DE1645291C - Process for the production of alternating copolymers - Google Patents

Description

A process of halogenating hydrocarbons of the general type has already been found and proposed by the inventors, in which a lower formula
Olefin with acrylonitrile in the presence of a catalyst rι

the general formula

₅ CH ₂ = CI

in which R is an organic radical and X is a halogen atom and / 7 is any number greater than 0, but in which R ^{1 is} a halogen atom or a halogenated less than 3, is mixed-polymerized. Hydrocarbon radical with 1 to 20 carbon characterizing the mentioned process is the ic atoms and R ² a hydrogen atom, a halogen successful successful interpolymerization of atom, a hydrocarbon radical with 1 to 20 carbon acrylonitrile with a lower olefin, like propylene material atoms or a halogenated one Hydrocarbon and isobutylene, although the former is usually a radical of 1 to 20 carbon atoms. with acrylic for unpolymerizable by cationic mechanisms nitrile or an acrylic compound of the general and the latter in general for unpolymerizable 15 formula

through anionic or radical mechanisms CH, - CH - C - Y

had been held. Another characteristic of the "II

Method is the fact that the mixture obtained 2

polymer is generally a so-called alternating copolymer, the alternating 20 in which Z has an oxygen or sulfur atom and consequences of the two monomers. Y the group ZR ³ , ZH, ZMe,

The inventors have further found that

Copolymers of Λ-olefins and common R ¹

Derivatives of acrylic acid using /

Organoaluminum halogen compounds as catalysis 25 IN. ·

gate can be obtained. The R ⁵

The olefins used are terminally unsaturated

Hydrocarbons, which generally denote a halogen or hydrogen atom in the presence of R ³ , of a cationic polymerization catalyst readily wherein R ^{3 is} an organic radical having 1 to 20 carbons are polymerized. The comonomers used together with the mentioned 30 substance atoms, R ⁴ and R ⁶ each hydrogen atoms len olefins are natural or organic radicals with 1 to 20 carbon atoms of acrylic acid, which are in contrast atoms, or R ¹ and R ^{5 are} mutually related Olefins are bound by means of an anionic catalyst and are readily polymerizable to form a heterocyclic catalyst. Because it was found. Ring with nitrogen, and Me is an ammonium that in the systems mentioned alternating mixed residue or a monovalent fraction of an element polymerisate are selectively obtained through the grains of groups I to III of the periodic table, bination ^ cr monomers whose reactivity varies in the presence of a catalyst which behaves in a manner that is contrary to the characteristics of olefin hydrocarbons, that the copolymerization in bulk substances with high cationic polymerizability or in an inert diluent for vinyl compounds, the carbonyl groups have a temperature in the range from -150 to + 100 ⁰ C, with high anionic polymerizability. Presence of (1) an organic aluminum one can see this as a specific mixed polymer halogen compound of the general formulas AIR ^e X ' _a , »ationsreaktion, which by the combination AIR'jX ¹ or Al ₂ R ^e ₃ X' ₃ , in where R "is a common olefinic hydrocarbon with a low organic radical and X ^{1 is} a halogen atom,« ■ value and an acrylic acid derivative of high 45 or for (2) a combination of at least two f-values, the r-value being achieved by the types of aluminum compounds with the general {Pr-Scrwma of the monomer reactivities expressed my formulas AIR ⁶ X ' _a , AlR ^e ₂ X', AI ₂ R ^ X ¹ ,,, AIR ⁷ ,., is given by Price - Alfrey suggested or AIX ² ,. ,, in which R 'and R' became ordinary (see Journal of Polymer Science, Vol. 2 [1947], organic radicals and X ¹ and X ^a halogen atoms p. 101) Catalyst is carried out.

In the course of further investigations, it is known that random copolymers

Range of ß-c values of available monomers (random copolymers) from halogenated olefins, tested and found that as olefins as well as vinyl chloride or vinylidene chloride with Acrylandere can be used as the hydrocarbons compounds or acrylonitrile, by usual radicals, namely, in particular, ethylenic 55 kaiische copolymerization can easily be obtained, unsaturated halogenated hydrocarbon compounds, on the other hand, it was not known that the named genes (hereinafter also as halogenated olefins bc monomers in the presence of an aluminum compound) effectively alternating copolymers can be mischpolymcrisiert as a catalyst with conjugated vinyl compounds such as Aerylvcr- can. That these monomers form alternating mixed bonds or acrylonitrile. Halogenated olefins form 60 polymers is a completely unexpected one have a larger i'-word than the corresponding result.

Olefin hydrocarbons, and most of them were also known to have alternating mixed poly positive values. This means that the e values merisatc some specific monomers selectively viin olefinic compounds are not necessarily obtained by being in the presence of must be wise negative. 65 of a free radical initiator copolymer

Accordingly, the invention relates to a method. For example, maleic anhydride, for the production of alternating copolymers malcimide and fumaric acid chloride, which are difficult by polymerizing an ethylenically unsaturated homopolymer, with styrene or «-methyl

I 645 291

styrene to alternating copolymers mixing ratios can be obtained. That according to the invention

are polymerized. It is also known that the method is, however, markedly different from that

an ester of fumaric acid with isobutylene or Pro- mentioned copolymerization, in which an I i: wis-

pylene is formed into a copolymer and an acid-vinylnionomcr complex. The

5 processes according to the invention which are independent of the mononization composition are

Composition can be copolymerized. good that the interpolymerization reaction is fast

Such known alternating copolymerization and takes place without the addition of a radical initiator,

tions produced by a radical mechanism This is one of the essential characteristics of the

arise are characterized in that one invention. Accordingly, the invention sets

those monomers are used that are not homopoly- io novel polymerization process available,

merisiurt and no random copoly- that was previously unknown. This polymerization

form merizates, even if the polymerization process is to be referred to in the following as »complex polymer

conditions varies. sation «. Because acrylic compounds

In contrast, one of the features of the invention and acrylonitrile tend to be with aluminum compounds

according to the method that selectively alternating fertilizing complexes are to be formed, such co-

Mixed polymers by combining such monomers as "complex-forming monomers"

Monomers obtained, the random copolymers are formed.

the. Such alternating copolymers are It is possible the fact that an aluminum is new, previously unknown compounds. You can connect with an acrylic compound or acrylic also say that the aforementioned phenomenon ao nitrile forms a complex, to prove experimentally, completely new and in the usual alternating mixing. For example, the infrared absorption polymerizations shifts has never been observed. band of nitrile group of acrylonitrile of 2220 cm '

Is not changed to 45 further tend allyl halides, which after 2270 ^"1 belong to the cm as a result of complex formation, while according to the invention the absorption usable ethylenically unsatu- the double bond at 1600 cm ¹ tigtcn halogenated hydrocarbons. It is concluded that a degradative chain transfer, which is ascribed to the allyl resonance, so called the aluminum compound, which is coordinated with the nitrile group. They are dinatively linked. It is of course assumed that the complex-forming monomer, the complex-forming monomer, is considered to be polymerizable by radical initiators only with great difficulty in such a bond state This is also the case when ionic catalysts are influenced. However, such a complex has to be used. According to the invention, generally no polymerization activity itself However, allyl halides show a pronounced effect. For example, a complex which, when mixed, has high polymerization activity and actually results in equimolar amounts of acrylonitrile and an aluminum-alternating copolymers. 35 miniumverbindungen was obtained at -78 ° C, at

It has recently been suggested that the polymer be solid at low temperatures and at room temperature

cation reactivity of vinyl monomers, which are all-liquid and do not result in polymerizate for a longer period of time

generally have a high anionic polymerizability. On the other hand, even then no essential

have, by complex formation with a metal borrowed amount of polymer in most cases

halide, such as zinc chloride or aluminum chloride, formed when a halogenated olefin with a

to change. Aluminum compound is mixed. At AlIyI-

For example, Kargin and coworkers have found only a violent reduction in reduction

tried a complex of methyl methacrylate and on. However, when a ternary system is formed

Radically homopolymerize zinc chloride (Vyso- by mixing an aluminum compound with a

komol. Soed., 2, p. 765 [I960]), and I mot ο and 45 acrylic compound or acrylonitrile and a halo-

Employees have a radical homopoly- genated olefin, so the system develops a high level

merization reported in which a complex formation polymerization activity, causing the polymerization

of zinc chloride and acrylonitrile or methyl meth- advances very rapidly and selectively an alternating one

acryte.t was carried out (Makromol. Chem., 65 Copolymer is formed. These many special

[1963], pp. 174, 180 and 194). Furthermore, in 50 the units are specific and are

British patent specification 946 052 a radical merization reaction has not yet been observed.

Copolymerization process described, with wcl- The obtained by the process according to the invention

chem distinguish between a first monomer and a second monomer, alternating copolymers

in the presence of a Friedel-CraftS metal halide differ in their properties from the corresponding

τ. B. zinc chloride, is copolymerized, with 55 homopolymers or the Ra ⁿ dom-Copo! Ymeri-

the first monomer is a polar vinyl or vinylidene seeds. The alternating copolymers obtained

is monomeric that is radically polymerizable, sate are generally amorphous and have none

and the second monomer is an olefin or substituted melting point. One observes this from

ated olefin, which is the result of a thermal differential analysis with Friedel-Crafts catalysts.

reacted. 60 Another feature of the inventive

In the process of the invention, the copolymers are also made that they are thermal

Complex formation between an aluminum compound are more stable and even at elevated temperature only

dung as a catalyst and acrylonitrile or a difficult to decompose. For example, it decomposes

Acrylic compound is of great importance for the mixed poly- a homopolymer of methyl acrylate in one

attributed to merization. This goes from the fact 65 nitrogen atmosphere at 350 "C, while an old

Lervor that excellent results when neering the copolymer from the same material

Turning an aluminum compound and an acrylic · replaced with vinyl chloride noticeably only at 400 "C /,

compound or acrylonitrile approximately equimolarcn Furthermore, the solubilities are according to the invention

iermade copolymers in various lithium, 1-bromo-1-iodethylene, 1-chloro-1-jocUUhylen,

Ingredients differ from those of the ent- 2-chloropropene-1,2-chlorobutene-1,2-bromododecene-1,2

corresponding homopolymers. From this result 1 - chlorine -1 - cyclohexylethylene, 1 - chlorine -1 - benzyl-

It is evident that the products of the ethylene according to the invention, η - chlorine - ρ - methylstyrene,, v - bromostyrene,

Process copolymers are. A homopoly- 5 "-chlorostyrene, p-bromo-α-chlorostyrene, 2-Chlnrnllyl-

The merisate of vinyl chloride is, for example, benzene chloride, 2,4-dichloropentene-1,2-chloromethylpropene-l, ^al5

insoluble and soluble in cyclohexanone, while 1,1 - bis (p-chlorophenyl) ethylene, a- (bromomethyl) - B ¹ ''

alternating copolymer of vinyl chloride and styrene, «- (chloromethyl / styrene, p-chloro-i \ -methylstyrene, B. ^c

Methyl acrylate both in benzene and in cyclo- 2,3-dichloro-A-methylstyrene and «-ätyl-m- (trichloro- Λ '

hexanone is soluble. The alternating copolymer io methyl) styrene. Of the compounds mentioned ^ac

sat is also soluble in tetrahydronaphthalene, preference is given to those whose e value is less than ^llt

while the corresponding homopolymers therein is 1.0, preferably less than 0.5. ^{a (}

are insoluble. The alternating copolymers The complex-forming monomers, the invention ^ai

of the process according to the invention have generally been used are acrylonitrile or acrylic ^a ;

common high molecular weights and a viscous compound of the general formula C

rate in the range 0.1 to 10. Cj ^ _ £ j_i q γ ^l )

The copolymers of the inventive pen ² '

driving have various superior characters- ^ll

ristic properties. You can for i ^ r different '

Purposes are used in which there are ao in the Y and Z have the aforementioned meaning. '

characteristic properties are particularly important. Such derivatives include acrylates, thioacrylates ^,!

In addition, thionacrylates, dithioacrylates, acrylamide, thioacrylic ^;

often achieved properties with individual homoamides, N-substituted acrylamides, N-substituted

polymerizaten could not be achieved. In addition to thioacrylamides, Ν, Ν-disubstituted acrylamides,

the use of the copolymers as such is »5 Ν, Ν-disubstituted thioacrylamides, acrylic acid halo-

it possible to improve their properties by mixing with genide, thioacrylic acid halide, acrylic acid, thiol-

other polymers or, through their reaction, acrylic acid, thionacrylic acid, dithioacrylic acid, salts

to modify. Even if a homopolymer of the named acids, acrolein and vinyl ketones,

of a certain monomer has insufficient consistency. As organic radicals with 1 to 20 carbon atoms,

has compatibility with another polymer, 30 by R ³ , R ¹ and R ^{B in} terms of meaning

it can nevertheless be expressed with the latter to a homogeneous of Y in the general formula,

Mixture can be processed by shaping it in the form of ordinary hydrocarbon radicals are preferred,

of a copolymer according to the invention, with derivatives thereof also being able to be included,

combined with the polymer in question. It can be, for example, alkyl, aryl,

also the copolymers in substances with three-dimensional aralkyl, alkylaryl and cycloalkyl groups. Stands

sional structure by using a crosslinker Y for a halogen atom, so chlorine, bromine,

over rcn. In general, the alternating iodine and fluorine are used. The rest of me in

Copolymers extensive use as a form connection with Y is an ammonium radical or

masses. Films or foils, plates, textiles, the monovalent fraction of an element of group I

such as threads and fibers, paints, additives 40 to III of the periodic table. Such elements

and adhesives. belong e.g. B. lithium, sodium, potassium, rubidium,

The unsaturated hydrocarbons halcgenierten h in crfindungsgemä (? S ^r s method vcrwendba cesium, copper, silver, beryllium, calcium, Stronäthyler.is tium, barium, have magnesium, zinc, cadmium, mercury materials of the general formula silver, boron, aluminum and gallium The imprint

45 The metal itself is a »single-valued fraction«

R ¹ in the case of a single-valued element (M = one element

Qft _ Q of groups 1 to 111 of the periodic table), M / 2 im

² \ in the case of a bivalent element and M / 3 in the case

R ^{2 is a} trivalent element. Therefore, the

50 general formula of the compound in the case of a

in which R ¹ and R ^{2 are} the above-mentioned meaning divalent elements of the form

have performance. _{The haloamines} of R ¹ and R ² / ΓΙ τ _r , for _Y1M

include chlorine, bromine, iodine, and fluorine. As coal ^l »""' ²
Hydrogen residues and halogenated hydrocarbon

icstc, R ¹ and R ² can include those that are alkyl, 55

Aryl, aralkyl, alkylaryl and cycloalkyl groups and, in the case of a trivalent element, of the form or their halide sub-products or derivatives. These halogenated olefins are at- (CH ₂ -CY) _n M.
spidswcisc vinyl chloride, vinyl bromide, vinyl iodide, | j
Allyl chloride, allyl chloride, allyl iodide, 4-chlorobutene-l, 60 χ
3-Chlorhutcn-1,3-Brcmpenten-i, 4,4,4-Trichlorobu

lcn-1, p-chlorostyrene, o-chlorostyrene, m-chlorostyrene, among these compounds are the monovalent ones

m-bromostyrene, p-iodostyrene, p-hurostyrene, p-chloro salts, d. Ii. the salts with an element from group I.

methylstyrene, 4-chloro-1-vinylcyclohexane, p-chlorallyl- of the periodic table and the ammonium salt, bcvor-

bcn / .ol, 2,4-dichloroslyrole, 2,6-dichlorostyrene, 2,4-di-65 plus. With regard to the meaning of NR ¹ R ⁶ , where

Huorslyrol. 3-Trifluormctliylsiyrol, 4-Chloro-1-vinyl- »R ¹ and R ⁶ are interconnected un'ir

iiiiphlhitlin. Vinylidene chloride, vinylidene bromide. Formation of a heterocyclic ring with the stick

ul. methallyl chloride, I-bromo-1-chloro-substance, "see, for example, the groups

7 8

CH ₂ - CH ₂ CH, - CH ₂ CH, - CH ₂

- N O, - N and - N CH,

CH ₂ - CH ₄ CH ₂ - CH ₂ CH, - CH ₂

i.e. the morpholines) -. Pyrrolidino- and piperidino- minium trichloride. Aluminum tribromide. Aluminum group, be understood. Typical examples of triiodide and aluminum trifluoride. The acrylic compounds mentioned are methyl acrylate. Against the arbitrary use of a single ethyl acrylate. Isopropyl acrylate. n-butyl acrylate. t-butyl component of the aluminum compounds of foracrylate. n-amyl acrylate. n-octyl acrylate. n-Dodecyl- io my AIR'X ¹ ». AIR ^e ₂ X '. AljR ^ X'j. AIR ^7, and A1X _^2: acrylate. Tetradecyl acrylate. Octadecyl acrylate. There are concerns about vinyl. The independent use of acrylate. Allyl acrylates. like phenyl acrylate. o-Tolyl- an aluminum compound of the formula AIR * X'j. acrylate. Benzyl acrylate. Cyclohexyl acrylate. Cyclopentyl AIR'jX ¹ and AI ₂ R ', X' is effective, but acrylate. U-ChloräthyD-acrylat, (/ J-ChlorallyD-aerylat. Are supposed to be the aluminum compounds of the formulas (Dimethylaminoäthyl) - acrylat. (2 - Ethoxyäthyl) - 15 AIR \ and AiX * ₃ each in a combination of acrylate, (2-Nitropropyb- . Methylthiolacrylat acrylate at least two compounds from the group Äthylthiolacrylat Isopropylthiolacrylat Phenylthiol- AIR ¹¹ X ^1, X ₂ AIR ^e ', Al ₄ Rf ₁ X ^1, AIR _^7:......, and AlX, ausacrylat Methylthionacrylat Methyldithioacrylat.. The use of, for example, acrylamide, thioacrylamide, N-methylacrylamide, only AIR ⁷ , or AIX'j alone does not result in the N-ethylacrylamide, Nn-butylacrylamide, Nn-hexyl-ao desired polymer. According to the invention, it is acrylamide , Nn-octylacrylamide, N-2-ethylhexyl acryl- namely required to use a system consisting of amide, Nn-dodecylacrylamide, N-stearylacrylamide. Of aluminum in a combination with an N-cyclohexyl acrylamide, N-tolylacrylamide, N-methyl- organic Group and a halogen atom bethi oacrylamide. NN-dimethylacrylamide, N-methyl-. This is one of the hallmarks of the pre-N-ethylacrylamide, N-acryloylmorpholine. N-acryloyl 25 invention.

pyrrilidine, NN-dimethylthioacrylamide. Acryloylchlo- The aluminum compound as a catalytic comride, acryloyl bromide, acryloyl iodide. Thioacryloyl component can be in a relatively broad chloride. Acrylic acid, thioacrylic acid, thionacrylic acid, amount range. based on the monomers, ver-dithioacrylic acid, sodium acrylate, potassium acrylate, are used. For example from 0.01 to 10 mol. Preferred zinc acrylate, aluminum acrylate, ammonium acrylate, 30 or 0.05 to 1.5 mol per mol of the complexing acrolein, methyl vinyl ketone. Ethyl vinyl ketone, phenyl monomer. According to the invention, the formation of a vinyl ketone, cyclohexyl vinyl ketone and vinyl 4-methyl complex from a complex-forming monomer naphthyl (1) ketone. The acrylic compounds. The meaning of the invention and an aluminum compound used in the invention are not limited to the compounds listed as the aluminum compound, which is a coordinate. The aluminum ratio used according to the invention to the complex-forming bonds are those of the general formulas monomer used, so the mixed polymer AlR'X'jt, AlRV, Al _t R * ₃ X ' ₃ . AIR ' ₃ and AIX ² ₃ , sation can be carried out effectively, and in which R ^e and R ^{7 are} each an ordinary organic copolymers with excellent properties nischer radical and X ¹ and X * each have a halogen atom 40 obtained. Mixing together the aluminum is. The usual organic radicals include connection with the monomers can occur in any hydrocarbon radical with 1 to 20 carbon in the usual manner.

atoms and their derivatives, such as. B. alkyl, alkenyl, the reaction will be particularly lower at one

Aryl, aralkyl, alkylaryl and cycloalkyl groups. Temperature carried out, then practically none

R * and R ⁷ include methyl, ethyl, propyl, butyl, 45 homopolymerization of the individual monomers. F .;

Hexyl, octyl, decyl, dodecyl, stearyl, phenyl, is therefore possible to dei an arbitrary order

ToIyI-, naphthyl-, benzyl-. Cyclopentadienyl and additives to choose at a low temperature

Cyclohexyl groups or their derivatives. Typical to obtain copolymers alone. Man canr

Compounds of the general formulas AlR ⁶ X ¹ J, for example first mix the monomers, given

AlR'tX ¹ and Al ₂ R ⁶ X ^ si.id Methylaluminiumdichon- 50 if necessary add solvent and finally

Ride, ethylaluminum dichloride, isobutylaluminiumdi- add the aluminum compound, or you came

chloride, hexylaluminum dichloride, dodecylaluminum acrylonitrile or an acrylic compound with an aluminum

dichloride, phenylaluminum dichloride, cyclohexylaluminum compound for the production of a complex?

Add minium dichloride, methyl aluminum dibromide, ethyl mix and a halogenated olefin, odei

aluminum dibromide, ethylaluminium diiodide, vinyl 55 one can use a halogenated olefin with an aluminum

First mix aluminum dichloride, AHylaluminum dichloride, ethyl minium compound and then acrylic

aluminum sesquichloride, ethylaluminum sesquibronitrile or an acrylic compound or continuous

add dropwise mid, ethyl aluminum sesquifluoride, methyl aluminum. or you can use this Ver

Carry out sesquichloride, methylaluminum sesquibromide, phenyl stages continuously and there:

Aluminum sesquiodide, diethylaluminum chloride, di- 80 process product continuously withdraw. Each the

ethylaluminum fluoride, ethylphenylaluminum chloride these procedures can be chosen,

and dicyclohexyl aluminum chloride. Typical connec- tion is premature contact of the aluminum

When fertilizing the general formula A1R ' ₃ , trimethyl compounds with one of the monomers are not advisable

aluminum, triethylaluminum, tripropylaluminum, the aluminum compound can initially irit the

Tributyl aluminum, trihexyl aluminum. Tridecylalu- 65 other monomer brought together geniuses, or

minium, triphenylaluminum.Tricyclohexylaluminium you can mix both monomers first and then dii

and tribocylaluminum. To the typical connec- mix with the AWminiiimverbindungen together

fertilizers of the general formula A1X ^S ₃ include aluminum bring. Does the Aliiminiiinivcrbiiuhing consist of a

If there are multiple components, each component can be added individually. In general, even with such an operation, an active complex is easily formed in the system. If a halogen-containing aluminum compound is added to a complex-forming monomer at relatively low temperatures, for example at a temperature below 0 ^° C., an alternating copolymer is easily formed.

If an alternating copolymer is obtained according to the invention, its composition changes not independent of the composition of the monomers used. However affected the mixing ratio of a halogenated olefin and an acrylic compound or acrylonitrile often the yield, molecular weight and other properties of the resulting polymer, so that a suitable mixing ratio of the monomers depending on the desired product should be determined. If the halogenated olefin is in excess over the acrylic compound or acrylonitrile applied, it is generally possible to determine the polymer yield based on the acrylic compound or to increase the acrylonitrile.

The polymerization temperature can be within relatively wide limits, namely between about -150 and about 4 100 C. The polishing system of the method according to the invention is occasional so active that the polymerization takes a few minutes or a few 10 minutes, e.g. B. even at -78 C, has completely expired. Since there is no homopolymerization at such a low temperature takes place, such a low one is preferably used to achieve a pure copolymer Temperature applied. The polymerization at low temperature also has the advantage that polymerized even such monomers in liquid phase polymerization at atmospheric pressure which are gaseous at room temperature. On the other hand, it is difficult to find low ones Temperature conditions are obtained so it is possible at room temperature or even higher To polymerize temperatures. If the monomers are gaseous at room temperature, one can carry out the polymerization under increased pressure. In general it is necessary to carry out the polymerization to be carried out in an inert atmosphere.

When carrying out the process according to the invention, it is possible to use liquid monomer to polymerize the mass or in a customary inert diluent. The polymerization is carried out in the absence of polar compounds such as water.

Such inert diluents include common hydrocarbons and halogen-containing ones Hydrocarbons. Typical examples are propane, butane, pentane, hexane, heptane, octane, ligroin, Petroleum oil and other petroleum solvents, benzene, toluene, xylene, cyclohexane, methylcyciohexane, Methylene dichloride, ethylene dichloride, trichlorethylene, Tetrachlorethylene, butyl chloride, chlorobenzene and ßrombenzene. Connections that are stable Forming complexes with the aluminum compound are not useful as diluents. In particular compounds that form more stable complexes than those that form between the conjugated vinyl compound or acrylonitrile and the aluminum compound Ethers such as diethyl ether or tetrahydrofuran are also unfavorable. Ketones and nitriles are also included not suitable.

After the polymerization reaction has been completed, the polymers obtained can be customarily used Submit post-cleaning treatments. Al such post-treatments can optionally include the those used with kationischet

ίο Polymerizations using Lewis acids and polymers sation by means of Ziegler-Natta catalysts have already been applied, such as the treatment mi Alcohol. Alcohol and hydrochloric acid, with hydrochloric acid, mi alkali or the like. You can also use the aluminum compounds Separate bonds and recover from the polymer obtained by, for example, a pre bond that forms complexes with it. without decomposing them.

The invention is illustrated by the following example

ao explained.

example 1

A 100 ml three-necked flask was evacuated, m

Flushed with nitrogen and with dry ice — Meth.i nol cooled to 78 C. In the flask was 20 ml of heptane and 4 g of methyl acrylate under nitrogen

given and mixed homogeneously. / 1

? Aiii'S ^{Un8 25mMo1} Ethylaluminiumsesquichloru (AI ₂ (C ₂ H) ₃ CI ₂ ) given. The temperature rose

0 C increased and gaseous vinyl chloride initiated continuously for polymerization. After 5 hours methanol was added to the contents of the flask to stop the polymerization. Then dci The contents of the flask are emptied and the insoluble product is separated off by a filter. The solid product was treated with hydrochloric acid-methanol, with Me ethanol carefully washed and be under reduced pressure. 5OX dried. It was 4.95 g of a obtained white copolymer.

The copolymer obtained was in benzo! and cyclohexanone soluble and possessed properties those of those of a vinyl chloride homopolymer * as well as those of a methyl acrylate homopolymer.sats were different. The elemental analysis

of the copolymer resulted in C 48.54% H 6 60 ° /, and Cl 22.68%. These values correspond to the theoretical Values of a 1: 1 alternating copolymer with C 48.50%, H 6.11% and Cl 23.86%.

Example 2

A equipped with an agitator 200-ml three-necked flask was evacuated, purged with nitrogen and 1 cooled to -78 ⁰ C with dry ice-methanol.

4 g of methyl acrylate was added to the flask under nitrogen and 30 g of vinyl chloride and kept at -78 ° C. A further 50 mmoles of ethylaluminum dichloride were added admitted and the mixture was polymerized for 2 hours. After the polymerization it was

Worked up similarly as in Example I, and 6.43 g of a white, solid copolymer were obtained. The results of the elemental analysis indicated a 1: 1 alternating copolymer. The viscosity of the copolymers measured at 30 ⁰ C in benzene solution was 0.96 dl / g. Similar results were obtained when ethyl acrylate was used instead of methyl acrylate under the same conditions.

Example 3 Example 9

In a manner similar to Example 2, using 50 mmoles of diethylaluminum chloride worked in place of the ethylaluminum dichloride, and 2.74 g of a copolymer were obtained.

Example 4

In a manner similar to Example 2, 25 mmoles of methylaluminum sesquibromide was substituted of ethylaluminum dichloride used and obtained 3.97 g of tines copolymer. From the results Elemental analysis revealed that the product had a composition in molar ratio 1: 1 owned. The viscosity number of the copolymer, measured at 3 (TC in benzene solution, was 2.76 dl / g.

Example 5

A 200 ml three-necked flask fitted with a stirrer was evacuated, purged with nitrogen and cooled to -78 "C with dry ice-methanol. 2 g of methyl acrylate and 30 g of vinyl chloride were added to the flask under a nitrogen atmosphere and kept at -78 ° C. 12.5 mmol of ethylaluminum sesquichloride were added to the flask, and the mixture was polymerized for 1 hour. After the polymerization it became similar Worked up as in Example 1, and 1.61 g of a white, solid copolymer were obtained. The results of the elemental analysis showed that the copolymer had a composition in a molar ratio of 1: 1.

Example 6

Similar to Example 5, the polymerization was carried out using 50 ml of heptane as a solvent. Polymerization was carried out for 1 hour and then in a manner similar to that in the example 1 worked up. 1.09 g of a white, solid copolymer were obtained. The results the elemental analysis showed that the copolymer had a composition in a molar ratio of 1: 1.

Example 7

A polymerization similar to that in Example 6 was carried out, 50 ml of toluene being used in place of the heptane, and 1.03 g of a white, solid copolymer was obtained. The results of elemental analysis indicated that the product had a composition in the molar ratio ⁿ : 1. The viscosity number of the copolymer, measured at 30 ⁰ C in benzene solution was 0.72 dl / g.

Example 8

A polymerization similar to that of Example 1 was carried out, except that 3 g of n-butyl acrylate was used in place of the methyl acrylate and the amount of the ethyl aluminum sesquichloride was reduced to 12.5 mmol. 3.38 g of a copolymer were obtained. The viscosity number of the copolymer, measured at 30 ⁰ C in benzene solution was 0.34 dl / g. The result of the elemental analysis showed that the product was a copolymer with a composition in a molar ratio of 1: 1. Polymerization was carried out in a manner similar to Example 1, except that 2 g of N-ethyl acrylamide was used in place of the methyl acrylate and the amount of ethyl aluminum sesquichloride was reduced to 12.5 mmol. 3 g of a white, solid copolymer were obtained. A similar result was obtained when NN ^ dimethylacrylamide was used in place of methyl acrylate under the same conditions.

Example 10

A 100 ml three-necked flask fitted with a stirrer was evacuated, flushed with nitrogen and cooled to -78 ° C with dry ice-methanol. Under a nitrogen atmosphere, 4 g of methyl acrylate, 15 g of vinylidene chloride and 20 ml were added to the flask

ao given heptane and kept at -78 ° C. Γη the Flask was further added 25 mmol of ethylaluminum sesquichloride and it was added with stirring Polymerized for 4 hours. After the polymerization, work-up was carried out as in Example 1, and there were

* 5 1.20 g of a white, solid copolymer obtained.

The copolymer was in acetone and benzene

soluble, and the elemental analysis values were C 39.11%, H 4.62% and Cl 39.90%. These values corresponded to the calculated values for a 1: 1 copolymer with C 39.37%, H 4.41% and Cl 38.74%.

Example 11

A 100 ml three-necked flask equipped with a stirrer was evacuated, flushed with nitrogen and cooled to −78 ° C. with dry ice-methanol. 3 g of n-butyl acrylate, 15 g of allyl chloride and 20 ml of heptane were added to the flask under a nitrogen atmosphere and kept at -78 ⁰ C. In the

12.5 mmol of ethylaluminum sesquichloride was further added to the flask and polymerized with stirring for 5 hours. After the polymerization, work-up was carried out in a manner similar to that in Example 1, and 2.48 g of a copolymer were obtained. The result of the elemental analysis showed C 59.64%, H 8.49%, Cl 16.79%. The values calculated for a 1: 1 copolymer are C 58.68%, H 8.37% and Cl 17.32%. The copolymer was soluble in acetone and benzene and had a viscosity number of 0.38 dl / g, measured at 30 ⁰ C in benzene solution.

Example 12

A similar polymerization and aftertreatment as in Example 10 was carried out, with the Exception that 3 g of n-butyl acrylate instead of methyl acrylate and of vinylidene chloride 15 g of vinyl bromide were used, and 4.25 g of a copolymer was obtained. After The result of the elemental analysis showed that the copolymer had a composition: m molar ratio 1: 1.

Example 13

A 100 ml three-necked flask fitted with a stirrer was evacuated, flushed with nitrogen and cooled to -78 ° C with dry ice-methanol.

2 g of methyl acrylate, 9.2 g of 2-chloropropene-1 and 20 ml

Heptane added and maintained at -78 ⁰ C. To the flask was further added 12.5 mmol of ethyl aluminum sesquichloride, and the contents were stirred for 2 hours to polymerize. After the polymerization, work-up was carried out in a manner similar to that in Example 1, and 2.78 g of a white, solid copolymer were obtained. The mixed polymer was soluble in acetone and benzene and showed the following values of the elemental analysis: C 52.12%, H 8.06%, Cl 21.99%, which agrees well with the calculated values for a 1 ^ mixed polymer with C 51.38 %. H 7.39 · / ,, Cl 21.67%.

Example 14

A 100 ml three-necked flask fitted with a stirrer was evacuated, purged with nitrogen, and cooled to -78 ° C with dry ice-methanol. 20 ml of butyl chloride and 3 g of methylthio'acrylate were placed in the flask under a nitrogen atmosphere and mixed homogeneously. To the mixture was added 12.5 mmol of ethyl aluminum sesquichloride. While stirring, the temperature was increased to ⁰ ° C. and 15 g of p-chlorostyrene were added to the liquid. After 2 hours, methanol was added to stop the polymerization. The contents of the flask were then emptied and the insoluble product was separated off by filtration. The solid obtained was treated with hydrochloric acid-methanol, carefully washed with methanol and dried under reduced pressure at 50 ° C. 2.50 g of a white copolymer were obtained.

Example 15

A equipped with an agitator 100-ml three-necked flask was evacuated, flushed with nitrogen and cooled with dry ice-methanol to -78 ⁰ C. 50 g of vinyl chloride and 2 g of acrylonitrile were added to the flask under a nitrogen atmosphere and kept at -78 ° C. Into the flask was added 25 mmol of methylaluminum sesquibromide, and polymerization was carried out with stirring for 5 hours. After the polymerization, an aftertreatment was carried out in a manner similar to that in Example 1, and a white, solid polymer was obtained. The polymer was soluble in dimethylformamide and had a viscosity number of 1.96 dl / g at 30 ^° C. in dimethylformamide solution. The results of the elemental analysis showed that the product was a copolymer with a composition in a molar ratio of 1: 1.

Example 16

A 300 ml glass autoclave was evacuated, flushed with nitrogen and cooled to -78 ° C. 100 ml of cyclohexane and 40 mmol of aluminum chloride were placed in the autoclave under a nitrogen atmosphere, and further 10.6 g of acrylonitrile were added. The temperature was raised to room temperature with stirring, and then 19.4 g of vinylidene chloride was added to the mixture. After the mixture had been cooled again to -78 ° C, 40 mmol of triethylaluminum were added, and polymerization was carried out for 24 hours at 20 ⁰ C. Thereafter, methanol was added to terminate the polymerization and the insoluble product was filtered off. The solid product obtained was worked up similarly to Example 1, and 1.32 g of its solid copolymer was obtained. The infrared spectrum showed that the product was a 1: 1 alternating copolymer. A similar copolymer was obtained by using aluminum bromide instead of aluminum-S chloride. On the other hand, a similar copolymer was also obtained by using trihexylaluminum or dibutylaluminum chloride in place of the triethylaluminum.

Example 17

20 ml of toluene and 3 g of sodium acrylate were placed at 0 ° C. in a 200 ml four-necked flask in a nitrogen atmosphere. The fine suspension was admixed with 12.5 mmol of ethylaluminum sesquichloride (Ala (CaHj) ₃ Cl ₃ ) and 15 g of p-iodostyrene and the mixture was polymerized for 2 hours with stirring. 3.27 g of a white copolymer were obtained. A similar result was obtained when instead of sodium acrylate

ao neither acrylic acid chloride, methyl vinyl ketone or acrolein were used under similar conditions.

Example 18

»5 A 300 ml pressure-resistant glass flask was flushed with nitrogen and charged with 20 ml of n-Hcptane and 3 g of acrylic acid. Then 10 g Vinyl chloride condensed and 25 mmol ethylaluminum sesquichloride added with stirring. the The contents of the flask were left to react for 5 hours at OC. 1.37 g of a white, solid Get mixed polymer that is soluble in water. According to the result of elemental analysis showed the copolymer has a composition in a molar ratio of 1: 1.

Claims (9)

Patent claims: 1. Process for the production of alternating copolymers by polymerizing a ethylenically unsaturated halogenated hydrocarbon of the general formula CH ₂ = c; R ¹ R ² in which R ^{1 is} a halogen atom or a halogenated hydrocarbon radical having 1 to 20 carbon atoms and R ^{2 is} a hydrogen atom, a halogen atom, a hydrocarbon radical having 1 to 20 carbon atoms or a halogenated hydrocarbon radical having 1 to 20 carbon atoms, with acrylonitrile or an acrylic compound of the general formula CH ₂ = CH-C -Y in which Z is an oxygen or sulfur atom and Y is the group ZR ³ , ZH, ZMe, R ^B R ³ , a halogen or hydrogen atom, where R ^{3 is} an organic radical with 1 to 20 carbon Substance atoms, R ⁴ and R ^{ü are} each hydrogen atoms or organic radicals with 1 to 20 carbon atoms or R ⁴ and R ⁶ are connected to one another, forming a heterocyclic ring with nitrogen and Me an ammonium radical or a monovalent fraction of an element from groups I to IU of the periodic table is, in the presence of a catalyst, characterized in that the copolymerization in bulk or in an inert diluent at a temperature in the range from - 150 to + 10ü ^r C in the presence of (1) an organic aluminum halogen compound of the general formula AlR ¹ X ¹ * A1R " ₂ X ¹ or AI ₈ RVO ₃ , in which R · is an ordinary organic radical u.id X ^{1 is} a halogen atom, or (2) a combination of at least two kinds of aluminum compounds with the general formulas A1R * XV AlR ^e , X \ Al ₁ RyO ₃ , A1R ⁷ ₃ or A1X * 3, in which R ″ and R ⁷ denote ordinary organic radicals and X ¹ and X ² denote halogen atoms, as a catalyst durc is managed. 2. Vetiahren according to claim 1, characterized in that the ethylenically unsaturated halogenated hydrocarbon added after as Acrylonitrile or the acrylic compound with the halogen-containing aluminum compound with each other came into contact. 3. The method according to claim 1, characterized in that the ethylenically unsaturated halogenated hydrocarbon by mixing the acrylonitrile or the acrylic compound added complex formed with the halogen-containing aluminum compound. 4. The method according to claim 1, characterized in that one acrylonitrile or the acrylic compound mixes with the ethylenically unsaturated halogenated hydrocarbon and the aluminum compound this mixture is added. 5. The method according to claim 1 to 4, characterized in that the halogen-containing aluminum compound and adding the organic aluminum compound separately. 6. The method according to claim I to 5, characterized in that the aluminum compound used in an amount of 0.01 to 10 moles per mole of the acrylic compound. 7. The method according to claim 1 to 6, characterized in that the ethylenically unsaturated halogenated hydrocarbon in excess of acrylonitrile or the acrylic compound used. 8. The method of claim 1 to 7, characterized in that one mixes the acrylonitrile or acrylic compound with the halogen-containing aluminum compound at a temperature below 0 ⁰ C. 9. The method according to claim 1 to 8, characterized in that the halogen-containing aluminum compound and the acrylonitrile or the acrylic compound in approximately equimolar proportions begins.