DE2511797A1 - PROCESS FOR THE MANUFACTURING OF VINYL POLYMERS PEROXIDATED AT THE END OF THE CHAIN - Google Patents

Description

R ¹⁹⁷⁵

8242-III / K

ATO CHIMIE fet, 92400 Courbevoie, Tour Aquitaine (France)

"Process for the preparation of vinyl polymers peroxidized at the end of the chain"

Priority from French patent application No. 74 09199 of March 19, 1974

The invention relates to a process for the production of vinyl polymers, which are peroxidized at the end of the chain. It also relates to peroxidized polymers obtained by this process will.

It is a method of making peroxidized on the 2nde of the chain Polymers known, which can be applied to polymers and copolymers, which one by a polymerization using can produce coordination catalysis. It consists of one or more unsaturated monomers, especially alpha olefins, polymerized with the help of a coordination catalyst of the Ziegler-Natta type, which by combining an organometallic Compound of a metal from Groups I to III of the Periodic Table of the Elements and a compound of a Transition metal of groups IV to VIII of the system mentioned is formed, the polymerization in the presence of a Carries out auxiliary means, which consists in particular of an organic compound of zinc, cadmium or boron, then the The polymers obtained are treated with a peroxidizing agent without deactivation and the peroxidized polymer formed is recovered. - 2 -

609825/0836

Such a method gives good results for manufacture of polymers which are peroxidized at the end of the chain and which are derived from mono-olefins, especially ethylene, propylene and butene-1 or derived from diolefins. Still, it can't with be used in a satisfactory yield to produce polar vinyl polymers which are peroxidized at the end of the chain, because the polar vinyl monomers react strongly with the coordination catalyst, in which they cause a rapid deactivation of said catalyst, with the result that it it is impossible to obtain polymer chains which have the desired degree of polymerisation and very often the polar ones themselves Polymerize vinyl monomers.

The invention is based on the object of a process for the production of vinyl polymers which are peroxidized at the end of the chain designed in such a way that polar polymers can be obtained which are peroxidized at the end of the chain without being put into operation having to accept the disadvantages of the above-mentioned known method.

This object is achieved in the process for the production of vinyl polymers peroxidized at the end of the chain in that according to the invention, one or more vinyl monomers are present in the presence polymerized with an aid of the formula M (X), in which M is an element from the group consisting of boron, aluminum and the metals of the group Hb of the periodic table of elements means, ρ indicates the valence of M, and the X, which is identical or can be different, each represent a monovalent organic radical or a hydrogen atom or a halogen, where the polymerization is carried out with the aid of a free radical initiator which has no effect on said auxiliary is that one then treats the polymer obtained, without having deactivated it, with a peroxidant and

60 9 8 25/0836

separating the peroxidized polymer formed.

Among the compounds that can be used as auxiliaries in the invention Processes are suitable, the hydrides, halides, halides mixed with boron, aluminum, cadmium may be mentioned or zinc or especially the organic compounds of the elements mentioned, in which the element boron, aluminum, cadmium or zinc to monovalent hydrocarbon or Hydrocar b oxylreste is bonded, said hydrocarbon radicals radicals of alkylene, arylene, aralkylene, alkarylene or cycloalkylene are which have up to 12 carbon atoms. Examples that are not intended to limit the compounds mentioned are in particular zinc diethyl, zinc dipropyl, zinc dibutyl, zinc diphenyl, cadmium diet, cadmium dibutyl, aluminum triethyl, Aluminum triisobutyl and boron triethyl.

The radical initiator, which is responsible for the polymerization of the vinyl monomer and has no effect on the auxiliary, is advantageously selected from the azo compounds of the formula RN = NR ¹ , in which R and R ¹ , which can be the same or different, denote monovalent hydrocarbon radicals, in particular alkyls, aryls, cycloalkyls, aralkyls and alkaryls which are optionally substituted by one or more groups which do not react with the auxiliary. It is possible in particular to use the nitrogen compounds mentioned for which the radicals R and R ', which can be identical or different, have the formula

IX

CN ^ά

have, in which R, and R ₀ , which may be the same or different

609825/0836

j can represent monovalent radicals selected from alkyl radicals from C ₁ to C ^ ₂ , or cycloalkyl _{radicals from C 1 to C 12} , or aryl, alkaryl or aralkyl radicals from ^C g to C 12 ^{JO (} ^ ^er ^ ^e _{3 in} order to form a ring-shaped hydrocarbon with 4 to 12 carbon atoms with the carbon atom to which they are bonded, said radicals or said ring being optionally halogenated Technology, Vol. 2, editors John Wiley and Sons (1965), pages 278 to 295, a more detailed description can be found in particular azobisisobutyronitrile, azobis-methylbutyronitrile, azobis-2-ethyl-butyronitrijil, azobis-2-methyl-heptonitrile, Azo-1-bis-1-cyclohexane carbonitrile and azo-1-bis-1-cycloheptane carbonitrile.

It is also possible in the context of this invention, the polymerization of the vinyl monomer by heat or photochemical To initiate rays. One can also consider the introduction of the thermal effect or the photochemical radiation or to combine the azo compounds with one another.

The ratio of the auxiliary to be used depends, among other things, on the degree of peroxidic groups that is found in desires to obtain the polymer which is peroxidized at the end of the chain. This is mostly in the order of magnitude of 0.1 to 100 millimoles and especially from 0.5 to 50 millimoles per mole of vinyl monomer to be polymerized.

The auxiliary can be added at the beginning of the polymerization. It can also be done gradually during the course of the polymerization add in such a way that a concentration of the auxiliary is established which remains practically constant over the entire duration of the polymerization.

609825/0836

2b \ 1797

The polymerization of the vinyl monomers can be carried out in the presence of the auxiliary, namely in emulsion, in suspension or in bulk, using the working conditions used in the art for the polymerization of vinyl monomers are known, in particular as regards the proportions of the catalyst and the type and amount of diluent for an emulsion or suspension polymerization, the temperature and the pressure.

Among the monomers that are used in the synthesis of vinyl polymerization can use to peroxidize these at the end of the chain, acrylic derivatives such as Acrylates, methacrylates, cyanoacrylates, especially methyl acrylate, Methyl methacrylate, hexyl methacrylate, methacrylate of tetraethylene glycol, Methylcyanaczylat, the nitriles of acrylic acid such as methacrylonitrile and acrylonitrile, the acrylamides, the vinyl ester derivatives, especially vinyl acetate and vinyl propionate, the vinyl chlorides such as vinyl chloride, vinylidene chloride, the vinyl aromatics such as Styrene, chlorostyrene, methylstyrene, the vinylpyridines, the Viny! Pyrrolidines and vinylsilanes.

The effect of the aid M (X) is not exactly known in detail. One suspects, however, without relying on this hypothesis to limit that in the radical polymerization of the vinyl monomer, said auxiliary to the extreme Part of the polymer chains attaches, thereby a bond carbon element M forms (M = boron, aluminum, metal of group Hb of the periodic table), and it thus forms a closure causes. The polymer obtained in this way therefore represents active sites at the end of the chain on which the peroxidized groups are located form when the polymer is treated with the peroxidant. So it is important that the moment you add the

- 6 609825/0836

2b I Ί797

Peroxidizing agent the polyirere has not been deactivated, d.ri. has not yet come into contact with an agent, that is capable of destroying the end bonds carbon element M in order to obtain the active sites that are at the end of the Chain in the polymerization of the vinyl monomer in the presence of the Resources have been made.

The auxiliaries for peroxidation that are used to peroxidize the non-deactivated polymer are air, oxygen, Ozone, peroxides and especially benzoyl peroxide or lauryl peroxide, the hydroperoxides such as cumene hydroperoxide or paramenthane hydroperoxide, Peracids, peresters, hydrogen peroxide, whereby the various auxiliaries mentioned are not restrictive Have meaning.

To carry out the peroxidation, one can use the peroxidant add directly to the reaction medium which contains the non-deactivated polymer after the polymerization.

The non-deactivated polymer that is obtained in the radical polymerization can also be separated off from the reaction medium before it comes into contact with the peroxidant. You can do this separation by filtration or Carry out centrifugation of the suspension of the polymer in the polymerization liquid under an inert atmosphere. Preferably the remaining polymer is washed with the same or a different liquid, thereby destroying the avoids active sites of said polymer. The non-deactivated polymer that is separated from the polymerization medium is, can optionally be used again in suspension or in a solution in a fresh, inert liquid will. This liquid can advantageously be an aliphatic one

- 7 -609825/0836

- τ -

or cycloaliphatic hydrocarbons such as hexane, heptane, cyclohexane or an aromatic hydrocarbon such as benzene or tolnene. It is also possible to use other liquids which do not deactivate the polymer, the liquids mentioned being, for example, dioxane, tetrahydrofuran or ether. The "tool for peroxidation is then added to the suspension or solution thus prepared of the non-deactivated polymer in the appropriate liquid, the temperature for the peroxidation can vary within wide limits It is in particular between -80 C and +100 C, and preferably between ^0.. - 20 ° C and +60 ⁰ C.

According to a preferred embodiment of the present invention the polymer that peroxidizes at the end of the chain and is treated by treating the non-deactivated polymer with the Peroxidation aid was obtained, subjected to hydrolysis in a polar medium in order to obtain a polymer, which contains hydroperoxide groups at the end of the chains.

Hydrolysis advantageous in neutral or slightly acidic aqueous phase to carry out, optionally in the presence of an emulsifying agent, and at a temperature between ⁰ C and 100 ⁰ C, and in particular between 15 ° C and 60 ° C.

The peroxidized or hydroperoxidized polymer is separated from the liquid medium in which it is dissolved or in itself is known to be suspended. If the peroxidation has been carried out in solution, the peroxidized polymer can precipitate either by pouring said solution into a liquid containing the peroxidized polymer does not dissolve, or by evaporating the solvent by distillation. The peroxidized polymer that is used in peroxy-

- 8 60982B / 0836

dation obtained in suspension, or the hydroperoxidized polymer can be separated from the peroxidation medium, and by simple filtration.

The polymeric carriers of the groups that peroxidize at the end of the chain and obtained by the process of the invention are stable at temperatures that are not too high, and can be stored at temperatures close to or below room temperature without special precautions.

These polymers with peroxidized end groups can, inter alia, be used as free-radical initiators for polymerization or find copolymerization of vinyl monomers, where block copolymers are obtained, one of which is one of the consequences of the polymeric part of the macromolecular initiator is formed and the other is derived from the vinyl monomer or monomers, which polymerizes with the aid of the macromolecular initiator mentioned became.

The following examples illustrate the invention without restricting it.

Example ei to 6

Various end-of-chain vinyl polymers were prepared by the following general preparation procedure was applied:

To 400 ml of anhydrous benzene, were placed in a temperature-controlled at 65 ⁰ C reactor, was mixed in an inert atmosphere, 40 g vinyl monomer and O.O8 g azobisisobutyronitrile. The auxiliary, namely zinc diethyl in solution in heptane, was added to the mixture thus obtained. The reaction mixture was then stirred for four hours at the temperature of 65 ^° C

- 9 -

609825/0836

500 revolutions / minute held to polymerize the vinyl monomer perform.

At the end of this period, air was added to the reactor until a pressure of 3 bar was reached, and at the same time it was lowered the temperature of the reaction medium up to a value of 4 5 C. The peroxidation was then allowed to proceed with stirring at this temperature for three hours. Then the contents of the Reactor into two liters of permuted water containing 0.2 g of lauryl sulfate and held the mixture at one for two hours Temperature of 40 C, with stirring at 750 revolutions / minute.

In this way a polymer was produced which hydroperoxidizes at the end of the chain was. This was separated from the aqueous phase by filtration and then recovered under a nitrogen atmosphere and dried.

For each example, a comparative test was carried out in the absence of the aid.

Each hydroperoxidized polymer produced was characterized by its intrinsic viscosity, which was determined at 25 ° C, and at the same time by its content of active oxygen, which is obtained by adding hydroperoxidized groups according to the method was determined in which the oxidation of potassium iodide or hydriodic acid by the hydroperoxidized polymer and the dosage carried out by thiosulphate of the released iodine.

The specific implementation conditions and the received

- 10 -

609825/0836

Results are shown in Table I. The solvents used to determine intrinsic viscosity were benzene (examples 1,3,5 and 6), butanone (example 2) and Tetrahydrofuran (Example 4).

Table

example Applied
Zinc diet
(Millimoles) vinyl
Monomer implementation
% Inner
Viscose
activity More active
oxygen
ρ.pm 1 0
1
3
6th
12th Methy1-
acrylate 50
50
51
44
32 0.54
0.53
0.38
0.17
0.14 150
850
2300
5300
9750 2 0
6th
12th Hexyl
methacry
lat 62
56
50 0.63
0.42
0.20 90
3700
6850 3 0
6th
12th Styrene 45
42
40 0.57
0.31
0.13 50
2850
6010 4th 0
6th vinyl
chloride 32
27 0.75
0.38 70
1850 5 0
6th Tetraethy-
lenglycol
methacryla 42
. 38 0.50
0.22 50
3500 6th 0
6th Methyl cyan
acrylate - 54
48 0.60
0.30 120
4800

60982B / 0836

2b1 1797 - left -

In the absence of the auxiliary, the ratio of the peroxidized groups is practically negligible. However, this ratio increases considerably when the solvent, here
Zinc diethyl, according to the invention, is present in the polymerization of the vinyl monomer. This is very clear, especially in the case of methyl polyacrylate, which is peroxidized at the end of the chain and obtained according to Example 1. This increases the salary
of active oxygen of 150 ppm (weight), since the polymerization is carried out in the absence of the auxiliary, to
to 9750 ppm when considering the polymerization of methyl acrylate
in the presence of 12 millimoles of auxiliary (zinc diet) executes.

At the end of the comparison, the polystyrene obtained by the polymerization of styrene, as indicated in the method of preparation of the comparative experiment of Example 3 (absence of zinc ethyl), and in solution in 400 ml of benzene in contact with 12 killimoles of zinc diethyl in heptane solution, the Contact at 65 ° C for four hours and with stirring at 500 revolutions / min,
was carried out. The polymer was then peroxidized and the peroxidized polymer was subjected to hydrolysis as indicated in the above examples.

The active oxygen content in the polystyrene obtained after these treatments was not significantly higher than that of the polystyrene
Product obtained after hydrolysis in the comparative experiment of Example 3.

This also shows that the aid is only used during the polymerization phase of the vinyl monomer acts.

Example 7

In order to explain the application of polymers, the invention

- 12 -

609825/0836

measured at the end of the chain for the synthesis of block copolymers had been peroxidized, the polymerization of styrene was carried out using methyl polyacrylate as the radical initiator applied, which was hydroperoxidized at the end of the chain with 5300 ppm active oxygen and obtained according to Example 1 was to form a block polymeric methyl polyarylate / polystyrene.

For this purpose, 20 g of styrene were added to a solution of 25 g of polyacrylate, which had peroxidized at the end of the chain, in 400 ml of anhydrous and oxygen-free benzene. The temperature of the mixture was set to 90 ^° C. and the mixture mentioned was kept at this temperature for four hours, with stirring.

The reaction mixture was then precipitated in alcohol, and the solid product obtained was washed and dried. After selective extractions with cyclohexane was carried out in order to extract the homopolymer, polystyrene, and in acetonitrile to extract the methyl polyacrylate, to give a copolymer Blockmethylpolyacrylat / polystyrene, which, like the infrared analysis showed 20 wt.% Polystyrene included that of polyacrylate was bound.

In a comparative experiment carried out under analogous conditions was, however, the methyl polyacrylate, which on The end of the chain was hydroperoxidized, replaced by non-peroxidized methyl polyacrylate, was the polymerization of styrene practically zero. In addition, the infrared analysis of the product obtained after the styrene had been separated off and extracted with cyclohexane fails to detect the presence of polystyrene. So there was no block copolymer formation.

- 13 -

2b11797

example

One worked under the same conditions as in general Production method for the implementation of Examples 1 to 6 were used, but zinc diet by a Auxiliaries such as aluminum triethyl (Example 8), boron triethyl (Example 9) and zinc diphenyl (Example 10) replaced.

The specific manufacturing conditions and the results obtained are given in Table II below.

Tabel

II

ι
example 8th Aids Aluminum Vinyl- implementation Inner More active Kind of amount umtri- 3 monomeric % Viscose Sour. ι (Mole) ethyl g activity ppm 0 12th 52 0.56 150 9 Boron ° Methyl- 50 0.54 190 tri- 1 acrylate 48 0.45 300 ethyl g 45 0.38 460 12th 43 0.37 500 10 Zinc- ° Methyl- 50 0.54 100 di- 6 acrylate 45 0.46 320 phenyl ₁₂ 35 0.30 800 30th 0.22 1130 Hexyl 58 0.62 80 metha- 53 0.54 270 crylate 50 0.49 410

609825/0836

- 14 -

The solvent used for viscosity measurements used to determine intrinsic viscosity passed from benzene (Examples 8 to 9) or butanone (Example 10). In the absence of the resource, the ratio of groups was that were peroxidized at the end of the chain.

However, this ratio is increased considerably if an inventive Auxiliaries, here aluminum triethyl, boron triethyl or zinc diphenyl in the radical polymerization of Viny! Monomers is present.

6098 2 5/0836

Claims (1)

PATENTANWÄLTE _{4S t} DlETf-: i CH LlWSNSKY / 011/3 / H-NZJOVCHiMKUBER Pure:.-. K 1 kiETSCH _l8 , _lg75 MONKS 2 1 Ι * GOTTHARDSTR. 81 ATO CHIMIE S.A. Patent claims: Process for the preparation of vinyl polymers peroxidized at the end of the chain, characterized in that one or more vinyl monomers are polymerized in the presence of an auxiliary of the formula M (X) in which M is an element from the group consisting of boron, aluminum and the metals from group Hb of the periodic System of elements means, ρ indicates the valence of M, and the X, which can be identical or different, each represent a monovalent organic radical or a hydrogen atom or a halogen, the polymerization being carried out with the aid of an initiator for the radical polymerization, which has no effect on said auxiliary, then treated the polymer obtained without deactivation with a peroxidizing agent and separating the peroxidized polymer formed. 2. The method according to claim 1, characterized in that the auxiliary is an organic compound of boron, aluminum, Zinc or cadmium is in which the element boron, aluminum, zinc or cadmium is only attached to monovalent hydrocarbon radicals is bonded, which have 1 to 12 carbon atoms, the radicals mentioned are alkyls, aryls, cycloalkyls, aralky-Ie and Alcaryle are. 3. The method according to claim 1 or 2, characterized in that the ratio of auxiliary between 0.1 and 100 MiI-limol and especially between 0.5 and 50 millimoles per mole of the vinyl monomer to be polymerized. - 2 - 60982b / 0836 "* '2b11797 4. The method according to any one of claims 1 to 3 _3, characterized in that the initiator of the polymerization is an azo compound of the formula RN = NR ¹ , wherein R and R ¹ , which can be the same or different, represent monovalent hydrocarbon radicals, in particular alkyls, Aryls, cycloalkyls, aralkyls and alkaryls which are optionally substituted by one or more groups without any effect on the auxiliary. 5. The method according to claim 4, characterized in that the radicals R and R ^{1 of} the azo compound of the formula RN = NR ^{1 has} the formula CN possess wherein R ₁ ^nd R _2, which may be the same or different, are monovalent radicals selected from alkyl radicals of C ₁ to C _12, cycloalkyl radicals of Cr to C _12, aryl, aralkyl or alkaryl from Cg to C ₁₂ , or which are bonded to form, with the carbon atom to which they are bonded, a cyclic hydrocarbon containing 4 to 12 carbon atoms the seated, with said radicals or / cyclic part optionally are halogenated. 6. The method according to claim 5, characterized in that the azo compound is azo-bis-isobutyrone-nitrile. 7. Process according to one of Claims 1 to 3 _5, characterized in that the initiator of the polymerization is used in the form of heat or photochemical rays. 609825/0836 8. The method according to any one of claims 1 to 7 _S, characterized in that the vinyl monomer is selected from the group of derivatives of vinyl chlorates, acrylates, methacrylates, vinyl esters, vinyl aromatics, vinyl pyridines, vinyl pyrolidines and vinyl silanes. 9. Method according to one of Claims 1 to 8, characterized in that that the peroxidation is carried out in an inert liquid phase, as an aid for the peroxidation Air, oxygen, ozone, hydrogen peroxide, peroxides, hydroperoxides, peracids or peresters are selected will. 10. The method according to any one of claims 1 to 9j, characterized in that that the non-deactivated polymer, which is obtained in the radical polymerization, from the Separates the polymerization medium before it is subjected to the treatment of peroxidation. 11. The method according to claim 9 or 10, characterized in that peroxidation at a temperature between - 80 C and + 100 C and in particular between -20 ⁰ C and + 80 ° C is carried out. 12. The method according to any one of claims 1 to 11, characterized in that that the polymer which has been peroxidized after the treatment is subjected to hydrolysis to form the polymer to form, which has been hydroperoxidized at the end of the corresponding chain. 13 · Method according to claim 12, characterized in that hydrolysis in neutral or slightly acidic ?, aqueous phase at a temperature between 0 ⁰ C and 100 ⁰ C, in particular between 15 ° C and 60 ° C, is performed. -H- 609825/08 3 6 lh. Vinyl polymers which are peroxidized at the end of the chain and are obtained by a process according to any one of Claims 1 to 13. 15. Block copolymers of vinyl monomers obtained by polymerization one or more vinyl monomers can be prepared with the aid of a free radical initiator and from a vinyl polymer exist, which is peroxidized at the end of the chain and obtained by the process of any one of claims 1 to 13 became. 60982b / 0836