DE1595672B2 - Process for the production of monoolefin-modified graft polymers of vinyl chloride on ethylene vinyl acetate copolymers - Google Patents

Description

Methacrylic esters, maleic or fumaric acid esters, half-esters, vinylidene chloride or vinyl isobutyl ether are possible. The amount of these additional monomers is then less than 10% of the vinyl chloride used. It is possible without difficulty to use partially saponified ethylene-vinyl acetate copolymers as the graft base. The resulting polymers can then be crosslinked via OH groups. The dispersants for the aqueous phase are used. A bead polymer is obtained which i. V. is ^{dried at 60 0} C and is composed as follows:

67.5% PVC polymer,
4.5% polyisobutylene,
28% ethylene vinyl acetate.

The K value is 52.
The product dissolves in

Methyl ethyl ketone and

Activator concentration
changes.

(based on vinyl chloride)

knew auxiliaries such as methyl cellulose, polyvinyl butyl acetate.

alcohol, partially saponified polyvinyl acetates, gelatine According to this regulation, the following variants are made

or polyacrylic acid. These substances are produced; the amount of isobutylene and the

for example in amounts of 0.1 to 2%, based on the water phase. The weight ratio of The water phase to the polymerizable phase is preferably between 1: 1 and 3: 1.

After the polymerization, finely divided products are produced more or less, which may contain between 0.5 and 10 ° / ₀ of the monoolefin. The polyvinyl chloride content is between 35 and 75% (percent by weight in the polymer). The K values of the graft polymer are approximately between 40 and 65 (measured on a 0.5 percent strength by weight solution in cyclohexanone at 25 ° C.). With an increasing content of olefins and ethylene vinyl acetate and with a decreasing K value, the solubility in the conventional solvents of the paint and coating industry improves.

The polymers according to the invention can either be used in substance for coating, lamination 3 " or gluing, inserted or applied from solution will. Mainly they are used for the production of paints and coatings. In the Processing is the addition of stabilizers, especially polyvinyl chloride stabilizers, dyes, Lubricants or fillers of the usual type are possible.

The polymers according to the invention can be addressed as soft polyvinyl chloride which can be used from solution which, however, does not contain any monomeric plasticizers and because of its physiological properties Safety especially in the food sector (e.g. for packaging) can.

example 1

mission
Isobutylene
Weight Activator
concentrate
tration K value Proc
together
Iso lukt-
netting
PVC share % butylene
% % a) _ 0.15 75 _ 72 b) 50 0.15 65 1.2 66.5 c) 100 0.15 55 3.5 65 d) 200 0.15 52 4.5 67.5 e) 300 0.15 50 7.7 59.5 f) 500 0.3 48 5.5 58 G) 750 0.4 45 4.9 45.5

Example 2

Analogously to Example 1, 2100 parts of vinyl chloride and 1800 parts of an ethylene-vinyl acetate copolymer are used (45% vinyl acetate) polymerized with the addition of different amounts of isobutylene. the Activator concentration (azodiisobutyronitrile, based on vinyl chloride) is 2%).

A stirred autoclave is filled with the following solutions:

a) Solution of 1000 parts of a copolymer of ethylene and vinyl acetate (vinyl acetate content 45%) and 4.5 parts of azodiisobutyronitrile in 2900 parts of vinyl chloride and 200 parts of isobutylene : the solution is prepared in the autoclave.

b) 4000 parts of a 1% solution of methyl cellulose in water.

The mixture is stirred vigorously for 4 hours at room temperature and then polymerized with further stirring 15 hours at 60 ° C.

45

mission K value Production PVC Isobutylene composition 54 Weight
share 80 Isobutylene 52 a) 77 37.2 b) 50 63 2.8 40.8 c) 100 61 4.3 41.0 150 56 8.2 e) 300 5.1

50

55 The products d) and e) dissolve z. B. in butyl acetate and toluene.

Example 3

Following the procedure of Example 1, the following components are reacted (activator 0.3%, azodiisobutyronitrile, based on vinyl chloride):

Ethylene vinyl

acetate
Parts by weight

1000
1000
1000

Vinyl acetate content

66 30 30

Vinyl chloride parts by weight

2800 2600 2600

Isobutylene parts by weight

200 400 100 K value

47 48 54

Product composition isobutylene

5.9 1.8 0.8

PVC

<7o

59.5 61.7 71

5 6

β
The K values of the products without added isobutylene butyronitrile as an activator in a mixture

are between 70 and 75. 3000 g vinyl chloride and 250 g propylene in 4000 g

a l ° / _o aqueous solution of methylcellulose dispersive

Example 4 yaws. Then the temperature increases

5 to 55 ° C for 20 hours with rapid stirring polymeric

Following the procedure of Example 1, a sier is carried out. A polymer is obtained which consists of
Solution of the following components in an aqueous 67 2 ° / PVC polymer

dispersed in methylcellulose solution and polymerized propylene,

15 hours at 6O ⁰ C polymer. 31.7% ethylene-vinyl acetate copolymer

1000 parts of ethylene vinyl acetate ¹⁰

composed.

f4S ° / Vnvlarptafi

2900 parts vinyl chloride ^{The product with a} K value of 67 (cyclo-

100 parts of isobutylene 'hexanone) dissolves in methyl ethyl ketone and butyl

150 parts of vinyl acetate, ^acetate

50 parts carbon tetrachloride, ¹⁵ bis ρ ie 1 6

9 parts of azodiisobutyronitil. ,, ■ τ, · ·, <■ j, _1cn

If the propylene is replaced in Example 5 by 150 g

A finely divided polymer which is soluble in ethylene is obtained, which gives a bead polymer which is

Methyl ethyl ketone and butyl acetate, with a K value from

of 53. The proportion of PVC is 71.5%. ₂ ° 71% PVC polymer, ^ ■

. . 0.7% polymerized ethylene and

B els ρ ι e 1 5 28.3 ° / ₀ ethylene-vinyl acetate copolymer

A solution of is composed in a stirred autoclave.

1000 g of a copolymer of ethylene and vinyl 25 The polymer dissolves in methyl ethyl ketone and

acetate (vinyl acetate content 45%) and 9 g azodiiso has a K value of 65.

Claims (3)

1 2 ethylene-vinyl chloride copolymers found that claims:; is characterized in that the vinyl chloride before the polymerization small amounts of a 1. Process for making improved graft monoolefins having 2 to 4 carbon atoms added polymers of vinyl chloride on ethylene-vinyl 5 and the mixture together with the ethylene-vinyl acetate copolymers, thus identified acetate copolymer polymerized. The Polymerisa marks that the vinyl chloride before the tion itself is carried out in a known manner. Polymerization 1.5 to 20 parts by weight, based on the Bfaipolymerization of the olefin in the on the total amount of a monoolefin with 2 to graft polymer, the solubility and the ver-4 Adds carbon atoms and this mixture sufficiently improves the workability of the product, together with the ethylene-vinyl acetate copoly- As olefins come z. B. ethylene, propylene and merisate polymerized. the butylenes into consideration; as particularly advantageous 2. The method according to claim 1, characterized in that isobutylene has been found. This is how it will be if draws that the monoolefin isobutylene used amounts of 1 to 2% isobutylene in the graft polymer will. 15 are included, the solubility is significantly improved, and 3. The method according to claim 1, characterized in a further increase in the amount of isobutylene in the draws that the solution of ethylene-vinyl graft polymer leads to products that acetate copolymer in the mixture isobutylene / itself in aromatic hydrocarbons or carbon vinyl chloride dispersed in water and after the hydrogen mixture up to a concentration Dissolve the method of suspension polymerization radika- 20 of 35%. is polymerized lisch. If you increase with given ratios of Vinyl chloride: ethylene-vinyl acetate copolymer the added amount of isobutylene, it is found that the The amount of polymerized isobutylene initially increases and after passing through a maximum Graft polymer of vinyl chloride on ethylene decreases again. This phenomenon occurs with con-vinyl acetate copolymer represent homogeneous products steadily, but also with increasing isobutylene, which due to their inherent physical components increase in the amount of activator. This indicates shafts, such as high strength, transparency, flexibility - point out that the paralleltät with the amount of olefin, Cold resistance and film-forming capacity for continuous solubility improvement initially on the Coating of flat structures from the incorporation of isobutylene and only with higher additions A wide variety of materials (e.g. textiles, wood, synthetic materials) have a strongly regulating effect of isobutylene materials) and for painting, especially due to the corrosion. ion protection sector. The polymers are The production of the olefin-modified grafts with regard to their mechanical behavior as soft polymers can be carried out in solution or after the polyvinyl chloride address, taking the hardness and driving the emulsion polymerization made the elongation from the ratio of polyvinyl chloride to be made by a mixture of vinyl chloride and Ethylene-vinyl acetate copolymer depend. In the gel olefin on a preformed ethylene-vinyl acetate set However, these products are latex grafted to polyvinyl chloride. Preferably, however, takes place Can be applied and processed without the addition of plasticizers. This is a particular advantage. sion polymerization, with a solution of the ethylene However, their processing and application makes vinyl acetate copolymer in the mixture of some difficulties, since the suspension polymerization predominantly obtained after the vinyl chloride and the olefin in the aqueous phase process is dispersed and polymerized. Preferably ver-graft polymers of vinyl chloride on ethylene 45 are used solutions of 20 to 50 parts by weight of vinyl acetate copolymers only in the typical poly of a copolymer of ethylene and vinyl acetate vinyl chloride solvents such. B. Tetrahydro with a vinyl acetate content of 25 to 70 weight furan or cyclohexanone are soluble, which are excluded for a percentage and a viscosity number [η] of 0.2 to 1.5 broad technical application. It was Γ _m ta] _{(en in χ lol) at 25} ° _{c and Ge} _ therefore already tried to determine the solubility and 50 [g J ν jj workability through the addition of regulators, in particular from 1.5 to 20 parts by weight of a single special of halogenated hydrocarbons, in the case of olefins with 1 to 4 carbon atoms and 80 to 98.5 weight of Polymerization and by polymerizing parts of vinyl chloride. The polymerization takes place on Additional monomers, such as vinyl acetate, acrylic or meth- best, free-radical using the usual acrylic acid esters or esters of unsaturated di- peroxidic initiators, such as benzoyl peroxide, lauroyl carboxylic acids, to improve. But regulators also have peroxide, dichlorobenzoyl peroxide, isopropyl peroxydibei Use of large quantities of an inadequate active carbonate, acetylcyclohexanesulfonyl peroxide (given. The copolymerization of the abovementioned, possibly in combination with more highly disintegrating Ini monomers of course changes the properties of stimulators) or thermally decomposable azo compounds Polymers, especially since they have a substantial 60 gene, such. B. azodiisobutyronitrile. The Polymerisa Improvement To achieve the solubility, in larger ion temperatures are preferably between about Quantities must be used. If you try the 30 and 80 ° C. The amounts of initiators are approximately Solubility by increasing the concentration of between 0.05 and 2 percent by weight, based on To improve the polymerization catalyst (reduced vinyl chloride used. supply of the molecular weight), one often obtains 65 regulators such as B. halogenated, aliphatic carbon networks Products. Hydrogen can also be used. Also the A process has now been established for the production of the addition of minor amounts of further mono-improvers Graft polymers of vinyl chloride on mers, especially vinyl esters, acrylic acid and