CS227315B2 - Stabilizer composition for shaping polyvinyl chloride - Google Patents

Abstract

1. A process for stabilizing polyvinyl chloride molding compounds, characterized in that a) 0.2 to 5 parts by weight of a synthetic, crystalline, finely divided sodium alumosilicate containing 13 to 25% by weight bound water and having the composition - based on the anhydrous form - 0.7-1.1Na2 O .Al2 O3 . 1.3-2.4SiO2 (zeolite 4A), b) 0.05 to 1.5 part by weight of the calcium salt of C8 -C22 fatty acids, c) 0.05 to 0.5 part by weight of the zinc salt of C8 -C22 fatty acids, d) 0.2 to 2.0 parts by weight of partial esters of C8 -C22 fatty acids and polyols containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups which, on average, contain at least one free polyol hydroxyl group per molecule and have OH values of 140 to 580, e) 0.1 to 1.0 part by weight of thioglycolic acid esters of polyols containing 2 to 6 hydroxyl groups and/or thioglycolic acid esters of monofunctional C8 -C22 alcohols are incorporated in the molding compounds to 100 parts by weight polyvinyl chloride.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to stebiliaate compositions for polyvinyl chloride molding processes which contain calcium and zinesin fatty acid salts as well as partial fatty acid esters of polyols.

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In practice, as stabilizers, mainly lead, zinc or barium / cadmium compounds, are used in the manufacture of articles of polyvinyl chloride. In practice, these heavy metal stabilizers have a completely satisfactory effect; however, there are some reservations about their use, particularly from a work - physiological point of view. For this reason, manufacturers have long sought to use the non-heavy metal stabilizers commonly used by others with less reservations. In this document, it has already been torn, to use, instead of heavy metal stabilizers, tfddl light alkaline earth metals. Calcium soaps are preferably used, optionally supplemented with secondary stabilizers such as zinc stearate, imino compounds and epoxy compounds.

The stabilizing effect of the calcium soap system is relatively dull compared to the effect of heavy metal compounds. Molded articles which have been produced using a stabilizer system on the same calcium mddl are often characterized by a dark coloration and a low residual stability. As a result, the scope of use of such stable systems is greatly reduced.

German Patent Publication 26 42 509 describes stabilizer combinations which, in addition to calcium stearate and / or zinc stearate, contain a partial ester of penteerythritol with a fatty acid of 12 to 22 carbon atoms, a waxy hydrocarbon and / or a free bridge acid of 12 to 22 atoms. as well as an antitxidant.

However, the desired effect, which is the same as that of non-heavy metal-based stabilizers, is not achieved by this combination.

U.S. Patent No. 4,000,100 discloses the so-called unactivated surfactant A in poly (vinyl chloride) resin stabilizer systems. The present invention is based on the discovery that by incorporating certain types of water-containing zeolites into stabilizer systems, a synargic increase in heat and light protection can be achieved. The zeoites developed for this purpose include types 3A, 4A and 5A. They are to be used together with any inorganic, organometallic or organic stabilizers or stabilizer components.

It was therefore an object of the present invention to improve the stabilization of iolyvinyl chloride by means of calcium- and optionally zinc-based combinations so that light pigments or white polyvinyl chloride articles with satisfactory stability can be produced without the aid of lead, zinc, barium or cadmium compounds. The object of the present invention was to surprisingly find that by selecting and combining most of the particular components of the composition, including the choice of a particular sodium aluminosilicate of the sodium type, the desired goal could be achieved.

Accordingly, the present invention provides a stabilizer blend for polyols of light-weight molding compositions which contain calcium and zinc fatty acid salts, as well as L partial esters of polyols with fatty acids, which composition is characterized in that it consists of

(a) 4 to 100 parts by weight of synthetic, finely crystalline, finely powdered sodium aluminosilicate, containing bound water in an evening mass of 13 to 25%, having a composition, on the anhydrous form, of 0,7 to 1,1 №20 · ^A 12 ° 3 · 1.3 to 2.4 SiO,

(b) 1 to 30 parts by weight of calcium salts of 2 to 22 carbon atoms;

(c) 1 to 10 parts by weight of zinc salt of ophthalted C 8 to 22 carbon atoms;

(d) 4 to 40 parts by weight of partial esters of polyols of 2 to 6 carbon atoms and 2 to hydroxyl groups of 8 to 22 carbon fatty acids having on average at least one free hydroxyl group in the moiety; and

e) 2 to 20 parts by weight of thioglycolic acid esters of polyols having 2 to 6 hydroxyl groups and / or of mono-thioglycolic acid esters. alcohols having 8 to 22 carbon atoms.

In the preparation of the iolyvioyl (molding compositions, sabatable sabbaths), the composition of the present invention is carried out by treating the molding mass with 100 parts by weight of polyvinyl chloride.

(a) a synthetic, finely crystalline, finely powdered sodium carbonate in an amount of 0.2 to 5 parts by weight containing bound water in a weight range of 13 to 15% and having a composition of: to anhydrous form - 0.7 to. 1.1 Νβ? Ο. AlgO ^. 1.3 to 2.4 Si ^,

b) calcium salt of a fatty acid of 8 to 22 carbon atoms, preferably 0.05 to 1.5 parts by weight;

(c) a zinc salt of a fatty acid of 8 to 22 carbon atoms, in the range 0,05 to 0,5% of the carrier;

d) C 1-6 polyol esters of 2 to 6 carbon atoms and 2-6 C-6 hydroxyl groups having a matt content of 8 to 8. up to 22 carbon atoms which, on average, contain at least one free polyhydroxy group in the moletail, in an amount of 0.2 to 2.0 parts by weight,

(e) thioglycolic acid esters of polyols of 2 to 6 hydroxyl groups and / or thioglycolic acid esters of isocarboxylic alcohols of 8 to 22 carbon atoms, in a number of forms. 0.1 to 10 parts by weight.

The sodium aluminosilicate used as component a) in the stabilizer composition of the invention has a particle size preferably in the range of 0.1 to 20 µm. Suitably it is a synthetic crystalline sodium aluminosilicate known as NaA type zeolite. These zeolites, also referred to as zeolites 4 A, have an average effective pore diameter of ⁴ . ^10-10 o. Second hlinitokřeoičitan sodium contains bound water in hmoonostním mnnožtví 18-25% ·

Such sodium aluminas may be prepared by known methods. Other synthetic methods are described, inter alia, in German publication DE 24 12 837.

Details of the properties and manufacture of these sodium aluminosilicates are given, for example, in the following patents: German publications DOS 26 51 485, 26 51 445, 26 51 436, 26 51 419, 26 51 420, 26 No. 51,437 in U.S. Patent 3,112,176.

In the manufacture, the amorphous, finely powdered sodium aluminosilicates formed by precipitation can be converted into a crystalline state by heating at a temperature ranging from 50 to 200 ° C. Thereafter, the crystalline sodium aluminosilicate is separated by filtration from the boiling aqueous solution and dried, as a rule, at a temperature in the range of 50 to 200 ° C until it contains water in an amount of 13 to 25% by weight. The crystalline products lived in accordance with the invention and described, for example, in German publication DE 24 12 837, have a particle size in particular in the range from 0.1 to 50 .mu.m. Sodium aluminosilicates having a particle size in the range of 0.1 to 20 µm are preferably used for carrying out the process of the invention.

The calcium binding ability of these sodium aluminum silicates, determined at 22 ° C, is at least 50 mg CaO / g anhydrous active and can reach values up to about 200 mg CaO / g active. Preferably, this calcium binding capacity is in the range of from 100 to 200 mg CaO / g of active ingredient, and more usually above 150 mg CaO / g. determinations of calcium binding capacity are disclosed in German Published Patent Publication No. 24 12 837 as well as in the further description relating to the production of suitable sodium silicate silicates.

The aluminum (a) stabillosulfate components of the present invention may also be of aluminum (rounded corners and edges). the molar composition is in the range

2.5 to 6.0 Na ₂ 0. AlgOj. 0.5 to 5.0 SiOg. 60 to 200 HgO.

This batch is crystallized by a conventional method. This is preferably done by heating the batch for at least half an hour from stirring at a temperature in the range of 70 to 120 ° C, preferably 80 to 95 ° C. The crystalline product is isolated simply by liquid phase separation, optionally washed with water and dried.

Furthermore, finely powdered, water-insoluble sodium aluminosilicates which have been precipitated and crystallized in the presence of water-soluble inorganic or organic dispersants can also be used as components a) of the stabilizer mixture according to the invention. Suitable water-soluble organic dispersing agents are surfactants, non-surfactant aromatic sulfonic acids and compounds with calcium-forming comolexing properties. The dispersants may be added to the reaction mixture at any time before or during precipitation; they can be used, for example, dissolved or dissolved in a solution of aluminum and / or creositen.

The monolithic level of the dispersing agent should be at least 0.05%, preferably 0.1 to 5, based on the entire batch. To precipitate out, the precipitated product is heated for 1/2 to 24 hours at a temperature in the range of 50 to 200 ° C. Among the large number of dispersing agents that can be used, sodium lithium ether sulfate, 1-hydroxy-ethane-1,1-diphosphonic acid sodium salt, sodium triacetate β, is exemplified.

Sodium silicates of the NaA type, suitable as component (e) of the stabilizer mixture according to the invention, contain bound water in a quantity of 13 to 25; preferably products having a water content in the range of 18 to 25 are used

The calcium and zinc salts of the fatty acids used as components b) and c) of the stebilizer composition of the invention are preferably derived from fatty acids such as ceprylic, capric, lauric, imyistic, pelmitic and steeric acids. Both salts of individual fatty acids and salts of mixtures of fatty acids are used, which are obtained, in particular, from natural fats and oils. Preferably, the calcium and zinc salts of palmitic acid and stearic acid are used.

The polyol partial esters constituting component (d) of the stabilizer composition according to the invention are prepared in a known manner by starching polyols having from 2 to 6 carbon atoms and from 2 to 6 hydroxyl groups with fatty acids having a chain length of 8 to 25 carbon atoms. . At the same time, the polyol and the fatty acid do not react in a molar ratio of 1: 1 to 1: (n-1), where n is the number of hydroxyl groups of the polyols.

Preferably, the reactants are used in an amount to give partial esters having a hydroxyl number of from 140 to 580, in particular from 170 to 540, which are particularly preferred as component d) of the stabilizer composition of the invention.

The reaction product, which is always a mixture of different esters, should have an acid number of less than 15, in particular less than 8. The aqueous polyol components are atylene glycol, propylene glycol-1,2, propylene glyco-1,3, butylene glyco-1,2, butylene glyco-1. 4, hexsadioo-1,6, neopentyl glycol, glycerol, erythritol, hexanol, andOTbitol.

Particularly important polyol components have 3 to 6 hydroxyl groups and preferably 3 or 4 hydroxyl groups. In this context, glycerol and pendeaeiltitoil may be particularly advantageously used in the present invention. Suitable acid components include, but are not limited to, caprylic, capric, lauric, myric, palmitic, stearic and behenic acids.

Synthetic fatty acids of the indicated chain length, such as montanoic acids, or unsaturated acids such as oleic acid, linolenic acid, or even fatty acid fatty acids, in particular hydroxylated acids such as 12-100 barric acid, may also be used. For practical reasons, most of the fatty acids are used, such as those obtained from natural fats and oils. Of course, component d) may also consist of the above-mentioned partial esters. Particularly preferred compounds within the meaning of component (d) may be in part esters of polyols having 3 to 6 hydroxyl groups, preferably 3 or 4 hydroxyl groups, and said fatty acids having an average of 2 to 3 free hydroxyl groups.

As component (e), thioglycolic acid esters of aliphatic polyols having 2 to 6 hydroxyl groups are suitable for carrying out the invention. Preferably these polyols have 2 to 36 carbon atoms, especially 2 to 18 carbon atoms. Examples of polyols having 2 to 6 carbon atoms are allylgol, propyleinglycol-1,2, propylene glycol-1,3, 1,2-diol, 1,2-butylene glycol-1,4, 2,4-diol, 1,2-butylene glycol. d 10-10-1.6, neopennyl glycol, glycolurol, trimethylollate, 1-propene, amidyltol, amenium! and μγΜΛοΙ.

In particular, polyols having a higher number of carbon atoms in the range, for example polyols having 8 to 18 carbon atoms, are also aqueous. Preferred polyols are in one embodiment polyols having from 2 to 4 hydroxyl groups and, in particular, from 1 to 4, 4 to 10, 1, 2, 4, 4, 4, 4, 6, 6, 6, 7, 10, 10

Especially preferred are alpha, Mege-81andiols and 8 to 18 carbon atoms, such as 1,10-dacandiol, 1,12-decanediol and 1,18-octadecanediol. Diols or polyols which are obtainable, inter alia, by other hydrolysis of longer-chain epoxyelkeols are suitable.

These are polyols with vicinal hydroxyl groups, which may or must be baths at the ends of the chain, such as, for example, ocio-10,2,2, Ес п пО ^ ^ tet, tetredecanediol-1,2, - сάββ ^ΛΛΛΟΟ. Mixtures of vicinal alkanes having unbranched hydroxyl groups having chain lengths of 12 or 14 carbon atoms, as well as chain lengths of from II to 14, from 14 to 16 and from 15 to 18 carbon atoms. The thioglycol acid esters to be considered are products which are obtained, for example, by:. The polyol of the type described above is reacted in a conventional manner with thioglycolic acid in a molar ratio of 1: 1 to 1: n, where n is the number of hydroxyl groups of the polyol.

All hydroxyl groups of the polyol can be esterified with thioglycolic acid. Preferably, however, according to the invention, thioglycolic acid esters are used which, on average, contain at most 3 thioglycolic acid residues in the polyol molecule and preferably one or at most two thioglycolic acid residues. When esters of thioglycolic acid with monovalent alcohols are used in component (e), the alcohol component of these esters consists of a straight or branched chain aliphatic, primary, secondary or tertiary alcohol of 8 to 22 carbon atoms. Examples of possible alcohol components are o-octanol, n-dodecanol, n-hexane decanol, n-octane decanol, and in particular 2-ethylhexanol.

Component e) of the stabilizer mixture according to the invention consists, in the simplest case, of a certain polyol thioglycolic acid ester or a thioglycolic acid ester with a mono-alcohol. However, it is possible. any combinations of these groups of substances may also be used, and the individual components may again be mixtures of substances.

Advantageously, the paternal ester of penneyltritol with C 8 -C 22 fatty acids in the molar ratio of penteerytharitol / urban acid in the range of -d 1: 1 to 1: 2 is returned to the polyvinyl chloride-based molding compositions as component d) of the ethanolized mixture according to the invention. and as component e) an ester of a C8-C18 thiol-glycol-1-acid ester of an aliphatic alkyl group. diols having from 2 to 6 carbon atoms or glycerol mololiool acetate.

The stabilizer composition according to the invention can be further decomposed by other known stabilizers and auxiliaries according to the purpose for which the stabilized semi-liquid molding compositions can be used.

Such known additives can be used in conventional onsoles, for example in the rank of 0.1 to 20 parts by weight of the non-100 parts by weight of the polylchloride resin.

While stabilizing the molding compositions intended for extrusion tube production, it is possible to return to the 100 parts by weight of the thimble-lime mixture, for example 0.5 to 10 parts by weight. 1 part by weight of paraffin having a melting point in the range of from 50 to 100 [deg.] C. and / or from 8 to 22 carbon atoms of free fatty acids, the fatty acids of which the abovementioned substances are suitable.

In polylioyl chloride (1) molding compositions which are intended for the production of hollow bodies by extrusion and blow molding, the poles of the chloride of vinyl chloride can still be worked per 100 parts by weight, for example 0.5 to 5 parts by weight of epoxidized reindeer oil and 0.1 to 5 parts by weight. 8 parts by weight of the wax ester wax. Possible ester waxes are the molar oil and paraffin oxides, but in particular the esopexic esters of

(a) aliphatic, cyclic-aliphatic and / or aromatic (C 2 -C 22) alkoxylic acids - in moleloil;

(b) aliphatic polyols having 2 to 6 hydroxyl groups per molecule; and

(c) aliphatic monocarboxylic acids having 12 to 30 carbon atoms in the molecule, the molar ratio of the substances referred to in (a), (b) and (ec) is approximately (n-1): n: [nm-2 (n-1) ], wherein n represents an integer from 2 to 11 and m represents the functionality of the polyol. These mixed esters have a hydroxyl number and an acid number in the range of 0 to about 15. They can be prepared by known methods described in German Patent Specification No. 19 07 766. Preferably, complex esters formed from adipic acid, penteetytritol and steeric acid are used. in the above molar ratio, wherein n is an integer from 2 to 8.

For example, 0.5 to 5 parts by weight of epoxidized soybean oil, 0.1 to 1 part by weight of high molecular weight ester wax as defined above and 0.2 to 5 parts by weight of the polyvinyl alcohol are added to the polyvinyl chloride molding compositions for the production of films by the ηβ rolling machine. 0.5 part by weight of alpha-phenylindole or benzoyl stearyl methane as co-stabilizers. In addition, from 0.05 to 0.2 parts by weight of calcium soaps and from 0.1 to 0.2 parts by weight of zinc soaps do not produce 100 parts by weight of polyvinyl chloride perfectly satisfying stabilization.

A preferred composition of the stebilizer composition according to the invention is one in which 100 parts by weight of polyvinyl chloride are worked into molding compositions for the production of pipes and profiles by extrusion.

(a) 1 to 2 parts by weight of sodium aluminosilicate;

b) 0.8 to 1.2 parts by weight of calcium salts of fatty acids,

c) 0.1 to 0.4 part by weight of zinc fatty acid salts,

d) 0.3 to 0.5 parts by weight of a partial ester of penteerythritol with fatty acids,

(e) 0.2 to 0.5 parts by weight of thioglycolic acid esters; and

f) 0.5 to 1 part by weight of paraffin and / or fatty acid.

The stabilizer compositions of the present invention can be obtained by simple mechanical mixing of the components in conventional mixers. They are obtained in the form of loose, non-dusting products.

The stabilizer compositions of the present invention are used to stabilize polyvinyl chloride or polyvinyl chloride copolymers having a predominantly wooll chloride content. These polymers can be made by slurry or block polymerization; their K value may be in the range of 35 to 80. The stebilizer compositions of the invention are suitable for stabilizing resin compositions containing predominantly such wooll chloride-based polymers.

The polyvinyl-lime-free molding compositions stabilized by the stabilizer composition according to the invention are used primarily in the manufacture of tubes and profiles by extrusion, for the manufacture of hollow bodies serving as wrappers and not for the production of rolled foils, as well as for the manufacture of arbitrarily shaped articles.

The processing properties of the polyvinyl chloride molding compositions which have been stabilized with the stabilizer composition according to the invention are quite comparable to those of the polyvinyl chloride molding compositions stabilized with heavy metal salts. This applies in particular to the original color, the original stability and the residual stability of the molding compositions. Therefore, the stabilizer composition according to the invention represents an equivalent substitute for the heavy metal stebilizer mixture hitherto used. The stabilizer composition according to the invention thus brings considerable progress, for example in the field of work physiology.

Next, the preparation of suitable sodium aluminosilicates is first described as an example

The production of suitable sodium precipitated product is transferred to a crystallization vessel, where it remains for 6 hours at 0 ° C to be shaken while stirring at 250 rpm. After suctioning off the mother liquor of the suspension of crystals and passing through demineralized water until the water has a pH of about 10, the residue on the filter is dried. The water content was determined by heating the 15 liter vessel for one hour to the silicate solution while stirring vigorously to the aluminate solution. The agitator impregnated with the dispersing disc rotates at a speed of 3000 rpm.

Both solutions have a temperature of m / m. The exothermic reaction is formed as the primary product of the precipitation of sodium aluminosilicate, as determined by X-ray analysis. After stirring for 1 / ml, the suspension of 90 has a pre-dried product. The resulting sodium aluminate, washed to pH 10, optionally neutralized and then dried, is then milled in a ball mill.

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The calcium-binding capacity of ΚΙ ^: ^ Ο ^^^^ ι ^ is determined as follows:

Κ 1 liter of an aqueous solution containing 0,549 g of CaCl2 (= 300 mg Ca / ltr = 30 ° dH), adjusted to pH 10 by addition of dilute sodium hydroxide solution, add 1 g of aluminum the edge of the michiten (referred to jlumtiiiЫt). The suspension was then stirred vigorously at 22 ° C (± 2 ° C) for 15 minutes. After filtration of the aluminum silicate, the residual hardness x final is determined. From this calculate the ability to bind calcium in mg CaO / g aluminosilices according to the formula:

(30 - x). 10

In addition, determinations capable of binding calcium at higher temperatures, for example at 60 ° C, are always found to be better than at 22 ° C.

Production conditions for ШпЮоО ^ гШШп sodium

All percentages

Precipitation

Ingredients:

the data are given in percent.

2,985 kg aluminate solution of composition

17.7% NaO, 15.8% AlgO-j, 66.6% HgO,

0.15 kg of sodium hydroxide,

9,420 kg of water,

2,445 kg 25 8% sodium silicate solution - composition

NagO · 6.0 SiOg, freshly made from commercial water glass and silicic acid, easily soluble in alkalis, 6 hours at 90 ° C 24 hours at 100 ° C

0,9 Νθ2θ. 1 Al ₂ ° 3. 2.04 SiOg. 4.3 HgO (= 21.6% HgO)

Degree of crystallization: Calcium binding capacity:

fully crystalline

170 mg CaO / g active substance.

When determining the layout. The particle size was determined by sedimentation analysis to provide a blend of 3 to 6 microns.

Sodium hinosilicate A shows the following interference lines in the X-ray diffraction pattern:

Riff Д detected with irradiation of Cu-K _and in 10 m

12.4

8.6

7.0

4.1

3.68 (+)

3.38 (+)

3.26 (+)

2.96 (♦)

2.73 (+)

2.60 (+)

It is quite possible that not all these interference lines are always present in the X-ray diffraction pattern, especially when the crystals are not perfectly pro-lycalated. Therefore, the values of d most important for the characterization of these types are marked (+).

Production conditions for sodium alumina

All percentages are given in% by weight.

Precipitation: 7.63 kg of an aluminate solution of 13.2? 4.0, 8.0? AlgOp 78.8% H _? 0.27 kg of sodium silicate solution of 8.0? No ₂ O, 26.9? SiO ₂ , 65.1% HgO Handle composition (in moles): ^^ seHzace: Drying: Composition of the dried product: Crystal shape: Mean particle diameter: Calcium binding ability: 3.24 Nb ₂ O, 1.0 Al ₂ O 3, 1.78 SiO ₂ , 70.3 HgO 6 hours at 90 ° C 24 hours at 100 ° C 0.99 Na ₂ 0. 1.00 A1 ₂ Og. 1.83 SiO ₂ . 4.0? 0 (= 20.9? HgO) cubic with strongly rounded corners and edges 5.4 172 mg CaO / g active ingredient.

minor conditions for sodium aluminum

All for cents data are expressed in percentages. Precipitation: 12.15 kg of an aluminate solution of 14.5 ₂ H ₂ O, 5.4 A1 A1 ₂ O ₃ , 80.1 H H ₂ O 237 kg of a sodium silicate solution of 8.0 N N ₂ 0, 26.9 SiOg, 65.1 HgO Handle composition (in moeech): Kryysalizace: Drying: 5.0 Na ₂ O, 1.0 Al ₂ O ₃ , 2.0 SiO ₂ , 100 HgO 1 hour at 90 ° C spraying the washed product suspension (pH 10) at 295 ° C; solids content in suspension 46 « Composition of the dried product: Crystal shape: Average particle diameter: Calcium binding capacity: 0.96 Ns ₂ O. AlgO ₃ . 1.96 SiOg. 4 HgO cubic with very rounded corners and edges, water content 20.5 5 5.4 / m 172 mg CaO / g active substance

Examples

In Examples 1 to 3, ее describes testing of the effect of a stabilizer composition manifested by static thermo-permeability of plastic skin test specimens. For this purpose, the polyvinyl chloride molding compositions containing the stabilizer mixtures are processed on a laboratory cylindrical machine having a size of 450. 220 mm (Berstorff) at a roller temperature of 170 ° C and a roller speed of 12.5 rpm in parallel for 5 minutes on test skin samples. From these skins with a thickness of approximately 0.5 mn, square samples of 10 mm edge length are cut and then exposed to a temperature of 180 ° C in a 6-rotary drying oven (Heraeus FT 420 R). At five minute intervals, samples are taken from the oven and the change in color is evaluated.

In Tables 2, 4 and 5 below, depending on the stabilizer mixture not used, the initial color is given first and then the time after which the test was discolored due to excessive color (stability disappears).

Table 1

Component Polyvinyl chloride molding compound AND В C D E F Suepensive polyvinyl chloride (K «65) 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! Sodium Aluminosilicate ¹ 2,0 2,0 2,0 - - - calcium stearate 1.0 1.0 ', 0 1.0 bo 1.0 zinc stearate 0.3 0.3 0.3 0.3 0.3 0.3 stearic acid ester with penteerythritol ² 0.3 - 0.3 0.3 0.3 0.3 wax ester (cetyl palmitate type) - 0.3 - - - - 2-ethylhexylthioglycolet 0.3 0.3 - 0.3 - - paraffin, m.p. 71 ° C 0.75 0.75 0.75 0.75 0.75 0.75 synthetic zeolite NaA; Na ₂ O: AlgO ₂ : SiOg «0,9 : 1 s 2, .04;

water content: 21.6% by weight maximum particle size: 3 to each

D molar ratio of pentaerythlt / stearic acid = 1: 1.5; hydroxyl number 212 Example 1

The polyvinyl chloride molding tips A to F, the composition of which is given in Table 1, were tested as described above.

Composition A is a polyvinyl chloride molding material stabilized by the stabilizer of the composition according to the invention, which is particularly suitable for the production of pipes and profiles by extrusion. The molding compositions of compositions V to F are comparative molding compositions which are obtained from Regulation A by omitting or replacing the individual components.

The values of “static thermostability” are given in Table 2.

221315

Table 2

Forming mass Initial color Back Stabblity (minutes) AND white 135 (B) white 105 C reddish 120 D white 45 E reddish 45 F reddish 30

Example 2

The polyvinyl chloride molding compositions G to L, the composition of which is given in Table 3, were tested as described above.

Composition G is a polyvinyl chloride molding compound; The stabilized stabilizer composition according to the invention is suitable for the production of packaging materials, in particular for the production of bottles by blowing and blowing. The letters H to L are denoted by the comparative molding compositions obtained from formula G by omitting or exchanging the individual components.

Table 3

Component Guilt poles Ι ^ Ιμ ^^ Α forming mass G H AND J TO L suspension polyvinyl chloride (K = 60) 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! hl ^and nitokřemičitan sl ^d Nu ^ 1.0 1.0 1.0 - - - calcium stearate 0.5 0.5 0.5 0.5 0.5 0.5 stearic acid ester with pennaerythri ^ ^{2) 2)} 1.0 1.0 1.0 1.0 1.0 wax ester (type Cetylpalmitan) - 1.0. - - - -, 2-ethylhexylthiogltktlate 0.3 0.3 - 0.3 - - oxi e ^{p d} portance incorporated with ^the oil; 4.0 4.0 4.0 4.0 4.0 4.0 com ^p leenní ester ⁴⁾ 0.5 0.5 0.5 0.5 0.5 0.5 synthetic zeoUt NeAj ItegO: AlgOj : SiO2 = 0,9: 1: 2.04

peuntserythrole: stearic acid molar ratio = 1: 1.5; hy <DRO: xplové number 212 ^{3) P} e oxi ^{d 6,3 4} memory ^number) mdlení Omer acid ^p ^ ^p ad network: ^p ent, eee tt ^{r i} ttl: Stearic acid "6: 7: 16 hydroxyl number of about 2 ; acid number approximately 10.

The static thermo-stability values found in this dilution of experiments are shown in Table 4.

Table 4

Forming mass Initial color Extinction of stability (minutes) G colorless 180 H colorless 150 AND nečervenelá 180 J colorless 105 К nečervenelá 105 L nečervenelá 60

Example 3

The molding compositions N to S are obtained by incorporating in the polyvinyl chloride molding composition M a composition

100 parts by weight of suspension polyvinyl chloride (K = 60)

0.75 part by weight of calcium stearate

0.25 part by weight of stearate stearate

0.3 parts by weight of stearic acid ester with penteerythltol (molar ratio of pentaerythritol: stearic acid = 1: 1.5; hydroxyl number 212)

0.3 part by weight of 2-ethylhaxylthioglycolate

0.75 parts by weight of paraffin, melting point 71 ° C, processed by zeolites n) to s) in an amount of 1 part by weight to 100 parts by weight of polyol;

(n) synthetic, non-activated Na-zeolite of the NaA type;

Na ₂ 0: Al ₂ 0 ₃ : SiO ₂ = 0.99: 1: 1.83; water content: 20.9%; mean particle diameter: 5.4 µm;

o) synthetic, non-activated Na-zeolite of the NaX type;

Na ₂ 0: Al ₂ 0 ₃ : SiO ₂ · 1: 1: (2.4 to 2.6);

p) synthetic, non-activated Na-zeolite of the NaX type;

Na ₂ 0: Al ₂ O ₃ : SiO ₂ = 1: 1: 4.3;

q) synthetic, non-activated KA-type K-zeolite;

K ₂ O: Al ₂ O ₃ : SiO ₂ = 1: 1: 2;

r) synthetic, non-activated Ca-type CaA zeolite; made from the zeolite referred to in (n) by ion exchange with calcium chloride;

s) synthetic, non-activated sodium aluminosilicate; amorphous

Na ₂ O: Al ₂ O ₃ : SiO ₂ =

1: 1: 2.

The stabilizing composition K is stabilized with a stabilizer according to the invention. Forming materials. M and P and Q represent the comparative compositions obtained by draining or replacing the sodium aluminosilicate referred to in (n). The molding compositions M to S are tested according to the above method for their static theomosstability. The results are shown in Table 5. *

Table 5

Forming mass Ze.ooit Initial color Extinction of stability (minutes) M - white 45 N n) On A white 90 0 o) NaX faintly yellowish 45 P p) Na X white 45 Q q) KA white 60 R r) CaA white 60 WITH s) Amoophobic white 60

Example 4

At high speed, 100 parts by weight of the suspension polyvinyl chloride (K = 65) are treated with 4.65 parts by weight of the stabilizer mixture of the composition of the non-activated Na8-type N8 zeoite synthetic, unactivated; Na _o 0: A1? 0 ^: SiOp = 0.99: 1: 1.83; .

20,9 fcRO 4 2 3 2 e. "Calcium molar stearate parts" molar parts of stearate zirconium parts by weight of the partial ester of tertiary acid with pentaerythritol (molar ratio of 1: 5: 1> hydroxyl number 212) swollen parts of 2-glycerol ethyl

7.5 parts by weight of paraffin with a melting point of 71 ° C per molding mass. A conventional twin screw extruder CN 55 (manufactured by Cincinnnti-Mlecron, Vienna) is used to process this molding composition. This extruder has the following technical parameters:

Screw diameter: Effective length: Arrangement: Screw direction: 55/110 mm 1,050 mm Coin / comb against each other, upwardly apart

Production of polyvinyl chloride pipes with a wall thickness of 5.3 mm and an outer diameter of 110 mo shall be subject to the following conditions:

cylinder:

inlet:

head:

nozzle:

thorn:

core: engine speed:

185/170/135 [deg.] C

140 DEG C. 190/190 DEG

200 ° C

190 ° C

140 [deg.] C

000 rpm Screw speed: engine load: fully filled Screws production:

rpm to 45 «

157 kg / h

Obtain white to caramel-colored tubes.

Example 5

A stabilizer mixture is prepared from the following ingredients:

hmoonoot parts of synthetic, non-activated Naa _Ze0 Naite type NaA;

NagO: Al2O3: SiOg = 0.99: 1: 1.83, -20.9 hooonoot% HgO calcium molar stearate parts by weight octoate zinc octoate parts by stnaic acid ester of pennaatritol (molar ratio 1: 1.5; hydroxyl number) 212) 2-ethylhexylthioglycoate 2-ethylhexyl thioglycoate moieties of adipic acid ester (β-β-triethylamine) and stearic acid (molar ratio 6: 7: 16; hydroxyl number about 2; approximately 10) parts by weight of epoxidized reindeer oil (epoxy number 6.3).

92 parts by weight of suspension polyvinyl chloride (K = 60), 8 parts by weight of methacrylate-styrene resin and 7 parts by weight of the above-mentioned stabilizer mixture are processed in a high-speed mixer to a free-flowing dry mixture, which is then extruded. it produces bottles of approximately 290 ml volume by means of a blow molding machine (cylinder diameter 40 mm, relative length of screw 20 D). Under constant processing conditions, bottles of good translucency, smooth, brilliant surface and high impact strength are produced from this polyvinyl chloride molding composition.

Example 6

From the following ingredients, a stabilizer mixture is prepared:

parts of synthetic, non-affinity NaA type Nae;

SiO 2 = 0.91: 1: 1.83; 20 wt% HgO of the calcium moieties tmoearate

5 parts by weight of stearate of zinc plated parts of stearate foal stearate (molar ratio of 1.5: 1) of carbon monoxide (2: 1) by weight of the ester parts of the ester edipic acid, pen08aeylrinsium and stearic acid (olar ratio 6: 7: 16; hydroxyl value approximately 2; acidity value approximately 10),. 3 parts of alpha-phenliindole parts of epoxidized soybean oil (epoxy number 6.3)

In a high-speed mixer, 100 parts by weight of the suspension pollvioyl chloride (K = 60) and 7.35% by weight of the above-mentioned stabilizer mixture are processed into a welding machine. 220 mm (Fa Bestorff) at a roller temperature of 170 ° C and a roller speed of 12.5 rpm - - softens and rolls in a conventional manner a translucent film having a thickness of approximately 0.5 mm. This foil has a smooth and brilliant surface.

Example 7

In a high-speed mixer with 100 parts by weight of suspension polyvinyl chloride (K = 65), 4.65 parts by weight of a stabilizer mixture having the composition of hmoonoot parts of synthetic, non-activated Naazzeoit, type NaA are processed;

Ni ^ O: A12 ° ^{3: Si0} 2 = ^{0) 99: 1:} 1.83 ^{20 9% H} ₂ ° H □ · Onostních parts of calcium steerátu hmoOnostní parts zinc steerátu h [DoSnootní ⁴ parts of a partial ester of glycerol and stearic acid (mercury ratio 1: 1.5) trimethylpropane proportions trimethylpropane proportions

7.5 parts by weight of paraffin with a melting point of 71 ° C per forming hmoo / µ. A conventional twin screw extruder CM 55 (manufacturer: Cincinnβti-Шlocrsn1 Vienna) is used to process this molding composition. This extruder has the following technical parameters:

Screw diameter: Effective length: Arrangement: 55/110 mm 1 050 mm conical / comb Direction of rotation: facing each other, upward apart

For the manufacture of polyiri.nyl chloride pipes with a wall thickness of 5,3 mm and an outer diameter of 110 mm, the following conditions shall be respected:

cylinder:

inlet: head: nozzle: mandrel: core: number of mooor revolutions: number of worms revolutions: load fully filled Screws production:

185/170/135 [deg.] C

140 DEG C. 190/190 DEG

200 ° C

190 ° C

40 ° C

000 rpm up to 45%

157 kg / h

White to caramel-colored tubes are obtained.

Example 8

The following ingredients are prepared from the following ingredients:

of the non-activated parts of synthetic, non-activated Nsezzooite type NaA; Neg0: AlgO3: SiO2 = 0.99: 1: 1.83, 20.9 hmoon% calcium stearate parts molar molar amounts of zinc to molar parts of glycorolri-12- of hydroxy steroid of the moieties of the recombinant to 1110-bis thioglycolate of the moieties of the edipic acid ester, the penoyltrosulfate and the stearic acid (molar ratio 6: 7 16; hydroxyl number about 2; the acid number of about 10) (epoxy number 6.3)

In a high-speed mixer, 92 parts by weight of suspension suspension (K = 60), parts by weight of meesacylate-styrene resin and 7 parts by weight of the above stabilizer combination are processed to a free-flowing dry mixture from which bottles of about 290 ml are then produced in a conventional extruder and blower (cylinder diameter 40 mm; screw length 20 D). Under constant processing conditions, bottles of good transparency, smooth, brilliant surface and high impact strength are obtained from this polyvinyl chloride molding composition.

Example 9

A stebilizer mixture is prepared from the following ingredients:

parts by weight of a synthetic, non-activated Na-zeolite of the NaA type;

Na ₂ O: Al ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83; 20 parts by weight H ₂ O parts by weight calcium stearate parts by weight zinc stearate by weight parts trimethylpropanlaurate (molar ratio i: 1.5) parts by weight n-octadecylthioglycoate parts by weight edipic acid ester, pentaerythritol and stearic acid (molar ratio 6: 7: 16; hydroxyl number about 2; acid number about 10) parts by weight of alpha-phenylindole parts by weight of epoxidized soybean oil (epoxy number 6.3)

In a high-speed mixer, 100 parts by weight of the suspension polyvinylchloride (K = 60) and 7.35 parts by weight of the above stabilizer mixture are processed into a molding composition. This molding mass is 450 in a laboratory rolling machine. 220 mm (manufactured by Berstorff) at a roller temperature of 170 ° C and a roller speed of 12.5 rpm in parallel, softens and rolls into a translucent film of 0.5 mm thickness. This foil has a smooth and glossy surface.

Claims (6)

SUBJECT OF THE INVENTION A stabilizer mixture for polyvinyl chloride molding compositions comprising calcium and zinc salts of fatty acids as well as partial esters of polyols with fatty acids, characterized in that it consists of: 4 to 100 parts by weight of a synthetic, finely crystalline, finely powdered sodium aluminosilicate, containing bound water in the amount of 13 to 25% by weight, having a composition - based on the anhydrous form - of 0.7 to 1.1 Na ₂ O. AlgO ^. 1.3 to 2.4 SiO ₂ , 1 to 30 parts by weight of a calcium salt of C8-C22 fatty acids, 1 to 10 parts by weight of a zinc salt of 8 to 22 carbon atoms, 4 to 40 parts by weight of partial esters of polyols having 2 to 6 carbon atoms; 6 hydroxyl groups with fatty acids of 8 to 22 carbon atoms, which on average contain at least one free polyol hydroxyl group per molecule, 2 to 20 parts by weight of thioglycolic acid esters of polyols having 2 to 6 hydroxyl groups and / or thioglycolic acid esters of monovalent alcohols having 8 to 22 carbon atoms. 2. The stabilizer mixture of claim 1, wherein the sodium aluminosilicate used has a particle size in the range of 0.1 to 20 .mu.m. 3. The stabilizer mixture according to claim 1, wherein the sodium aluminosilicate used is zeolite 4A containing bound water having a water content in the range of from 18 to 25%. The stabilizer mixture according to claims 1 to 3, characterized in that the partial esters of polyols with fatty acids used are partial esters having a hydroxyl number in the range of from 140 to 580, preferably from 170 to 540, which have an acid number in particular of less than 15. , expediently less than 8. 5. A stabilizer mixture as claimed in claim 1, wherein the thioglycolic acid ester is a thioglycolet of linear or branched monovalent alcohols and / or mono- and / or di-thioglycoletes of said polyols. 6. A stabilizer mixture as claimed in any one of claims 1 to 5, wherein the partial ester of the fatty acid and polyols comprises a partial ester of a fatty acid of 8 to 22 carbon atoms at a fatty acid of 8 to 22 carbon atoms. a pentaerythritol / urban acid molar ratio ranging from 1: 1 to 1: 2 and as the thioglycolic acid ester comprises a thioglycolic acid ester with a C8-C18 monovalent alcohol, a monoeser of thiogylcolic acid with aliphatic diols of 2 to 6 carbon atoms, or a monohioglycooeth glycerol .