DD153556A5 - METHOD FOR STABILIZING POLYVINYL CHLORIDE MOLD - 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

Process for stabilizing polyvinyl chloride molding compounds

Field of application of the invention

The invention relates to a process for the stabilization of molding compositions based on polyvinyl chloride or in v / vinyl chloride vinyl-containing copolymers, agents for carrying out the method and articles produced therewith.

Characteristic of the known technical solutions

In the manufacture of articles made of polyvinyl chloride, lead, tin or barium / cadmium compounds are used in practice predominantly as stabilizers. These heavy metal stabilizers show a thoroughly satisfactory action in practice; However, there are some concerns about their use, in particular those of a work-physiological nature. For this reason, attempts have long been made to replace the commonly used heavy metal stabilizers with less hazardous substances. In this connection, it has already been proposed to use soils of the light alkaline earth metals instead of the heavy metal stabilizers , Calcium soaps are preferably used, which are optionally supplemented by co-stabilizers such as zinc stearate, imino compounds and 1 / poxyverb indungen.

The stabilizing effect of the calcium soap system is comparatively low compared to that of the heavy metal compounds. Molded articles made using a calcium soap-based stabilizer system often show dark discoloration and have a low content

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EestStabilität, As a result, the scope of such stabilizer systems is considerably limited ·

In the DjEhOS 26 42 509 a stabilizer combination is described, in addition to calcium and / or -zinkstearat a partial ester of pentaerythritol with a ^ 12 ~ ^ 22 ~ "^ ^e ^ ^s ^ ^{ure> β ί- Ώ & Ώ} waxy hydrocarbon and / or a free However, the desired equality with stabilizer systems based on heavy metal compounds is not reached hereby

The US-PS 4 000 100 describes the use of so-called non-activated zeolite A in stabilizer systems for resin compositions on PVC BasiSo The teaching of this document is based on the finding that the incorporation of certain hydrous zeolite types in stabilizer synergistic increases in heat and light protection can be achieved. The zeolites proposed for this purpose • include types 3A ₁ 4A and 5A «They are to be used in conjunction with any inorganic, organometallic or organic stabilizer or» stabilizer component »

Object of the invention

It is the object of the present invention to improve the stabilization of polyvinyl chloride with the aid of combinations based on calcium and optionally zinc soaps, that without the concomitant use of lead, tin, barium or cadmium compounds, the production of lightly pigmented or white polyvinyl chloride with satisfactory reserve stability is made possible

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Explanation of the essence of the invention

The invention has for its object to achieve the desired goal by selecting and combining a plurality of certain components, including the selection of a particular sodium aluminosilicate zeolite type.

The invention accordingly provides, in a first embodiment, a process for the stabilization of polyvinyl chloride molding compositions, which is characterized in that in the molding compositions per 100 parts of polyvinyl chloride

a) 0.2 - 5 parts by weight of a synthetic, crystalline, 13 to 25 wt .-% bound water-containing, finely divided NatriumalumoSilikats, which - based on the anhydrous form - the composition

0.7-1.1 Na ₂ O. Al ₂ O ₃ . Has 1.3-2.4 SiO ₂ ,

b) 0.05-1.5 parts by weight calcium salt of fatty acids having 8 to 22 carbon atoms,

c) 0.05-0.5 parts by weight of zinc salt of fatty acids having 8 to 22 carbon atoms,

d) 0.2-2.0 parts by weight of partial esters of fatty acids having 8 to 22 carbon atoms and polyols of 2 to 6 carbon atoms and 2 to 6 hydroxyl groups containing on average at least one free polyol hydroxyl group per molecule,

e) 0.1-10 parts by weight of thioglycolic acid esters of polyols having 2 to 6 hydroxyl groups and / or thioglycolic acid esters

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monofunctional alcohols having 8 to 22 carbon atoms incorporated.

The invention further provides a stabilizer combination of the composition

a) 4-100 parts by weight of synthetic, crystalline,

13 to 25 wt .-% of bound water-containing, finely divided sodium aluminosilicate, which - based on the anhydrous form, the composition 0.7 - 1.1 Na _? 0 · Al ₂ O ₃ . Has 1.3-2.4 SiO ₂ ,

b) 1 to 30 parts by weight of calcium salt of fatty acids containing 8 to 22 carbon atoms,

c) 1-10 parts by weight of zinc salt of fatty acids having 8 to 22 carbon atoms,

d) 4 to 40 parts by weight of partial esters of fatty acids having 8 to 22 carbon atoms and polyols of 2 to 6 carbon atoms and 2 to 6 hydroxyl groups containing on average at least one free polyol hydroxyl group per molecule,

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

The invention, finally, the stabilized in the context of the teaching of the invention articles of resin compositions based on PVC. In this case, both the correspondingly stabilized molding compositions as such and the molded articles obtained therefrom by any desired deformation are included.

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The synthetic crystalline sodium aluminosilicates defined above are ITaA type zeolites which are known per se and have an average effective pore diameter of 4 Å, which is why they are also referred to as zeolites 4 A. Such ITatriumalumoSilikate can be prepared by known methods · Suitable synthesis methods are u. a. in DE-OS 24 12 837. ^ eitere details on the nature and preparation of these sodium aluminosilicates can be found for example in the following literature parts: DE-OS 26 51 485, DE-OS 26 51 445, DE-OS 26 51 436, DB-OS 26 51 419, DS-OS 26 51 420, DE-OS 26 51 437, US-PS 3,112,176.

In the production caused by precipitation, amorphous, finely divided liatriumalumo silicates by heating at 50 to 200 ⁰ C in the crystalline state are transferred. Thereafter, the kristattine sodium aluminosilicate is separated by filtration from the remaining aqueous solution and usually dried at 50 to 200 ⁰ C until it has a water content of 13 to 25 weight percent. The crystalline production described for example in DE-OS 24 12 837 and used according to the invention have in particular a particle size in the range of 0.1 to 50 / i. For carrying out the process according to the invention sodium aluminosilicates are preferably used with a particle size of 0.1 to 20 ^ i «The particular at 22 ⁰ C calcium binding capacity of IiatriumalumoSilikate is at least 50 mg CaO / g of anhydrous active substance and can reach values of about 200 mg CaO / g reach active substance. Preferably, this Galciumbindeabmögen is in the range of

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100-200 mg CaO / g active substance and usually in the range above 150 mg CaO / g. Details for determining the calcium binding capacity can be found in the cited DE-OS 24 12 837 and the following information on the preparation of suitable sodium aluminosilicates.

In a preferred embodiment of the process according to the invention, sodium aluminosilicates with rounded corners and edges can also be used. To prepare such zeolites, it is advantageous to start from an approach whose molar composition is in the range

2.5-6.0 Na ₂ O "Al ₂ O ₃ . 0.5 - 5.0 SiO ₂ . 60-200 H ₂ O

is · This approach is brought in the usual V / else for crystallization · This is advantageously characterized in that the approach long least 1/2 hour at 70 - 95 ⁰ C under heated Kühren · The crystalline product - 120 ⁰ G, preferably 80 is easily isolated by separating the liquid phase, optionally washed with water and then dried «

When carrying out the process according to the invention, it is also possible to use finely divided water-insoluble sodium aluminosilicates which have been precipitated and crystallized in the presence of water-soluble inorganic or organic dispersants. Suitable water-soluble organic dispersants are surfactants, non-surfactant aromatic sulfonic acids and compounds with complexing properties with respect to calcium may be introduced into the reaction mixture in any manner before or during the precipitation; they may, for example, be presented as a solution or dispersed in the aluminate

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and / or silicate solution should be dissolved. The amount of dispersing agent should be at least 0.05% by weight, preferably 0.1-5% by weight, based on the total precipitation batch. For crystallization, the precipitation product is brought to 50 to 200 hours to 24 hours ⁰ C heated. from the large number of dispersants are as examples Natriumalaurylethersulfat, sodium polyacrylate and the sodium salts of 1-hydroxyethane-1,1-diphosphonic acid may be mentioned ₀

The sodium aluminosilicates of the NaA type, which are suitable according to the invention, contain from 13 to 25% by weight of bound water; Preferably, those products are used whose water content is in the range of 18 to 25 weight percent.

The fatty acid calcium and zinc salts used according to the invention are preferably derived from fatty acids such as caprylic, capric, lauric, myristic, palmitic and stearic acid. Both salts of individual fatty acids and salts of fatty acid mixtures are used, as are natural ones Fats and oils can be used. The calcium and zinc salts of palmitic and stearic acid are preferably used.

The polyol partial esters of component d) are prepared in a manner known per se by esterification of polyols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups with fatty acids having a chain length of 8 to 22 carbon atoms, whereby customary esterification catalysts can be used. Polyol and fatty acid are in a molar ratio of 1: 1 to 1: (n-1)

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reacted with one another, where η is the number of hydroxyl groups of the polyol Preferably, the ReaktionssteilnehEier in such amounts that partial esters having an OH number between 140 and 580, in particular between 170 and 5 ^ 0 form, The Beaktionsprodukt, each one Mixture of different esters, should have an acid number which is below 15, in particular below 8. Suitable Polyo components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, butylene glycol-1,4, 1,6-hexanediol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, srythritol, mannitol and sorbitol. Particularly important polyol components have 3 to 6 hydroxyl groups, and preferably 3 or 4 hydroxyl groups. Glycerol and pentaerythritol may be included in the invention within the context of the invention find particular advantage in use "Suitable fatty acid components are, for example, caprylic, oaprinic, lauric, myristic tin-, palmitic, stearic and behenic acid. It is also possible to use synthetic fatty acids of the mentioned chain length, such as montanic acids, or unsaturated acids, such as oleic acid and linolenic acid, or else substituted fatty acids, in particular hydroxylated acids, such as 12-hydroxystearic acid. For practical reasons, mixtures of fatty acids are usually used, as they are obtained from natural fats and oils. "Of course, the component d) may also consist of a mixture of the aforementioned partial esters _β partial esters of polyols having 3 ~ 6 hydroxyl groups, preferably 3 or 4 hydroxyl groups and The fatty acids mentioned, which contain on average 2 to 3 free hydroxyl groups, may be particularly preferred compounds in the sense of component d).

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As component e), in one embodiment of the invention, thioglycolic acid esters of aliphatic polyols having 2 to 6 hydroxyl groups are considered. Preferably, these polyols contain 2 to 36 carbon atoms, in particular 2 to 18 carbon atoms. Examples of polyols having 2 to 6 carbon atoms are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 4-butylene glycol, 1,6-hexanediol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, Pentaerythritol, mannitol and sorbitol "Polyols of higher carbon number of the stated range, for example those having 8 to 18 carbon atoms, are particularly suitable. Preferred polyols in one embodiment are those having 2 to 4 hydroxyl groups, in particular ethylene glycol, glycerol and / or pentaerythritol. Also particularly suitable are CC , Φ-alkanediols having 8 to 18 carbon atoms, such as 1,10-decanediol, 1,12-decanediol and 1,18-octadecanediol. Also suitable are diols or polyols which are obtained, inter alia, by hydrolysis of longer-chain epoxyalkanes / can ground. These are polyols with vicinal OH groups, which may be arranged end and not terminal, for example, octanediol-1,2, 1,2-decanediol, 1,2-tetradecanediol, octadecanediol-1,2, mixtures of vicinal alkanediols with non-terminal OH groups of the chain lengths Cj ^ or G ^ ₁ , and the chain length ranges C ^ to C ^ j C ^ to C ^ and CL ₁ - to CLq. The thioglycolic acid esters coming in stage are products which are obtained, for example, by reacting a polyol of the type defined above in a customary manner with thioglycolic acid in a molar ratio of 1: 1 to 1: η, where η is the number of hydroxyl groups of the polyol means. In this case, all the hydroxyl groups of the polyol can be esterified with thioglycolic acid. Prefers

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According to the invention, however, such thioglycolic acid esters are used which have an average of at least 3 thioglycolic acid residues per polyol molecule and preferably one or a maximum of two thioglycolic acid residues. If thioglycolic acid esters of monofunctional alcohols are used in component e), the alcohol component of these esters consists of an aliphatic, straight-chain or branched, primary, secondary or tertiary alcohol having 8 to 22 carbon atoms. Examples of possible alcohol components include n-octanol, n-dodecanol, n-hexanedecandol, n-octadecanol and especially 2-ethylhexanol.

In the simplest case, component e) consists of a specific poly (thioglycolic acid ester or a thioglycolic acid ester of a monofunctional alcohol. However, it is also possible to use any desired combinations of these substituent groups, the constituents in turn being able to represent mixtures of substances.

In a preferred embodiment of the process according to the invention, a pentaerythritol partial ester of fatty acids having 8 to 22 carbon atoms with a molar ratio of pentaerythritol: fatty acid in the range from 1: 1 to 10 is worked into the molding compositions based on polyvinyl chloride as component d)

1: 2 and as component e) a thioglycolic acid ester of a monofunctional alcohol having 8 to 18 carbon atoms, a Monothioglykolsäureester of aliphatic diols with

2 to 6 carbon atoms or a glycerol monothioglycolate.

The stabilizer combination used in the process according to the invention can be prepared by further known go-stabilizers

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and adjuvants, modified depending on the intended use of the stabilized polyvinyl chloride molding compositions. Such additives known per se can be used in conventional amounts, for example in amounts of from 0.1 to 20 parts by weight / 100 parts by weight of PVG resin composition.

In the stabilization of molding compositions, which are intended for the production of pipes and profiles by extrusion, for example, with the stabilizer mixture per 100 parts by weight of PVC, 0.5 to 1 parts by weight paraffin of melting point 50 - 100 ⁰ C and / or free fatty acid with 8 to 22 carbon atoms incorporated v / earth, as fatty acids again the substances mentioned above come into consideration.

In Polyvinylchloridform mm assen, which are intended for the production of hollow bodies by extrusion blow, for example, 0.5-5 parts by weight of epoxidized soybean oil and 0.1-8 parts by weight of high molecular weight ester wax can be incorporated per 100 parts by weight of PVG · High molecular weight ester wax are montan waxes and paraffin oxidates but especially complex esters

a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids having 2 to 22 carbon atoms in the molecule,

b) aliphatic polyols having 2 to 6 hydroxyl groups in the molecule and

c) aliphatic monocarboxylic acids having 12 to 30 carbon atoms in the molecule,

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in which the molar ratio of the substances mentioned under a), b) and c) about

η - 1: η: nm - 2 (n-1)

where η is an integer from 2 to 11 and m is the functionality of the polyol. These mixed esters have hydroxyl and acid numbers in the range of 0 to about 15. They can be prepared by known processes, for example, in DS-PS 19 07 768 described method «. Complex esters of adipic acid, pentaerythritol and stearic acid are preferably used in the abovementioned molar ratio, where η is an integer from 2 to 8.

In polyvinyl chloride molding compositions for the production of films in Kalanderwalzverfahren be example for 100 parts by weight of PVC additionally 0.5 to 5 parts by weight of epoxidized soybean oil, 0.1 to 1 parts by weight of the above-defined high molecular weight ester wax and 0.2 to 0.5 parts by weight of QC-phenylindole In addition, 0.05 to 0.2 parts by weight of calcium soaps and 0.1 to 0.2 parts by weight of zinc soaps per 100 parts by weight of PVC cause completely adequate stabilization here.

In a preferred embodiment of the process according to the invention werd'en in molding compositions, which are intended for the production · of pipes and profiles in the extrusion process, per 100 parts by weight of polyvinyl chloride

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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 parts by weight of zinc salts of fatty acids,

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

e) 0.2 to 0.5 parts by weight of thioglycolic acid ester,

f) from 0.5 to 1 part by weight paraffin and / or fatty acid incorporated

The stabilizer mixtures according to the invention can be obtained by simple, mechanical mixing of the constituents in conventional mixers. They are produced as free-flowing, non-dusting products during production *

The process according to the invention is used for stabilizing polyvinyl chloride or copolymers of vinyl chloride with a predominant vinyl chloride content. These polymers can be prepared by suspension or bulk polymerization; her K-Y / ert can be between about 35 and 80. Within the scope of the invention is the stabilization of resin mixtures containing predominantly such polymers based on vinyl chloride.

The stabilized polyvinyl chloride molding compositions according to the invention are mainly used for the production of drilling

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and extruded profiles, used for the production of packaging hollow bodies and for the production of rolled foils. Arbitrarily shaped articles fall within the scope of the invention,

The processing properties of the PVC molding compositions which have been stabilized with the aid of the process according to the invention are quite comparable with the properties of the heavy metal-stabilized PVC molding compositions. This applies in particular to the initial color, the initial stability and the residual stability of the molding compositions. Accordingly, the stabilizer combination used in the process according to the invention represents a complete replacement for the heavy metal stabilizer combinations used hitherto. The process according to the invention thus brings considerable progress, for example in the field of occupational physiology ·

embodiment

The invention will be explained in more detail below with reference to some examples. The production of suitable sodium aluminosilicates is described below by way of example.

Preparation of suitable sodium aluminosilicates

The silicate solution was added to the aluminate solution while stirring vigorously. Stirring was carried out with a stirrer at 3000 revolutions / min. Both solutions had room temperature. An X-ray amorphous sodium aluminosilicate was formed under exothermic reaction as the primary precipitation product. After stirring for 10 minutes, the suspension of the precipitate was poured into a crystalliser.

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transferred tion container, where she with stirring (250 revolutions / min ·) remained for 6 hours at 90 ⁰ O for the purpose of crystallization · After aspirating the liquor from the crystal slurry and washing with deionized v / ater, until the effluent wash water has a pH of about 10, the filter residue was dried. The water contents were determined by heating the predried products to 800 ^° C. for one hour. The sodium aluminosilicates which had been washed or neutralized to a pH of about 10 and then dried were then ground in a ball mill. The particle size distribution was determined by means of a sedimentation process.

The Ca-binding capacity of the Al silicates was determined in the following manner:

1 .1 of an aqueous, containing 0.594 g CaCl ₂ (= 300 mg CaO / 1 = 30 ° dH) and adjusted with dilute EaOH to a pH of 10 solution is mixed with 1 g of aluminosilicate (based on AS). Then the suspension is 15 minutes at a temperature of 22 C (-2 ⁰ C) stirred vigorously · Filtration of the alumino-silicate determining the residual hardness χ of the filtrate · Hence the calcium binding capacity is calculated in mg CaO / GAS according to the formula: (30 - x). 10 ·

Determining the calcium binding capacity at higher temperatures, for example at 60 ⁰ C, you will find consistently better values than at 22 ⁰ C.

Manufacturing conditions for the ITatriumalumo silicate A: All percentages are by weight

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Precipitation: 2.985 kg Alumnat Composition solution:; 17.7% Na ₂ O, 15.8% Al ₂ O ₃ ,

66.6% H ₂ O 0.15 kg caustic soda 9.420 kg water 2.445 kg one of commercial water glass

and slightly alkali-soluble silica freshly prepared, 25 »8% sodium silicate solution of the composition 1 Na ₂ O. 6.0 SiO ₂

Crystallization: 6 hours at 90 ° C. Drying: 24 hours at 100 ^° C.

Composition: 0.9 Na ₂ O. 1 Al ₂ O _3. 2.04 SiO ₂ .

4.3 H ₂ O (= 21.6% H ₂ O)

Degree of crystallinity: fully crystalline Calcium binding capacity: I70 mg CaO / g active substance ₀

In the particle size distribution determined by sedimentation analysis, the particle size maximum at 3 - 6yu,

The sodium aluminosilicate A shows the following interference lines in the X-ray diffraction diagram:

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d values recorded with Cu K radiation in A

12.4 (+) 8.6 (+) , 7.0 (+) 3.68 (+) 3.38 (+) 3.26 (+> 2.96 2.73 2.60

It is quite possible that not all of these interference lines will appear in the X-ray diffraction pattern, especially if the aluminosilicates are not fully crystallized. Therefore, the most important d values for the characterization of these types were marked with a "(+)".

Production conditions for the sodium aluminosilicate B:

All percentages refer to percent by weight precipitation: 7.63 kg of an aluminate solution of the composition 13.2 % Na ₂ O; 8.0% Al ₂ O ₃ ; 78.8% H ₂ O

2.37 kg of a sodium silicate solution of the composition 8.0% Na ₂ O; 26.9% SiO ₂ ; 65.1 % H ₂ O;

approach ratio

in moles: 3.24 Na ₃ O; 1.0 Al ₂ O ₃ ; 1.78 SiO ₂ ; 70.3 H ₂

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Crystallization: 6 hours at 90 ⁰ G; Drying: 24 hours at 100 ^° C. Composition of the dried product:

0.99 Na ₂ O, 1.00 Al ₂ O. «1.83 SiO ₂ . 4.0 H ₉ O; (= 20.9% H _p O

Crystal shape: cubic with strongly rounded corners

and edges;

average paricle diameter: 5 »4 / u

Calciumbinde-

capacity: 172 mg CaO / g active substance.

Production conditions for the sodium aluminosilicate G:

All percentages are by weight. Precipitation: 12.15 g of an aluminate solution of the composition 14.5 % of a ₂ O; 5.4% Al ₂ O ₃ ; 80.1 % H ₂ O;

237 kg of a sodium silicate solution of the composition 8.0 NapO; 26.9 % SiO ₂ ; 65.1 % H ₂ O;

approach ratio

in moles: 5.0 Na ₂ O; 1.0 Al ₂ O ₃ ; £, 0 SiO ₂ ? 100 H ₃ O

Crystallization: 1 hour at 90 ⁰ G;

Drying: hot atomization of a suspension of the

washed product (pH 10) at 295 ⁰ C; Solids content of the suspension 46%;

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Composition of the dried product:

0.96 Na ₂ O c 1 Al ₂ O ₃ .1.96 SiO ₂ , 4 H ₂ O;

Crystal shape: cubic with strongly rounded corners

'and edges; Water content 20.5 %

average particle diameter: 5 | 4 / u calcium binding properties: 172 mg CaO / g active substance.

Examples of the effect of the stabilizer combinations

In Examples 1 to 3 static thermostability "of rolled sheets" the effect of the stabilizer combinations on the basis of was "tested. For this purpose Polyvinylchloridformmassen containing stabilizer mixtures were run on a laboratory roll mill of dimensions 45O χ 220 mm at a roll temperature of 1? 0 ⁰ G and a roller speed The roughly O ₁ ^ mm thick skins were cut into quadratic specimens with 10 mm edge length, which were subsequently dried in a drying oven with 6 rotating trays (Heraeus FT 420 E) at a temperature of 12.5 rpm were exposed to 180 ⁰ C. At intervals of I5 minutes samples were removed and examined for changes in color.

In the following Tables 2, 4 and 5, depending on the stabilizer mixture used initially the initial color is given and then the time after which the test was terminated because of excessive discoloration (stability termination).

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Examples 1

The polyvinyl chloride molding compositions A to II, the compositions of which are shown in Table 1, were investigated by the method indicated above.

Table 1

Component PVC molding compound

ABCDEF

Suspension PVC (K value 65) 100 100 100 100 100 100

Sodium aluminosilicate 2.0 2.0 2.0 -

Calcium stearate 1.0 1.0 1.0 1.0 1.0 1.0 i \>

Zinc stearate 0.3 0.3 0.3 0.3 0.3 0.3

Pentaerythritol stearic acid ester 0.3-0.3 0.3 0.3.

Wax ester (type cetyl palmitate) - 0.3 - - -

2-Kthylhexylthioglycolate 0.3 0.3 - 0.3 - - _xn

Paraffin, mp 71 ⁰ C 0.75 0.75 0.75 0.75 0.75 0.75

1) Synthetic zeolite NaA; Na ₅ O: Al ₅ Oo: SiO ₅ = 0.9: 1: 2.04 x;

Water content: 21.6% by weight; Particle size maximum: 3 - 6 / U \

/ 'ro

2) molar ratio pentaerythritol: stearic acid = 1: 1.5, OH number 212 "^

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Composition A is a PVC substance stabilized by the process according to the invention, which is particularly suitable for the production of pipes and profiles by extrusion. The compositions 'B to F' represent comparative molding compositions obtained from formulation A by omitting or replacing individual components.

The values found for the "static thermal stability" are reproduced in Table 2 _o

Table 2 • Stability s abbr uch. (Minutes) molding compound Initial color «ι 135 105 120 45 45 30 A B O D E F white white reddish white reddish reddish Example 2

The polyvinyl chloride molding compositions G to L, the compositions of which are given in Table 3, were investigated by the method indicated above ».

j G 1.0 table PVC For mmas se I 1.0 : Stearic acid logo CNRS logo INIST J K : 16 , 5   _- ro ro Suspension PVG (K value 60) 100 0.5 100 100 0.5 100 100 3 VJI to component Hatrium salumo silicate ₅ O, 3 1.0 0.3 - - OO VAS calcium stearate "1.0 H 0.5 1.0 4) adipic acid pentaerythritol stearic acid ester OHZ ca. 2; SZ approx. 10. 0.5 0.5 L zinc stearate - 0.3 - 0.3 0.3 100 Pentaerythritstearinsäureester ' 0.3 - - 1.0 1.0 - , 0 I ro Y-axis ester (type cetyl palmitate) 4.0 1.0 4.0 - - O , 5 vj 2-ethylhexyl 0.5 0.3 0.5 = 1: 0.3 - O epoxidized soybean oil 1) synthetic zeolite NaA; Na ₂ O 4.0 : Al 0: SiO ₂ = 4.0 4.0 - Jx complex ester 0.5 Water content 21.6% by weight; Teilchengrölienmaximum: 0.5 0.5 - 2) molar ratio of pentaerythritol 0.9: 1: 2, 04 - 3) Bp oxide number 6.3 3 - 6 yu - 4 ζ VjJ 1.5; OHZ 212 O Ω year O - *> OO VD ro ; Molar ratio 6 : 7: 51 L / 22 * vj

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The composition G is a stabilized by the process according to the invention polyvinyl chloride molding composition, which is suitable for the production of packaging material, in particular for the production of bottles by extrusion blow molding. Under H to L comparative compositions are listed, which were obtained from the formulation G by omission or replacement of individual components.

The values for the "static thermal stability" found in this test series are summarized in Table 4.

Table 4-

Porm masses initial color stability termination

(Minutes)

G colorless 180

H colorless I50

I reddish 180

J colorless 105

K reddish 105

L reddish 60

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Example 3

The molding compositions N to S were obtained by adding in portions of a PVC composition M of the composition

100 parts by weight of suspension PVC (K value 60)

0.75 parts by weight of calcium stearate

0.25 parts by weight of zinc stearate

0.3 part by weight of pentaerythritol stearic acid ester

(Molar ratio pentaerythritol: stearic acid = 1: 1.5, OH number 212)

0.3 weight st 0.75 Gewientsteile paraffin rush 2-ethylhexyl thioglycolate, mp _o 71 ⁰ C

the following zeolites η to s were incorporated in amounts of 1 part by weight per 100 parts by weight of polyvinyl chloride:

n) synthetic, non-activated Na zeolite, type ITaA Na ₂ O: Al ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83 »water content: 20.9%> mean particle diameter: 5» 4

o) synthetic non-activated Na zeolite; Type NaX; Na ₂ O: Al ₂ O ₃ : SiO ₂ = 1: 1: 2.4 - 2.6,

p) synthetic, unactivated Na zeolite, type NaY Na ₂ O: Al ₂ O.,: SiO ₂ = 1: 1: 4.3 _C

q) synthetic, unactivated K zeolite, type KA; K ₂ O:; α ₂ θ: SiO ₂ = 1 :, 1 1 2.

r) synthetic, unactivated Ca zeolite, type CaA from n) prepared by ion exchange with calcium chloride

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s) synthetic non-activated sodium aluminosilicate, amorphous NapO: Al ₂ O ₃ : SiO ₂ = 1: 1: 2.

The molding compound N was stabilized by the process according to the invention. The molding compositions M and O to Q ₁ are comparative compositions us exchange of Natriumalumo silicate n) were obtained by omitting or A * _0, the molding materials M to S were tested for their "static thermostability" out according to the method specified. The results found are summarized in Table 5.

table 3

Molding Complex Zeolite Initial Color Stability Demolition

  '(Min,)

M - White 45 N n) NaA White 90 O 0) NaX pale yellow 45 chig P p) NaI White 45 Q q) KA White 60 e r) CaA White 60 S sj na amorphous White 60

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Example 4

In a snow-running oven, 100 parts by weight of suspension PVC (EItert 65) were mixed with 4.65 parts by weight of a stabilizer blend of composition (GT weight steep).

20 GT synthetic non-activated Na zeolite,

Type NaA; Na ₂ O: -Al ₂ ⁰ S ^{: Si0} 2 ^{= 0>} ^ ^{: 1:} ^ ¹ » ⁸ ^» 20.9 %

10 GT calcium stearate 3. GT zinc stearate

3 pb pentaerythritol stearic acid partial ester (molar ratio 1: 1.5, OHZ 212)

3 GT 2-Bthylhexyl thioglycolate 7 _f 3 GT paraffin, mp 71 ⁰ U

Processed into a molding compound · A commercially available CH 55 twin-screw extruder was used in the processing of the molding compound. This extruder has the following technical data:

Screw diameter: 55/110 mm

effective length: "IO5O mm

Arrangement: conical / combing

Direction of rotation: opposite, upwards apart.

In the production of PYC-Eohren of 5j3 now wall thickness and HO mm outside diameter, the following conditions were met:

t + H ο η -28- 42 - 45% 03/13/1981 snails AP C 08 L / 224 434 157 kg / h ^ 7 854/11 Cylinder: 185/170/135 ⁰ C Enema: 140 ⁰ G Head: 190/190 ⁰ G Jet: 200 ⁰ C Mandrel: - 190 ⁰ G Core: 140 ⁰ C Engine speed: 2000 rpm Screw speed: 35 rpm Engine load: fully filled up emissions:

This resulted in white to k & ramel-colored tubes.

Example 5

A stabilizer combination was prepared from the following ingredients (GT = parts by weight);

10 GT synthetic non-activated Na zeolite,

Type NaA; ITa ₂ O: Al ₃ O ₃ : SiO ₂ = 0.99: 1 'x 1.83; 20.9 parts by weight for H ₂ O,

2 parts of calcium stearate, 4 parts of zinc octoate,

20 pentaerythritolstearic acid ester (molar ratio 1: 1.5, OHZ 212)

4 GT 2-ethylhexythioglycolate, 10 GT adipic acid pentaerythritol stearic acid ester

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(Loading ratio 6: 7: 16, OHZ about 2, S ₀ Z. about 10) 80 GT epoxidized soybean oil (epoxy number 6.3).

92 parts by weight of suspension PVC (K-'7ert 60), 8 parts by weight of methacrylate-butadiene-styrene resin and 7 parts by weight of the stabilizer combination vorstehfinden were processed in a schneilaufenden mixer to a free-flowing dryblend composition, which then on a conventional Extrusionblasanlage (cylinder diameter 40 2 to 0 ml of contents, under constant processing conditions this PVC molding compound provided bottles of good transparency, smooth and brilliant surface and high impact strength.

Example 6

A stabilizer combination was prepared from the following ingredients (GT parts by weight);

10 GT synthetic non-activated Na zeolite,

Type NaA; Na ₃ O: Al ₃ O: SiO ₂ = 0.99: 1: 1.83; 20% by weight of H ₂ O.

6 GT calcium tar ar at

5 GT zinc stearate

24 pb pentaerythritol stearate (boiling ratio 1: 1.5)

6 GT 2-ethylhexyl thioglycolate

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10 parts by weight of adipic acid pentaerythritol-stearic acid ester (molar ratio β: 7: 16, OHZ about 2, SZ about 10)

3 GT & phenylindole 40 GT epoxidized soybean oil (epoxide number 6.3)

Parts by weight of suspension PVC (K value 60) and 7.35 parts by weight of the above stabilizer combination were processed in a blender mixer to form a molding compound. This molding material was plasticized on a laboratory rolling mill with the dimensions 450 220 mm (Berstorff) at a roller temperature of 17Ο ⁰ G and a roller speed of 12.5 rpm in the usual manner in a conventional manner and to a translucent film about 0.5 mm thick rolled out. This film showed a smooth and brilliant surface.

Example 7

In a cold running mixer, 100 parts by weight of suspension PVC (K value 65) was mixed with 4.65 parts by weight of a stabilizer mixture of the composition (GT = parts by weight).

20 GT synthetic non-activated Na zeolite, type KaA; Na ₂ O ₃ : SiO ₂ = 0.99 * 1: 1.83; 20.9%

10 GO · calcium stearate, 3 GT zinc stearate,

2 parts of glycerin stearate (boiling ratio 1: 1.5 »1 part by weight of trimethylolpropane,

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3 parts by weight of ethylene glycol monothioglycolate, 7.5 parts by weight of paraffin, mp 71 ^° C.

When processing the molding compound, a commercially available twin-screw extruder CM 1 was used. This extruder has the following technical data:

Tail diameter: 55/110 mm

effective length: 'IO5O mm

Arrangement: conical / combing

Direction of rotation: opposite, upwards apart.

In the production of PVC pipes of 5 * 3 nua wall thickness and 110 mm outer diameter, the following conditions were met:

Cylinder: 185/170/135 G Enema: 140 ⁰ C Head: 190/190 ⁰ C Jet: 200 ⁰ C Mandrel: 190 ⁰ C Core: 140 ⁰ G Engine speed: 2000 rpm Screw speed : 35 rpm Engine load: '42 - 45 % fully filled up snails emissions: 157 kg / h

This resulted in white to karame colored tubes,

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Example 8

A stabilizer combination was prepared from the following ingredients (GT = parts by weight):

10 GT synthetic non-activated Na zeolite,

Type NaA; Na ₃ O: Al ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83; 20.9% by weight

2 parts of calcium stearate, 4 parts of zinc octoate,

20 parts by weight of glycerol-12-hydroxystearate, 4 parts by weight of decanediol-ijiO-bis-thioglycolate 10 parts by weight of adipic acid pentaerythritol stearate ester

(Molar ratio 6: 7: 16, OHZ about 2, S "Z _e about 10)

80 GT epoxidized soybean oil (epoxy number 6.3) »

92 parts by weight of suspension PVC (K-V / ert 60), 8 parts by weight of methacrylate-butadiene-styrene resin and 7 parts by weight of. The stabilizer corotation described above was processed in a high-speed mixer to form a free-flowing dry-blend composition, which was then processed on a conventional extrusion blower unit (cylinder diameter 40 mm, relative screw length 20 D) into bottles of about 290 ml. Under constant processing conditions, this PVC molding compound provided bottles of good transparency, smooth and brilliant surface and high impact strength.

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Example 9

A stabilizer combination was prepared from the following ingredients (GT = parts by weight):

10 GT synthetic non-activated Sa zeolite,

Type NaA; Ha ₂ O: Al ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83; 20% by weight of H ₂ O.

6 GT Calciuinstearat

5 GT zinc stearate

24 g. Of trimethylolpropane laurate (molar ratio .1: 1.5)

6 GT n-octadecyl thioglycolate

10 GT adipic acid-pentaerythritol-stearic acid ester (molar ratio 6: 7: 16; OHZ approx. 2; SC approx. 10)

3 GT cC-phenyiindole 40 GT epoxidized soybean oil (epoxy number 6.3)

100 parts by weight of suspension PVG (K value 60) and 7.35 parts by weight of the above stabilizer combination were processed into a molding compound in a high speed Icscher. This molding material was on a Laborwalswerk nut dimensions 450 χ 220 mm at a roll temperature of 170 ⁰ C and a roller speed of 12.5 rpm in synchronism else plasticized in a usual V / and rolled 0.5 thick translucent film into a ca ". This film showed a smooth and brilliant surface,

Claims (8)

invention claim 1. "Process for the stabilization of polyvinyl chloride molding compositions, characterized in that in the molding compositions per 100 parts by weight of polyvinyl chloride a) 0.2 to 5 parts by weight of a synthetic, crystalline, 13 to 25 percent by weight of bound water-containing, finely divided, sodium aluminosilicate, which - based on the v / bererfreie form the composition 0.7 - 1 »1 Ha ^ O · ΑΧ? 0- · 1 | 3 has, b) 0.05-1.5 parts by weight of calcium salt of fatty acids having 8 to 22 carbon atoms, c) 0.05-0.5 parts by weight of zinc salt of fatty acids having 8 to 22 carbon atoms, d) 0.2-2.0 parts by weight of partial esters of fatty acids having 8 to 22 carbon atoms and polyols of 2 to 6 carbon atoms and 2 to 6 hydroxyl groups containing on average at least one free polyol hydroxyl group per molecule, e) 0.1 to 10 parts by weight of thioglycolic acid esters of polylols having 2 to 6 hydroxyl groups and / or thio glycoic ester of monofunctional alcohols having up to 22 carbon atoms incorporated. 2 2 4434 -3 ^ - 13.3.1981 AP O 08 L / 224 4-34 57 854/11 · 2. The method according to item 1, characterized in that one uses the component a) in a particle size of 0.1 - 20 / u 3. The method according to points 1 and 2, characterized in that as component a) a bound water-containing zeolite 4 A with a water content of 18 25 Ge v / i ent spr ο ζ ent used. 4 _e method according to the items 1 to 3 »characterized in that one uses as component d) partial ester of a hydroxyl number of between 140 and 580, in particular between 170 and 540, whose acid value is suitably below 13, in particular below 8 5. The method according to items 1 to 4, characterized in that one uses as component e) thioglycolates of aliphatic straight-chain or branched monoalcohols and / or mono- and / or di-thioglycolates of said polyols « 6. The method according to points 4 to 5 », characterized in that in the molding compositions as component d) a pentaerythritol partial ester of fatty acids having 8 to 22 carbon atoms with a molar ratio of pentaerythritol: fatty acid in the range of 1: 1 to 1: 2 and as Component e) incorporates a thioglycolic acid ester of a monofunctional alcohol having 8 to 18 carbon atoms, a monothioglycolic acid ester of aliphatic diols having 2 to 6 carbon atoms or a glycerol monothioglycolate » 2 2 443 A -36- 13.3.1981 AP C 08 L / 224 57 854/11 7 «method according to the points 1 to 6, characterized in that in molding compositions, which are intended for the production of pipes and profiles in the Bxtrusionsverfahren, per 100 parts by weight of polyvinyl chloride additionally 0.5 - 1 parts by weight of paraffin melting at 50 - 110 ⁰ G. and / or free fatty acid containing 8 to 22 carbon atoms « Process according to points 1 to 6, characterized in that in molding compositions which are intended for the production of hollow articles in the extrusion blown, in addition to 100 parts by weight of polyvinyl chloride in addition 0.5 to parts by weight of epoxidized soybean oil and 0.1 to 0.8 parts by weight of high molecular weight ester wax incorporating " 9 «method according to the points 1 to 6, characterized in that in molding compositions, which are intended for the production of films calender rolling process, • for 100 parts by weight of polyvinyl chloride additionally 0.5 to 5 parts by weight of epoxidized soybean oil, 0.1 to 1 part by weight high molecular weight ester wax and from 0.2 to 0.5 part by weight of OC-phenylindole or benzoylstearoylmethane incorporated « 10 * Process according to items 1 to 7 », characterized in that in molding compositions, which are intended for the production of pipes and profiles by extrusion, for 100 parts by weight of polyvinyl chloride 2 4 4 3 4 -37- 13.3.1981 AP C 08 L / 224 434 57 854/11 a) 1 - 2 parts by weight sodium aluminosilicate, b) 0.8-1.2 parts by weight calcium soap of fatty acids, c) 0.1-0.4 parts by weight of zinc salt of fatty acids, d) 0.3-0.5 parts by weight of polyol partial ester of fatty acids, e) 0.2-0.5 parts by weight of thioglycolic ester, f) 0.5-1 part by weight paraffin and / or fatty acid einarbeitete β stabilizer combination for polyvinyl chloride molding compositions, characterized in that they have the following composition: a) 4 - 100 parts by weight of synthetic, crystalline, 13 to 25 percent by weight of bound water containing, feint hasty sodium aluminosilicate, which - based on the anhydrous form - the composition 0.7 - 1.1 ^ a ₂ O _o Al ₂ O ₃ . Has 1.3-2.4 SiO ₂ , b) 1 to 30 parts by weight of calcium salt of fatty acids having 8 to 22 carbon atoms, c) 1-10 parts by weight of zinc salt of fatty acids having 8 to 22 carbon atoms, d) 4 to 40 parts by weight of partial esters of polyols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups and fatty acids having 8 to 22 carbon atoms which contain on average at least one free polyol-hydroxyl group per molecule, e) 2 - 20 parts by weight of thioglycolic acid esters of polyols having 2 to 6 hydroxyl groups and / or thioglycolic acid monofunctional alcohols with 2 2 4434 _ ₃₈ _ 13.3.198I AP C 08 L / 224 434 57 854/11 8 to 22 carbon atoms. 12 · stabilizer combination according to item 11, characterized in that component a) is present in a particle size of 0.1 - 20 μ . 13. Stabilizer combination according to items 11 and 12, characterized in that component a) is a bound water-containing zeolite 4A having a water content of 18-25% by weight. 14. A stabilizer combination according to items 11 to 13, characterized in that component d) consists of partial esters of a hydroxyl number between 140 and 580, preferably between 170 and 540, in particular an acid number below I5, advantageously below 8 on / off. 15. Stabilizer combination according to items 11 to 14, characterized in that component e) is the thioglycolate of aliphatic straight-chain or branched monoalcohols and / or mono- and / or di-thioglycolates of said polyols. 16. A stabilizer combination for polyvinyl chloride molding compositions according to items 11 to 15, characterized in that they contain as component d) a pentaerythritol partial ester of fatty acids having 8 to 22 carbon atoms with a molar ratio of pentaerythritol:. Fatty acid in the range of 1: 1 to 1: 2 and as component e) a thioglycolic acid ester of a monofunctional alcohol having 8 to 18 carbon atoms, a Monothioglykolsäureester of 2 2 A A3 A -39- 13.3.1981 AP C 08 L / 224 37 854/11 aliphatic diols having 2 to 6 carbon atoms or a Glycerinmonothioglykolat contains © 17 · molding compounds or moldings based on polyvinyl chloride or copolymers of vinyl chloride with a predominant content of vinyl chloride »characterized in that they contain a stabilizer combination according to items 11 to 18 · molding compounds, or moldings according to item 17j, characterized in that they are free of heavy metal-containing stabilizers »