteristic of metallizovannogo polymer, instantly disappeared. Within 30 minutes of continued intensive stirring, after which was added 10% aqueous Hcl solution in the amount of approximately half of the volume of the organic phase. Mix the suspension gently warmed to room temperature. The aqueous phase after 3 h was separated from the organic phase and in acetone was besieging the polymer from the second washing of the remaining polymer used methanol. The sample was dried at room temperature in vacuum for at least 24 h Dried polymer was impossible to re-dissolved in hydrocarbon solvents or THF. During this process was carried out by metallation of the isobutylene-parameterstyle, differing from those described in the sections entitled "General method" that was used only 1.25 equiv. sec-BuLi and 1.50 EQ. tert-Reach.1-Formylpiperidine
Reaction conditions and the observed results are identical to those specified for the case of the use of DME as an electrophilic compounds.D2O
In the solution metallizovannogo polymer was added in considerable excess of D2O (PMS/second-uLi/tert-Reach in the ratio of 1/1,5/3). Dark red color of the solution changed to colorless. Deuterated copolymers were isolated in 70% yield. 1. The method of introducing the functional group in the copolymer isoolefine and alkylthiol in place of the carbon atom alkyl group side chain, which is directly connected to an aromatic ring, comprising preparing a solution of this copolymer in a hydrocarbon solvent, an introduction to polymer solution alkaline alkoxide m the solution and the introduction of such alkaline polymer solution electrophilic compounds.2. The method according to p. 1, where the molar ratio of coronoary and alkylthiol is from about 1: 1 to about 2: 1.3. The method according to p. 1, where the alkali metal alkoxide and litearcy injected sequentially.4. The method according to p. 1, where the first by the interaction of alkali metal alkoxide and litiialkilov getting coronoary and this Verhoeven added to the polymer solution.5. The method according to p. 1, where the alkali metal alkoxide is an alkoxide of cesium or potassium.6. The method according to p. 5, where the alkali metal alkoxide is an alkoxide of cesium.7. The method according to p. 5, where socialscience connection is a secondary socialscience connection.8. The method according to p. 7, where socialscience connection is a second-utility.9. The method according to p. 1, where alkylthiol is a p-alkylthiol.10. The method according to p. 1, where p is alkylthiol is a p-methylsterol.11. The method according to p. 1, where the copolymer is an isobutylene-para - methylstyrene copolymer.12. The method according to p. 1 wherein the electrophilic compound selected from the group including acylchlorides, CO2CS2the electron group, siliclone, aldehydes, ketones, carbonates, esters and anhydrides.13. The copolymer produced by the interaction of electrofishing reagent with metilirovaniem copolymer, which is obtained by the reaction of a solution of a copolymer of Monoporeia and alkylthiol with sverhsoznanie obtained from one alkoxide from the group of alkoxides Cs or Na and sociallising connection.14. The copolymer under item 13 of the formula
< / BR>where a= 1-70000;
R1and R2each independently from each other - FROM1-C5alkyl or hydrogen, provided that at least one of R1and R2- alkyl and R1+ R25 carbon atoms;
R3and R4each independently of one another is hydrogen or C1-C4alkyl group;
Q - electrophilic fragment.15. The copolymer according to p. 14, where the fragment is selected from the group including aldehydes, ketones, esters, organic halides, acylhomoserine, trialkylsilanes, sulphonylchloride, benzylchloride, aliphatic halides, silicalite, Tony, fluoroaromatic compounds, epoxides, amisulpride, CO2and polymer fragments containing ASS="ptx2">17. Statistical copolymer of the formula
< / BR>where a= 1-70000;
R1and R2each independently from each other - FROM1-C5alkyl or hydrogen, provided that at least one of R1and R2- alkyl and R1+ R25 carbon atoms;
R3and R4each independently from each other hydrogen, C1-C4alkyl group;
M is an alkali metal other than lithium, or 10-100% M replaced by an electrophile.18. The copolymer under item 17, where M Is Na, K or Cs.19. The copolymer under item 18, where alkylthiol and metallizovannyj alkylthiol represent n-alkyl - and n-metallizovannyj alkylthiol.20. The copolymer under item 17, where alkylthiol and the functionalized alkylthiol represent n-alkyl - and n-functionalized alkylthiol.21. How metallation copolymer isoolefine and alkylthiol in place of the carbon atom alkyl group side chain, which is directly connected to an aromatic ring, which is provided by the preparation of a solution of this copolymer in a hydrocarbon solvent, an introduction to polymer solution of alkali metal alkoxide and sociallising connection with obtaining SV is about on p. 21, where the alkoxide of an alkali metal and litearcy injected sequentially.23. The method according to p. 21, where the first by the interaction of alkali metal alkoxide and litiialkilov getting coronoary and this Verhoeven added to the polymer solution.
FIELD: polymers, in particular method for production of random copolymers from one or more conjugated diene monomers, usable in rubber mixtures.
SUBSTANCE: target copolymers are obtained in continuous reactor for slurry polymerization. Method includes reaction in polar solvent of isoolefinic and diene monomers, Levis acid and initiator. Conjugated diene monomers are selected from group containing isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylsulfene, hexadiene; piperilene. Initiator has general formula , wherein X represents halogen atom; R1 represents C1-C8-alkyl and C2-C8-alkenyl; R3 represents C1-C8-alkyl, C2-C8-alkenyl, and phenylalkyl; R2 represents C4-C200-alkenyl, phenyl, phenylalkyl, alkylphenyl, C3-C10-cycloalkyl and group of formula , wherein X represents halogen atom; R5 represents C1-C8-alkyl and C2-C8-alkenyl; R6 represents C1-C8-alkyl, C2-C8-alkenyl, and phenylalkyl; R4 represents phenylene, diphenyl, ω,ω-diphenylalkane and group of formula -(CH2)n-, wherein n = 1-10, integer number. R1 R2 and R3 groups may also form adamantyl or bornyl rings, wherein X group in position of tertiary carbon atom. Reacted monomers in reactor form slurry in concentration of 20-50 % calculated as total mass of slurry, diluents, unreacted monomers and catalyst system.
EFFECT: improved heat transfer in reactor; production of copolymers at relatively high slurry concentration.
23 cl, 2 tbl, 5 ex, 6 dwg
FIELD: polymer materials.
SUBSTANCE: invention relates to air bladders such as inner tire cover or pneumatic tire tube including composition based on halogenated terpolymer constituted by units derived from C4-C8-isoolefins, units derived from C4-C14-multiolefins, and units derived from p-alkylstyrene. Compositions based on halogenated terpolymer are characterized by low air permeability, good adhesion to tire body, and acceptable longevity, which all allows their use in manufacture of air bladder.
EFFECT: improved performance characteristics of air bladders.
11 cl, 1 dwg, 8 tbl
FIELD: polymer production.
SUBSTANCE: invention relates to superhigh-molecular weight copolymer constituted by an α-olefin monomer with carbon chain length 4 to 9 carbon atoms and another comonomer, which is α-olefin with carbon chain length 2 to 20 carbon atoms or containing vinylaromatic monomer. Copolymer has molecular mass above 1000000 and no more than 25 mol % monomers with carbon chain length 12 carbon atoms or more. Copolymer of invention is completely dissoluble in heavy aromatic hydrocarbons at low temperatures such as 0°C. Another advantage of the copolymer consists in that it can be transported either in stable suspension or can be preliminarily dissolved in small amount of heavy hydrocarbon. Suspension of polymer lowering resistance of a medium is stable so allowing longer storage time and thereby enabling agreement between consumer's demand and delivery time. Secondary agglomeration of polymers leading to lower resistance of medium is considerably reduced ensuring easier processing in the production process.
EFFECT: facilitated flowability control.
14 cl, 1 dwg, 2 tbl, 4 ex
FIELD: chemical industry; method of production of the highly-active polyisobutenes.
SUBSTANCE: the invention is pertaining to production of the highly active polyisobutenes. The A method of production highly-active homo- and interpolymers of isobutene with the contents of the tail vinyliden groups exceeding 80 molecular percent, and number-average molecular mass from 500 to 10000 Da by the cationic polymerization of isobutene or the isobutene with the monomers suitable for the copolymerization in the presence of the complexes of the stabilized in the dissolvent transition metal containing the weakly coordinated anions. The technical result consists in development of the economical method of production of the highly active polyisobutene at the temperatures exceeding 0°С.
EFFECT: the invention ensures development of the economical method of production of the highly active polyisobutene at the temperatures exceeding zero degree Celsius.
4 cl, 1 tbl, 5 ex
SUBSTANCE: invention concerns a method for obtaining rubbers, particularly an uninterrupted obtaining of butyl rubber, and the butyl rubber. Butyl rubber with Mooney viscosity of at least 25 units and gel content of at least 15 mass % is obtained at the transformation degree within 50% to 95%. The butyl rubber includes repeating links derived from at least one isoolefine monomere, over 4.1 mol % of repeating links derived from at least one multiolefine monomere including isoprene, and optionally other co-polimersable monomers. The butyl rubber is obtained by polymerisation of respective monomers in the presence of initiating agent, which is a system containing AlCl3 and at least one proton source, e.g. water, and/or cation-generating substance capable of polymerisation initiating. The method is implemented in the presence of at least one multiolefine binding agent.
EFFECT: higher degree of butyl rubber transformation.
13 cl, 4 tbl, 4 ex
SUBSTANCE: method includes contacting of (i) C4-C7 isomonoolefin and p-alkylstyrole, or (ii) C4-C6 isoolefin and multiolefin, one or more Lewis acid, one or more initiator, and solvent, including one or more hydrofluorocarbons (HFC) in reactor. As hydrofluorocarbon, compounds, represented with general formula CxHyFz, are used, where x is an integer from 1 to 40, and y and z are integers. Solvent additionally includes non-reactive olefin, one or more other hydrocarbons, and/or inert gas.
EFFECT: reduction of particle agglomeration and reactor blocking, without degradation of process parameters, conditions or components, productivity of reactor capacity and ability to produce polymers with great molecular weight.
23 cl, 25 tbl, 148 ex, 3 dwg