DE2012953C - Process for the production of high impact vinylchloridpfropfpoly mers - Google Patents

Description

The inventive method for production. · 1 1

of vinyl chloride graft polymers is thereby Example 1

indicates that polymeric tetrahydrofuran or In a cylindrical stainless steel vessel

a copolymer of tetrahydrofuran and ethylene-65 was added to 117 g of tetrahydrofuran. After that oxide, propylene oxide or epichlorohydrin, which were each 16.2 ml of triethylaluminum, water and added in a known manner by catalytic ring-opening poly-epichlorohydrin. The mixture remained merization are produced, with the poly- 24 hours at 0 ° C. During this time po-

polymerized the monomers. After removing unreacted tetrahydrofuran in vacuo 48 g of polymeric tetrahydrofuran were obtained. This polymer had a molecular weight of 150,000, which was calculated using the following equation

[η] = 0.00131 · Μ »βο (in _{benzene at} 30 oq

20 g of the above polymeric tetrahydrofuran were placed in a 2 liter autoclave equipped with a Stirrer was equipped. The air was then displaced with nitrogen, which in turn was evacuated was removed. Then there was 400 g of monomeric vinyl chloride added. The mixture was stirred at 70 ° C. for 2 hours to give the polymeric tetrahydrofuran to solve. The solution was then cooled to room temperature. 1200 ml of water were then added 0.56 g of tert-butyl perpivalate and 0.2% hydroxypropylmethyl cellulose (from which the dissolved oxygen had been removed), with the help of a metering pump added

The system was reheated to 60 ° C. The mixture was polymerized at this temperature for 170 minutes. The polymer product obtained was washed with water and dried. 357 g were obtained. 100 parts by weight of this polymer were mixed well with 3 parts by weight of dibutyltin mercaptide stabilizer, 1 part by weight of dibutyltin laurate stabilizer and 0.5 part by weight of butyl stearate. The mixture was then milled at 170 ° C. for 10 minutes. The mixture obtained was deformed at 170 ° C. to give 2 mm thick plates. The tensile impact strength test of the plates was carried out in accordance with ASTM-D-1822-61T. It was found that the average tensile impact strength of 10 S-shaped specimens of the same plate was 138 kg cm / cm ² . The tensile strength of the same plate was determined by the method JIS-K-6745 (1963) and was 478 kg / cm *.

The mean transmittance of the same test pieces at the wavelength 650 πιμ was 70 · / · ..

Comparative example 1

ίο Following the procedure of Example 1, vinyl chloride was polymerized for 230 minutes at 60 ° C. without polymeric tetrahydrofuran. 328 g of polymeric vinyl chloride were obtained. This polymer was formed into sheets 2 mm thick in accordance with Example 1. The average tensile impact strength of ten test specimens from the above sheet was 65 kg cm / cm ² . The mean tensile strength and permeability (at 650 πιμ) of the same test pieces were 560 kg / cm * and 80%, respectively.

* ° Examples 2 to 7

It was polymeric tetrahydrofuran after Bei-. game 1 made. Following the procedure of example 1 wuide vinyl chloride in the presence of this po-S5 polymerized polymerized tetrahydrofuran In these examples, however, the temperature of the polymerization of tetrahydrofuran to influence the molecular weight of the polymeric tetrahydrofuran changed. The ratio of polymeric tetrahydrofuran to mono- • meren vinyl chloride Samples were prepared and tested according to the procedure described in Example 1. The results are given in the table.

Examples 2 to 7 General conditions for the polymerization of vinyl chloride

Vinyl chloride monomer 400 g

Water (hydroxypropyl ethyl cellulose, 0.2% solution) 1200 ml

tert-butyl perpivalate 0.56 g

example Polyi
Tetrahyi
Mole
Weight
10 » leres
rofuran
Gram Polymeric
station
tempe-
temperature ⁰ C Polymes
Zl
hours isation
: it
Minutes yield
to graft
poly-
meren · / · Polymeres
THF in
Plug
polymers Surcharge
toughness
kg / cm'cm ¹ Tensile strength
speed
kg / cm » Through
nonchalance
(65 Οίημ)
· /. Deh
tion
O/. 2 13.6 20th 60 4th 10 369 5.4 165 483 61 158 3 14.5 40 60 1 50 369 10.8 166 411 40 142 4th 14.5 10 60 5 00 340 2.9 145 549 79 170 5 21 5 60 2 30th 322 1.6 86 570 78 195 6th 21 20th 64 1 30th 332 6.0 100 506 64 ? 80 7th 4th 20th 60 4th 00 357 5.6 115 560 62 19C

A different polymerization temperature was chosen for example 6.

Comparative example 2

100 parts by weight of the vinyl chloride polymer from Comparative Example 1 were mixed with the various stabilizers from Example 1. Then 3 parts by weight of the polymeric tetrahydrofuran prepared in Example 1 were added. The obtained mixture was ground and compression molded on a mixing roll. The product had a tensile impact strength of 110 kg cm / cm ² . However, it was white in color and completely opaque.

Example 8

The inside of a 2 liter detachable flask was dried. Then τ / urde the Air displaced by nitrogen. 1400 g of tetrahydrofuran was added to the flask and a stream of nitrogen was introduced

With stirring, 24.5 g of triethylaluminum, 3.9 g of water and 19.8 g of Bpichlorohydrin in the specified Order added. The mixture was held at 15 ° C for 48 hours. During this time

polymerized the monomers. The unreacted tetrahydrofuran was removed under reduced pressure. 744 g of crude polymeric tetrahydrofuran were obtained. This polymer had a molecular weight of 114,000 calculated according to the equation of Example 1. 20 g of this polymeric tetrahydrofuran, 390 g of vinyl chloride and 10 g of vinyl acetate were polymerized by the method of Example 1 for 220 minutes. 369 g of graft polymer were obtained. According to the test methods of Example 1, this polymer had an ^{impact strength of 120 kg cm / cm 2} , a tensile strength of 472 kg / cm ² and a permeability (at 650 μm) of 76%. D ^; e Permeability was measured on a 2 mm thick plate.

Example 9

A 300 ml separable flask was charged with 125 g of tetrahydrofuran, 2.0 g of triethylaluminum, 0.3 g of water and 16.1 g of epichlorohydrin. The whole was polymerized at 0 ° C. for 48 hours. 91.6 g of crude polymer were obtained. This polymer had a molecular weight of 123,000, calculated according to the formula of Example 1. 20 g of this polymer and 400 g of monomeric vinyl chloride were polymerized according to the method of Example 1 for 210 minutes. 371 g of graft polymer were obtained which had a tensile impact strength of 111 kg cm / cm ² , a tensile strength of 495 kg / cm ² and, measured on a 2 mm thick plate, a permeability (at 650 πΐμ) of 70%.

Example 10

In a 300 ml separable flask was placed 100 g of tetrahydrofuran, 1.6 g Trif'hylalumuiium and 16.1 g propylene oxide mixed. After a polymerization time of 90 hours, 27 g of crude polymer were obtained. This Polymers had a molecular weight of 237,000, calculated according to the formula given above.

Following the procedure of Example 1, 20 g of this polymer and 400 g of vinyl chloride were obtained Polymerized for 210 minutes. In this example, however, the polymer was used in the monomeric vinyl chloride dissolved at room temperature in the course of 3 hours 330 g of polymer were obtained. The "pro-

Lo duct had a tensile strength of 121 kg cm / cm ² , a tensile strength of 469 kg / cm ² and, measured on a 2 mm thick plate, a permeability (at 650 πιμ) of 73 Va.

Example 11

Into a detachable 300 ml flask which had been filled with nitrogen Given 100 g of tetrahydrofuran. After that were under Stirring in a stream of 18 g of boron trioxide

ao fluoride added. The system remained at 0 ° C. for 8 days to polymerize the monomers.

The obtained polymer was put into a large amount of methanol. The polymer was separated and drained in a vacuum. There were 43 g

as received.

This polymer had a molecular weight of 360,000 as calculated from the above formula. 20 g of this Polymers and 400 g of monomeric vinyl chloride were polymerized according to Example 1. As a catalyst however, 0.8 g of lauroyl peroxide were used instead of tert-butyl perpivalate.

The polymerization was carried out at 60 ° C. for 260 minutes. 350 g of polymer were obtained in this way. This product had to the previously described test methods a Zugsch'ngzähigkeit of 130 kg cm / cm ^2, a tensile strength of 467 kg / cm ² and, measured on a 2 mm thick plate, a transmittance (at 650 ΐημ) 70 ⁰ Zo.

Claims (1)

mere tetrahydrofuran or the copolymers a Mo claim: have a gross weight of 20,000 to 400,000, Throw dissolved in monomeric vinyl chloride and that Process for the production of vinyl chloride monomers vinyl chloride or a mixture of vinyl graft polymers, characterized thereby marked S chloride or vinyl acetate or vinylidene chloride _m net that polymeric tetrahydrofuran or the presence of polymerization catalysts under copolymer of tetrahydrofuran and ethylene formation of graft polymers throw polymerized, oxide, propylene oxide or epichlorohydrin, which are produced in the 1 to 15 percent by weight polymeric tetrahydro-known manner by catalytic ring-opening furan, based on the weight of the graft polymerization, the io polymer. polymeric tetrahydrofuran or the copolymers a molecular weight of 20,000 to 400,000 based polymeric tetrahydrofuran can prove Throwing dissolved in monomeric vinyl chloride can be produced using conventional methods. Monodes and the monomeric vinyl chloride or a meres tetrahydrofuran can, for. B. in the presence of a Mixture of vinyl chloride or vinyl acetate or 15 ring-opening polymerization catalyst among vinylidene chloride throw in the presence of polymerisation throws. The catalysts are, for example, anti-ionic catalysts with the formation of graft polyethylaluminum and water or Bortnfluond Throw polymerized, the 1 to 15 suitable. weight percent polymeric tetrahydrofuran contains- To strengthen the impact strength of the vinyl th, based on the weight of the graft polymer ao chloride polymer, it is necessary that the polymer ren. Tetrahydrofuran has a sufficiently high molecular weight weight, which makes the consistency rubbery or plastic. The polymers have a MoIe- Cell weight from 20,000 to 400,000, preferably a ₅ from 100,000 to 200,000. According to the method according to the invention, polymeric tetrahydrofuran in monomeric vinylchjo At present in general use only solved. Thereafter, the vinyl chloride is polymerized on traditional vinyl chloride polymers in those conventional ways,
which are based on a hard, transparent recipe, 30 This polymerization can be carried out according to block, solution, advantages with regard to increased transparency and suspension or emulsion processes. A major disadvantage, however, is throwing. In industry, suspension polymerisation is becoming its generally low impact resistance. tion preferred. As a polymerization initiator you can use In order to overcome these disadvantages, the known radical-forming polymers were advantageously used, Throw vinyl chloride polymers with various 35 risationskatalysatoren used. Suitable elastinizing polymers, e.g. B. Ethylenvinylacetat- are z. B. azo-bis-isobutyronitrile, butyl perpivalate copolymers or acrylate polymers. and benzoyl peroxide. The amount of used However, these formulations lead to products that are polymeric tetrahydrofuran depending on the desired one have significantly reduced transparency. th conversion of the vinyl chloride to the polymer. in the To increase the impact strength of vinyl chloride 40 generally throw 1 to 15 percent by weight, vorridpolymeren without loss of transparency was preferably 2 to 10 percent by weight, based on the proposed vinyl chloride polymers with 10 to the weight of that obtained after the polymerization 15 weight percent of a methyl methacrylate buta graft polymer is used. diene-styrene copolymers or an acrylonitrile-buta articles made by throwing to mix diene-styrene copolymers. However, since the polymeric tetrahydrofuran is mixed only with virtylchlo-butadiene copolymers in their moriclpolymeren and the mixture contains pressure-sticking, their impact resistance decreases, although increased impact resistance very quickly rejects the influence of sunlight. It was on, but is white and opaque,
However, not only mixtures of polymers, but also those according to the grafting process according to the invention which also proposed graft polymers. For example, the products obtained not only have an improved solution of ethylene-vinyl acetate-co-impact strength, their transparency is also only slightly polymeric or a polymeric acrylic acid ester. diminishes. They are also used in monomeric vinyl chloride. The obtained substantially free from unsaturation, WOdUrCh ₁ the polymers, however, consistently have a poor polymer an excellent weather-resistant transparency. 55 have the ability. The in the: according to procedure The object of the present invention is to include tetrahydrofuran polymers used in Verren drive to produce clear, high impact not only polymeric tetrahydrofuran, but also Graft polymers of vinyl chloride on polytetra copolymers of tetrahydrofuran with ethylene oxide, hydrofuran. Propylene oxide and epichlorohydrin. Monomer This object is achieved by the present invention. A mixture of vinyl chloride can also be used realized. be rid and vinyl acetate or vinylidene chloride.