KR840001537B1 - Stabilizer compositions for polyvinyl cheroide - Google Patents

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Description

Stabilizer Composition of Polyvinyl Chloride Casting Mixture

The present invention relates to a stabilizer composition of a polyvinyl chloride casting mixture. More particularly, the present invention relates to a stabilization process of a casting mixture based on polyvinyl chloride or vinyl chloride copolymers, wherein the mixture contains alkali metal aluminosilicates, calcium and zinc salts of fatty acids, partial esters of fatty acids and polyols, and polyols. And / or the process of adding thioglycolates.

Lead, tin, barium, or cadmium compounds are excellently used as stabilizers in making polyvinyl chloride materials. Stabilizers in these metals have indeed shown a very satisfactory effect. However, they have some problems with their use, especially related to occupational diseases such as addiction. For this reason, efforts to replace heavy metal stabilizers have been continued for a long time. The use of metal salts as light alkalis of fatty acids instead of heavy metal stabilizers has already been proposed. From this point of view, the calcium salts of fatty acids are better, and if desired, common stabilizers such as zinc stearin salts, amino compounds, or epoxy compounds may be used as an aid.

The stability and effectiveness of the fatty acid calcium salt system are relatively low compared to the heavy metal compounds. Casting materials prepared using stabilizers based on calcium salts often exhibit dark bleaching and low secondary safety. Therefore, the range of use of such stabilizers is very limited.

US Pat. No. 834,515, stabilizers containing partial esters of pentaerythritol with fatty acids having 12 to 20 carbon atoms, beeswax hydrocarbons and free fatty acids having 12 to 22 carbon atoms, calcium stearate and / or zinc stearate, and antioxidants. The composition of is shown.

However, this formulation is less efficient than stabilizers based on heavy metals.

US Pat. No. 4,000,100 describes the use of the so-called inert zeolite A as a stabilizer for resin compounds mainly based on polyvinyl chloride. A characteristic aspect in the notification of this document is that an increase in the action on the protection of heat and light can be achieved by any combination of zeolite forms containing water in the stabilizer. Zeolites used for this purpose are proposed in 3A, 4A, and 5A forms. These may be used with the necessary inorganic, organometallic, or organic stabilizer or stabilizer components.

So stabilization of polyvinyl chloride with the help of formulations based on calcium and zinc fatty acids, such as the production of polyvinyl chloride articles with weak coloration or whiteness and satisfactory pre-stability without the use of lead, tin, barium or cadmium compounds There remains a need for improvement.

It is an object of the present invention to develop a stabilizer combination for addition to a main formulation based on polyvinyl chloride or vinyl chloride copolymers. This stabilizer combination is a castable composition that has a good initial color when cast, is readily deformable, shows long-term stability under heat and is low in toxicity.

In addition, the present invention per 100 parts of the polymer to stabilize the casting composition based on polyvinyl chloride:

(a) A synthetic crystalline sodium aluminosilicate, consisting of about 0.2-5 parts by weight of small sized particles and containing 13-25% by weight of crystalline water, expressed in anhydrous form as follows.

0.7-1.1Na ₂ O. Al ₂ O ₃ 1.3-2.4 SiO ₂

(b) 0.05-1.5 parts by weight of one or more calcium salts of fatty acids having 8-22 carbon atoms.

(c) about 0.05-0.5 parts by weight of one or more zinc salts of fatty acids having 8-22 carbon atoms.

(d) 0.2-2.0 parts by weight of a partial ester of a polyol having 2-6 carbon atoms and 2-6 hydroxyl groups and a fatty acid having 8-22 carbon atoms, including at least one free polyol-hydroxy group per molecule on average; Have.)

and (e) 0.1-10 parts by weight of esters of polyols having 2-6 hydroxyl groups and thioglycolic acid esters of mono-functional alcohols having 8-22 carbon atoms.

It is also an object of the present invention to develop a stabilizer composition of a cast composition based on polyvinyl chloride or vinyl chloride copolymer, the stabilizer composition comprising:

(a) Synthesis of a small particle size containing 13-25% by weight of crystalline water having a composition of 0.7-1.1 Na ₂ O. Al ₂ O ₃ 1.3-2.4 SiO _{2 in} anhydrous form, about crystalline sodium aluminosilicate 4-100 parts by weight,

(b) about 1-30 parts by weight of one or more calcium values of 8-22 fatty acids,

(c) about 1-10 parts by weight of one or more zinc salts of fatty acids having 8-22 carbon atoms,

(d) about 4-40 parts by weight of a partial ester of a polyol having 2-6 carbon atoms with 2-6 hydroxyl groups and a fatty acid having 8-22 carbon atoms, including an average of at least one free polyol-hydroxy group per molecule Has),

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

Improvements in the stabilization of polyvinyl chloride compounds can be achieved by selecting a combination of complexes of certain components, including the selection of any aluminosilicate in zeolite form. More specifically, the present invention relates to a process for stabilization of polyvinyl chloride casting mixtures, per 100 parts of polymer.

(a) 0.2-enzymatically prepared sodium crystalline aluminosilicate of small particle size containing 13-25% by weight of crystalline water having a composition such as 0.7-1.1 Na ₂ O. Al ₂ O ₃ 1.3-2.4 SiO _{2 in} anhydrous form. 5 parts by weight,

(b) about 0.05-1.5 parts by weight of one or more calcium salts of fatty acids having 8-22 carbon atoms,

(c) about 0.05-0.5 parts by weight of one or more zinc salts of fatty acids having 8-22 carbon atoms,

(d) 0.2 to 2.0 parts by weight of a partial ester of a polyol having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups and a fatty acid having 8 to 22 carbon atoms, having an average of at least one free polyol-hydroxy group per molecule. ),

(e) 0.1-10 parts by weight of thioglycolic acid esters of polyols having 2-6 carbon atoms and 2-6 hydroxyl groups and / or monoglycolic alcohols having 8-22 carbon atoms in the casting mixture. Characterized in that.

In one embodiment of the invention components (a)-(e) were used in total with respect to 100 parts by weight of polyvinyl chloride or vinyl chloride copolymer, preferably 1-5 parts by weight in total.

The invention also

(a) Synthetic crystalline sodium aluminosilicate 4-100 of small particle size containing 13-25 mu% of crystal water with composition of 0.7-1.1 Na ₂ O. A1 ₂ O ₃ 1.3-2.4 SiO ₂ in anhydrous form. Weight,

(b) 1-30 parts by weight of one or more calcium salts of fatty acids having 8-22 carbon atoms,

(c) 1-10 parts by weight of one or more zinc salts of fatty acids having 8-22 carbon atoms,

(d) 4-40 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, having an average of at least one free polyol-hydroxy group per molecule; .

(e) and a stabilizer comprising 2-20 parts by weight of thioglycolic acid ether of polyol having 2-6 hydroxyl groups and or thioglycolic acid ester of monofunctional alcohol having 8-22 carbon atoms.

Materials made from a polyvinyl chloride based collection compound stabilized according to the invention are another aspect of the invention.

Synthetic crystalline sodium aluminosilicates as defined above are prideful zeolites of NaA type with an average actual pit diameter of 4A and are called zeolite 4A. Such sodium aluminosilicates can be prepared by known methods.

Aluminosilicates produced as a precipitate and present in the form of finely dispersed suspensions can be converted from the amorphous form to the crystalline state by heating from 50 ° to 200 ° C. These crystalline sodium aluminosilicates are then separated from the remaining aqueous solution by filtration and dried at 50 ° -200 ° C. until the water content reaches 13-25% by weight.

As used herein, the crystal product prepared according to US Pat. No. 458,306 has a particle size in the range of 0.1-50 mu. Sodium aluminosilicate with a size of 0.1-20 μ is preferentially used to carry out the process according to the invention. The calcium binding capacity of sodium aluminosilicates, measured at 22 ° C., is at least 50 mgCaO per gram of anhydrous substance and may reach 200 mg CaO. Usually this calcium binding capacity is in the range of 100-200mg CaO per gram of active substance and normally in the range of 150mg CaO / g or more.

Sodium aluminosilicates with curved corners and edges can also be used in the preferred embodiment of the process according to the invention. The preparation of such zeolites starts with group 1 having the following range of molecular compositions.

2.5-6.0 Na ₂ O. A1 ₂ O ₃ . 0.5-5.0 SiO ₂ . 60-200 H ₂ O

This product is crystallized in a conventional manner. Heat at least 1/2 hour with stirring at 70 ° -1200C, preferentially 80-95 ° C. The crystal product is extracted in a simple manner by separating the liquid phase. It is also advisable to rinse the product again with water and to dry it before use if desired.

Sodium aluminosilicates of small sized particles precipitated in the presence of water-soluble, inorganic or organic dispersants and insoluble in crystallized water can also be used in the process according to the invention. These can be obtained by technically simple methods. Suitable water soluble dispersants include tensides, non-surfactant aromatic sulfonic acids, and compounds capable of forming calcium complex compounds. The dispersant may be added to the reaction mixture in a desired manner prior to or during precipitation, in solution form or they may be dissolved in the aluminate solution and the silicate solution. In particular, satisfactory results were obtained when the dispersant was dissolved in the silicate solution. The amount of dispersant used should be at least 0.05% by weight, usually 0.1-5% by weight, based on the total amount of precipitation obtained. The precipitate product is determined by heating at a temperature of 50 ° -200 ° C. for 1 / 2-24 hours. Suitable dispersants include sodium laurylether sulfate, sodium polyacrylate, and sodium salts of 1-hydroxy-ethane-1,1-diphosphate.

NaA type sodium aluminosilicate suitable for carrying out the process of the present invention contains about 13-25% by weight of crystalline water. More preferred is a product having a water content of 18-25% by weight.

The calcium and zinc salts of fatty acids used in the process according to the invention are generally derived from fatty acids such as caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Popular salts include salts of monofatty acids as well as salts of mixtures of fatty acids such as those obtained from natural fats and natural oils. It is common to use calcium or zinc salts of saturated fatty acids such as palmyric acid and stearic acid.

The polyol partial esters of component (d) are prepared by a known method of esterifying polyols having 2 to 6 carbon atoms and also having 2 to 6 hydroxyl groups having long chain fatty acids having 8 to 22 carbon atoms. In this process, conventional esterification catalysts can be used. To this end, the polyols and fatty acids are reacted in a molar ratio of 1: 1-1: (n-1) (n is the number of hydroxyl groups in the polyol). The amount of reaction combinations used is such that partial esters with an OH number of 140-580, preferentially 170-540, are formed. The reaction product, a mixture of different esters, should contain 15 or less acids, preferably 8 or less.

Examples of suitable polyol components include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl Glycols, glycerol, trimethylolethane, trimethylpropane, pentaerythritol, erythritol, mannitol, and sorbitol. Particularly important polyol components are the number of hydroxyl groups of 3-6, generally 3 or 4. In the case of the present invention, it is advantageous to use glycerol or pentaerythritol. Suitable fatty acid components include caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Synthetic fatty acids having a chain of the aforementioned length, such as mineral acids, unsaturated acids such as oleic acid and linolenic acids, and saturated fatty acids, in particular 12-hydroxystearic acid, may also be used. Indeed, mixtures of natural fats and fatty acids from natural oils are most frequently used. Component (d) also constitutes a mixture of the aforementioned partial esters. Particularly preferred compounds of component (d) comprise polyols having 3-6 hydroxyl groups, preferentially 3 or 4 hydroxyl groups, partial esters of the fatty acids already mentioned which have an average of 2-3 free hydroxyl groups. Have

Suitable materials as component (e) include thioglycolic acid esters of aliphatic polyols having 2-6 hydroxyl groups in one embodiment of the invention. Carbon number of these polyols is 2-36 and patent 2-18. Examples of polyols having 2 to 6 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexane Diol, neopentylglycol, glycerol, trimethyloletane, trimethylolpropane, pentaerythritol, mannitol, and sorbitol.

Polyols with 8-18 carbon atoms are also suitable. Suitable polyols in one embodiment of the present invention have been found to be those having 2-4 hydroxyl groups, in particular ethylene glycol, glycerin, and pentaerythritol. Α, ω-alkanediols having 8-18 carbon atoms, i.e., 1,10-decanediol, 1,12-dodecanediol, and 1,18-octadecanediols, are also suitable polyols. In addition, suitable compound groups include diols and polyols obtained by hydration of long chain epoxy alkanes. These diols and polyols contain adjacent hydroxyl groups at the terminal or non-terminal positions. Among these groups are compounds having 8-18 carbon atoms, namely 1,2-octanediol, 1,2-decanediol, 1,2-tetradecanediol, 1,2-octadecanediol, and C ₁₁ -C ₁₄ , Mixtures of adjacent alkanediols with OH groups distributed irregularly at non-terminal positions having carbon chain lengths in the range of C _{14 to} C ₁₆ and C _{15 to} C ₁₈ or carbon chain lengths of C _{12 to} C ₁₄ are preferred. Such suitable thioglycolic acid esters can be obtained by reacting the polyol of the above-mentioned form with thioglycolic acid in a molar ratio of 1: 1: 1-1: n in a conventional manner. Where n represents the number of hydroxyl groups of the polyol. All hydroxyl groups of the polyol can be esterified with thioglycolic acid. According to the present invention, however, thioglycolic acid esters constituting at most three thioglycolic acid groups are used, preferably esters constituting at most 1-2 thioglycolic acid groups per molecule. When thioglycolates of monofunctional alcohols are used in component (e), the alcohol components of these esters consist of fatty acids, linear or branched, primary, secondary or tertiary alcohols having 8 to 22 carbon atoms. . Examples of possible alcohol components are n-octanol, n-dodecanol, n-hexadecanol, n-octadecanol, and in particular 2-ethylhexanols and paid alkanols.

In the simplest case, component (e) consists of a polyol thioglycolic acid ester or thioglycolic acid ester of a monofunctional alcohol. However, double and triple combinations of these substance groups can also be used.

In a preferred embodiment of the present invention, a pentaerythritol partial ester of a fatty acid having 8 to 22 carbon atoms as a component (d) is contained in a polyvinyl chloride-based casting compound, and the molar ratio of pentaerythritol to fatty acid is 1: 1-1: 2. As the component (e), a thioglycolic acid ester of a monofunctional alcohol having 8 to 18 carbon atoms, a monothioglycolic acid ester of an aliphatic diol having 2 to 6 carbon atoms, or glyceryl monothioglycolate is used.

Combination stabilizers used in the process according to the invention can be made new by the addition of common stabilizers or auxiliaries, depending on the use of the stabilized polyvinyl chloride casting mixture. The amount of such additives used is, for example, an amount of 0.1-20 parts by weight per 100 parts by weight of the polyvinyl chloride resin compound.

For the stabilization of the casting mixture for the tube and the like in the extraction method, for example, 0.5-1 parts by weight of paraffin having a freezing point of 50 ° -100 ° C. and free fatty acids having 8-22 carbon atoms are stabilizers for 100 parts by weight of polyvinyl chloride. Suitable fatty acids include those mentioned above, with palmitic acid and stearic acid being preferred.

For example, 0.5-5 parts by weight of epoxidized soybean oil, 0.1-8 parts by weight and polymer ester wax may be used for 100 parts by weight of polyvinyl chloride in the polyvinyl chloride casting mixture for the production of pupillary wire by the extrusion method. Suitable polymeric ester waxes include mineral waxes and paraffin oxides, and in particular,

(i) aliphatic, cycloaliphatic and aromatic dicarboxylic acids having 2 to 22 carbon atoms in the molecule,

(ii) aliphatic polyols having 2-6 hydroxyl groups in the molecule,

(iii) complex esters of aliphatic mono carboxylic acids having 12-30 carbon atoms in the molecule.

Wherein the molecular ratios of components (i), (ii), and (iii) are approximately n: 1: n: nm-2 (n-1), where n is a number up to 2-11 and m is the hydroxyl in the polyol The number of groups. These mixed esters have about 0-15 hydroxyl and acid water. They can be prepared by known methods such as those shown in German Patent No. 1,907,768. Adipic acid and pentaerythritol acid of the said molecular ratio. And complex esters of stearic acid are used preferentially. In this case n is a number from 2-8.

The use of polyvinyl chloride casting mixtures for the production of foils by the rotary calender method involves 0.5-5 parts by weight of epoxidized soybean oil, 0.1-1 parts by weight of the aforementioned polymeric ester waxes, and α-phenyllindol or benzoyl. 0.2-0.5 parts by weight of stearoylmethane is added as a common stabilizer per 100 parts of polyvinyl chloride. When used together with 0.05-0.2 parts by weight of calcium salt and 0.1-0.2 parts by weight of zinc salt, complete stabilization is achieved.

In the general process according to the invention, the following listed per 100 parts by weight of polyvinyl chloride are used in casting mixtures for the production of tubes and foils by extraction.

(a) 1-2 parts by weight of sodium aluminosilicate.

(b) 0.8-1.2 parts by weight of one or more calcium salts of fatty acids.

(c) 0.1-0.4 parts by weight of one or more zinc salts of fatty acids.

(d) 0.3-0.5 parts by weight of pentaerythritol partial ether of fatty acid.

(e) 0.2-0.5 parts by weight of thioglycolatin acid ester.

(f) and 0.5-1 part by weight of paraffins and fatty acids.

The stabilizer mixture according to the invention can be obtained by a simple method of mechanically mixing the components with a common mixer.

The mixtures according to the invention show a good stabilizing effect on polyvinyl chloride and mixtures of polyvinyl chloride and vinyl chloride polymers. The mixed polymers in question are preferred to acrylic esters and vinylidene chloride in addition to vinyl esters such as vinyl acetate. The polymer and mixed polymers can be prepared by known processes such as suspension or zone polymerization. Their K value is between 35-80. Stabilization of such resin mixtures is another concern of the present invention.

The polyvinyl chloride casting mixtures stabilized by the present invention are mainly used for the production of tubes and the like by extrusion method, the production of pupil storage materials, and the production of wound plates.

The process properties of the polyvinyl chloride casting mixtures stabilized using the process according to the invention can be compared well with those of the casting mixtures stabilized with heavy metals. This includes initial color, initial stability, and residual stability of the cast mixtures. Thus, the combination stabilizers according to the process of the present invention are complete replacements for the heavy metal combinations used so far. The process of the present invention shows significant progress in terms of occupational disease.

[Preparation of Appropriate Sodium Aluminosilicates]

The silicate solution was added to the aluminate solution with vigorous stirring in a 15 L vessel. Stirring was performed at a speed of 3000 revolutions per minute with a winged stirrer. The two solutions are at room temperature. As an exothermic reaction, an X-ray amorphous sodium aluminosilicate was produced as a secondary precipitate. After stirring for 10 minutes, the suspension of the precipitate product was transferred to a crystallite and left at 90 ° C. for 6 hours with stirring. The alkaline aqueous solution constituting the mother liquor is drained from the debris and the filter residue is washed with non-ionized water to bring the pH of the washed water to about 10. The washed filter residue was then dried. The product was heated to 80 ° C. for 1 hour to determine the water content. Sodium aluminosilicate was washed and neutralized until pH was about 10 and then ground in a ball mill. The particle size distribution was determined by sedimentation balance method.

Calcium binding capacity, ie complexing capacity, can be determined according to the following calcium binding test.

A 5 L aqueous solution containing 0.594 g of CaCl ₂ (300 mg CaO / L = 30 ° dH) is normalized with dilute NaOH until the pH value is 10 and mixed with 1 g of aluminosilicate. Shake this suspension vigorously at 22 ° C (± 2 ° C) for 15 minutes. The aluminosilicate is filtered off and the hardness X of the filter residue is determined. The calcium binding force is calculated from the number of mg of CaO per gram of aluminosilicate according to the structure of (30-X) x 10 therefrom.

If calcium binding capacity is determined at high temperature, ie 60 ° C, the result is better than that at 22 ° C.

[Production Conditions of Sodium Aluminosilicate A]

Precipitation: 2.985 kg of aluminate solution, 17.7% Na ₂ O, 15.8 Al ₂ O ₃ , 66.6% H ₂ O, 0.15 kg sodium hydroxide, 9.420 kg water, prepared in immediate soluble silicic acid and sodium silicate 2.445 kg of sodium silicate solution, 25.8% with a composition of 1Na ₂ O, 6.0 SiO ₂ .

Crystallization: 6 hours at 90 ° C.

Drying: 24 hours at 100 ° C.

Composition: 0.9Na ₂ O. 1Al ₂ O ₃ . 2.04 SiO ₂ . 4.3H ₂ O (= 21.6% H ₂ O).

Crystallinity: Complete crystal.

Calcium binding capacity: 170mg CaO per 1g active substance.

The particle size distribution by sedimentation analysis is in the range of 3-6μ curve. The interference line of the X-ray diffractogram of sodium aluminosilicate A is as follows.

D value taken with C ₁₁ -Kα radiation, Å, I,-, 12.4,-, 8.6, 7.0. -, 4.1 (+),-, 3.68 (+), 3.38 (+), 3.26 (+), 2.96 (+),-,-, 2.73 (+),-, 2.60 (+).

It is possible that all these interfering lines will not appear in the X-ray diffractogram, especially if the aluminosilicates are not fully crystallized. Therefore, the most important d values that characterize these forms are marked with (+).

Preparation Conditions of Sodium Aluminosilicate B.

Precipitation: 13.2% Na ₂ O 8.0% Al ₂ O ₃ Aluminate solution with a composition of 78.8% H ₂ O 7.63kg, 8.0% Na ₂ O, 26.9% SiO ₂ , 65.1% Sodium silicate solution with a composition of H ₂ O 2.37.

Molding ratio: 3.24 Na ₂ O: 1.0 Al ₂ O ₃ : 1.78 SiO ₂ : 70.3 H ₂ O.

Crystallization: 6 hours at 90 ℃.

Drying: 24 hours at 100 ° C.

Composition of dry product: 0.99 Na ₂ O, 1.00 Al ₂ O ₃ , 1.83 SiO ₂ , 4.0 H ₂ O (= 20.9% H ₂ O).

Crystal Form: Square with corners and corners before bending.

Average particle diameter: 5.4 μ.

Calcium binding capacity: 172mg CaO per 1g active substance.

Preparation Conditions of Sodium Aluminosilicate C

Precipitation: 14.5% Na ₂ O: 5.4% Al ₂ O ₃ : 80.1% H ₂ O aluminate solution 12.15 kg, 8.0% Na ₂ O: 26.9% SiO ₂ : 65.1% Sodium with H ₂ O 2.37 kg of silicate solution.

Production molar ratio: 5.0 Na ₂ O: 1.0 Al ₂ O: 2.0 SiO ₂ : 100 H ₂ O.

Crystallization: 1 hour at 90 ℃.

Drying: The content of solids in the heated grinding suspension of the product (pH 10) suspension washed at 295 ° C .: 46%.

Preparation Conditions of Sodium Aluminosilicate C

Composition of dry product: 0.96 Na ₂ O. 1 A1 ₂ O ₃ . 1.96 SiO ₂ . 4 H ₂ O

Crystal form: square with curved corners and edges.

Moisture content: 20.5%.

Average site diameter: 5.4μ.

Calcium binding capacity: 172mg CaO per 1g active substance.

In Examples 1-3 below, the effect of the combination stabilizer was tested with the static thermal stability of the wound foil. For this purpose, the polyvinyl chloride casting mixture containing the stabilizer mixture was made into test foil under the experimental rate at 450 × 220 mm standard with the rotation speed of the roller at 12.5 rpm and the temperature of 170 ° C. over 5 minutes. The thickness was 0.5 mm. This was cut into a square test sample having a corner of 10 mm and left at a temperature of 180 ° C. in a drying chamber equipped with six rotary blades. Samples were taken out at 15-minute intervals and examined for color change.

Example 1

The polyvinyl chloride casting mixture of A-F (the composition thereof is shown in Table 1) was tested by the above method.

Composition A is a PVC cast mixture stabilized according to the invention, which is particularly suitable for making tubes or piles by extrusion. The composition of B-F is a cast mixture according to structure A, but with any of its components removed or substituted.

TABLE 1

1: Synthetic zeolite NaA: Na ₂ O: Al ₂ O ₃ : SiO ₂ = 0.9: 1: 2.04, water content: 21.6 wt%, maximum particle size: 3-6μ.

2: molar ratio pentaerythritol: stearic acid 1: 1.5: OH number 212 The determined static thermal stability values are shown in the following table.

TABLE 2

Example 2

Polyvinyl chloride casting mixture G-L (the composition thereof is shown in Table 3) was tested by the above method.

Composition G is a polyvinyl chloride casting mixture stabilized by the process of the present invention, which is suitable for the production of packaging materials and bottles by extrusion.

The cast mixes to be compared are marked with H-L, which is consistent with structure G except for the exception of any of the components being removed or substituted.

TABLE 3

1. Synthetic zeolite NaA: Na ₂ O: Al ₂ O ₃ : SiO ₂ = 0.9: 1: 2.04 Moisture content: 21.6% by weight, maximum particle size: 3-6μ.

2. molar ratio pentaerythritol: stearic acid 1: 1.5; OH number 212.

3. Number of epoxides 6.3.

4. adipic acid; Pentahenititol: stearate molar ratio 6: 7: 16, OH number; About 2, acid number; About 10.

The static heat stability values measured in this test are summarized in Table 4.

TABLE 4

Example 3

PVC casting mixtures have the following composition:

100 parts by weight of the PVC suspension (K is 60), 0.75 parts by weight of calcium stearate, 0.25 parts by weight of zinc stearate, 0.3 parts by weight of pentaerythritol stearate (molar ratio of pentaerythritol to stearic acid = 1: 1.5 OH number =). 212) 0.3 parts by weight of 2-ethylhexyl thioglycolate, and 0.75 parts by weight of paraffin having a melting point of 70 ° C., the NS mixture is added to the casting mixture of structure M by 1 part by weight of the following zeolite ns per 100 parts by weight of polyvinyl chloride. It was prepared by.

(n) synthesized inert Na-zeolites of type NaA; Na ₂ O: Al ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83, Moisture content: 20.9 wt%, Maximum particle diameter: 5.4μ.

(o) synthesized inert Na-zeolites of the NaX type; Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 1: 1: 2.4-2.6;

(p) synthesized inert Na-zeolites of the NaY type; Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 1: 1: 4.3;

(q) synthesized inactive K-zeolites of type KA; K ₂ O: A1 ₂ O ₃ : SiO ₂ = 1: 1: 2;

(r) Synthesized inert Ca-zeolites of the CaA type (prepared from (n) by ion exchange with calcium chloride).

(s) synthesized inactive aluminosilicates; Na ₂ O: Al ₂ O ₃ : SiO ₂ = 1: 1: 2.

Casting mixture N was stabilized by the process according to the invention. Casting mixtures M and 0-Q are comparative mixtures obtained by the removal or substitution of sodium aluminosilicate (n).

The cast mixture M-S was tested for its static thermal stability by the method mentioned above. The results are summarized in the following table.

TABLE 5

Example 4

Using a quick mixer, 100 parts by weight of the PVC (65 K) suspension was mixed with 4.65 parts by weight of the stabilizer mixture having the following composition and placed in the casting mixture.

(a) 20 parts by weight of the synthesized inert Na-zeolite (NaA type): Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83; Moisture Content: 20.9%

(b) 10 parts by weight of calcium stearate.

(c) 3 parts by weight of zinc stearate.

(d) 3 parts by weight of pentaerythritol stearic acid partial ester (molar ratio = 1: 1.5, OH number = 212).

(e) 3 parts by weight of 2-ethylhexyl thioglycolate.

(f) 7.5 parts by weight of paraffin having a melting point of 71 ° C.

An industrial double reduction gear extruder was used to treat the casting mixture. Technical data on the extruder is as follows:

Worm gear diameter: 55 / 110mm Array: Cone / consumption

Actual length: 1050mm Direction of rotation: opposite type, diverging upward

The following conditions were applied to the fabrication of a PVC tube with a wall thickness of 5.3 mm and an outer diameter of 110 mm.

Cylinder: 185/170/135 ℃ Core: 140 ℃

Raw material: 140 ℃ Motor speed: 2,000rpm

Head: 190/190 ℃ Worm Gear Speed: 35rpm

Jet: 200 ℃ Motor Load: 42-45%

Cone: 190 ℃ Fully filled worm gear: 157kg / hr

Example 5

Combinations of age agents were made from the following ingredients.

(a) 10 parts by weight of synthesized inactive NaA type Na-zeolite, Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 0.99: 1: 1: 1.83; Moisture content: 20.8 weight;

(b) 2 parts by weight of calcium stearate;

(c) 4 parts by weight of zinc octoate;

(d) 20 parts by weight pentaerythritol stearate (molar ratio = 1: 1.5; OH number = 212);

(e) 4 parts by weight of 2-ethylhexyl thioglycolate;

(f) 10 parts by weight of adipic acid / pentatritritol stearate (molar ratio = 6: 7: 16, OH number = about 2, acid number = about 10);

And

(g) 80 parts by weight of epoxidized soybean oil (epoxide number = 6.3).

92 parts by weight of PVC (K value = 60) suspension, 8 parts by weight of methacrylate-butadiene-styrene resin, and 7 parts by weight of the combination stabilizer were mixed in a fast mixer until a dry mix composition was obtained. With this, a bottle having a capacity of about 290 ml was prepared using a conventional extrusion apparatus.

Under certain operating conditions, this PVC casting blend produced bottles with excellent permeability, smooth and glossy surfaces, and high hardness.

Example 6

A combination stabilizer having the following composition was made.

(a) 10 parts by weight of synthesized inert NaA zeolite of NaA; Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 0.99: 1: 11.83; Moisture Content: 20.9 wt%

(b) 6 parts by weight of calcium stearate;

(c) 5 parts by weight of zinc stearate;

(d) 24 parts by weight of pentaerythritol stearate (molar ratio = 1: 1.5);

(e) 6 parts by weight of 2-ethylhexyl teroglycolate;

(f) 10 parts by weight of adipic acid / pentaerythritol stearate; (Molar ratio = 6: 7: 16, OH number = about 2, acid number = about 10)

(g) 3 parts by weight of α-phenylindole: and

(h) 40 parts by weight of epoxidized soybean oil (epoxide number = 6.3)

100 parts by weight of the PVC (K value 60) suspension and 7.35 parts by weight of the combination stabilizer were mixed with the casting mixture in a fast mixer. The cast mixture was plasticized under a condition of a roller of 450 × 200mm, roller temperature was 170 ℃, and roller speed was 12.5rpm. This gourd had a smooth, glossy surface.

Example 7

A cast mixture was prepared from 100 parts by weight of PVC (65 K) suspension and 4.65 parts by weight of a stabilizer mixture having the following composition in a fast mixer.

(a) 20 parts by weight of synthesized NaA inert Na-zeolite: Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 0.99: 1: 1: 1.83; Moisture content = 20.9 wt%;

(b) 10 parts by weight of calcium stearate,

(c) 3 parts by weight of zinc stearate,

(d) glyceryl stearic acid partial ester (molar ratio = 1: 1.5) 2 parts by weight,

(e) 1 part by weight of trimethylol propane,

(f) 3 parts by weight of ethylene glycol monothioglycolate, and

(g) 7.5 parts by weight of paraffin having a melting point of 71 ° C.

In order to process the casting mixture, the industry used a dual reduction worm gear extruder.

Worm gear diameter: 55 / 110mm, actual length: 1050mm, arrangement: cone / consumption, direction of rotation: opposite, top divergence type,

Wall thickness: The following conditions were applied to the manufacture of PVC tubes with a thickness of 5.3mm and 110mm.

Cylinder: 185/170/135 ℃ Core: 140 ℃

Raw material: 140 ℃ Motor speed: 2,000rpm

Head: 190/190 ℃ Worm Gear Speed: 35rpm

Jet: 200 ℃ Motor Load: 42-45%

Cone: 190 ℃ Fully filled worm gear: 157kg / hr

A white-caramel colored tube was obtained.

Example 8

A combination tablet having the following composition was prepared.

(a) inert Na-zeolites of synthesized NaA type; Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83; Moisture content: 20.9%.

(b) 2 parts by weight of calcium stearate.

(c) 4 parts by weight of zinc octoate,

(d) 20 parts by weight of glyceryl di-12-hydroxystearate,

(e) 4 parts by weight of 1, 10-decanediol dithioglycolate,

(f) 10 parts by weight of adipic acid / pentaerythritol stearate (molar ratio 6: 7: 16, number = about 2, acid number = about 10), and

(g) 80 parts by weight of epoxidized soybean oil (6.3 number of epoxides)

92 parts by weight of the PVC (K value 60) suspension, 8 parts by weight of the methacrylate-butadiene-styrene resin, and 7 parts by weight of the combination stabilizer were mixed to obtain dry mix in a fast mixer. Using this, a bottle having a capacity of 290 ml was manufactured by an industrial extrusion device. Under certain operating conditions, the gauze bottle was produced with excellent permeability, smooth and glossy surface and strong hardness in this PVC-mainly mixture.

Example 9

A combination stabilizer having the following composition was prepared.

(a) 10 parts by weight of synthesized NaA inert Na-zeolite; Na ₂ O: A1 ₂ O ₃ : SiO ₂ = 0.99: 1: 1.83; Moisture content: 20.9 wt%.

(b) 6 parts by weight of calcium stearate,

(c) 5 parts by weight of zinc stearate,

(d) 24 parts by weight of trimethylolpropane laurate (molar ratio 1: 1.5),

(e) 6 parts by weight of n-octadecyl thioglycolate,

(f) 10 parts by weight of adipic acid / pentaerythritol stearate (molar ratio; 6: 7: 16, OH number; about 2, acid number; about 10),

(g) 3 parts by weight of 2-phenylindole, and

(h) 40 parts by weight of epoxidized soybean oil (number of epoxides 6.3)

100 parts by weight of the PVC (K value 60) suspension and 7.35 parts by weight of the combination stabilizer were mixed with the cast mixture. The casting mixture was plasticized under a test roller of 450 × 220 standard at a temperature of 170 ° C. and a roller speed of 12.5 rpm, and wound around 0.5 mm thick.

The surface of this foil was smooth and glossy.

Claims (1)

4-100 parts by weight of anhydrous synthetic crystalline sodium aluminosilicate containing 13-25% by weight of water of crystallization and having the following structure of small sized particles 0.7-1.1 Na ₂ O. Al ₂ O ₃ 1.3- 2.4 SiO ₂ , 1-30 parts by weight of one or more calcium salts of fatty acids having 8-22 carbon atoms, 1-10 parts by weight of one or more zinc in fatty phase having 8-22 carbon atoms, 2-6 hydroxyl groups and carbon atoms Thioglycolic acid esters of polyols having 2-6 and 4-40 parts by weight of partial esters having at least one free polyol-hydroxyl group per molecule of fatty acids having 8-22 carbon atoms, and polyols having 2-6 hydroxyl groups And or 2-20 parts by weight of a thioglycolic acid ester of a monofunctional alcohol having 8-22 carbon atoms.