DE1669975A1 - Process for the stabilization of polymers and copolymers based on vinyl chloride and / or vinylidene chloride and their chlorination products - Google Patents

Description

Process for stabilizing polymers and misen polymers based on vinyl chloride and / or vinylidene chloride and their chlorination products Vinyl chloride polymers and copolymers and their chlorination products tend easy to decompose when processed in the melt flow. Experience has shown that these products only with the addition of var: mestabilistors and lubricants above deformable at the freezing temperature. Stabilizers are among numerous others Connections also pole. ; : ole as @entaerythrit, sorbitol, glycerin, described (British Patent 857,382, U.S. Patent 2,943,070). Serve as a lubricant for example longer-chain fatty acids.

The stabilizers and lubricants mentioned have no * transferring properties Effect, but are among the few physiologically approved in Germany harmless compounding. Pentaerythritol also comes in because of it syrergic effect in connection, inter alia. with Ba-Cd soaps and also with organic ones Tin compounds used.

Besenders are annoying with pentaerythritol, the most effective stabilizer from the group of polyols, high melting point, strong tendency to sublimation and water solubility. Due to the high melting point, with higher desed additives above approx. 1% the risk of insufficient solubility in the polymer. Especially when it comes to processing as agglomerates or powder, undigested white ones then appear in the finished product Pentaerythritol types. The tendency to sublimation of unsolved Pantaerythritol leads to an increased extent to deposits on tools or calibration nozzles. Another disadvantage of pressurized water pipes is PVC containing pentaerythritol, There is a gradual seepage of water, which appears in the form of tears (Weeping effect) on the outer wall. This phenomenon is likely to occur the high affinity for water of the Penta. erythrits based.

The invention now relates to a method for stabilization of polymers or copolymers based on vinyl chloride and / or Vinylidene chloride and its chlorination products, which are characterized by that one esterified and / or falsified pentaerythritol in amounts of 0.3 to 8% by weight incorporated mechanically.

The use of the compounds of pentaerythritol mentioned results There are physiologically harmless polymers. The one with the use of pentaerythritol The associated disadvantages are avoided and stabilization is achieved at the same time. and lubricant wi. improvement achieved.

From the large number of possible compounds with the properties described, the following may be mentioned: mono- to tetraesters of pentaerythritol of monocarboxylic acids with Cl to C30 in pure or mixed form, mono- to tetraesters of pentaerythritol of dicarboxylic acids, the second carboxylic acid radical of which is unbound or also esterified, the second alcohol component made from monohydric or polyhydric alcohols, preferably from fatty alcohols. Pentaerythritol or Snrbit is made. It is also. @ possible to use esters of pentaerythritol or acetals, the alcohol component being the one already mentioned and preferably consisting of fatty alcohols, pentaeryth @@@ or serbit, and the yeast component consisting of the monocarboxylic acids already mentioned. Particular mention may be made of esters, especially fatty acid esters of ipentaeryturite or tentaerythritol sorbitol. Pentacrythritol can also be used, the second alcohol component consisting of the alcohols already mentioned. Furthermore, inner rler ', in which: can be used in which R1 and R2 are a hydroxyl group or a fatty acid residue of a fatty acid with C1 to C30, preferably C10 to C20. Such compounds have a low melting point, do not sublime and are not soluble in water. Particularly preferred are the monofatty acid esters of pentaerythritol with 10 to 20 carbon atoms. These can be obtained by simply reacting the fatty acid with pentaerythritol.

It was also found that the stabilizing power of @entaerythritol in a mixture with pentaerythritol esters is increased, especially in the case of pentaerythritol quantities of over 1%, the addition of pentaerythritol esters facilitates the solubility in PVC, its copolymers and their chlorination products, and reduces the tendency to limation and water solubility. The ratio of such mixtures is preferably at 1: 3 to 1: 1 from pentaerythritol to pentaerythritol esters or ethers.

D mentioned pentaerythritol ester or pentaerythritol alone odeur It together with pentaerythritol can be used with other usual stabilizer systems can be combined, e.g. with barium-cadmium soaps, calztum-zinc soaps, organic Sulfur-tin compounds, lead salts. epoxidized oils or fats, compared to the use of these stabilizer systems, the stabilization alone is pre-improved. In some cases there are pentaerythritol / pentaerythritol esters compared to the comparison mixture Only Iceine ttart parts recognizable in the oven test, but can change during processing by adding conventional stabilizers to the advantages according to the invention e.g. specify against the influence of friction.

The heat stabilizing effect of conventional stabilizer systems falls different for different vinyl chloride polymers and their chlorination products the end. This is the case for atactic and tactical PVC, which are quick organic Sulfur-tin compounds are not used in post-chlorinated PVC. From the gorge of the epoxy compounds has proven its worth with tactical PVC epoxidized soybean oil better than with post-chlorinated PVC, while glycidyl ether is the opposite achieve better effect in post-chlorinated PVC and polyvinylidene chloride.

3c4 polyvinyl chloride and chlorinated polyvinyl chloride and their Copolymers result in an improved stabilization through the use of Carboxylic acid esters or @ of pentaerythritol alone or together with pentaerythritol. When additionally using glycidyl ethers of / diphenolpropane (e.g. in the form the commercial products Epicote 828 or Witolen 53) results in a further synergistic effect Reinforcement of the stabilization described.

The pentaerythritol esters or ethers mentioned or their mixtures with pentaerythritol are used as stabilizers for PVC and its copolymers especially for stereoregulated polyvinyl chlorides, post-chlorinated polyvinyl chlorides and their copolymers and polymers or mixed polymers of 1,1 and 1,2 vinylidene chloride, suitable. As comonomers of the copolymers mentioned, vinyl chloride, vinyl acetate, Vinyl propionate, vinyl cetyl ether, acrylic acid ester, substituted acrylic acid ester such as 2-ethyl-hexyl-acrylic acid ester, acrylonitrile, dichloroethylene, trichlorethylene, Maleic and fumaric acid esters, ethylene, propylene and others, in Marger. from 0, 1 to 20 % By weight can be used.

@odertactic polyvinyl chloride with 55-85% syndiotactically arranged Chlorine atoms can e.g. B. according to the German Auslegeschrift 1 187 374, the Belgian Patent Document 627,674 or British Patent S; 15 y obtain will. Post-chlorinated polyvinyl chlorides are obtained by hate or dry chlorination obtained from PVC. A method for this can be found in the German Auslegeschrift 1 210 561 described. As a P-R game for polyvinyl 1,1 "djchlorid is a commercial product Saran Ku to name.

Modifying. Additions to such polymer bases, for example to improve the impact strength, do not affect or only inevitably the stabilizing effect of Pentaery. thritesters or ethers or their mixed tongues with Pentyerythri-t.

Such modifying additives are, for. B. chlorinated polyethylene, Co from ethylene and vinyl acetate, from acrylonitrile-butadiene-styrene (ABS) and methacrylate-butadiene-styrene.

The following are three series of examples (tables, 2 and 3) of the most varied Listed stabilizer approaches that have the stabilizing influence of pentaerythritol fatty acid esters and their mixtures with pentaerythritol are supposed to show, The first series contains. according to as a base polymer a stereoregulated or tactical polyvinyl chloride, the should apply as an example of vinyl chloride polymers and copolymers. That higher chlorinated vinyl chloride polymer of the second row should generally behave of highly chlorinated vinyl pro. identify products that have a chlorine content of 56-72%, with the chlorine atoms of the vinyl unit in the 1.1 or 1.2 position arranged could be. The heat stabilizing effect of the systems described shows the so-called oven test. To do this, the specified mixtures of the first and second Example series 10 min. Plasticized on a roller at 185 ° C and to a 0.5 mm thick rolled head pulled out. Strips of these rolled sheets were placed in warm air at 190 ° C (Drying cabinet) and removed at intervals of 20 minutes.

The polymers in the third series of examples are copolymers of vinylidene chloride (Saran 864 from Dow Chemicals) with a chlorine content of 71 1% by weight and a vinylidene chloride / vinyl chloride ratio of approx. 87:13 and a suspension copolymer with the designation LDC 142, consisting of 80 t Vinylidene chloride, 10% vinyl chloride and 10% 2-ethyl-hexyl-acrylic acid ester. the The specified mixtures were plasticized for 10 minutes on a 17ale at 160 ° C. or 140 ° C. and pulled out to 0.5 mm thick rolled heads. Strips of this are then rolled heads stored horizontally in warm air (Trookenschra. nk) at 170 ° C and removed every 10 minutes been. The zest until the onset of a dark discoloration is called Therctostabile designated.

1st sample series (1-14) 100 g of stereoregulated (tactical) PVC from K value 62 and a Vicat value (5 kp) of 96 ° are achieved with 1 g hard wax (OP ~ wax) and with stabilizers of the corresponding example numbers added, plasticized on the roller and subjected to the oven test in the manner described, 2nd series of examples (15-28) 100 g post-chlorinated PVC with K value 60, 67% chlorine, Vicat (5 kp) 120 ° C with 1 g of hard wax (surgical wax) and stabilizers of the associated Sample numbers on the roll plastified and dansch in the raised way tested in the oven.

. ' 3. Example grate (29-43) 100 g of Saran 864 with a K value of 49.6 (1% in cyclchexanone) and a chlorine content of 71.0% by weight or LDC 142 with a K value of 43, 8 (1% in cyclohexanone and a chlorine content of 64.2% by weight are. With 0.3 Ca stearate and 0.3 g of Hartrrachs (Advawachs 280 from Advance) and 5 g of acetyl tributyl citrate (Citroflex A 4 from Ciba) and stabilizers according to the example numbers Plactified on the roller at 160 ° C (Saran 864) or 140 ° C (LDC 142) on the roller and then, in the manner indicated, the thermal stability through warm storage determined at 170 ° C.

The numbers given in the respective examples denote the . Amounts of the stabilizers used in% by weight, based on the polymers.

In the examples in addition to pentaerythritol esters in @@ .- ethers known stabilizers used in combination with pentaerythritol it is inter alia around: Dialkyltin - dimerkaptocarboxylic acid ester e.g. around di-n-butytin dimerkaptocarboxylic acid ester in the form of the.

1Adväntab 17M-marked as 1 \; basic lead results, whereby the The preceding number indicates the PbO PbSO4 ratio, e.g. in the form of the commercial product Bärostab V 220 - 3); Glycidyl ethers, such as glycidyl ethers of 2,2-bis (4-hydroxyphenyl) propane with an epoxy value of 0.53 / 100g z. B. in the form of the commercial product Witolen 53 -4); and epoxidized fats and ad oils such as epoxidized soybean oil, e.g., in the form of the commercial product Advaplast 39-marked as 5).

Table 1 tactical (70% Tacti- K value 60 Vicat 96 ° C Polyvinylchloride rate) + 1% hard wax Example 1 2 3 4 5 6 7 8 9 Pentaerythritol 1 2 1 1 1 Pentaerythritol monostearate 3 3 3 3 Org.sulfur tin compound1) 2 2 Barium-Cadnium Soap 2) 2 2 2-basic lead sulphate 3) 2 Glycidyl ether 4) Epoxy fatty acid ester 5) Thermostability min at 190 ° C 20 30 50 90 70 50 70 50 Table 2 Post-chlorinated K value 60, 67% chlorine, Polyvinyl chloride + 1% hard wax Example 15 16 17 18 19 20 21 22 2 Pentacrythritol 1 2 1 1 1 Pentaerythritol monostearate 3 3 3 3 Org.sulfur tin compound 1) 2 2 Barium-Cadnium Soap 2) 2 2 2-base lead salad 3) Glyoidyl ether 4) Epoxyfottic acid ester 5) Thermostability min at 190 ° C 40 45 50 90 15 30 30 55 1 Table 3 Copolymers Saran 864 K-Wart: 49.6 LDC 142 71.0 wt% Cl. of vinylidene chloride Example 29 30 31 32 33 34 35 36 37 38 Pentacrythritol - 1 2 - - - - 1 2 - Pentacrythritol- - - - 3 - 3 - - - 3 Glycidyl ether 4) - - - - - 1 - - - - Epoxy fatty acid esters 5) - - - - 3 - - - - - ß - aminocrotonic acid 6) - - - - - - - - - - Thermostability 10 10 10 35 30 40 10 15 15 30 min at 170 ° C

Claims (4)

Pttppriiche 1 :) Process for the stabilization of polymers or low) fish polymorianten on the banis of vinyl chloride and / or vinylidene chloride and their chlorination products, characterized in that one esterified and / or Etherified pentaerythritol is incorporated mechanically in amounts of 0.3 to 8% by weight. 2.) The method according to claim 1, characterized in that d - t, 8 man Fatty acid esters of pentaerythritol with 3 to 30 carbon atoms, preferably with 10 to 20 carbon atoms in the fatty acid residue used. 3.) Method according to claim 1 and 2, characterized in that one esterified and / or etherified pentperythritol mixture in the ratio of the face 0.1 to 10 to 10 zix 0.1, preferably fatty acid esters of pentaerythritol in a mixture with pentaerythritol in a ratio of 3 su 1 to 1 to 1, used. 4.) The method according to claim 1 to 3, characterized in that da3 known stabilizers of polyvinyl chloride are also used.