DE3720590A1 - STABILIZED POLYMER COMPOSITIONS - Google Patents

Abstract

Unplasticized halogen-containing polymer compositions comprise: a) 100 parts of an unplasticized, chlorine-containing thermoplastic, b) 0.7-2 parts of thiodiethylene glycol bisacetoacetate of the formula (H3CCOCH2COOCH2CH2)2S, c) 0-0.5 part of a Ca, Ba and/or Mg salt of an aliphatic C8-C24-monocarboxylic acid or C8-C24-hydroxymonocarboxylic acid or of benzoic acid or tert.-butylbenzoic acid, d) 0.01-0.2 part of a Zn salt of an aliphatic C8-C24-monocarboxylic acid or C8-C24-hydroxymonocarboxylic acid, or of benzoic acid or tert.-butylbenzoic acid, and e) 3-10 parts of epoxidized unsaturated fatty acid esters. These compositions can be employed for the preparation of PVC sheeting for food packaging and PVC bottles.

Description

The present invention relates to stabilized compositions from plasticizer-free chlorine-containing thermoplastics, the thiodiethylene glycol bis- acetoacetate, epoxidized unsaturated fatty acid esters, a Zn carboxylate and optionally a Ca, Ba or / and Mg carboxylate included as stabilizers.

From US-A-43 27 000 stabilizer mixtures of β-ketocarboxylic acid esters of di- and polyols with thioether structure and metal-containing stabilizers, for. B. Ca and Zn carboxylates known. These mixtures show a good stabilizing effect in chlorine-containing thermoplastics, e.g. B. in PVC and PVC containing polymers. As an example of the β-ketocarboxylic acid esters mentioned, it is described, among others, as thiodiethylene glycol bis-acetoacetate. Despite the intrinsically interesting properties of the stabilizers described in US Pat. No. 4,327,000, the latter have not hitherto been commercialized, since their effect has not yet been sufficient for practical purposes. In particular, the polymers stabilized with it yellowed a little too much, especially under prolonged thermal stress. In addition, the transparency of the articles produced using the stabilized polymers left something to be desired. These findings also apply to the two stabilizer mixtures specifically described in application examples A and B of US-A-43 27 000, especially also with regard to the initial color and color retention. Similar compositions are also known from JP-A-54-11 948, which however additionally contain free aromatic carboxylic acids.

It has now been found that the properties of stabilizer mixtures, the ingredients described in US-A-43 27 000 included, can be improved so that they are for a large-scale use come into question, and surprisingly in that a very specific β-ketocarboxylic acid ester Zn and optionally Ca, Ba or / and Mg carboxylate primary stabilizers in very specific concentrations and mixing ratios is combined.

The present invention relates to stabilized polymer compositions, the

• a) 100 parts of a plasticizer-free chlorine-containing thermoplastic,
• b) 0.7-2 parts of thiodiethylene glycol bis-acetoacetate of the formula (H ₃ CCOCH ₂ COOCH ₂ CH ₂ ) ₂ S,
• c) 0-0.5 parts of a Ca, Ba or / and Mg salt of an aliphatic C ₈ -C ₂₄ monocarboxylic acid or hydroxymonocarboxylic acid or benzoic acid or tert-butylbenzoic acid,
• d) 0.01-0.2 parts of a Zn salt of an aliphatic C ₈ -C ₂₄ monocarboxylic acid or hydroxymonocarboxylic acid or benzoic acid or tert-butylbenzoic acid, and
• e) 3-10 parts of epoxidized unsaturated fatty acid esters

contain.

Thiodiethylene glycol bis-acetoacetate (component b) is preferred in an amount of 0.8-1.5 parts, especially about 1 part.

Component c) is preferably in a concentration of 0-0.4, e.g. B. 0-0.35 parts available. The preferred ones contain Compositions a component c) (concentration ≦ λτ0). The Component c) is then z. B. in an amount of 0.001-0.5, preferably 0.01-0.5, especially 0.05-0.4, especially 0.1-0.35 parts available.  

Component c) is a Ca, Ba or Mg salt or a mixture of such salts, preferably a Ca or Mg, in particular a Ca salt, an aliphatic C ₈ -C ₂₄ monocarboxylic acid or hydroxymonocarboxylic acid or Benzoic acid or tert-butylbenzoic acid.

The aliphatic monocarboxylic acids or hydroxycarboxylic acids are saturated or unsaturated and in particular have 8-22 carbon atoms. As hydroxycarboxylic acid, especially hydroxystearic acid, e.g. B. 12-hydroxystearic acid. Of the monocarboxylic acids are 2-ethylhexanoic, lauric, stearic and behenic acids preferred. Prefers component c) is Ca, Ba or / and Mg, preferably Ca or / and Mg, in particular Ca octoate (salt of 2-ethylhexanoic acid), Laurate, stearate or behenate. Of course, too Mixtures of salts of different acids can be used.

Component d) is preferably contained in an amount of 0.05-0.2, in particular 0.1-0.2 parts. It is the Zn salt of an aliphatic C ₈ -C ₂₄ monocarboxylic acid or hydroxycarboxylic acid or of benzoic acid or tert-butylbenzoic acid. The aliphatic monocarboxylic acids or hydroxycarboxylic acids are saturated or unsaturated and in particular have 8-22 carbon atoms. As hydroxycarboxylic acid, especially hydroxystearic acid, e.g. B. 12-hydroxystearic acid to name. Of the monocarboxylic acids, 2-ethylhexanoic acid, lauric acid, stearic acid and behenic acid are preferred. Preferred component d) is Zn octoate (salt of 2-ethylhexanoic acid), basic Zn octoate, Zn stearate, laurate, behenate or benzoate, in particular Zn octoate, basic Zn octoate, Zn stearate or Zn -Benzoat, used. Zn stearate is particularly preferably used in an amount of about 0.2 part, Zn octoate of about 0.1 part and basic Zn octoate of about 0.05 part.

Component e) is preferably epoxidized soybean oil. These Component is especially in an amount of 4-7, especially about 5 parts, before.  

In the case of the stabilized, plasticizer-free chlorine-containing thermoplastic polymers (component a) especially to vinyl chloride homopolymers, copolymers of Vinyl chloride with unsaturated comonomers, mixtures of the above Polymers with each other or mixtures of the polymers mentioned with other copolymers. The preferably according to the invention Polymers that can be used as component a) can also be used as rigid PVC be designated.

Of the vinyl chloride homopolymers and copolymers, especially suspension and bulk polymers and emulsion polymers to mention. As Comonomers for the copolymers come, for. B. in question: Vinyl acetate, vinylidene chloride, transdichlorethylene, ethylene, Propylene, butylene, maleic acid, acrylic acid, fumaric acid, itaconic acid. Other suitable chlorine-containing polymers are post-chlorinated PVC and chlorinated polyolefins, also graft polymers of PVC with ABS, EVA and MBS.

Compositions according to the invention which additionally contain an impact modifier are to be mentioned, in particular in an amount of up to 15, for example from 0.1-15, preferably from 1 to 15, in particular 3-10, for. B. 6-8 parts. Examples of such modifiers are copolymers of esters of methacrylic acid and / or acrylic acid (in particular of monohydric aliphatic C ₁ -C ₁₈ alcohols) with butadiene and styrene. These copolymers are generally referred to as ABS and MBS.

The compositions according to the invention can also be used for chlorine-containing thermoplastics contain the usual stabilizers. So for example, they contain 0-1.5 parts, especially 0-1 parts one or more phosphites. Such phosphites can be found in one Amount of 0.01-1.5, especially 0.01-1, preferably 0.1-0.6, e.g. B. 0.2-0.5 parts may be included. Examples of such phosphites are those of the formulas

wherein R ¹ , R ² and R ^{3 are the} same or different and are C ₆ -C ₁₈ alkyl, C ₆ -C ₁₈ alkenyl, a substituted or unsubstituted phenyl radical or C ₅ -C ₇ cycloalkyl.

R ¹ , R ² and R ^{3 are} C ₆ -C ₁₈ alkyl, it is, for. B. n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. Alkyl groups with 8 to 18 carbon atoms are preferred.

As substituted phenyl, R ¹ , R ² and R ³ mean, for example, tolyl, ethylphenyl, xylyl, cumyl, cymyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl, pn-octylphenyl, pn-nonylphenyl or pn-dodecylphenyl .

Particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, Tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, Tris-p-nonylphenyl or tricyclohexyl phosphite and especially aryl-dialkyl and alkyl-diaryl phosphites are preferred, such as B. phenyldidecyl-, (2,4-di-tert-butylphenyl) -di-dodecylphosphite, (2,6-di-tert-butylphenyl) di-dodecyl phosphite and the dialkyl and diaryl-pentaerythritol diphosphites such as distearylpentaerythritol diphosphite.

Preferred organic phosphites are distearyl pentaerythritol diphosphite, Trisnonylphenyl phosphite and phenyl didecyl phosphite.

Furthermore, further compositions can be used in the compositions according to the invention known costabilizers may be included, for example 0-2, especially 0-1.5 parts. They are then preferably in a lot from 0.01-2, especially 0.05-1.5, e.g. B. 0.1-1, especially 0.1-0.5 parts available. As such costabilizers  Aminocrotonic acid esters, dehydroacetic acid, 1,3-diketo compounds, 2,4-dihydroxybenzophenone, 2,4-dihydroxy-4'-tert-butylbenzophenone and called pyrrole derivatives, the latter being preferred.

Particularly suitable aminocrotonic acid esters are the esters with monovalent straight-chain C ₈ -C ₂₀ , in particular C ₁₂ -C ₁₈ alcohols and / or with 1,3- or 1,4-butanediol and / or 1,2-dipropylene glycol and / or Thiodiethylene glycol into consideration.

1,3-Diketo compounds which can be used as costabilizers are in particular those described in DE-B 26 00 516 and EP-A 35 268 are described, e.g. B. those of the in the claim DE-B 26 00 516 given formula. Preferred 1,3-diketo compounds are benzoylstearoylmethane, 2-benzoylacetoacetic acid alkyl (e.g. ethyl) esters and triacylmethanes.

As pyrrole costabilizers, special mention should be made of those in EP-A 22 087 and GB-A 20 78 761 are described, e.g. B. the Formula I given there, preferably those pyrrole derivatives which are in Claims 2-9 of EP-A 22 087 are defined. As an an example be called 2-methyl-3-cyclohexyloxycarbonyl-4-phenyl-1H-pyrrole.

In addition to the the aforementioned optional costabilizers or other Place additional optional components, e.g. B. Organotin stabilizers, such as. B. butylthiostannonic acid, mono- [n-octyl] tin tris [isooctyl thioglycolate], di-n-octyl tin-bis- [isooctyl thioglycolate], di-butyltin sulfide, di-butyltin thioglycolate or mono [butyl] tin sulfide and mono [methyl] tin tris [alkyl thioglycolate], mono- [n-butyl] tin tris [alkyl thioglycolate], Mono- [carb-n-butoxy-ethyl] tin tris [alkyl thioglycolate], Bis- [methyl] tin-bis- [alkyl thioglycolate], bis- (n-butyl) - tin bis [alkyl thioglycolate], bis [carb-n-butoxyethyl] tin bis [alkyl thioglycolate], mono [methyl] tin tris [alkyl thiopropionate], Mono [n-butyl] tin tris [alkyl thiopropionate], mono [carb-n-butoxy-ethyl] tin tris [alkyl thiopropionate], bis [methyl] -  tin bis [alkyl thiopropionate], bis [n-butyl] tin bis [alkyl] thiopropionate], bis- [carb-n-butoxyethyl] tin-bis- [alkyl thiopropionate], where alkyl, for example 2-ethylhexyl, dodecyl, Means tridecyl or tetradecyl, and also organotin carboxylates, in particular maleinates or half-ester maleinates, or mixtures of the the aforementioned organotin stabilizers, or organic antimony compounds, like antimony tris [isooctyl thioglycolate] (Isooctyl = 2-ethylhexyl).

Furthermore, the compositions according to the invention can be customary Contain antioxidants. Examples include:

1.1. Alkylated monophenols, e.g. B. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) - 4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol.

1.2. Alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis- (6-tert.- butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio- bis- (6-tert.butyl-3-methylphenol), 4,4'-thio-bis- (6-tert.butyl-2- methylphenol).

1.4. Alkylidene bisphenols, e.g. B. 2,2'-methylene-bis- (6-tert.butyl-4- methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis- [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'- Methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (6- nonyl-4-methylphenol), 2,2'-methylene-bis- (4,6-di-tert.butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert.butylphenol), 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2′-methylene-bis- [6- (α-methylbenzyl) - 4-nonylphenol], 2,2'-methylene-bis- [6- (α, α-dimethylbenzyl) -  4-nonylphenol], 4,4'-methylene-bis- (2,6-di-tert.butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis- (5-tert.- butyl-4-hydroxy-2-methylphenyl) butane, 2,6-di- (3-tert.butyl-5-methyl- 2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-tert.butyl-4- hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2- methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis- [3,3-bis- (3'-tert.butyl-4'-hydroxyphenyl) butyrate], di- (3-tert.butyl-4- hydroxy-5-methylphenyl) dicyclopentadiene, di- [2- (3'-tert.butyl-2'- hydroxy-5'-methyl-benzyl) -6-tert-butyl-4-methyl-phenyl] terephthalate.

1.5 benzyl compounds, e.g. B. 1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) - 2,4,6-trimethylbenzene, di- (3,5-di-tert-butyl-4-hydroxybenzyl) - sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester, bis- (4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl) - dithiol terephthalate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) - isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) - isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, calcium salt.

1.6. Acylaminophenols, e.g. B. 4-hydroxy lauric anilide, 4-hydroxy stearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-di-tert.butyl-4- hydroxyanilino) -s-triazine, N- (3,5-di-tert-butyl-4-hydroxyphenyl) - carbamic acid octyl ester.

1.7. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as. B. with methanol, Octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate, di-hydroxyethyl oxalic acid diamide.  

1.8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such as. B. with methanol, Octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate, di-hydroxyethyl-oxyalsiamide.

1.9. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as B. N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - trimethylene diamine, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hydrazine.

Depending on the intended use, the compositions according to the invention can also incorporated other common additives be such. B. lubricants (e.g. montan waxes or glycerol esters), Fatty acid esters, paraffins, fillers, soot, asbestos, kaolin, talc, Glass fibers, optical brighteners, pigments, light stabilizers, UV absorbers, flame retardants and / or antistatic agents, in particular Lubricants, pigments, processing aids, fillers, antioxidants and / or light stabilizers.

The compositions according to the invention preferably contain no free aromatic carboxylic acids, especially not those as described in JP-A-54-11 948 as component (d).

The compositions according to the invention can be according to the Common shaping processes, e.g. B. by extrusion, injection molding or calendering into molded parts. Also the Use as plastisols is possible. From this are preferred PVC films for food packaging and PVC bottles.

The following examples serve to further explain the Invention. Parts and percent relate to it as well as in the remaining description and in the claims to the weight, unless otherwise stated.  

Examples 1-5:

The PVC compositions given in Table 1 by dry mixing the individual components produced.

Table 1

Each 68 g of the compositions of Examples 1 and 2 are in a Brabender plastograph and 40 revolutions per minute and a kneader temperature of 180 ° C processed. Every 5 minutes a sample was taken and pressed into a plate 5 mm thick. The discoloration of the samples is determined by measuring the optical Remission according to the standard method ASTM D 1925-70, Yellowness Index of Plastics. Yellowness Index (YI) values obtained are given in Table 2. The compositions of Examples 3 to 5 are processed into plates in the same way.  

Examples 6-14:

The given in Table 3 PVC compositions are made by dry mixing the Individual components manufactured.  

Table 3

The compositions given in Examples 6-10 are based on rolled in a mixing mill for 5 minutes at 180 ° C. From the educated 0.3 mm thick rolled skin is used to test film samples in a test oven 180 ° C thermally stressed. Before treatment in the test oven (0 minutes) and after 10, 20 and 30 minutes the test samples will be the Yellowness index (YI) determined according to ASTM D 1925-70. The received Results are shown in Table 4.

Table 4

The compositions of Examples 11-14 are made analogously on a Mixing mill processed into foils.

Claims (16)

1. Stabilized polymer composition containing

• a) 100 parts of a plasticizer-free chlorine-containing thermoplastic,
• b) 0.7-2 parts of thiodiethylene glycol bis-acetoacetate of the formula (H ₃ CCOCH ₂ COOCH ₂ CH ₂ ) ₂ S,
• c) 0-0.5 parts of a Ca, Ba or / and Mg salt of an aliphatic C ₈ -C ₂₄ monocarboxylic acid or hydroxymonocarboxylic acid or benzoic acid or tert-butylbenzoic acid
• d) 0.01-0.2 parts of a Zn salt of an aliphatic C ₈ -C ₂₄ monocarboxylic acid or hydroxymonocarboxylic acid or benzoic acid or tert-butylbenzoic acid, and
• e) 3-10 parts of epoxidized unsaturated fatty acid esters.

2. The composition of claim 1, wherein component c) Ca or / and Mg salt. 3. The composition of claim 1 or 2, wherein the chlorine-containing Thermoplastic is a vinyl chloride homopolymer, a copolymer of the Vinyl chloride with unsaturated comonomers, a mixture of the mentioned polymers with each other or a mixture of the above Polymers with other copolymers. 4. The composition of claim 1 or 2, wherein component b) is contained in an amount of 0.8-1.5 parts. 5. The composition of claim 1 or 2, wherein component c) contained in an amount of 0.01-0.5, in particular 0.05-0.4 parts is. 6. The composition of claim 1, 2 or 5, wherein the component c) is a Ca salt. 7. The composition of claim 1, 2, 5 or 6, wherein the Component c) a salt of lauric acid, 2-ethylhexanoic acid, Is stearic acid or behenic acid.   8. The composition of claim 1 or 2, wherein component d) in an amount of 0.05-0.2, in particular 0.1-0.2 parts, is included. 9. The composition of claim 1 or 2, wherein component d) Zinc octoate, basic zinc octoate, zinc stearate or zinc benzoate. 10. The composition of claim 1 or 2, wherein component e) is contained in an amount of 4-7 parts, in particular 5 parts. 11. The composition of claim 1, 2 or 10, wherein the component e) is epoxidized soybean oil. 12. The composition according to any one of claims 1 to 11, which to 15 parts, in particular 3-10 parts, of an impact modifier contains. 13. The composition of claim 12, which as an impact modifier a copolymer of esters of acrylic acid and / or methacrylic acid with butadiene and with styrene (ABS or / and MBS) included. 14. The composition according to any one of claims 1 to 13, which up to 1 part, in particular 0.1-0.6 parts, of an organic phosphite stabilizer contains. 15. The composition according to any one of claims 1 to 14, up to Contains 1.5 parts of another costabilizer. 16. The composition of claim 15, wherein the further costabilizer an aminocrotonic acid ester, dehydroacetic acid, a 1,3-diketo compound, 2,4-dihydroxybenzophenone, 2,4-dihydroxy-4'-tert-butylbenzophenone or / and is a pyrrole derivative.