Method for preparing block-copolymers

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of block-copolymers based on vinylaromatic monomers and monomers representing derivatives of (meth)acrylic acid. Invention describes a method for synthesis of block-copolymers by means of radical polymerization involving the following steps: (a) polymerization of vinylaromatic monomer at temperature 120°C or above in the presence of the radical-initiating system consisting of a compound of the general formula (I) given in the invention description and wherein R1 and R2 are similar or different and represent methyl or ethyl radical; X1 represents hydrogen atom; X2 represents hydrogen atom or hydroxyl, or X1 and X2, similar or different, represent (C1-C4)-(iso)alkyl radicals, or they form in common aromatic ring; n = 0 or 1; R3 represents radical chosen from one of the following groups: -C(CH3)2-CN, -CHCH3-Ph, or R3 is absent as unpaired electron occupies its place, and used in mixture with compounds (G) generating radicals chosen from peroxides, peracid esters, percarbonates, azobisdialkyldinitriles in the molar ratio (I)/(G) less 4 up to the conversion degree of monomer from 5 to 99.9%; (b) feeding a monomer representing a derivative of (meth)acrylic acid to polymerization mixture from step (a) after the necessary conversion degree in the amount providing the total mass of block-copolymer Mw is less 500000 Da, and this step is carried out at the same temperature and in the presence of the same initiating system; (c) isolation of synthesized block-copolymer after termination of the polymerization reaction. Also, invention describes a block-copolymer. Invention provides synthesis of block-copolymer comprising the decreased amount of homopolymer and statistic copolymer, elimination of the precipitation step and isolation of the first polymeric block.

EFFECT: improved method of synthesis.

11 cl, 11 ex

 

This invention relates to a process for the preparation of copolymers.

More specifically, this invention relates to a process for the preparation of copolymers based on vinylaromatic monomers and monomers derived from (meth)acrylic acid.

More specifically, this invention relates to a process for the preparation of copolymers based on styrene and/or α-methylstyrene and Acrylonitrile.

As you know, the classic way obtain copolymers involves the use of anionic polymerization. However, it has various disadvantages, such as a thorough and time-consuming purification of the monomers from the trace amounts of impurities and moisture. In addition, not all polar monomers can be subjected to anionic polymerization in good yield and acceptable reaction conditions due to their interaction with the originating system. An example of such a monomer is Acrylonitrile.

Over the last few years appeared in the literature where the copolymers synthesized by living radical polymerization is a more flexible technique as compared with the previous one, which also does not require excessive purity monomers.

Among the scientific literature on radical polymerization are, for example, Makromolecular Chemistry, Rapid Communication, 1982, 127 in which is described the use of so-called "interferon"who ve the ut itself as thermal and/or photochemical initiators, and also as agents of transfer circuit and agents, chain breakage and Makromolecular Chemistry, 1983, 184, 745, which describes thermal decomposition of tetraacrylate obtaining diphenylethylene radicals. These products are another example of initiators capable of "living" radical polymerization; in Journal of Polymer Science, Polymer Chemistry Ed., 1986, 24, 1251 described "living" radical polymerization by similarbank of pinecones, which behave similarly to the aforementioned tetraacrylate.

European patent 135280, international patent application WO 96/30421 and U.S. patent 4581429 are other examples of scientific literature describing the "living" radical polymerization.

The lack of "living" radical polymerization is that upon receipt of the copolymers it is necessary to carry out the synthesis and release of the first block, and then dissolving the thus obtained macromolecule in the second monomer or mixture of monomers, resulting after polymerization of the second block is formed.

This technique not only has technical flaws, which consists in conducting two different types of polymerization, which requires the use of two serially connected reactors, polymerization, but also leads to the formation of such end product which must be further treated to remove more and the less visible traces of homopolymer, or when working in the presence of a mixture of monomers) statistical copolymer, which are inevitably formed during the second phase polymerization.

Another known drawback, which are essential to ensure successful use of the products associated with the formation of polymers is usually yellow in color (due to decomposition). To solve this problem, WO 01/38431 proposed to mix the polymer agents reducing agents, such as phosphites or antioxidants (alkylated monophenol, hydrochinone, triazine, benzylphosphonate, ascorbic acid, amine antioxidant, etc.) or UV-stabilizers, hydroxylamine or Nitron. The stabilizer can be added to the polymer in the molten state, if he has a crystalline structure, and the polymer is heated to temperatures above Tgif it is amorphous.

Therefore, the objective of the invention is a method of producing copolymers by radical polymerization, which is free from the disadvantages inherent in the known solutions.

More specifically, the objective of the invention is a method of producing copolymers by radical polymerization, which allows to obtain products containing a reduced number of homopolymer or statistical copolymer, and furthermore has the advantage that it eliminates the time-consuming stage of deposition and release of the first polymer clay is tion of the block.

The applicant has found that this problem can be solved through the effective and efficient receipt of copolymers based on vinylaromatic monomers, such as styrene or α-methylsterol, and monomers derived from (meth)acrylic acid such as (meth)Acrylonitrile, consisting of at least two parts: the first containing only vinylaromatic links, and the second containing (meth)acrylic or vinylaromatic and copolymerizable (meth)acrylic units.

Therefore, the objective of the present invention relates to a method for producing block copolymers by radical polymerization, which includes:

a) polymerization vinylaromatic monomer at a temperature above or equal to 120°With, in the presence of a radical initiating system,

comprising the compound of General formula (I):

where R1and R2identical or different, represent a methyl or ethyl radical, X1represents a hydrogen atom, X2represents a hydrogen atom or hydroxyl, or X1and X2identical or different, represent a C1-C4(ISO)alkyl radical, or together they form an aromatic ring, n is zero or one and R3represents a radical selected from one of with EBUSY groups:

- (CH3)2-CN;

- (CH3)2-Ph;

-SSN3-Ph;

or R3no, because in its place is an unpaired electron;

until you achieve the degree of conversion of monomer is from 5 to 99.9%, preferably from 8 to 95%;

b) feeding a polymerization mixture of stage (a), after achieving the necessary degree of conversion of monomer - derived (meth)acrylic acid in such a quantity that at the end of the polymerization, the total mass of blockcopolymer Mwis less than 1000000, and at the same temperature and in the presence of the same originating system;

C) allocation upon completion of polymerization of the thus obtained of blockcopolymer.

In accordance with this invention, when the product of General formula (I) there is no R3because this place is unpaired electron corresponds to a stable radical compounds, known as "nitroxide or nitroxyl radicals", as described in "Advanced Organic Chemistry", J.March, fourth edition, str-191.

The term "vinylaromatic monomer", as used in the description and the claims, essentially refers to the product corresponding to the following General formula (II):

where R is a hydrogen atom or a methyl group, n is zero or an integer between 1 and d is 5, a Y is halogen, such as chlorine or bromine, or alkyl or CNS radical having from 1 to 4 carbon atoms.

Examples vinylaromatic of monomers having the General formula above are: styrene, α-methylsterol, methylsterol, atillery, butalbiral, dimethylstyrene, mono-, di-, tri-, Tetra - and pentachlorophenol, Postira, mitoxantron, acetoxystyrene etc. styrene and α-methylsterol are preferred vinylaromatic monomers.

Any monomer, which is derived from (meth)acrylic acid, can be used in the proposed method of obtaining copolymers, although the preferred Acrylonitrile and Methacrylonitrile. Other derivatives of (meth)acrylic acid is alkalemia esters in which the alkyl group contains from 1 to 4 carbon atoms, such as methyl acrylate, methyl methacrylate, acrylate, butyl acrylate, etc.

Polymerization as in stage (a)and stage (b) is conducted at temperatures above 120°C, preferably between 120 and 150°With, in the presence of an initiator having the General formula (I). The latter is present in such concentrations to activate the polymerization reaction to continue until the desired molecular mass Mw. Typical concentrations are in the range from 0.01 to 2 mol.% in relation to the total amount of mo is she coming monomers.

To facilitate implementation of the polymerization reaction initiator of General formula (I) can be used in a mixture with the compounds (G)generating radicals, such as peroxides, hydroperoxides, esters of percolat, percarbonate, assistancincinnati etc., when the molar ratio I/G below 4. In particular, the initiator of General formula (I) can be used with generators (G) free radicals such as peroxide of Dibenzoyl, peroxide of Dicumyl, N,N'-azobis(diisobutyrate) with molar ratios I/G in the interval from 1 to 3. The initiator (I) can also be generated "in situ"on the basis of the corresponding nitroxyl radical. Examples of the initiators of the General formula (I) as follows:

2-methyl-2-(2,2,6,6-tetramethylpiperidine-1 yloxy)propionitrile;

2-methyl-2-(4-hydroxy-2,2,6,6-tetramethylpiperidine-1 yloxy)propionitrile;

N-(2-phenylethane)-2,2,6,6-tetramethylpiperidine;

N-(2-phenylethane)-4-hydroxy-2,2,6,6-tetramethylpiperidine;

N-(2-phenylprop-2-hydroxy)-2,2,6,6-tetramethylpiperidine;

N-(2-phenylprop-2-oxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine;

1,1,3,3-tetraethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetraethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetraethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole.

After polymerization of the first vinylaromatic polymer block this method involves feeding the second monomer in the quantities listed above. During this stage acrylic monomer is mixed with unpolymerized vinylaromatic monomer, if any, and continuing the polymerization in the presence of the same initiating system.

At both stages of the polymerization can be periodic, continuous or semi-continuous manner at temperatures above 120°and when such pressure to keep the monomers in the liquid phase. Furthermore, the polymerization can occur in the presence of an organic solvent, in suspension or in bulk.

In the periodic process, the initiator system is added to vinylaromatic the polymer either in pure form or in the form of a solution or suspension in quantities indicated above. The reaction continues at the required temperature during the time from 15 minutes to 24 hours. When the desired degree of conversion, add a second monomer and complete the polymerization. At the end of the produce thus obtained block copolymers.

In a continuous process vinylaromatic the monomer, the initiator system and, possibly, the solvent is continuously fed into the polymerization reactor at such a flow rate to provide a residence time sufficient for the achievement of degrees of conversion in the range of from 5 to 99.9%. Then the reaction product serves in the second reactor together with acrylic monomer at such a flow rate, to ensure the required final composition of blockcopolymer. The reaction mixture at the outlet of this second reactor is treated to separate the product.

Optional, but not necessarily, the initiating system can slowly add in for the entire duration of the reaction or in part. One or both of the two monomers can also be dosed portions through successive intervals of time in order to modify the microstructure of the second unit, as necessary. At the end of the polymer is recovered from the polymerization mixture by one of the known in the field of methods, for example, by deposition of a suitable antibacterial or by distillation and removal of impurities under vacuum at high temperature.

Upon completion of the process, which is the task of the present invention, receive extremely clean copolymers in amounts of more than 50 wt.% from the whole product. The molecular mass Mweach of the blocks can vary from 1000 to 500,000, preferably 5,000 to 200,000, while the molecular mass of the polymer Mwcan vary from 10000 to 1000000, preferably from 20,000 to 500,000.

Polymer block at the stage (b) may contain a proportion vinylaromatic links in the interval from 30 to 90 wt.%, preferred is compulsory from 55 to 85%.

When radical initiating system, having the General formula (I), X1and X2together form an aromatic ring, and n is equal to zero, get completely unpainted products. Therefore, these products do not need to be subjected to further processing to remove yellow staining, which is in accordance with well-known in this area is characteristic of the polymers synthesized in this way, and thus, it simplifies the process of obtaining the polymer. Specific examples of these initiators are the following:

1,1,3,3-tetraethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetraethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetraethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole.

For a better understanding of the present invention and to describe the variant of the invention, the following are illustrative examples, not limiting the scope of the invention.

EXAMPLE 1

920 g of styrene were placed in a nitrogen atmosphere at room temperature (20° (C) in a two-liter steel autoclave, stable at a pressure of 20 bar (2 MPa), equipped with anchor stirrer and immersed tube for sampling at high pressure, as well as the shirt, cooled by circulating silicone oil. When applying nitrogen and stirring at a speed of 100 rpm and the temperature was raised to 60°and added 2.28 g (7,06 mmol) of benzoyl peroxide (as such, stable 25.1% of water), and 1.24 g (of 7.95 mmol) 2,2,6,6-tetramethylpiperidinyloxy radical (TEMPO), dissolved in 80 g of styrene; the concentration of initiator TEMPO in relation to the total number of moles of monomers comprised of 0.07 mol.%.

Then, the autoclave was closed and by means of nitrogen brought the pressure up to 2 bar (0.2 MPa). The reaction temperature was raised to 130°C for 25 minutes. Upon reaching this temperature through an immersion tube, fitted with a valve, removed 85 g sample of the reaction mixture. The same sampling was repeated every 30 minutes until the end of the test and for each sample gravimetrically measured the degree of transformation (conversion). After 1 hour 30 minutes after reaching 130° (the degree of conversion = 34%) by means of a pump was administered to 132 g of Acrylonitrile within 10 minutes (so that the residual mixture of styrene/Acrylonitrile corresponded to the composition of the azeotropic mixture). After 3 hours after reaching 130°With the reaction mixture (containing 59% of polymer) was extracted under pressure of nitrogen in a glass vessel with a volume of 0.33 liters (810 vessels, each of which contained about 50 g of the reaction mixture).

Then, to separate the copolymer, contained in the reaction mixture, 10 vessels were immersed in a thermostatted bath with silicone oil, connected to a vacuum pump and brought a residual pressure of 10 mbar (1 kPa). Temperature controlled bath was raised to 220°C for 1.5 h and after reaching this temperature was cooled for 30 minutes.

As soon as the pressure is brought back to atmospheric, the vessels broke at room temperature, the copolymer was removed and crushed in a mill. To estimate the output of blockcopolymer, the resulting copolymer was then dissolved in cyclohexane (solvent polystyrene) and acetone (solvent for SAN), which received 56% of insoluble blockcopolymer, which, as was proven by using gel permeation chromatography (GPC), had Mw=102000 and Mw/Mn=1,18.

COMPARATIVE EXAMPLE 1

20 ml (175 mmol) of styrene, 30 mg (0,124 mmol) of benzoyl peroxide and 26 mg (0,166 mmol) 2,2,6,6-tetramethylpiperidinyloxy radical TEMPO (the concentration of the initiator TEMPO in relation to the total number of moles of monomers comprised of 0.07 mol.%) were placed in a reactor with a volume of 100 ml, equipped with a magnetic stirrer. The reactor was immersed in an oil bath at 125°and conduct a reaction for 5 hours.

After cooling, to the solution was added such an amount of EtOH, which is necessary for the deposition of polyster the La. Then the product was filtered and dried in a vacuum oven (30 Torr) for 8 hours. Cleaning of the sample was performed by dissolving in methylene chloride.

1.5 g PS, obtained as described above was dissolved in of 14.2 ml (124 mmol) of styrene, and 5 ml (76 mmol) of Acrylonitrile (which corresponds to the composition of the azeotropic mixture were placed in a reactor of 100 ml, equipped with a magnetic stirrer.

The reactor was heated on an oil bath to 125°C for 70 minutes. After cooling, the mixture was treated with 100 ml of EtOH. The product was filtered and dried in a vacuum oven (30 Torr) at 60°C for 8 hours. The degree of conversion was 48.1%.

Then, in order to estimate the output of blockcopolymer, the resulting polymer was dissolved in cyclohexane (solvent for polystyrene) and acetone (solvent for SAN), and received 25% of insoluble blockcopolymer, which, as was proven with the aid of gel permeation chromatography, had Mw=338000 and Mw/Mn=1,78.

COMPARATIVE EXAMPLE 2

Repeated the procedure described in comparative example 1, except that the first stage of the synthesis lasted 1.5 hours, the second stage is 1.5 hours, and the temperature at both stages was equal to 130°C.

Mw=360000; Mw/Mn=1,83; output blockcopolymer PS-SAN=20%.

EXAMPLE 2

Repeated the procedure described in example 1, adding acrylonitril after 30 minutes, not Celestin hour thirty minutes. The product had the following characteristics: Mw=71000; Mw/Mn=1,17; output blockcopolymer PS-SAN=64%.

EXAMPLE 3

Repeated the procedure described in example 1 by adding Acrylonitrile in two hours thirty minutes. The product had the following characteristics :

Mw=to 136,000; Mw/Mn=1,29; output blockcopolymer PS-SAN=52%.

EXAMPLE 4

Repeated the procedure described in example 1 by adding Acrylonitrile and conducting the reaction for three hours, not one hour thirty minutes. The product had the following characteristics :

Mw=153000; Mw/Mn=1,21; output blockcopolymer PS-SAN=51%.

EXAMPLE 5

Repeating example 1, using of 7.95 mmol 2-methyl-2-(2,2,6,6-tetramethylpiperidine-1 yloxy)propionitrile instead TEMPO and benzoyl peroxide.

Share blockcopolymer in the final reaction mixture was equal to 79%.

Mw=125000; Mw/Mn=1,31.

EXAMPLE 6

250 g of styrene containing dissolved 400 mg of 1,1,3,3-tetraethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole, pre-treated by bubbling nitrogen for 15 minutes, placed at room temperature in a steel autoclave with a volume of 600 ml, equipped with anchor stirrer, electrically heated jacket, internal cooling coil cooling system inlet and bottom discharge. The concentration of initiator relative to the total number of mole the monomers comprised of 0.038 mol.%.

For 50 minutes the reaction mixture was heated to 120° (h "0" counted from the time when the temperature reached 118°). 4 hours after hours of "0" was added to 51.3 g of Acrylonitrile. The temperature was maintained at 120°C for 1.5 hours, then the reaction mixture was cooled. 50 g of the mixture were taken for analysis. Of the remaining mixture of volatile components were removed at 14 mbar (1,4 kPa) and heated to 230°C for 2 h, maintaining these conditions for 30 minutes. At the end of the isolated product was cooled and granulated.

Received a colorless polymer having the following characteristics: output blockcopolymer PS-SAN=86%; Mw=115000; Mw/Mn=1,35.

EXAMPLE 7

Repeating example 6, using 200 mg of 1,1,3,3-tetraethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole, and leave the mixture to reaction for 6 h in the first stage and 2.5 h in the second stage. The final product had the following properties:

Mw=325000

Mw/Mn=1,56

the output of blockcopolymer PS-SAN=79%.

EXAMPLE 8

Repeating example 1, using, however, 4.40 mmole 2,2'-azobis(2-methylpropionitrile)and (AIBN) instead of benzoyl peroxide. The final product had the following properties:

Mw=126000

Mw/Mn=1,21

the output of blockcopolymer PS-SAN=58%.

EXAMPLE 9

Repeating example 1, using of 7.95 mmol 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy and 4.4 mmole 2,2'-azo is IP(2-methylpropionitrile)and (AIBN) instead of TEMPO and benzoyl peroxide. The final product had the following properties:

Mw=97000

Mw/Mn=1,33

the output of blockcopolymer PS-SAN=49%.

EXAMPLE 10

Repeating example 1, using of 7.95 mmol 4-butyl-2,2,6,6-tetramethylpiperidinyloxy instead TEMPO. The final product had the following properties:

Mw=111000

Mw/Mn=1,22

the output of blockcopolymer PS-SAN=62%.

EXAMPLE 11

Repeating example 1, using of 7.90 mmol of N-(2'-venlafaxi)-2,2,6,6-tetramethylpiperidine instead TEMPO and benzoyl peroxide. The final product had the following properties:

Mw=168000

Mw/Mn=1,19

the output of blockcopolymer PS-SAN=63%.

1. A method for production of block copolymers by radical polymerization, including

a) polymerization vinylaromatic monomer at a temperature higher than or equal to 120°in the presence of a radical initiating system consisting of compounds having General formula (I)

where R1and R2the same or different, represent a methyl or ethyl radical, X1represents a hydrogen atom, X2represents a hydrogen atom or hydroxyl, or X1and X2identical or different, represent a1-C4(ISO)alkyl radicals, or together they form an aromatic ring, is equal to zero or one, and R3represents a radical selected from one of the following groups:

- (CH3)2-CN;

-SSN3-Ph;

or R3no, because in its place is an unpaired electron;

used in a mixture with the compounds (G)generating radicals selected from peroxides, esters of percolat, percarbonates, assistancebbilateral, when the molar ratio I/G below 4; until not achieved the degree of conversion of monomer is from 5 to 99.9%;

b) feeding a polymerization mixture of stage (a), after achieving the necessary degree of conversion of monomer - derived (meth)acrylic acid in such a quantity that at the end of the polymerization, the total mass of the block copolymer Mwis less than 500000, and the stage is carried out at the same temperature in the presence of the same originating system;

C) allocation upon completion of polymerization of the thus obtained block copolymer.

2. The method according to claim 1, where the group R3represents-C(CH3)2-CN.

3. The method according to claim 1, where the group R3represents-SSN3-Ph.

4. The method according to claim 1, where the group R3is missing.

5. The method according to claim 1, where the polymerization as in stage (a)and stage (b) is conducted at a temperature in the range from 120 to 150°C.

6. The method according to claim 1, where the initiator has the speaker of the General formula (I), is present in concentrations in the range of from 0.01 to 2 mol.% in relation to the total number of moles of the incoming monomer.

7. The method according to claim 1, where the initiator having the General formula (I), use with generators (G) free radicals, selected from a peroxide of Dibenzoyl, peroxide of Dicumyl, N,N'-azobis(diisobutyrate), with molar ratios I/G in the interval from 1 to 3.

8. The method according to claim 1, where the polymerization as in stage (a)and phase (b) conduct periodic manner at temperatures above 120°and when such pressure to maintain the monomers in the liquid phase.

9. The method according to claim 1, where in radical initiating system, having the General formula (I), X1and X2together form an aromatic ring, and n is equal to zero.

10. The method according to claim 9, where the initiator having the General formula (I), choose from

1,1,3,3-tetraethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetraethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetraethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;

1,1,3,3-tetramethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole.

11. Block copolymers based on vinylaromatic monomers and monomers derived from (meth)acrylic acid obtained p the means of the method according to any of the preceding paragraphs.



 

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29 cl, 4 tbl, 4 dwg, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to photoinitiating agents of phenylglyoxylic acid order used in polymerizing compositions to be subjected for hardening. Invention describes a photoinitiating agent of the formula (I): wherein Y means (C3-C12)-alkylene, butenylene, butinylene or (C4-C12)-alkylene that are broken by groups -O- or -NR2- and not following in sequence; R1 means a reactive group of the following order: -OH, -SH, -HR3R4, -(CO)-OH, -(CO)-NH2, -SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)-NH-R8-NCO and -O-(CO)-R-(CO)-X; R2 means hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R3 and R4 mean hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R, R and R mean hydrogen atom or methyl; R8 means linear or branched (C4-C12)-alkylene or phenylene; R9 means linear or branched (C1-C16)-alkylene, -CH=CH-, -CH=CH-CH2-, C6-cycloalkylene, phenylene or naphthylene; X, X1 and X2 mean -OH, Cl, -OCH3 or -OC2H5. Also, invention describes a method for synthesis of a photoinitiating agent, polymerizing composition and substrate covered by its. Proposed photoinitiating agent possesses the effective introducing capacity and absence of migration in thermal treatments.

EFFECT: improved and valuable properties of agent.

13 cl, 1 tbl, 16 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: polymer production.

SUBSTANCE: invention relates to high-stereospecific 1-butene (co)polymer and a high-activity process for producing the same. Process comprises polymerization of reactive monomer 1-butene in presence of catalyst including solid component containing titanium compound and in presence of inert gas, the latter being introduced into reactor together with hydrogen in order inert gas to be present in reactor during polymerization. This step is performed at elevated pressure in polymerization reactor owing to use inert gas at higher pressure than equilibrium pressure of gas-liquid reactant system at reaction temperature from 10 to 110°C. High-stereospecific polybutylene obtained in this process is characterized by that it is 1-butene homopolymer or copolymer including up to 40 wt % α-C2-C20-olefins other than 1-butene and shows following properties: titanium does nor present in catalyst residues at the ppm level, stereospecificity expressed through content of isotactic pentads (mmmm%) and measured using 13C-NMR technique equals 96 or higher, and molecular mass distribution (Mw/Mn) is 3-6.

EFFECT: enabled effective process for production of high-stereospecific polybutylene essentially free of catalytic residues.

3 cl, 4 dwg, 11 ex

FIELD: polymer production.

SUBSTANCE: invention relates to high-stereospecific 1-butene (co)polymer and a high-activity process for producing the same. Process comprises polymerization of reactive monomer 1-butene in presence of catalyst including solid component containing titanium compound and in presence of inert gas, the latter being introduced into reactor together with hydrogen in order inert gas to be present in reactor during polymerization. This step is performed at elevated pressure in polymerization reactor owing to use inert gas at higher pressure than equilibrium pressure of gas-liquid reactant system at reaction temperature from 10 to 110°C. High-stereospecific polybutylene obtained in this process is characterized by that it is 1-butene homopolymer or copolymer including up to 40 wt % α-C2-C20-olefins other than 1-butene and shows following properties: titanium does nor present in catalyst residues at the ppm level, stereospecificity expressed through content of isotactic pentads (mmmm%) and measured using 13C-NMR technique equals 96 or higher, and molecular mass distribution (Mw/Mn) is 3-6.

EFFECT: enabled effective process for production of high-stereospecific polybutylene essentially free of catalytic residues.

3 cl, 4 dwg, 11 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to preparation of cellular polymer particles suited to be used in coating deposition compositions. Cellular polyesters-based polymer particle according to invention including spherical particles having numerous air hollows and long-chain aliphatic groups and/or spatially hindered branched-chain hydrophobic groups associated with surface of said spherical particles is proposed. A composition for preparing indicated cellular particles and a method of preparing the same are developed.

EFFECT: enlarged assortment of starting materials for polymeric coating compositions.

11 cl, 10 tbl, 17 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to emulsion method for co-polymerization of acrylic monomers. Invention proposes a method involving preliminary emulsification of mixture of butyl acrylate with (meth)acrylic and/or vinyl monomer in water in the following mass ratio co-monomer : water = 1:(0.2-0.3) in the presence of 3.4-4.0 wt.-% of sulfooxyethylated alkylphenol ammonium salt wherein (C8-C10)-alkyl has the alkylation degree 18-26 wt.-%, the following emulsion co-polymerization at temperature 78-82°C for 3-10 h at continuous dosing of preliminary prepared co-monomers emulsion and 0.3-0.6 wt.-% of ammonium or potassium persulfate in the total ratio to the reaction mass co-monomer : water = 1:(0.4-0.5) followed by additional polymerization of the reaction mixture in addition of 0.1 wt.-% of ammonium or potassium persulfate after keeping the reaction mixture for 0.5 and 1.5 h and its final temperature keeping for 2 h. Invention provides increasing concentration of acrylic copolymer aqueous dispersion at low content of coagulum and improving its adhesion properties. Invention provides the development of a method for preparing highly concentrated aqueous dispersion with the content of acrylic copolymer 60 wt.-%, not less, for glues showing sensitivity to pressure.

EFFECT: improved preparing method, improved and valuable properties of dispersion.

2 cl, 1 tbl, 13 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

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