DE1241991B - Process for the production of homo- or copolymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 c -25/01

Number: 1241991

File number: H 53498IV d / 39 c

Filing date: August 10, 1964

Open date: June 8, 1967

Polymers of the vinyl ester of trimethyl acetic acid, known as pivalic acid, with a wide variety of comonomers are known. These known products are thermoplastic polymers which have a relatively low softening point and are therefore unsuitable for many uses. The softening point of from 85 to 88 ⁰ C. Further, it was known that produced by bead polymerisation polyvinyl pivalate shows a softening point of about 94 to 96 ⁰ C.

There has now been a process for the production of homopolymers or copolymers by polymerization of vinyl pivalates, optionally together with at least one polymerizable double bond containing compounds, found under the action of radical formers, in which then thermoplastic, Polymers or copolymers containing bound chlorine with a high softening point are obtained when the vinyl ester of ^, ^ ', ^ "- trichloropivalic acid as vinyl pivalate is polymerized.

In the following the ^, ^ ', ^ "- trichloropivalic acid briefly referred to as trichloropivalic acid.

The monomeric vinyl ester of trichloropivalic acid was just like the polymers obtained from it up to now not known. The monomeric vinyl ester can be prepared in various ways known per se have been. So z. B. the trichloropivalic acid have been reacted with acetylene to form the vinyl ester. It is also possible that the free acid with a lower vinyl ester, such as vinyl acetate or vinyl propionate, has been transesterified.

The vinyl ester should be present in pure form for the polymerization. For this reason it is supposed to be manufactured Trichloropivalic acid as pure as possible can be used. It is also often useful that the Vinyl ester of trichloropivalic acid shaken out with concentrated aqueous alkalis before the polymerization and then fractionally distilled. The homopolymerization of the vinyl ester of trichloropivalic acid is carried out according to the usual methods.

It is also possible to carry out the polymerization together with further, at least one polymerizable Perform double bond containing compounds. Examples of suitable comonomers are Vinyl esters of long- or short-chain aliphatic carboxylic acids, but in particular vinyl acetate, vinyl propionate or vinyl butyrate. Acrylic or methacrylic esters are also suitable as comonomers short-chain aliphatic alcohols, especially processes for the production

of homo- or copolymers

Applicant:

Henkel & Cie. GmbH.,
Düsseldorf-Holthausen, Henkelstr. 67

Named as inventor:
Dipl.-Chem. Dr. Ernst Klesper,
Düsseldorf-Eller

special methyl acrylate, ethyl methacrylate or butyl acrylate.

The polymerization is carried out in a manner known per se. It can be used as a block polymerization, under Certain circumstances also in the form of a bead polymerization, as a polymerization in solution, optionally as a precipitation polymerization, or also preferably as an emulsion or Suspension polymerization can be carried out.

The known radical formers or radical generating agents are suitable for stimulating the polymerization Systems, including exposure to short-wave light or other high-energy radiation. By which Means the stimulation of the polymerization is carried out depends, among other things, on the respective Polymerization method. The following catalysts can be used in many cases: hydrogen peroxide, Potassium peroxydisulfate, possibly with the addition of reducing agents such as sodium dithionite, Sodium hydrogen sulfite, sodium thiosulfate, formaldehyde sodium sulfoxylate and divalent ones Iron salts, as redox systems. In addition, there are organic compounds that generate radicals when heated suitable for initiating the polymerization, for example diacetyl peroxide, dilauroyl peroxide, Acetyl lauroyl peroxide, dibenzoyl peroxide, dicumol peroxide, cyclohexanone peroxide, butyl hydroperoxide, Cumene hydroperoxide. Furthermore, non-peroxidic organic compounds can also be used as radical formers in question, such as azo-isobutyric acid dinitrile or the corresponding dimethyl ester. Furthermore, to initiate the polymerization, irradiation with customary quartz lamps which deliver UV light is necessary possible.

The actual block polymerization is preferably triggered by irradiation with ultraviolet light. It can also take the form of a bead polymerization in

709 589/358

Water can be made. In this case it is advisable to use free radical formers soluble in the monomers, mentioned above are used. It may also be advisable to use protective colloids or so-called Use grit.

In the case of polymerization in solution, it is possible to use solvents which are both the monomeric as well as the polymeric vinyl ester of trichloropivalic acid or the vinyl ester of trichloropivalic acid Dissolve containing copolymer. For example, the following can be used as such: Benzene, toluene, xylene, dioxane, acetone, methyl ethyl ketone, ethyl acetate.

Used in the emulsion or suspension polymerization of the vinyl ester of trichloropivalic acid primarily water is used as the reaction medium. But it is also possible to use organic liquids such as Use glycol or glycerin. Known ones can be used for emulsifying or dispersing the monomers Emulsifiers, in particular anionic and nonionic compounds, are used. For example alkali salts of fatty acids or alkylarylsulfonates or of half-esters of sulfuric acid are suitable with longer-chain fatty alcohols such as lauryl, myristyl, palmityl, stearyl or oleyl alcohol. The surface-active ethylene oxide addition products to the above can also be used Alcohols or an alkylated phenols such as nonylphenol. In some cases it can be useful be to use protective colloids in addition to the emulsifiers, especially if you wants to obtain a stable emulsion or dispersion.

The polymerization temperature depends on the polymerization process used. She is about between 0 and 150 ° C, but especially 30 and 100 ° C.

The work-up of the polymers depends on the polymerization method used. If solvent or diluents have been used, the reaction products can be used in a suitable manner Way, for example by precipitation with nonsolvents or when using water by adding Saline solutions, are deposited. In some cases you can also use the solvents Remove distillation. The purification of the obtained polymers, which for some purposes is necessary, can in a manner known per se by dissolving in a solvent and precipitating with a non-dissolving, miscible liquid. In addition to about not implemented Monomers also separated low molecular weight fractions.

The polymers or copolymers of the vinyl ester of trichloropivalic acid which can be prepared according to the invention have a very high softening point compared to other vinyl polymers. Compared with polyvinyl similar molecular weight, the softening points of about 60 to 9O ⁰ C higher, namely between about 130 and 155 ° C.

The polymers, but especially the homopolymers, show good thermal stability and good light resistance, which is particularly noteworthy compared to polyvinyl chloride. So occur with the same temperature stress in the vinyl ester of trichloropivalic acid only after considerably the same discoloration for a long time. The good thermal properties can be attributed to that the polymers prepared according to the invention have little or no tendency to split off HCl.

The polymers produced according to the invention are suitable for producing moldings and hard, chemically resistant coating agents. The homopolymers are generally hard and brittle. However, they can easily be converted into hard, but at the same time tough, products using known plasticizers to process. In addition, you can by polymerizing the already mentioned comonomers obtained internally plasticized genuine copolymers.

Production of the vinyl ester
of trichloropivalic acid

255 g of trichloropivalic acid, 25.5 g of HgO and 5.1 g of Hg (OOCCH3) were combined and heated to 120.degree. 0.69 ml of concentrated sulfuric acid were added to this in order _{to form finely divided HgSO 4} in situ. After the atmospheric oxygen had been displaced, _{acetylene was passed in for 3V for 2} hours at 110 to 120.degree. C. with rapid stirring until the acetylene uptake had slowed down considerably. The product was distilled at 1 to 2 torr. Yield 164 g (57.5% of theory).

For further purification, fractionation was carried out over a 30 cm high Raschig ring column with a reflux to decrease ratio of 2: 1 to 1: 1. The purified ester boils at 63 to 66 ^° C. and 0.2 torr. Refractive index: n% ⁵ = 1.4848.

Analysis:

Found
calculated

C 36.30%, Cl 46.31%;
C 36.28%, Cl 46.00%.

example 1

15 g of vinyl ester of trichloropivalic acid were emulsified in 150 ml of water by rapid stirring using 1.5 g of sodium lauryl sulfate. Then, 150 mg potassium peroxydisulfate were added, the oxygen in the air displaced with nitrogen and heated to 7O ⁰ C. After 1 ^x / ₂ hours and continuous stirring, the polymer formed was precipitated with concentrated sodium chloride solution, washed out with water and dried.

Yield 11g, K value 62 (0.5% in dioxane), Softening point between 135 and 145 ° C. The polymer was soluble in benzene, xylene, acetone and chloroform, insoluble in ethanol, glycerine, heptane.

Example 2

The above example was repeated, but with the difference that the polymerization was carried out ^{at 70 °} C. for 2 hours and at 95 ^{° C. for a further 2 hours.} The polymer was crystallized by adding 15 g. Aluminum sulfate is precipitated into the hot emulsion and immediately filtered, washed with water and dried.

Yield 13.2 g, K value 53 (3% in dioxane), softening point between 140 and 150 ° C.

Example 3

6 g of vinyl ester of trichloropivalic acid were emulsified in 60 ml of water by rapid stirring using 600 mg of the sodium salt of lauryl sulfate. 60 mg of potassium peroxydisulfate and 100 mg of Fe (NH ₄ ) JJ (SO ₄ ) JJ 6H ₂ O were added, the air

oxygen displaced by nitrogen, kept for 2 hours at 70 ⁰ C and 2 hours at 95 ° C with constant stirring. It was crystallized by adding 6 g. Aluminum sulfate is precipitated into the hot emulsion.

Yield 5 g, K value 54 (3% in dioxane), softening point between 135 and 145 ° C.

Example 4

7 g of vinyl ester of trichloropivalic acid were placed in a test tube with a combined UV and IR light source irradiated for 6 hours. The monomer turned into a clear, hard mass.

For purification, the substance was dissolved in dioxane and precipitated with methanol. Yield 4.1g. The K value of the precipitated polymer was 62 (3% in dioxane).

Example 5

6 g of vinyl ester of trichloropivalic acid and 6 g of vinyl acetate were emulsified in 60 ecm of water using 600 mg of sodium lauryl sulfate with rapid stirring. There were added 60 mg of potassium persulfate, oxygen in the air displaced with nitrogen, and held for 2 hours at 70 ⁰ C, 1 hour at 95 ° C under stirring ständigern. While it was still hot, it was precipitated with a saturated saline solution. Yield 10.1g. The polymer was soluble in dioxane, ethyl acetate, acetone, trichlorethylene or benzene and insoluble in methanol, ethanol or heptane. It is not a mixture of homopolymers, but a real copolymer.

Example 6

35

Example 7

2.15 g of vinyl ester of trichloropivalic acid and 0.86 g of vinyl acetate were in the test tube for 18 hours irradiated with a combined UV and IR lamp until it hardens completely. The polymer was dissolved in dioxane and precipitated with methanol. It is a real copolymer.

Example 8

6 g of vinyl ester of trichloropivalic acid and 6 g of freshly distilled acrylic acid methyl ester were emulsified with 300 mg of Na lauryl sulfate and 300 mg of a nonionic emulsifier (nonylphenol with 2.5 ethylene oxide units per mole of nonylphenol) in 60 ecm H ₂ O with stirring. There were then added 60 mg of potassium peroxydisulfate, the oxygen in the air displaced with nitrogen and kept under stirring for 2 hours at 7O ⁰ C, 2 hours at 95 ° C. Then it was precipitated with saturated sodium chloride solution, washed with water and dried.

Yield 11.5 g (= 96%), K value 63 (3% in Dioxane). The polymer was hard and tough. It was soluble in dioxane, ethyl acetate, acetone, trichlorethylene or benzene, insoluble in methanol, ethanol or heptane. It is a real copolymer.

Example 9

10 g of vinyl ester of trichloropivalic acid and 10 g of vinyl acetate were diluted with 30 ecm of dry toluene and 20 mg of azo-bis (isobutyric acid nitrile) were added. Polymerization was carried out under reflux for 3V for _{2 hours.} The polymer was precipitated with heptane and ^{dried at 70 °} C. in a vacuum drying cabinet. Yield 10 g, K value 17 (3% in dioxane).

45 9 g of vinyl ester of trichloropivalic acid and 3 g of freshly distilled acrylic acid n-butyl ester were emulsified with 450 mg of sodium lauryl sulfate, 450 mg of a nonionic emulsifier (nonylphenol with 2.5 ethylene oxide units per mole of nonylphenol) in 90 ml of water with stirring. There were then added 120 mg of potassium peroxydisulfate, the oxygen in the air displaced with nitrogen and kept under stirring for 2 hours at 70 ⁰ C and 1 hour at 95 ° C. Then it was precipitated with saturated sodium chloride solution, ^{washed with water at 70 °} C. and dried. Yield 10.5g. The polymer was hard and tough.

Claims (1)

Claim: Process for the production of homopolymers or copolymers by polymerizing vinyl pivalates, optionally together with compounds containing at least one polymerizable double bond, with the action of Radical formers, characterized in that that the vinyl ester of /?, / f, ^ "- trichloropivalic acid is polymerized as vinyl pivalate. Considered publications:
U.S. Patent No. 2,381,338;
Die Makromolekulare Chemie, Vol. 69, p. 135 (1963). 709 589/358 5.67 © Bundesdruckerei Berlin