DE1025146B - Process for the production of polymers and copolymers - Google Patents

Description

This invention relates to a process for the preparation of polymers and copolymers in which by implementing an ester of the formula

R ₁ OOCR

with an alcohol of the formula

CH ₂ : CHO (AO) _m H.

in the presence of a basic, anhydrous alcoholysis catalyst esters of the formula prepared in a conventional manner

CH ₂ : CHO (AO) _m OCR,

in which R is an acyclic unsaturated hydrocarbon radical with at least 2 carbon atoms, A is an alkylene group with not more than 14 carbon atoms or a vinyl-substituted or a phenyl-substituted alkylene group, m is an integer not more than 6 and R _{1 is} a lower alkyl group, as such or be polymerized together with another unsaturated polymerizable compound in the presence of a polymerization catalyst.

The esters CH ₂ : CH O (AO) _m O CR form polymers both under the influence of catalysts of the acid type and under the influence of catalysts which form free radicals. Under the influence of catalysts of the acid type, polymers are formed which are reactive due to the unsaturated bond in the carboxylic acid part. They can be reacted with other substances at this bond, or they can react with themselves to form crosslinked, insoluble polymers. The polymers as well as the mixed and heteropolymers described below are used to produce adhesives, coatings, moldings and the like. Polymers of the first stage can be modified chemically, ie permanently. The above esters also form copolymers with other unsaturated compounds, the copolymers prepared under the influence of acid-type catalysts being particularly useful. Furthermore, the esters form heteropolymers with reaction participants such as maleic anhydride, citraconic anhydride, chloromalic anhydride, etc.

If you use the monomeric ester according to the claimed process with a free radical Reacts catalyst, you get directly to an insoluble, crosslinked polymer, while one with a Acid-type catalyst produced polymer upon further treatment with a free radical-forming one Catalyst is crosslinked. The process of this invention provides a way of producing addition polymers, both homo- and copolymers, which can ultimately be networked and thus made insoluble. That is in the cases of

for the production of polymers
and copolymers

Applicant:

Rohm & Haas Company,
Philadelphia, Pa. (V. St. A.)

Representative: Dr.-Ing. H. Ruschke, Berlin-Friedenau,

and Dipl.-Ing. K. Grentzenberg, Munich 27,

Pienzenauerstr. 2, patent attorneys

Claimed priority:
V. St. v. America March 9, 1951

La Verne Norman Bauer, Philadelphia, Pa.,

and Harry Trainer Neher, Bristol, Pa. (V. St. A.),

have been named as inventors

Advantage in which high-resistance coatings, adhesives or moldings are required, where e.g. high temperatures require the use of a thermoplastic Exclude resin or the products must withstand the action of solvents. The polymers of the invention can be prepared in situ and are insoluble in a single process step be made. Or it can be done by using an acid type catalyst in the first stage first produce soluble polymers and then make them insoluble if necessary.

The reactions are double bonds due to the different reactivities of the different species easily controllable in the molecule. Thus the vinyl ether group speaks easily to acid-type catalysts with the formation of addition polymers at this point. These polymers can then be attached to the double bond of the acid group can easily be converted further. Where the double bond of the acid group is proportionate Activated quickly by a free radical forming catalyst will turn out to be at this point easily form addition polymers, whereupon the other point, which is unsaturated, comes into action. As a result These differences in reactivity can keep the entire polymerization well under control will.

709 907/44 *

3 4

Esters of unsaturated carboxylic acids with the vinyloxy-like oxide to achieve longer ether chains or containing alcohols are best modified by alcoholysis of mixed ether chains. Suitable of an ester from an unsaturated carboxylic acid and oxides include ethylene oxide, propylene oxide, a lower monovalent saturated aliphatic butylene oxide, styrene oxide, butadiene monoxide and the like. Alcohol with a vinyloxy-containing alcohol in counter-5 vinyloxy-containing alcohols with mixed ether ware of an alkaline reaction or alcoholysis group are produced, for example, by reacting a catalyst produced. The lower aliphatic alcohol vinyloxyalkanol with any of those mentioned above is replaced by the alcohol with the vinyl ether group as oxides under the influence of an alkali hydroxide and conveniently removed by distillation, catalyst. So give / 3-vinyloxyethanol and Pi owodurch the alcoholysis conversion up to the completion of io pylenoxyd vinoxyethoxypropanol with a boiling point of 66 ° / progresses. The alkaline catalyst can then be from 1.2 mm to 7571.5 mm; Removes vinyloxyethanol and butadiene or destroyed and give the monomer monoxide in many cases

purified by distillation under reduced pressure _{CH <} . CHOCh ₂ CH ₂ OCHXH (OH) CH: CH ₃

will. "

Catalysts for promoting alcoholysis are 15 with a boiling point of 68 to 69 ° / l mm; Vinyloxyethanol and strongly basic, anhydrous compounds such as sodium oxide and styicloxide produce vinyloxyethoxy (phenyl) ethanol Potassium or other alkali alcoholates, e.g. potassium with a boiling point of 130 to 142 ° / 1 mm, and vinyloxyethanol butylate, sodium methylate and potassium propylate. Be and allyl glycidyl result

The alkali alcoholates of vinyl qjj .qjjq q j ^ q qjj CHiOH) CH can also be used

oxy-containing alcohols. Quaternary ammonium alcoholates 20 ² 'V) - CH CH "CH *

are because of their good solubility in the conversion ² ' ² '

systems of interest. Typical quaternary ammo - A long chain glycol can be mixed with 1 mole of acetylene too

nium alcoholates are e.g. Tetramethylammoniummethy- a vinyloxyalkanol, e.g. vinyloxy-5-pentanol, umlat, Tetramethylammonium tert. -butylate, trimethyl- are set, which in turn with one of the above benzylammonium methylate.Dimethyldibenzylammonium oxide with formation of a compound, e.g. of vinyl ethylate, Diniethyldi- (chlorobenzyl) ammonium methylate oxypentyloxyethanol and the like., Can be implemented. and the like. Those required to replace the alcohol groups. A suitable method for carrying out alcoholysis

The amount of catalyst borrowed is small; the presence of a lower aliphatic alcohol ester 0.05 to 1% catalyst in a mixture of the reaction and an unsaturated monocaibonic acid with a participant is usually sufficient to convert the vinyloxy-containing alcohol is a vinyl substitution to advance. It is advisable to put ether alcohol in a reaction vessel and to give it a add alkaline alcoholysis catalyst from time to time as the reaction progresses. Through this small amounts of catalyst too. the conversion mixture remains alkaline from the start,

Esters of lower aliphatic alcohols with unsaturated ones, which is desirable because vinyl ethers as well as vinyl carboxylic acids, how they are sensitive to acid as reaction participants 35 ether alcohols. Should an alcohol des Have the formula that will act as a catalyst, so will vinyl ether alcohol

R OOCR sodium as a typical alkali metal to the vinyl ether

¹ 'alcohol added and reacted with it. Otherwise

where R _{1 is} a lower alkyl group, such as methyl, ethyl, an anhydrous alkaline catalyst, for example propyl or butyl, and R is an acyclic unsaturated alkali metal alcoholate of a lower alcohol. So-hydrocarbon group with at least 2 carbon atoms is then meant as an ester of an unsaturated carboxylic acid. The acid residue of these esters corresponds to that of set, usually in an amount which is at least equivalent to that of vinyl acrylic, α-methacrylic, α-ethacrylic, α-phenylacrylic, cro-ether alcohol. The reaction clay, cinnamon, ß-ethacryl, β, / 9-dimethylacryl, vinyl acetic, mixture is stirred and heated. Implementation tempe-allylacetic, 2-methyl-2-butene, hydrosorbin, 2-ethyl 4-5 temperatures between 50 and 180 ° below normal, vermin-2-hexene, undecylene, myristolein, oil, sorbin -, 2,4-pendulum or increased pressures can be used. The tadiene, geranium, linoleic, linolenic, elaostearic, procatalyst can also be added from time to time to piolic, methylpropiolic, 10-undecinic, stearolic acids and, especially if the reaction becomes sluggish, similar acids . So R fluctuates in the preferred seems. It is often very advantageous if between 2 and 17 carbon atoms during the acid components. 50 Implementation of a successful amount of a polymerization

Vinyloxy-containing alcohols used herein inhibitors such as / 3-naphthol is present. have the general formula The alcohol split off from the original ester

P ₁ T rxxr \ / \ r \\ tr hol is removed by distillation. If this alcohol

and the ester intended to be reacted em azeotropes

in which A form an alkylene or a hydrocarbon sub-mixture, the alcohol is expedient in this substituted alkylene group with a chain of at least form removed, and there must be enough ester applied Means carbon atoms between oxygen atoms. They are going to allow this procedure. If not Group A can contain up to 14 carbon atoms. This alcohol is split off more, is the conversion alcohols are exhausted from the reaction of acetylene with a glycemic mixture. The catalyst can be removed or kolen in the presence of a strongly alkaline catalyst 60 destroyed by washing or neutralization, available. Thus, in the presence of sodium or this can be an organic acid or carbonic acid or Potassium hydroxide 1 mole of acetylene with 1 mole of ethylene, a strong acid can be used. Becomes a strong acid Propylene, trimethylene, butylene, hexylene, octylene, used, an excess must be avoided. Ob-decamethylene, Tetradecylene, diethylene, triethylene, although it is usually appropriate to use the alkaline Destroying pentaethylene, dipropylene, phenylene glycol or the catalyst is not always essential similar glycol to the monovinyl ether thereof. borrowed as the new ester in many cases from the alkaline Such vinyl ethers can be used directly to replace the lower reaction mixture by distillation below low Alcohol group of a monocarboxylic acid ester related to pressures can be isolated.

will. On the other hand, the monovinyl ether alcohol can use the transesterification process described above

by reaction with an alkylene oxide or a 70 is not the subject of the invention.

5 6

The esters described give under the influence of in which vinyloxymethyl methacrylate solidifies) cooled. Acid type catalysts, usually at low temperatures. The solid melted at about -18 °. About 45 parts ratur, particularly advantageous polymers. The poly-liquid propane was added; However, since this does not dissolve the merization reaction best in the presence of a solid, 45 parts of liquid organic methylene solvent, especially one with a low level of 5 chloride at -50 °, were added. This mixture resolved the temperatures remaining fluid, running. About this ester. 70 parts of solid carbonic acid and 1 part of a purpose can liquids such as propane, methyl chloride 15% boron trifluoride-ethyl ether solution were zuu. Like., are used. Temperatures between + 50 given. The mixture was stirred and in a bath and -80 ° are applicable. As catalysts can be cooled. A polymer formed which was deposited as boron trifluoride and its coordination complexes with a white solid. After 4 hours, the oxygen-containing compounds such as ethers, ketones, liquid in the vessel were poured off the solid, the alcohols or carboxylic acids, iodine, phosphoric acid, with 50 parts of a 5% sodium hydroxide solution and p-toluenesulfonic acid, aluminum chloride, stannous chloride, 20 parts of benzene to dissolve of the polymer treated and the like., Can be used. The more effective cata- lyst was. The aqueous layer was drawn off. The catalysts require lower temperatures than the less 15 benzene solution was dried over sodium sulfate, effective. filtered and evaporated. The residue obtained was freed of volatile constituents by heating to 50 ° / l mm, the polymers obtained by acid catalysis are thermoplastic, in organic solvents, and formed a sticky mass. A soluble resin. They can owned by free radical catalysis 30 ° / ₀ solution thereof in toluene had a viscosity or by oxidation into insoluble polymers vice 20 of 23.4 cSt at about 38 °.

to be changed. The soluble polymers can be used for films of this polymer from a toluene

Coatings and films and applied to metal foils for gluing or similar solutions. The films were

Process in which crosslinking and later insoluble - air-dried for 9 days, after which time

are desired to be used. they are clear, hard and insoluble in the usual solutions

The polymerization can also be averaged with free radicals. The presence of cobalt dryers

forming catalysts, including both organic, accelerated air drying significantly. Was that

Peroxides as well as azo type catalysts, such as azodiiso polymer with benzoyl peroxide for 15 minutes

butyronitrile and dimethylazodiisobutyrate, when heated to 150 °, an extraordinarily hard, un-

will act. These catalysts lead to insoluble soluble film being obtained.

Polymers and copolymers. 30 In the same way, from the other vinyloxy

The following are examples of the preparation of the various esters of unsaturated acids.

which polymers. be asked. Vinyloxyethyl crotonate also supplies

Example 1 usually hard, insoluble films. Vinyloxyethyl oleate

are films that are produced in the presence of traces of cobalt

A mixture of 15 parts by weight of Vinyloxyäthyl 35 dryers become insoluble. Increasing the number of acrylate, 68 parts of liquid methyl chloride and 70 parts of ether bonds or the length of the alkylene chain of solidified carbonic acid was cooled to -71 ° and the toughness and adhesive strength of the final poly-1 part of a 15% boron trifluoride-ethyl ether solution was added and prevents shrinkage at the end offset. The temperature of the approach rose with continued treatment,
gradual polymerization to -66 °. The poly- 40.
merizing mixture was 2.5 hours at lower example ά
Maintained temperature and then a slow temperature rise 10 parts of vinyloxyethyl linolate (containing some oleate) with evaporation of methyl chloride were dissolved in 44 parts of methyl chloride. Leave to the mixture. At + 5 °, 20 parts of benzene and 50 parts were added at -15 ° to 0.695 parts of a 20% boron tri-part of water, to which 0.264 parts of sodium hydroxide were added to the fluoride-ether complex. Over the course of 2.5 were added. The resulting mixture was allowed to have a temperature of 17 ° for hours and was stirred well for 20 minutes. Then they would achieve. The polymer formed was allowed to settle in 10 parts of layers and separated. The benzene and benzene was added at 10 ° / ₀ hydrochloric Natriumbicarbo solution of the polymer was dried over anhydrous bicarbonate solution. After removal of the sodium sulfate solution, dried, filtered and concentrated under reduced pressure under reduced pressure. The residue was replaced by liquid polymer. Films of this polymer were broken down by heating to 45 ° / l mm and resulted in an amber layer, applied to metal foils and air-dried, colored, very viscous liquid, the polyvinyloxyethyl they remained sticky for a few days. One made with benzoylacrylate. The yield was 96%. The vis- peroxide-treated sample formed a solid, insoluble film after 15 minutes of viscosity of a 32.8% solution of this polymer in mild heating at 150 °. Toluene was 3.6 cSt at about 38 °. Another sample treated with a cobalt drier. This polymer becomes insoluble within 2 days when heated with a dried to form a resistance organic peroxide, such as benzoyl peroxide. capable, insoluble film.
Films air-dried on metal foils for 7 days.
of the polymer became solid and insoluble in benzene. 60 Example 4

Containing a trace of cobalt naphthenate, 2 days at 30 °.

air-dried films were cooled on mild heating on ice-bath, it formed a glass-like solid

150 ° insoluble in 15 minutes. These films were solid. Treatment of a methyl chloride solution this

shiny, extremely hard and abrasion-resistant. Ester with 1% of its weight of a 20 ° / ₀ sodium boron

65 trifluoride ether catalyst caused in the cold

Example 2 Polymerization with a rise in temperature. The polymer

was taken up in benzene and this solution became

A polymerization vessel was washed with 15 parts / S-vinyl with 10% sodium bicarbonate solution. the

Oxyäthylmethacrylat charged and in a bath of benzene solution was applied to metal. In 2.5

Acetone and solid carbonic acid to -62.2 ° (the point 70 hours a non-sticky film formed. After

7 8

For 3 days the film was very hard and insoluble in benzene. methacrylate content could - as with similar mixed Das the same result was achieved with the addition of a small amount of benzoyl polymers ■ - improved hardness, peroxide and mild heating to 150 ° in 15 minutes.

achieved. Cobalt dryers had the same effect. Example 9

5 From a mixture of 5 parts of vinyloxyethyl

Beisüiel 5 methacrylate and 10 parts of styrene was a mixed poly

merisat produced. The mixture was made in propane and

10 parts of vinyloxyethyl methacrylate were dissolved with 0.01 methylene chloride and at -71.1 ° with 0.3 parts Treated parts of azodiisobutyronitrile and treated aluminum chloride for 4 hours. Under various heated to 60 to 70 ° for a long time. It became a hard, insoluble additions of small amounts of aluminum chloride Lich polymer formed. the temperature rise to 20 °. The implementation

mixture was mixed with a dilute sodium hydroxide

Beismel 6 solution, washed, dried and concentrated. A dry

A white, non-sticky resin was obtained. One

A solution of 15 parts of 4-vinyloxybutylmeth- 15 30% strength solution of this polymer in toluene had a Acrylate in 49 parts of methyl chloride was reduced to -78.3 °, viscosity of 16.6 cSt at about 38 °. This polymer cooled and with a portion of a 20% boron trifluoride was in toluene solution with 0.1% benzoyl peroxide ether catalyst treated. The solution failed and yielded films that were mild after 15 minutes heat up over the course of 4 hours. During this time, heating to 150 ° found hard and insoluble. Polymerization takes place. The polymer was with 15 20

Share a 10% sodium bicarbonate solution. Example IU

delt and dried under reduced pressure. Copolymers can also be made from polyvinyloxy

20 ° / ₀ by weight solution of this polymer in Methylmetha- containing esters of unsaturated carboxylic acids and ungecrylat had a viscosity of 6.3 cSt at about 38 °. Saturated polymerizable compounds, such as vinyl. If this solution was treated with benzoyl peroxide and heated to esters, allyl esters, acrylic acid esters, methacrylic acid, it formed a solid, hard, insoluble ester, styrene or the like, with the aid of peroxide catalyst. manufacture sators.

B eis el η a) From 25 parts of polyvinyl oxyethyl acrylate and 75

Parts of vinyl acetate was at 80 to 96 ° with Benzoylper-

5-vinyloxypentyl methacrylate was prepared as a copolymer as above pory-30 oxide as a catalyst, merized. The polymer was taken up in benzene- The product was a translucent, rubber-coated, by washing with sodium bicarbonate solution from the like, non-sticky, insoluble resin. Freed catalyst and dried over potassium carbonate. b) A copolymer of 18 parts of polyvinyloxy

The benzene solution was ethyl acrylate with 0.05% benzoyl peroxide and 82 parts of styrene was a clear, glassy treated and applied to a metal foil. A resin that is insoluble in acetone, toluene or ethylene chloride hard, resilient, adhesive film was after was. It was so hard that it was with a pencil 15 minutes of mild heating of the metal foil to 135 ° hardness 5 H could no longer be scratched, obtain. c) A copolymer of 15 parts of polyvinyloxy

With other unsaturated polymerizable diethyl acrylate and 85 parts of methyl methacrylate, the same was true bonds, such as vinyl ethers, vinyl aryl compounds, 40 previous copolymer, only that there is an 8 H entz.B. Styrene, isobutylene, etc., form vinyloxy-containing speaking hardness possessed.

Esters of unsaturated acids, fast copolymers. The hardness terms used here mean

As an example of the typical copolymerization, the hardest pencil with which the here are the details of the production of mixed polymer! - plastic just couldn't be scratched anymore.

sowed. 45. .

Example 11

5.75 parts of vinyloxyethyl crotonate, 19.25 parts of styrene,

A mixture of 15 parts of vinyloxyethyl methacrylate, 50 parts of methyl chloride and 0.5 part of boron trifluoride was mixed with 45 parts of allyl vinyl ether and 240 parts of n-butyl vinyl at -71.1 °. The temperature was allowed to slowly rise in an ether made from acetone to 5 °. Mixed polymerization took place. Cooled 74.6 parts of benzene were added to a solid carbon dioxide bath, and the methyl chloride polymerization vessel was added and the 1200 parts of liquid evaporated. This benzene solution was washed with a 5 ° / _o by weight of methylene chloride, 20 parts of a 15 ° / ₀ aqueous sodium carbonate solution and boron trifluoride powdered over sodium sulfate getrock-ethyl ether complex and 750 parts of an integral net. A 25 ° / ₀ by weight solution of the copolymer in carbon dioxide contained. The resulting mixture was 55 benzene had a viscosity of 99.1 cSt at about 38 °. Maintained at -78 ° for 40 minutes and then while evaporating from the benzene solution, films made of methyl chloride were left to heat. after heating with a cobalt dryer or a then about 500 parts of benzene and 500 parts of an organic peroxide hardened. The films showed, upon introduction, 2% strength aqueous sodium hydroxide solution was added. do not put a source in benzene. The above mixed polymer mixture was stirred for 15 minutes and then 60 sat can be used as a molding powder which is left to stand with Perfor to form layers. The organic oxides, such as tert-butyl hydroperoxide, is activated. The layer was dried over sodium sulfate and filtered. molded products are hard and insoluble. The benzene was evaporated and the residue at. .

407I mm dismantled, with 250 parts of copolymer Example 12

were obtained. A 30% solution of the same in 65 A equipped with a stirrer and through a bath Toluene had a viscosity of 5 cSt at about 38 °. The acetone and solid carbon dioxide cooled reaction copolymer could with the help of an organic vessel was with 127 parts of liquid methyl chloride, Peroxide or a cobalt drier quickly made insoluble 27 parts of pure isobutylene and 27 parts of vinyloxy will. Films of the above copolymer are charged with ethyl methacrylate. At this point we were at - 74 ° somewhat soft. By increasing the vinyloxyethyl-70 cooled feed, over 17 minutes

Claims (6)

9 10 Given 2.7 parts of boron drifturide. While the polymer acrylate, allyl methacrylate, ethylene diacrylate, allyl croton considerable heat development took place, so nat, allyl vinyl ether, diallylsuccmat, glycolic acid allyl that the temperature rose to -70 °. Some mixed ether allyl ester and the like are typical for making polymer separated out in the solvent. Can be used after copolymers. The reaction mixture of the er- 5 The vinyloxy-containing esters also form heteropoly- heating with evaporation of methyl chloride over- merisate. permit. The approach was at 29 ° under a pressure of Beismel 14 30 mm freed from volatile constituents and resulted in " 41.2 parts resin. This was with a solution of 10 parts of vinyloxyamyl methacrylate, 10 parts of maleic 11 parts of sodium bicarbonate in 140 parts of water, acid anhydride, 20 parts of dry benzene and 0.5 parts acts and dissolved in benzene. The benzene solution benzoyl peroxide were mixed. The mix was was dried over potassium carbonate, filtered and heated to 80 ° at reflux for 15 minutes, with one 557IO mm freed from the solvent and resulted in 34.6 conversion took place which made the mixture semi-solid Parts of a clear, brownish, liquid resin that let in. It was then 3 hours at 81 to 82 ° and Toluene was soluble. From the solution, films were heated to 118 ° for 30 minutes at a pressure of 30 mm. Metal foils produced a) without a catalyst, b) with 19 parts of a solid heteropolymer were formed. Cobalt dryer, c) with benzoyl peroxide. After 40 minutes instead of Vinyloxyäthylmethacrylat can also After mild heating to 150 °, the films were used with other hard vinyloxy esters of unsaturated acids and in all cases insoluble. A cobalt dryer can be removed, and maleic anhydride can be used by others holding film was replaced in 4 days at room temperature 20 a, /? - unsaturated anhydrides. These two hard. A film without a dryer remained sticky. Starting materials form heteropolymers in a mol ..,. . ,., ο ratio of about 1: 1. Example 13 A stirrer equipped with an acetone example 15 Carbon dioxide bath cooled reaction vessel was 25,312 parts of vinyloxyethyl crotonate, 392 parts of Maleinmit 83.7 parts of methyl chloride, 7.5 parts of vinyloxyethyl anhydride and 200 parts of dry benzene were methacrylate, 42.5 parts of freshly distilled styrene and mixed and mixed with 10 parts of benzoyl peroxide. 55 parts of powdered solid carbon dioxide charged. The mixture was heated on the water bath. Between At a temperature of the mixture of -80 °, a violent reaction set in at 70 and 80 °, at which point 1.63 parts of boron trifluoride was formed in the course of 15 minutes to 30 heteropolymer, which was added to a cream. An exothermic reaction took place which was a colored, brittle, glassy resin insoluble in benzene. brought the reaction mixture to a boil. After 1.5 A similar type of copolymer is produced, For hours it became so viscous that it could no longer be stirred by adding a soluble vinyl polymer to the first could be. At this point, 9 parts of the stage (from one of the Vinyloxyalkylcarboxylate) were with Sodium bicarbonate added. The temperature of the maleic anhydride type anhydride is below the Mixture was increased to 0 °, converted 120 parts of benzene and the influence of a free radical type catalyst. So 30 parts of water were added. For example, the benzene layer becomes a soluble polymer such as polyvinyloxy separated, dried over sodium sulfate and ethyl acrylate or polyvinyloxypropyl methacrylate, with filtered through a layer of diatomaceous earth. The filtrate contained maleic anhydride, chloromaleic anhydride, citra 20.4% resin. It had a viscosity of 40% acid anhydride or the like, preferably in an orga-70 cSt at about 38 °. mixed solvents, the aromatic With the addition of hydrocarbons in many proportions, 50 parts of benzene solution 160 parts of methanol precipitated a copolymer. It is particularly suitable was dried at 50 ° for 12 hours to give 9.6. . Parts of a dry white powder. One at 150 ° 45 Example 16 A sample pressed under a pressure of 560 atm gave a In a reaction vessel 3 parts of maleic Product with a hardness of 2 H that swells in benzene. To an acid anhydride with 9 parts of a liquid polymer Part of the powdered copolymer was mixed with 1.2% of 5-vinyloxypentyl methacrylate, the last- tert-Butylhydrcperoxyd given. As the so treated res is a polyvinyl resin which is under the influence of Powder was pressed, a hard and in toluene 50 a boron trifluoride-ethyl ether complex, 0.02 parts insoluble product obtained. Benzoyl peroxide and 50 parts of dry toluene in the The copolymers from vinyloxyhaltigen esters cold was produced. This mixture was based on the unsaturated acids and polymerizable vinyl water bath heated to 80 to -85 °. After about 15 minutes compounds, especially monovinyl compounds, vigorous conversion took place, with a white, can in a wide range of proportions 55 solid reaction product formed and deposited. To getting produced. You can benefit from 0.3 to 95% of the decanting solvent was the product the starting ester contained, while the remainder was dried for 18 hours at 80 °. There were 8 parts or more other polymerizable monovinyl of a hard, brittle, glassy resin. Compounds such as styrene, p-methylstyrene, a-methyl- styrene, isobutylene, vinyl methyl ether, vinyl butyl ether, 60 claims: Vinyl octyl ether, vinyl dodecyl ether, octyl allyl ether, vinyl acetate, vinyl butyrate, methyl acrylate, ethyl acrylate, 1. Process for the production of polymers Methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixed polymers, characterized in that lat and the like. The one for the preparation of the mixed that by reaction of an ester of the formula The catalyst used in the polymerizate will of course be 65 chosen that he for the chosen compilation K ₁ UULK suitable is. with an alcohol of the formula Instead of one of the above-mentioned monovinyl connections Polyvinyl compounds for which CH ₂ : CHÜ (AU) _TO H Diallyl phthalate, dimethallyl phthalate, vinyl acrylate, allyl 70 in the presence of a basic, anhydrous alcoholysis catalyst in a conventional manner prepared esters of the formula CH ₂ : CHO (AO) _1n OCR, where R is an acyclic unsaturated hydrocarbon group with at least 2 carbon atoms, A is an alkylene group with not more than 14 carbon atoms or a vinyl-substituted or a phenyl-substituted alkylene group, m is an integer not more than 6 and R _{1 is} a lower alkyl group, as such or together be polymerized with another unsaturated polymerizable compound in the presence of a polymerization catalyst. 2. The method according to claim 1, characterized in that R is an acyclic unsaturated hydrocarbon group with 2 to 17 carbon atoms, A is an alkylene group with 2 to 14 carbon atoms or a vinyl-substituted or a phenyl-substituted alkylene group, m is an integer not exceeding 6 and R ₁ means an alkyl group with not more than 4 carbon atoms. 3. The method according to claim 1, characterized in that the further unsaturated polymerizable Compound a vinyl compound such as styrene, a vinyl alkyl ether, a vinyl ester, an acrylic acid ester or is a methacrylic acid ester. 4. The method according to any one of the preceding claims, characterized in that the polymerization catalyst a free radical forming catalyst, e.g. a peroxide, especially an organic one Peroxide, or an azo catalyst, e.g. azodiisobutyronitrile or dimethylazodiisobutyrate. 5. The method according to claim 4, characterized in that the polymerization catalyst is a Is acid type catalyst. 6. The method according to claim 5, characterized in that the by treatment with a Acid type catalyst is treated with a peroxide catalyst. © 709 907/444 2.58