CS207426B1 - Compounds containing the homopolymeres and/or copolymeres of the vinylchloride and subsequent current admixtures resisting the oxidation,extraction,actions of light and atmospheric ageing - Google Patents

Description

THE CZECHOSLOVAK REPUBLIC (18) DESCRIPTION OF THE FOLLOWING COPYRIGHT CERTIFICATE 207426 (11) (Bl) (22) Registered 04 06 79 (21) (PV 3837-79) (51) Int. Cl.3 C 08 L 27/06 OFFICE AND DISCOVERY (40) Published 31 03 80 (45) Published 01 07 84 1 ------------ 1 (75)

Author of the invention MALÁČ JIŘÍ ing. CSc., GOTTWALDOV, BELYUSOVÁ MARIE ing.,

BRATISLAVA and RUDOLF BATTERY, ADAPTERS (54) Mixtures containing homopolymers or copolymers of vinyl chloride and other conventional additives and resisting oxidation, extraction, light effects and weathering The present invention provides compositions comprising vinyl chloride copolymers or copolymers and other conventional oxidation, extrusion, and other additives. the effects of light and weathering, which are highly protective of light and air oxygen degradation by the addition of mixed tris (1-phenylethyl-phenyl) phosphites.

The use of phosphites in mixtures for the preparation of plastic products is justified by their ability to decompose hydroperoxides in a non-random manner, by inhibiting kinetic degradation processes by direct reaction with free radicals and by deactivating metal chlorides. The antioxidant action of the phosphites in the mixture is used in particular in diene rubbers and polyolefins. The ability of phosphites to bind metal chlorides catalytically accelerating the dehydrochlorination of polymers under thermal stress and formed in the presence of primary thermal stabilizers is used in the thermal stabilization of chloro-containing polymers, of mainly homopolymers and copolymers of vinyl chloride. The stabilization systems for polyvinyl chloride and vinyl chloride co-polymers are combinations of phosphites with all common types of metal organic compounds that are applied as heat stabilizers.

Particular attention has been paid to organic phosphite systems with thermal stabilizers based on organic salts of alkaline earth metals, barium, cadmium, calcium, magnesium, zinc or organic compounds (US Pat. No. 2,564,646, British Patent 803 081). , German Pat. No. 1,262,590). Organic phosphite and epoxy compound soaps have become one of the standard stabilization systems (US Pat. No. 2,997,454, Belgian Pat. No. 5,595,409).

Also known are mixtures with four-component combinations in which the preceding system is supplemented with a phenolic antioxidant (British Pat. No. 841,890, U.S. Pat. No. 1,149,164, Belg. Pat. No. 615,535), optionally with a hydrocarbon solvent (Belgian Pat. 621 848). Combinations of trialkylphosphine with 2-hydroxybenzophenone derivatives have been proposed to achieve the luminous stability of metal soap-containing polyvinyl chloride mixtures (U.S. Pat. No. 2,828,712). At the same time, a large number of two-component and multi-component stabilizing systems have been described containing the organotin compound as the primary stabilizer, the organic phosphite as the secondary stabilizer with other additives such as phenolic antioxidants, epoxide compounds, nitrogen organic compounds (α-phenylindole), oxides. or metal alkali hydroxides, light stabilizers and the like (German Pat. Nos. 2,538,409; 2,256,575; 207426,207,426,175,874; US Pat. No. 3,919,165; USSR Pat. No. 3,881,223).

Mixtures of triphenyl phosphite with lead carboxylates (US Pat. No. 2,752,319) and stabilization systems comprising various combinations of organic compounds of zinc, calcium and tin with organic phosphites have also been described (German Pat. No. 2,546,900). In the context of the chelating action, the organic phosphites are regarded as secondary stabilizers, in mixtures of polymers and copolymers of vinyl chloride and are in the range of 0.5 to 1.0 wt. % is used to improve the thermal stabilizing effect of primary heat stabilizers.

The light-stabilizing effect of phosphites in mixed chlorine-containing polymers is used in technical practice with pentaerythritol phosphoric acid esters (U.S. Pat. No. 2,961,454, 3,047,608).

Many of the hitherto mentioned mixtures contain phosphates which are difficult to obtain or whose use is economically disadvantageous. A number of the disclosed mixtures are physiologically harmful and therefore unusable for non-toxic products. The higher volatility of some phosphites results in a deterioration of the working environment in addition to the lower active ingredient content of the final product. Other disadvantages of some phosphorus derivatives include their low hydrolytic stability. Some of the phosphites are easily extracted from the mixture, again reducing the active ingredient in the product during application.

The drawbacks of prior art mixtures containing homopolymers or copolymers of vinyl chloride and other conventional additives and resistant to oxidants, light and weathering are eliminated according to the invention by using from 0.1 to 100 parts by weight per 100 parts by weight of homopolymer or copolymer vinyl chloride, preferably 2 to 10 parts by weight of mixed tris (1-phenylethylphenyl) phosphites, having a number of advantageous properties, act as a light stabilizer in the mixture and are already industrially manufactured according to the art. pat. 115 828.

Improvements in the oxidative and light stability of their weathering blends refer to both the copolymers and the copolymers of vinyl chloride. The most common are copolymers of vinyl chloride with vinyl carboxylic acid esters, for example, with vinyl acetate, vinyl propionate, vinyl butylate, with unsaturated carboxylic acid esters, e.g. methacrylate, butyl acrylate, methyl methacrylate, with styrene, propylene, with dienes, such as butadiene, with acrylonitrile, with maleic or fumaric acid esters. A particular group of vinyl chloride copolymers are vinyl chloride grafted polymers and copolymers, such as vinyl chloride grafted ethylene-vinyl acetate copolymer, or vinyl chloride-grafted chlorinated butyl rubber. A typical example of vinyl chloride copolymers is vinyl chloride / vinyl acetate 98-80: 2-20, vinyl chloride / vinyl acetate / maleic anhydride 86: 13: 1, vinyl chloride / vinylidene chloride 95: 5, vinyl chloride / propylene in 97: 3 ratio and vinyl chloride grafted ethylene / vinyl acetate copolymer in a ratio of 90-95% VC: 5-10% E / VAC.

The protective action of mixed tris (1-phenylethylphenyl) phosphites also occurs in mixtures where chlorine-containing polymers are modified by the addition of macromolecular substances that are mechanically mixed into the base polymer base. The modifying component used is, for example, chlorinated polyethylene, ethylene / vinyl acetate copolymer, acrylonitrile / butadiene / styrene terpolymer, nitrile or butadiene / styrene rubber, acrylic acid and methacrylic acid derivatives and the like.

Mixtures comprising homopolymers or copolymers of vinyl chloride and mixed tris (1-phenylethylphenyl) phosphites may contain, among other conventional additives, plasticizers such as arorate and aliphatic carboxylic acid esters and alkyl aryl phosphates. By way of example, dioctyl phthalate, phthalates obtained by esterification of linear alcohols, dioctyl adipate, tricresyl phosphate, or polymeric type plasticizers obtained by esterification of bifunctional acids with bifunctional alcohols.

In the compositions according to the invention, the addition of epoxide compounds of natural or biosynthetic origin is advantageous. Examples of such compounds are the epoxidized esters of fatty acids, soybean, sunflower, olive oil, and synthetically prepared epoxide compounds, for example, glycidylepoxystearate.

Increasing the resistance of the compositions of the invention to degradation in the heat treatment process, especially for compositions which do not contain plasticizers, can be achieved by dosing 0.1 to 5% by weight of thermal stabilizers. Organic salts of barium, cadmium, calcium, zinc, magnesium, antimony, lead stabilizers and organotin compounds are particularly suitable for this purpose.

Further enhancement of the light stabilizing effect can be achieved by combining mixed tris (1-phenylethyl-phenyl) phosphites with UV absorbers, for example benzophenone such as 2-hydroxy-4-methoxy-benzophenone, or benztriazole, such as 2 ( 2'-hydroxy-5-methylphenyl) benztriazole, optionally substituted substituted acrylonitrile or oxanilide derivatives may be used.

Other processing aids may be included in the composition of the invention, such as lubricants, additives such as fillers, pigments, antistatic additives, thickening additives, and the like. An advantage of blends containing mixed tris (1-phenylethylphenyl) phosphites is that an economically advantageous and technically readily available phosphite is used as the light stabilizer and antioxidant. Compositions containing said phosphite exhibit excellent exposure to oxidation and weathering conditions. For example, high potency blends of polyvinyl chloride containing 20 to 60% by weight plasticizer with only 2% by weight of mixed tris (1-phenylethyl) -phenyl) phosphites without additional additives. 3

In addition to the high protective effect against oxidation and the action of weather factors, in particular light and oxygen, and the reduction of stabilization costs, the use of mixed tris (1-phenylethylphenyl) phosphites also provides other advantages. The compositions according to the invention may also be prepared as harmless, since said phosphite blend is physiologically safe, oxidation and extraction resistant and also suitable for use in food contact packaging materials. The high oxidation resistance of the excellent hydrolytic stability of the mixed tris (1-phenylethylphenyl) phosphite is the cause of good shelf life and, in conjunction with low extractability, guarantees a number of advantageous application properties of the products prepared from the compositions of the invention. Due to the high chemical and thermal stability of the tris (1-phenylethylphenyl) phosphites, volatile products which could adversely affect the working environment do not result in the processing of the compositions of the invention. During the weathering of the compositions of the present invention, there is no cloudiness or migration of the (1-phenylethylphenyl) phosphites to the surface of the article, and mixtures without fillers and pigments retain the initial grain. Since the mixed tris (1-phenylethylphenyl) phosphites are difficult to extract, hydrolytically and thermally stable, there is no significant loss of active ingredient in the mass during processing or during the use of the plastic articles. Phenyl) phosphites are also distinguished by good compatibility with other ingredients of the composition, such as plasticizers, lubricants, heat stabilizers, modifying agents, fillers, pigments, and the like.

A method of carrying out the invention is described in the following practical examples. Example 1

A mixture was prepared containing 100 parts by weight of polyvinyl chloride, 50 parts by weight of dioctyl phthalate as plasticizer and 2 parts by weight of mixed tris (1-phenylethyl-phenyl) phosphites. The mixture was stirred in a fluid mixer at < 110 ° C and rolled at 150-160 ° C. Bylatak prepared a high transparency film (light transmittance 86.2%). The film obtained was exposed for 5 years in a slightly warm climate. During the exposure, it remained transparent, with no significant change in color and surface quality. Neither point degradation centers characteristic of long-term softened polyvinyl chloride appeared, nor did the mechanical properties of the specimens evaluated during the exposure change significantly. Example 2 Addition of a heat stabilizer to a mixture of Example 1 in an amount of 0.3 to 0.5 parts by weight increased the thermal stability of the composition without affecting the weathering resistance. The mixture with higher thermal stability can then be safely processed at a higher temperature. 207426 dibutyltin bis (isooctyl maleate) and complex barium-cadmium stabilizer were used as heat stabilizers:

Composition of the mixture Heatstab.180 ° C The permeability of the mixture was mixed. 1 8 min. 86.2% additive mixture 1 + 0.3 wt. d. Dibutyltin 12 min. 87.3% mixture added. 1 + 0.5 wt. d. Dibutyltin 16 min. 90.1% add. 1 + 0.5 wt. d. Ba-Cd stab. 15 min. 90.6% Example 3

A further increase in the thermal stability of the mixture of Example 1 was achieved by the addition of 1 part by weight of diatomaceous stabilizer in combination with 5 parts by weight of epoxidized soybean oil and 0.5 parts by weight of 2-hydroxy-4-methoxybenzophenone. This blend had a high transparency with a thermal stability of 90 minutes and high weathering aging. Example 4

An unplasticized mixture of 100 parts by weight of polyvinyl chloride, 2 parts by weight of lubricant, 3 parts by weight of lead stearate and 5 parts by weight of mixed tris (1-phenyl-ethyl-phenyl) phosphites was prepared. After mixing in a fluid mixer, the mixture was granulated and then used to extrude tubes that were later exposed to long-lasting weathering from the outside and an aqueous medium. The stability of their properties was very good in these conditions. EXAMPLE 5 Softened Mixtures containing 100 parts by weight of vinyl chloride / graft copolymer of ethylene / vinyl acetate, 50 parts by weight of plasticizer ester type, 2 parts by weight of bamboo stabilizer, 0.2 parts by weight of UV absorber, 5 parts by weight of epoxy compound and 0, 5 parts by weight of the mixed tris (1-phenyl-ethyl-phenyl) -phosphite were rolled, after mixing, with a translucent film which was used to cover the agricultural structures. Her light stability was very good. EXAMPLE 6 A plasticized composition containing 100 parts by weight of polyvinyl chloride, 20 parts by weight of chlorinated polyethylene, 50 parts by weight of an ester type, 2 parts by weight of an organic stabilizer, 0.4 parts by weight of UV absorber, 3 parts by weight of epoxy resin. 5% by weight of the soybean oil, 5 parts by weight of pigment and dyes and 5 parts by weight of mixed tris (1-phenylethyl-phenyl) phosphites were laminated to colored water films used for assembly. The film obtained was highly resistant to oxidation and extraction with aqueous media at very good stability under weather conditions.

Claims (1)

4 í 207426 Example7! By direct mixing of a mixture containing 100 parts by weight of paste-forming PVC, 5 parts by weight of a vinyl chloride / vinyl acetate copolymer, 80 parts by weight of mixed tris (1-phenylethylphenyl) phosphites and 2 parts by weight of organotin 1 · 1 '' ARTICLE Mixtures comprising homopolymers or copolymers of vinyl chloride and other conventional additives which are resistant to oxidation, extraction, light and weathering, characterized in that they contain from 0.1 to 100% by weight of 100% by weight of homopolymer or copolymer of vinyl chloride Particularly, from 2 to 10 parts by weight of the mixed tris (1-phenylethyl-phenyl) phosphites of the stabilizer formula have been obtained with a PVC paste which has been deposited on a textile backing and gelatinized at 170 ° C. The prepared product had a high resistance to the effects of surface, oxidation, hydrolysis and liquid media extraction. THE INVENTION wherein R1; R2, R3 represent 1-phenylethyl substituents, or one or two of the substituents are 1-phenylethyl and the remaining hydrogen atoms. Printed by Moravské tiskařské závody, provoz 12, Leninova 21, Olomouc Price: 2,40 Kčs