DE1569407C - Stabilizer mixtures for vinyl chloride polymers - Google Patents

Description

The invention relates to new stabilizer mixtures for vinyl chloride polymers and containing them Vinyl chloride polymer compositions which have improved color and clarity, in particular new stabilizers containing a ketoacetic acid compound and a metal salt of an organic acid for polyvinyl chloride as well as those stabilized with such a stabilizer combination, one polyvinyl chloride compositions having excellent heat resistance and improved clarity.

In U.S. Patent 2,564,646, stabilization of polyvinyl chloride using a Heavy metal salt of a higher fatty acid proposed, the polymer with this stabilizer an organic phosphite is also incorporated which serves as an opacifying agent and which Precipitation of metal halide from the stabilizer polymer mass as a cloud or turbidity in the crowd inhibits. The phosphites described in the patent include prim., Sec. And tertiary alkyl and aryl phosphites. In addition, can according to US Pat. No. 2,716,092, improved stabilization is obtained by combining with such phosphites salts of polyvalent metals with hydrocarbon-substituted phenols begins. These compositions are used extensively today to stabilize polyvinyl chloride against discoloration during processing and against blooming due to the separation of components used from the polymer.

US Pat. No. 2,711,401 describes the stabilization of polyvinyl chloride by means of a combination of polycrl with certain organic salts Acids provided with polyvalent metals. However, these stabilizer combinations are, as in the U.S. Patents 3,003,998, 3,003,999 and 3,004,000 at 191 ° C and above, the increased processing temperatures required for hard polymers, not sufficiently effective.

Polyvinyl chloride develops in the course of mixing at elevated temperatures and in many cases before the mixed mass is heated for any duration, a pale yellow color and loses clarity. You have this initial discoloration and this initial opacity so far not considered disadvantageous for many purposes, and the basis of the above-mentioned patents Lying work was accordingly aimed at intensifying this discoloration long-term exposure to heat, such as grinding, to a minimum. However, one has reason this initial discoloration does not result in an essentially clear and colorless polyvinyl chloride composition in all cases can get. So it is z. In U.S. Patent 2,867,594 as a significant improvement felt when the polymer only a very light yellow color after 15 minutes of heating accepts (example). It would obviously be one represent a considerable improvement if one could produce a polymer composition that after 15 minutes Heating to temperatures of the order of magnitude of 177 ° C is still clear and no noticeable Has yellowing or other discoloration. Even if such masses are heated for a long time would prove to be less stable if a mass that, though prolonged heating to a high Temperatures is not as stable as known masses, but when heated briefly on such

4U7

Temperatures not discolored, have definite and distinct advantages.

Recent developments in the field of stabilizers for vinyl polymers have led to additives which are non-toxic and useful for food packaging. As a plasticizer or additive for those masses used in the food packaging field Only certain, tested materials can be used which have been found to be completely free from migration or non-toxic have proven. Examples of these new types of non-toxic stabilizers can be found in U.S. patents 3 0.03 998, 3 003 999 and 3 004 000 can be taken. With these developments you get to which the mixture of the fatty acid salts of magnesium, zinc and calcium with a polyvalent one Alcohol is one, however, not the clarity required for various uses of the finished material 'required will.

According to the present invention, it has been found that polyvinyl chloride compositions which have an excellent Have initial color and clarity and even after 15 minutes of heating at 177 ° C and moreover show essentially no discoloration or turbidity, are obtainable if one of the polymers incorporates a stabilizer combination, the essential components of which are a ketoacetic acid compound, which may represent an ester or an anhydride dimer of the acid, and a metal salt of a contains organic acid. You only need this combination in very small amounts to achieve this improvement of stabilization against discoloration, and amounts in the range are usually sufficient from 0.005 to 5 parts by weight per 100 parts by weight of polymer.

According to the invention, using non-toxic ketoacetic acid compounds and non-toxic Metal salts also achieve polyvinyl chloride compounds that are used for food and luxury goods packaging are safe to use. Such nontoxic masses possess even at the elevated temperatures of 191 ° C and above, which are required for processing rigid polyvinyl chloride, is a remarkable one Heat resistance and clarity.

The ketoacetic acid compound is said to be at. the processing temperatures not be fleeting and permanent. It should also be nitrogen-free .. Generally sufficient these conditions compounds that contain at least 8 carbon atoms in the molecule. the For unknown reasons, free ketoacetic acids have the stabilizing effectiveness of the esters or anhydride dimers. However, one can use metal salts of these keto acids as the metal salt component Use the stabilizer combination according to the invention and in combination with the Esters and / or anhydride dimers achieve excellent stabilizing effectiveness.

The ketoacetic acid esters according to the invention have the general formula

/ R-c -CH ₂ -C-OVR '; ...

where R is an organic group having 1 to about 30 carbon atoms, R 'is an organic radical having 1 to about 30 carbon atoms and χ is a number from 1 to 10. The total carbon number of the ester molecule is at least 8.

R and R 'can represent hydrocarbon groups and are selected from alkyl, alkenyl, aryl, alkylaryl, arylalkyl, Cycloalkyl, cycloalkenyl and heterocyclic groups are formed. The groups with open Chain can be straight or branched, or the cyclic and alicyclic groups can be saturated or be unsaturated. The groups R and R 'can also be replaced by groups such as halogen (fluorine, chlorine, Bromine and iodine), alkoxy or epoxy, formation of a polyhydric alcohol become mixed esters of acid and alcohol according to their respective molar proportions, and in most In some cases, there are also mixtures of the various possible esters

Typical esters are

- C-

-c -

IO

(1) CH ₃ CCH ₂ COCH ₂ CHc ₄ H ₉

O O

• ^N o ^/

Hydroxy, OH and ether groups = C - O - C = be substituted. Usually there are no more than ten such substituents, the number being natural is influenced by the number of available substituent sites in the groups R and -R '.

So z. B. the radical R 'have free hydroxyl groups (OH), their number practically at most 10, but generally no more than one hydroxyl group present per carbon atom, and the radical R 'a number of'

(R-C-CH ₂ -C-0- \ - ester groups C ₂ H ₅

. (2) Is ₀ -C ₄ H ₉ -C-CH ₂ -CO- C ₂ H ₅ OO

(3)

C-CH ₂ -CO

Il Il

ο ο

up to a total of about 10, the value of x. If R 'has more than one OH group, the value of χ represents only an average of the number of possible ester types that can exist (depending on the total number of OH groups in R') In the case of a diester (x = 2) For example, in which R 'has three free OH groups, the penta-, tetra-, tri- and monoester types can also be present. χ can indeed be a decimal number in such cases, e.g. Equal to 2.5, indicating the presence of a mixture of monoester, diester, triester and higher ester species in proportions leading to the average value of χ. The possibilities that increase with an increase from χ to values of 10 or more are clear. .

Examples of hydrocarbon groups R and R 'are methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, tert-amyl, hexyl, heptyl, tert. -Octyl, 2-ethyl-hexyl, isononyl, decyl, undecyl, dodecyl, palmityl, stearyl, oleyl, ricinoleyl, linoleyl, linolenyl, behenyl, tridecyl, phenyl, xyIyI ₅ ToIyI, naphthyl, cyclohexyl, methylcyclopentyl, tetrahydropentyl, cyclopentyl, cyclopentyl , Cycloheptyl, isononylphenyl, furyl and pyranyl.

Examples of hydroxy-substituted groups R 'are hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyamyl, 2-hydroxyamyl, 2,2-dimethylolpro- ' pyl, 2,2-dihydroxyamyl, 1,1-methylolriydroxybutyl, 2- (dihydroxyethyl) butyl, 1- (dihydroxyethyl) propyl, 3,4-dihydroxyheptyl, 4,5-dihydroxyoctyl, 7,8-dihydroxyheptadecyl, 6,7-dihydroxytetradecyl, 1,2,3-trimethylol - octadecyl, 1,2,3,4,5,6 - hexahydroxyheptyl, 10-hydroxyeicosyl, 2,3-dihydroxypropyl, 4-hydroxybutyl, 3,4-dihydroxybutyl, 2,3,4-trihydroxybutyl and 1,3,4-trihydroxybutyl. \ r:

These esters are easily converted into the corresponding ester by transesterification of a simple ester according to known methods Ketoacetic acid, such as ethyl acetoacetate, can be obtained with the corresponding alcohol. If the If the corresponding ketoacetic acid is stable, a direct esterification can be carried out. When using

(4) <s VC-CH ₂ -CO-CH ₃

C - CH, - C - O - CH

(7) CH ₃ CCH ₂ C-O

O O

C - CH ₂ C - OCH ₂ CH ₂ OH

Il Il ^: r:

OO

CH, -C-CH ₂ -CO- CH ₂ "

(9)

CCH,

O O

(10) C ₁₈ H ₃₇ CCH ₂ C-O-C ₃ H ₇ -ISO

O O

(11) C ₁₂ H ₂₅ C-CH ₂ CO-CH ₂ -CH-CH ₂ OH

OO OH

(12) CH ₃ CCH ₂ C - O - CH ₂ CH ₂ OH

O O

(13) C ₂ H ₅ CCH ₂ C - O - CH ₂ CH ₂ CH ₂ OH

O O

CH ₂ OH

(14) CH ₃ - CCH ₂ CO - CH ₂ - C - CH ₂ OH 0

CH ₂ OH.

CH, C ~ CH, - C - 0 - CH, -

(16) CH ₃ C - CH ₂ - 'C - 0 - CH ₂

Il Il

ο ο

CH ₃ C - CH ₂ - C - 0 - CH

Il Il

0

_CH3 - C - CH ₂ - C - 0 - _CH2 0

Il Il

O

"C ₂ H ₅ - C - CH ₂ - C - OCH ₂ " Ο "

CHOH

(19)

(20)

C - CH ₂ - C - O - CH ₂ -

Il Il

οο J ₂

Wt -C ₄ H _{9 -C -C H 2} -C -C OCH ₂ I CHOH

ο ο J ₂

IO

(21) C-CH ₇ -CO-CH-

O O

-C-CH ₇ OH

(22) TCH ₃ -C-CH ₂ -C-OCH ₂
OO

-C- (CH ₂ OH) ₂

20th

0 0

CH ₃ - C - CH ₂ - C - 0 —'CH '

0 0 '_

(24) CH ₃ -CH CH-CH ₂ -C-CH ₂ -C-OC ₂ H ₅

\ / IL Il

ο ο

(25) CH ₃ CH-CH ₂ CH ₂ C-CH ₂ -COC ₅ H ₁₁ -IsO Cl OO

CH ₃ CH ₂ O CH ₂ CH ₂ C CH ₂ CO CH ₂ CH ₂ OH

O

CH CH, C CH, C O CH, CH, Ο— CH, CH, OH

CH,

OO CH ₃ CH ₂ - [O - CH ₂ CH ₂ L - O - CH ₂ C - CH ₂ - COCH ₃

O O

_"CH3 - C - CH ₂ - C - O - ⁷ J CH ₂ CH ₂ [OCH ₂ CH _{2] 2} OCH ₂ CH _3.

O

CH ₃ CH ₂ - CH ₂ -C-CH ₂ -CO - CH ₂ CHOHCH ₂ OH OCH ₃ OO

The keto acid anhydride dimers have the formula: or

■ -'O- "■ ■ '- ■ ■■ · ■■■ ·" ■■ -

C-R

^ O

Here, R again has the above meaning, while R ₁ is hydrogen or R '.

Examples are dehydroacetic acid, isodehydroacetic acid, dehydropropionylacetic acid, dehydrobenzoylacetic acid, Isodehydro - 3,4 - dichlorobenzoyl acetic acid and esters of isodetiydroacetic acid, such as methyl, Ethyl, η-butyl, 2-ethylhexyl and glyceryl esters.

The organic acid anion of the metal salt component usually contains from about 6 to 24 carbon atoms. The metal can be any alkali or alkaline earth metal from Groups I or II of the Periodic Systems like the sodium, potassium, lithium, calcium, barium, magnesium and strontium. The acid can be any organic, non-nitrogen-containing monocarboxylic acid with 6 to 24 carbon atoms being. The aliphatic, aromatic, acyclic and oxygenated heterocyclic organic Acids are suitable as a class. Under the »aliphatic Acid «is to be understood as any open-chain carboxylic acid which, if desired, does not include reactive groups such as halogen, sulfur and hydroxyl may be substituted. The term "alicyclic" is intended to include any cyclic acid, the ring of which is not aromatic and of carbon atoms alone is formed; such acids can, if desired, non-reactive substituents such as Halogen, hydroxyl, alkyl radicals, alkenyl radicals and other carbocyclic ring structures condensed with them, exhibit. The oxygen-containing, heterocyclic compounds can be aromatic or not be aromatic and may contain oxygen and carbon in the ring structure like. the alkyl substituted furancarboxylic acid. The aromatic acids can be used in a corresponding manner non-reactive ring substituents such as halogen, alkyl and alkenyl groups, and others with have condensed saturated or aromatic rings. .

Examples of the acids that can be used in the form of their metal salts are hexanoic acid, 2-ethylhexanoic acid, n-octanoic acid, isooctanoic acid, capric acid, undecylic acid, lauric acid, myristic acid, Palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, chlorocaproic acid, Hydroxycapric acid, ethylacetoacetic acid, benzoic acid, phenylacetic acid, butylbenzoic acid, Ethy! Benzoic acid, propylbenzoic acid, hexylbenzoic acid, Salicylic acid, naphthoic acid, 1-naphthaleneacetic acid, o-Benzoylbenzoic acid, petroleum-based naphthenic acids, abietic acid, dihydroabietic acid, Hexahydrobenzoic acid and methylfurancarboxylic acid as well as partially esterified, dibasic ones Acid, such as monobutyl phthalate, isooctyl maleate, ethylene glycol maleate and 2-ethoxyethyl maleate. · ■ ^

The water-insoluble salts are preferred because they are not subject to leaching when the molded body is in contact with water. These salts are available through the usual types of reactions, such as by mixing the acid, acid chloride or anhydride with the corresponding oxide or hy-

droxyd the metal in a liquid solvent and, if necessary, heating until the salt formation is complete.
A metal salt of a hydrocarbon-substituted phenol can be used in combination with or in place of the above-mentioned metal salts of organic acids. The hydrocarbon substituents can each contain 4 to 24 carbon atoms. The metal can be an alkali or alkaline earth metal such as sodium, potassium, lithium, calcium, strontium, magnesium and barium. Of these phenolates of polyvalent metals, the magnesium, barium, calcium, strontium, cadmium, lead, tin and zinc salts of n-butylphenol, isoamylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, n- Decylphenols, tert-dodecylphenols, tert-octylphenols, isohexylphenols, octadecylphenols, diisobutylphenols, methylpropylphenols, diamylphenols, methylisohexylphenols, methyl-tert-octylphenols, di-tert-nonylphenols, di-tert-dodecylphenols and o- phenylphenols and o- specifically called. The metal phenate should be compatible with the chlorine-containing polymer.
It is also possible to use mixtures of salts of different metals and achieve enhanced effects with many such mixtures, such as mixtures of zinc, cadmium, tin, lead, antimony, manganese, bismuth, iron, cobalt, nickel and copper salts with the alkali or alkaline earth salts, e.g. B. of potassium and zinc stearates (US Pat. No. 2,446,976) and mixtures of cadmium, lead or calcium and alkali salts, such as of sodium and potassium (US Pat. No. 2,181,478).
Usually, even with a relatively small amount of the stabilizer combination according to the invention, a considerable improvement in clarity is obtained. Usually, based on the total weight of the mass, amounts in the range from about 0.005 to 5% are used, with 0.05 to 2% being particularly preferred. The larger quantities generally do not have a negative effect on the product quality, but are not worth the increased effort.

The present invention applies to any polyvinyl chloride applicable, the term polyvinyl chloride in the sense used here any polymer should include that at least in part from the recurring group

'; ■: ■ " ^x "
^C1 :. '■■ ^x _

is formed and has a chlorine content of over 40%. The groups X in this group can each formed by hydrogen or chlorine. With the vinyl chloride homopolymers all Groups X formed by hydrogen. The above term includes in this way not only the vinyl chloride homopolymers, but also post-chlorinated ^ polyvinyl chlorides as a class. e.g. those according to British patent specification 893 288, and also copolymers with a larger proportion of vinyl chloride and a smaller proportion of other copolymerizable Monomers, such as copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride with maleic or fumaric acid or their esters and copolymers of

109 536/379

Vinyl chloride with styrene. The invention is also applicable to blends of a major proportion of polyvinyl chloride and a smaller proportion of other plastics such as chlorinated polyethylene or a copolymer of acrylonitrile, butadiene and styrene.

The invention is directed to the stabilization of hard polyvinyl chloride compositions, ie compositions which are designed to withstand high processing temperatures of the order of 191 ° C. and above, as well as of plasticized polyvinyl chloride compositions of conventional composition for which heat resistance is not a requirement. Rigid polyvinyl chloride and the plasticized polymers are defined as follows: Hartpolyvinylchloride are polymers which no plasticizer is added and the processing is carried out generally at 191 ⁰ C. The ASTM definition (1961 D-883, part 9, p. 804) is as follows:

"A polymer having a stiffness or _2Q apparent modulus of elasticity greater than 7,000 g / cm ² (1,000,000 pounds / square inch) at 23 ° C."

The plasticized polymer is accordingly to be defined in such a way that it has a modulus of elasticity of less than 7000 g / cm ² and contains an additive of the plasticizing compound. One can use the conventional plasticizers familiar to the person skilled in the art, such as. B. dioctyl phthalate, octyl diphenyl phosphate and epoxidized soybean oil.

The higher epoxy esters with 22 to 150 carbon atoms are particularly valuable plasticizers Such esters initially contain unsaturated in the alcohol or acid part of the molecule Components that are absorbed through the formation of the epoxy group.

Typical unsaturated acids are acrylic, oil, Linoleic, linolenic, erucic, ricinoleic and brassidic acids; they can be monovalent or polyvalent with organic Alcohols, the total carbon number of the acid and alcohol in the mentioned area. Typical monohydric alcohols include butyl alcohol, 2-ethylhexyl alcohol, Lauryl alcohol, isooctyl alcohol, stearyl alcohol and oleyl alcohol. The octyl alcohols are preferred. Typical polyhydric alcohols include pentaerythritol, glycerine, ethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, neopentyl glycol, ricinoleyl alcohol, Erythritol, mannitol and sorbitol. The glycerin is preferred. These alcohols can be epoxidized with the Acid be fully or partially esterified. The epoxidized mixtures of higher fatty acid esters, that occur in naturally occurring oils, such as epoxidized soybean oil, epoxidized olive oil, epoxidized cottonseed oil, epoxidized valley oil fatty acid esters, epoxidized coconut oil and epoxidized Tallow are useful, of which epoxidized soybean oil is preferred.

The alcohol can contain the epoxy group and be long or short chain, and so can the acid have a short or a long chain, such as epoxystearyl acetate, epoxystearyl stearate, glycidyl stearate and polymerized glycidyl methacrylate.

The ketoacetic acid compounds according to the invention can, if desired, in conjunction with other stabilizers for polyvinyl chloride are used, albeit in most cases the stabilization achieved with the ketoacetic acid compound is sufficient. However, in some cases special uses, special stabilization effects may be desired.

The stabilizer combinations according to the invention give without the presence of any others Additive to improve the clarity of the polyvinyl chloride. However, it has long been recognized that polyvinyl chlorides containing several types of heat stabilizers are better than just one Heat stabilizer containing polymers are protected. It represents an important one in this regard Feature of the invention is that the stabilizer combinations according to the invention in use along with other heat stabilizers, significantly improved resistance to deterioration result in heat that cannot be achieved with the other heat stabilizers alone is.

A large number of thermal stabilizers are known. Among the more important, technically used Heat stabilizers include weak alkalis, such as sodium carbonate, disodium phosphate, and sodium and potassium salts of partially esterified phosphoric acids, inorganic and organic lead salts, Organotin carboxylate (U.S. Patent

2 307 157), organotin mercaptide. (U.S. Patent 2,641,588 and 2,641,596), various metal-free, organic compounds, such as polyols, e.g. B. Mannitol, sorbitol, glycerine, pentaerythritol, 1,2-epoxides, e.g. B. soybean oil epoxide, isooctyl epoxystearate and the diglycidyl ether of 2,2-bis (p-hydroxyphenyl) propane, and nitrogen compounds, e.g. B. phenylurea, Ν, Ν'-diphenyl thiourea and 2-phenylindole. A detailed discussion of the thermal stabilizers for vinyl halide polymers is given in N. L. Perry, "Barium-Cadmium Stabilization of Polyvinyl Chloride", Rubber Age, 85, pp. 449 bis 452 (June 1959), and H. V e r i t y - S m i t h, British Plastics, 27, pp. 176 to 179, 213 to 217, 307 to 311 (1954), as well as in a brochure "The Development of the Organotin Stabilizer" (Tin Research Institute, 1959) by the same author and the work "La Stabilization des Chlorures de Polyvihyle" by F. Chevassus (Amphora, Paris, 1957).

Preferred classes of additional heat stabilizers used include the phenols and the organic triphosphites and acid phosphites.

The phenolic stabilizers contain one or more phenolic hydroxyl groups and can be one or have more than one phenolic nucleus. In addition, the phenolic core can be an oxy or Thioether group included. The alkyl substituted phenols and polynuclear phenols have due to Their molecular weight has a higher boiling point and are therefore lower in view of their Volatility preferred. It can be one or a number of alkyl groups with one or more carbon atoms are present. The alkyl group or groups including any alkylene groups between Phenolic nuclei preferably contain at least 4 carbon atoms together; Compatibility with the polymer is the better, the longer the alkyl or alkylene chain, since the phenolic compound here ih to a greater extent the character of a aliphatic hydrocarbon, whereby the number of alkyl carbon atoms is unlimited is. Usually the connection from

ftU /

From the standpoint of availability of no more than about 18 carbon atoms in an alkyl, alicyclidene and alkylene group and no more than about 50 total carbon atoms. The connections can contain one to four alkyl radicals per phenol nucleus.

The phenol contains at least one and preferably at least two phenolic hydroxyl groups, if only one ring is present, the two or more hydroxyl groups are in the same ring and in the presence of more than one ring are in the same ring or in different rings. In the case of bicyclic phenols, the rings can be replaced by thio or oxyether groups or by alkylene, Alicycliden- or arylidene groups be linked. Such phenols because of their superior Stabilizing effect can be preferred by the formula

OH _V

represent, in which X represents an oxygen or sulfur atom or an alkylene or alicyclidene or arylene or mixed alkylene-alicyclidene or alkylene-arylidene group with a straight or branched chain of 1 to about 18 carbon atoms in total, y _t and y ₂ denotes the number of phenolic hydroxyl groups OH and H ₁ and n _{2 denotes} the number of groups R and R ₁ and R ₂ denote hydrogen or alkyl having 1 to about 18 carbon atoms. The OH groups are preferably in the ortho and / or para position to X.

The sum of y and η in each ring naturally cannot exceed 5.

Typical groups X are

■ CH ₂

- CH ₂ CH ₂
OH

CH,

CH

-CH

- CH ₂ - S CH ₂

H - C -

CH

CH, -CH

OH

CH,

Examples of the various groups X and R are given by the following compounds.

Examples of satisfactory monohydric phenols are

2,6-di-tert-butyl-4-methyl-phenol, 2-tert-butyl-4-methoxyphenol, Nonylphenol, dodecylphenol, dinonylphenol, phenylphenol, tetradecylphenol and Tetrahydro-a-naphthol.

Examples of the polyhydric phenols are

- S -

- CH ₂ 55 Orcin, - CH- Propyl gallate, Catechol, CH ₃ Resorcinol, fin 4-octyl resorcinol, 0— -CH ₂ -O OU 4-dodecylresorcinol, 4- octadecyl catechol, ^/ \ _ II 4-isooctyl-phloroglucine, Pyrogallol, Hexahydroxybenzene, CH ₂ (CH ₂ J ₃ CH ₂ ? 4-isohexyl catechol, 2,6-di-tert-butyl-resorcinol, CH ₃ 2,6-diisopropyl-phloroglucine, I. Methylene bis (2,6-di-tert-butyl-m-cresol), - c - Methylene-bis- (2,6-di-tert-butyl-phenol), ' I. 2,2-bis (4-hydroxyphenyl) propane, ^v CH ₃ Metb.ylen-bis- (p-cresol), '

4,4'-thio-bis-phenol,

4,4'-oxo-bis (3-methyl-6-isopropyl-phenol), 4,4'-thio-bis- (3-methyl-6-tert-butyl-phenol), 2,2'-oxo-bis (4-dodecyl-phenol), 2,2'-thio-bis- (4-methyl-6-tert-butyl-phenol), 2,6-diisooctylresorcinol,

4,4'-n-butylidene-bis- (2-tert-butyl-5-methyl-

phenol),
4,4-benzylidene-bis- (2-tert-butyl-5-methyl-

phenol),
2,2'-methylenebis (4-methyl-6- (l'-methylcyclohexyl) phenol),

4,4'-cyclohexylidene-bis- (2-tert-butyl-phenol), 2,6-bis- (2'-hydroxy-3'-tert-butyl-5'-methyl-

benzyl) -4-methylphenol,
4-octylpyrogallol and
3,5-di-tert-butyl catechol.

10

15th

The triphosphite can be any organic triphosphite in which aryl, alkyl, cycloalkyl, aralkyl or alkaryl groups in any combination, such as three monovalent groups, (RA) ₃ P, a monovalent group and a divalent group forming a heterocyclic ring with the phosphorus,

-AR

30th

a number of _% divalent groups forming polymers with it

35 14th

-AR ₁ -AP phenyl dicyclohexyl phosphite, phenyl diethyl phosphite, triphenyl phosphite, tricresyl phosphite, tri- (dimethylphenyl) phosphite, trioctadecyl phosphite, triisooctyl phosphite, tridodecyl phosphite, isooctyl diphenyl phosphite , Diisooctyl-phenyl-phosphite, tri- {tert-octylphenyl) -phosphite, tri- (tert-nonylphenyl) -phosphite, benzyl-methyl-isopropyl-phosphite, butyl-dicresyl-phosphite, isooctyl-di- (octylphenyl) -phosphite, di- (2-ethylhexyl) - (isooctylphenyl) -phosphite, tri- (2-cyclohexylphenyl) -phosphite,

Tri-a-naphthyl-phosphite, tri- (phenylphenyl) -phosphite, tri- (2-phenylethyl) -phosphite, Tridodecyl thiophosphite, tri-p-tert.-butyl-phenyl-thiophosphite, Dodecyl-thiodiphenyl-phosphite, tert-butyl-phenyl-thio-di-2-ethylhexyl phosphite, Ethylene-phenyl-phosphite, ethylene-tert-butyl-phosphite, ethylene-isohexyl-phosphite, Ethylene isooctyl phosphite, ethylene cyclohexyl phosphite, 2-phenoxy-l, 3,2-dioxäphosphorinane, 2-butoxy-1,3,2-dioxaphosphorinane, 2-octoxy-5,5-dimethyldioxaphosphorinane and 2-Cyclohexyloxy-5,5-diethyldioxaphosphorinane.

The acid phosphites of U.S. Pat. No. 197,454 can also be used. examples for this are

a trivalent group

/ ^A \

RAP

4 °

or a number of polymers forming with it, trivalent groups

/ A \ / ^A \ / ^AH '

HA-R ₂ PAR ₂ PAR ₂

and any combinations of mono-, di- and trivalent groups are bonded to form monomeric and polymeric phosphates (A = oxygen or sulfur). The term "organic phosphite triester" as used here also includes oxo- and thiophosphites and, oxo-thio-mixed phosphites. Usually the carbon number of the phosphite is no more than about 60.;. ■: .. Examples are; _;

Monophenyl-di-2-ethyl-hexyl-phosphite, piphenyl-mono-2-ethyl-hexyl-phosphite,. Di-isooctyl-monotolyl-phosphite, Tri-2-ethyl-hexyl-phosphite,

Di- (phenyl) -phosphite, monophenyl-phosphite, mono- (diphenyl) -phosphite, Dicresyl phosphite, di- (o-isooctyl-pheriyl) -phosphite, di- (p-2-ethylhexylphenyl) -phosphite, Di- (p-tert-octylphenyl) phosphate, Di- (dimethylphenyl) phosphite, di-n-butyl phosphite, di-2-ethylhexyl phosphite, Mono-2-ethyl-hexyl-phosphite, diisooctyl phosphite, monoisooctyl phosphite, Monododecyl phosphite,

2-ethylhexylphenyl phosphite, 2-ethylhexyl (n-octylphenyl) phosphite, Monocyclohexyl-phosphite, dicyclohexyl-phosphite, di- (2-cyclohexyl-phenyl) -phosphite, Di-a-naphthyl-phosphite, diphenylphenyl-phosphite, di- (diphenyl) -phosphite, Di- (2-phenyl-ethyl) -phosphite, dibenzyl phosphite, Monobenzyl phosphite, n-butyl cresyl phosphite, didodecyl phosphite, Di-tetrahydrofurfuryl phosphite and difuryl phosphite.

15 16

You can use 100 parts by weight of the polymer. So you can with all non-toxic ali-

a total of 0.5 to 10 parts by weight of the combined phatic compounds work, at least

Stabilizer combination according to the invention and two and preferably not more than ten hydroxyl

use on auxiliary stabilizers. have groups. Mannitol, sorbitol and glycerin

The use of larger amounts of Stabili- 5 are particularly preferred polyols. Pentaery-

Sator composition is possible, but leads to thrrite, dipentaerythritol and tripentaerythritol are in

homely to no better results, so that the stabilizer compositions according to the invention

Such larger quantities are not economical and effective and can be used in the field of

cannot be justified. Food packaging according to the respective

You can also use a small amount, usually in compliance with food law regulations.

Do not use more than 1.5% of a release agent. Find a twist.

Typical release agents are the higher aliphatic. The stabilizer should be added to the polymer in one

Acids with 12 to 24 carbon atoms, such as stearin, are added in sufficient quantities to ensure that the

acid, lauric acid, palmitic acid and myristic acid, stabilized polyvinyl chloride mass the necessary

Mineral lubricating oils, polyvinyl stearate, and polyethylene can be heated for 15 times without a thermal

Paraffin wax. Decomposition occurs. Usually 2 to 6% is enough

According to a preferred embodiment of the Erfrn stabilizer based on the weight of the polymer to

polyvinyl chlorides, which are responsible for most of the requirements and use

in the packaging of foodstuffs or luxury foods to be fair training purposes. A sufficient one

are safe to use and have a remarkable 20 resistance to thermal degradation

Heat resistance at elevated temperatures can be achieved even with small amounts of the stabilizer

wise, obtainable by being used as an auxiliary stabilizer to sators, e.g. B. about 0.25 weight percent based on

the ketoacetic acid compound, a combination of the polymer, achieve. The resistance to

non-toxic (non-toxic) salt polyvalent m-thermal deterioration gets better the more

tails that at least one calcium and / or 25 more stabilizer is used. Amounts over

Magnesium salt and at least one zinc salt to about 10% stabilizer are im. generally unnecessary

contains together with a polyol. That and accordingly cannot economically

Anion part of the calcium and / or magnesium should be justified. The stabilization of soft

and zinc salts can be obtained from benzoic acid and from established polymers which require less stabilization

edible fats and oils, and they are usually not needed

acids are obtained. more than about 3% of the weight of the polymer.

The full details of many such non-toxic The stabilizing effects of these stabilizers

Stabilizer combinations can the USA. Patent according to the invention can be strengthened by

Writings 3 003 998, 3 003 999 and 3 004 000 - you can take small amounts of non-toxic antioxidant

to which reference is made here. The 35 medium adds. When using such antioxidants

The present invention thus also includes stabilizers, their amount being about 0.5% of the mass

sators ,. which do not exceed a ketoacetic acid compound, CaI-. You can do any known

Use cium and / or magnesium and zinc benzoate antioxidants, as far as it is in the

plus a polyol, calcium and / or amounts used is non-toxic. Too exemplary

Magnesium and zinc fatty acid salts plus one of 40 antioxidants are included

Polyol and mixtures of calcium and / or 2,6-di-tert, butyl-4-methylphenol,

Magnesium and or or Zmkbenzoaten and Mert-Butyl-4-methoxyphenol,

Magnesium and / or zinc fatty acid salts to 3-tert-butyl-4-methoxyphenol,

also contain a polyol. One obtains with n-Propvlgallat

this combination has a good, long-term resistance - 45 n-dodecyl gallate,

^ Jf ™, ^d % heat. Dilauryl thiodipropionate and

Such stabilizer compositions according to the nordihydroguaiaretic acid.

Invention contain about 4 to 80 parts Ketoessig- ^J

acid compound, about 25 to 40 parts calcium and also the 'following antioxidants appear

or or magnesium salts, about 25 to 40 parts 50 nen in small amounts as non-toxic, however

Zinc salts and about 20 to 80 parts of the polyvalent naturally their approval for use too

Alcohol. .When using glycerine, the following is important: '

one is preferably with a ratio of zinc 4,4'-methylene-bis- (2,6-di-tert-butylphenol),

salt voa, at least ^: 1 , and optimally ^ at least ₄ 4 '. _Thio X _is . _{(2-t e} rt-butyl-5-methyl-phenol),

4: 1. Under "salt" are the calcium and / or 55 44'-butylidene-bis- (2-tert-butyl-5-methylphenol),

Magnesium and Zmksate of benzoic acid and i _J l, 3-Tris- (3-tert-butyl-4-hydro _X y-6-methyl-

the fatty phenol butane, which can be traced back to edible fats and oils

acids to understand Examples are the mixed fat- ^ '- methylene-bis - ^ - methyl-o-U'-methyl-

^ acidic consisting of tallow, lard, Sardinenol, olive _C yclohexyl) phenol], and

oil, babassuol, coconut oil cottonseed oil, soy-60 ₂ , 2'-methylene-bis- (4-nonyl-phenol).

bean oil, corn oil and peanut oil can be obtained. ^J

The oils from which the fatty acids are obtained, The manufacture of the stabilized mass allows; If desired, they can be hydrogenated.- Also distil- _v easily accomplished by conventional methods, lated, fractionated fatty acids; or mixtures j. Usually, one mixes the selected fatty acid combination, which is derived from such fats and oils, with the _: plasticizer and the base are suitable. :; , ^tene mixture then with the polyvinyl chloride, for example in these stabilizer compositions according to using plastic mixing rollers in one of the invention, all non-toxic polyols can be temperature at which the mixture is flowable and a

. 109 536/379

thoroughly mixing is facilitated, and, to form grinding the plasticizer and the stabilizer with the polymer on a two-roll mill at 121-177 ⁰ C (250 to 35O ⁰ F) and of sufficient duration, usually from 5 minutes to a homogeneous coat. After the mass is even, it is removed in the usual way.

The following examples serve to illustrate preferred embodiments of the polyvinyl chloride compositions according to the invention.

example 1

A series of four compositions is produced, each 100 parts of vinyl chloride homopolymer

in a mixture with a stabilizer of (based on 100 parts of polymer) 45 parts of dioctyl phthalate, 1.5 parts of calcium stearate and the other ingredients according to Table I contains. A fifth sample is then prepared with the homopolymer, omitting the calcium stearate and replacing it with a sample of 1.5 parts calcium ethyl acetoacetate. Each sample is heated to 177 ° C in an air oven to determine its heat resistance; The color fastness of all samples on extended heating is given in Table I. In order to show the initial color and clarity of each sample, a pressed, polished film is produced ^{after heating the sample to 177 ° C. for 3 minutes.}

Table I.

ICetoessis acid Press polished 0 Discoloration in the Heat at 177 ° C 15th 30th • Red with 45 60 j sample JtVVWvJÜlgÜU U JL W
Component of the Foil,
clarity Weak after a heating time of ... minutes Pale orange dark reddish Dark U Stabilizer and coloring pink orange redden coloring red with,. Vt
75 1 Control sample I. pink Put black strong more colorful stains Dark Sound, very orange Red easy Gloomy Red Dark strong cloudy White red with Dark red 2 Control sample II darker orange black strong (1.5 parts calcium pink stains Dark red ethyl acetoacetate) more colorful Volume, Weak very Red Red cloudy pink Pale Bright 3 0.25 parts of dehydrating clear orange orange strong acetic acid colorless very Red Red Dark red Pale amber 4th 1 part 2-ethylhexyl- clear stone strong acetoacetate Colours Dark red Weak Pale yellow Pale- . Red yellow orange 5. 1 part glyceryl tri- clear Red _Λ acetoacetate

As shown in the table above, the composition containing a ketoacetic acid compound according to the invention has a much better coloration and clarity in the early stages of heating compared to the addition of heat stabilizer, the ketoacetic acid ester compound nevertheless not adversely affecting color and Clarity when heated for a long time. In addition, the table shows that the calcium ethyl acetoacetate brings no improvement in terms of clarity and thus none in the direction of this property Represents stabilizer.

Example 12

A mixture containing 100 parts of vinyl chloride homopolymer and the stabilizers according to Table II is prepared on a two-roll grinder at 191.degree. Each sample is then divided into 2 parts, one of which to test the heat resistance to 177 ° C and the other is heated to 191 ⁰ C in an air oven. In addition, a press-polished, rigid film 1 mm thick is produced from each batch by heating it to 191 ° C. for 3 minutes; The color and clarity of the press polished film are compared. Each sample contains 0.67 parts of mixed zinc and calcium salts of hydrogenated tallow acids plus 0.67 parts of sorbitol. The composition corresponds to US Pat. No. 3,003,999. One checks for discoloration (Tables II and III).

19th

Table II

20th

Per-
U ". , Ketoacetic acid
component clarity
and coloring
the press 0 15th Discoloration when heated at 177 ° C
after a heating time of ... Minutes 45 60 . 75 90 105 DC of the stabilizer polished pink orange orange orange Bright Bright- charred foil 30th orange orange 1 Control sample very orange With weak Points cloudy, Pale very Pale Pale Bright Bright charred orange pink Pale yellow yellow orange orange 2 0.25 parts clear, yellow Pale With Dehydrated Pale yellow yellow Points acid very very Pale Pale Pale charred Pale Pale yellow yellow yellow 3 0.5 parts clear, pink yellow Pale Dehydroacetic very yellow ■ acid pale cream very Pale Pale Pale Pale charred Colours Pale yellow yellow yellow yellow 4th 0.5 parts clear, yellow Pale Glyceryl tri- Light yellow ■ yellow acetoacetate

Table III

Ketoacetic acid component
of the stabilizer Press polished
Slide, clarity
and coloring 0 pink Discoloration in the warmth at: 91 ° C 60 sample after a hit; training period from ...] Minutes _ Control sample very easy 15th 30th 45 ' 1 cloudy, Pale pink orange yellow charred orange 0.25 parts of dehydrating clear and. very 2 acetic acid Pale yellow Pale pink Light yellow Yellow with charred 0.5 parts dehydrating clear and Points 3 acetic acid. very pale very Light yellow Yellow with charred cream colored Pale yellow Points 0.5 parts glyceryl clear and 4th triacetoacetate Light yellow Light yellow Yellow with charred Points

The results show the effectiveness with which the additives according to the invention improve the clarity of the polyvinyl chloride at the processing temperatures of 177 and 191 ° C without impairing the heat resistance of the polymer while falling short of the time required for processing

will. '''' ^r - ■ ■ ""''.". ■■■■■■ ... · ■., - .. ■

B e i s ρ i e 1 3

A series of compositions is produced, each of which contains 100 parts of vinyl chloride homopolymer and a stabilizer composed of 2 parts of a mixture of magnesium benzoate, zinc stearate and mannitol (quantitative ratio 3: 4: 5) and the additional ingredients according to Table IV and Grinder is mixed ^{at 191 0 C.} Each sample is then divided into 2 parts, one heated to 177 ° C and the second to 191 ° C in an air oven to test its heat resistance. Check for discoloration (Tables IV and V).

Ketoacetic acid
Component '
of the stabilizer: - Beginning
liche
clarity
and
coloring 0 Table IV 15th Ve
after
30th r staining ir
a hit
45 ι the Wan
time ν
60 ne at 177
on ... Mn
75 ° C
chime;
90 105. 120 sample Control sample cloudy,
pink very
Pale pink Pale
orange Bright
yellow Bright-
orange Bright-
orange orange orange orange
yellow orange
yellow with
Points A.

i bt> y 4Ü7

continuation

sample Ketoacetic acid
component Beginning
liche
clarity 0 15th Discoloration when heated at 177 ° C
after a heating time of ... minutes 45 60 75 90 105 120 of the stabilizer and colorless cloudy yellow Dark orange Light yellow Light yellow Light yellow coloring 30th yellow B. 1 part glycerin cloudy, colorless Pale yellow yellow Pale yellow yellow yellow yellow yellow Margins Pale pink charred C. 1 part 2-ethyl-hexyl- very Pale yellow acetoacetate weak cloudy, very colorless very Pale yellow Pale yellow yellow yellow Margins charred Pale yellow Pale yellow charred D. 1 part mixed clear, . very Glyceryl mono- and very very Pale yellow Pale yellow Pale yellow yellow yellow yellow Margins charred -di-acetoacetate Pale yellow Pale yellow charred E. 1 part glyceryl triaceto clear, Pale yellow acetate very very very Pale yellow yellow yellow yellow Margins charred Pale yellow Pale yellow ■ Pale yellow charred F. 1 part propylene glycol very very di-acetoacetate easy Pale yellow cloudy, very colorless very yellow yellow yellow Margins Margins charred Pale yellow Pale yellow charred charred G 1 part dehydrated clear, Pale yellow acetic acid nearly colorless

Table V

• Initial 0 very Discoloration in the warmth ϊ at 191 ° C 60 Sample. Ketoacetic acid component
of the stabilizer clarity
and coloring Pale pink after an ErI litzungszeitvo ι ... minutes colorless 15th 30th 45 A. Control sample cloudy, Bright yellow charred charred pink colorless orange B. 1 part glycerin cloudy, Bright yellow Margins - Pale pink orange charred C. 1 part of 2-ethyl hexylacetoacetate very Pale yellow yellow charred IClWiil
cloudy, colorless very Pale yellow very D. 1 part mixed glyceryl clear, very Pale yellow Pale yellow Margins charred mono- and di-acetoacetate Pale yellow very charred E. 1 part glyceryl triacetoacetate clear, very Pale yellow Pale yellow ' charred charred Pale yellow F. 1 part propylene glycol very Pale yellow charred diacetoacetate easy cloudy, colorless very Pale yellow G 1 part dehydroacetic acid sure, almost yellow charred colorless

The results of this test show the effectiveness with which the stabilizers according to the invention improve the clarity, and explain the ineffectiveness of adding more, pure glycerine to improve clarity. The addition of a mixture of fatty acid salt and glycerine is described in the USA patent 2 711 401. By adding glycerine to the one containing the mixed salt stabilizer Polymer is the additive according to this patent without the surprising increase in clarity, obtained according to the invention occurs.

23

As in Example 3, a series of belle VI is made.

24

Example 4 Masses using the additional ingredients according to Ta-

Table VI

sample

Ketoacetic acid

Component of the stabilizer

Initial

Clarity and

coloring

0.5 part of glyceryl triacetoacetate

0.5 part of glyceryl triacetoacetate, 0.5 parts of free glycerin

0.5 part glyceryl triacetoacetate, 0.5 part

Mannitol
0.5 part of 2-ethyl-hexyl-

acetoacetate
0.5 part of 2-ethyl-hexyl-

acetoacetate, 0.5 part

free glycerol 0.5 parts 2-ethyl-hexylacetoacetate, 0.5 parts of mannitol

clear cloudy

cloudy

clear clear

clear

Discoloration when heated at 177 ° C after heating for ... minutes

clear cloudy

cloudy

clear clear

clear

15 clear

Pale yellow

Pale yellow

Pale yellow

Pale yellow

30th 45 60 75 90 105 120 very Pale Pale yellow Pale yellow Pale yellow yellow charred Pale yellow yellow Pale- yellow Dark Dark dumped black black . yellow yellow yellow celtic Stripes Stripes Yellow with black Stripes yellow yellow Yellow with Yellow with Yellow with Yellow with Yellow with black black black black black Stripes Stripes Stripes Stripes Stripes Pale Pale Pale yellow yellow yellow Dark charred yellow yellow yellow Pale yellow yellow yellow Dark Dark Dark yellow yellow yellow yellow yellow yellow Dark Dark Dark- Dark Dark yellow yellow yellow' . yellow yellow

This test shows the relative ineffectiveness and in some cases, particularly in Examples C and F, in who are worked with mannitol, the unfavorable heat resistance, which can be seen with the addition of further, free polyhydric alcohol to the clarity-improving additives according to the invention.

Example

The following tests illustrate that the salts of the keto acid anhydride dimers according to the invention are only in admixture with the ketoacetic acid compound according to the invention to improve clarity and Color fastness are suitable. A series of compounds is produced, each of which contains 150 parts of vinyl chloride homopolymer, 0.8 part of zinc stearate, 0.7 part of mannitol and 0.05 part of 2,6-di-tert-butyl-4-methyl-phenol as well contains the additives according to Table VII and on a two-roll grinder at .Temperaturen up to 191 ° C is mixed. Each sample is then divided into 2 parts, one at 177 ° C and the other at 191 ° C heated in an air oven to determine heat resistance. The discoloration is checked (Tables VII and VIII). ':

Table VII

Ketoacetic acid Initial 15th 30th Discoloration in the heat at 177 ° C ■. ■■ · .- ■: · 60 75 90 ^Λ 105 Per-
U- component clarity Pale Pale after a heating time of ... minutes yellow ver De of the stabilizer and coloring yellow yellow carbonates very Pale 45 yellow yellow ver A. 0.5 parts magnesium cloudy ■ Pale yellow Pale carbonates benzoate yellow yellow B. 0.5 parts magnesium clear, yellow benzoate colorless Bright yellow Dark ver " ^r - 0.25 parts of dehydrating yellow yellow • coal acetic acid C. 0.6 parts magnesium very yellow yellow Yellow"; Dark Dark Dark charred dehydroacetate cloudy, yellow - yellow yellow ^ ^; colorless ■ '■■ · ■■ ^: D. ■ 0.6 parts calcium " Pink, nearly very Yellow ; Pale yellow Dark black benzoate; weak White Pale yellow yellow cloudy yellow E. 0.6 parts calcium clear, Pale benzoate colorless yellow 0.25 parts of dehydrating acetic acid

109536/379

continuation

Ketoacetic acid Initial 15th 30th Discoloration when heated at 177 ° C 60 75 90 105 Per component clarity Pale Pale after a heating time of ... minutes Dark easy Ver Ver be of the stabilizer and coloring yellow yellow yellow Ver carbonization carbonization 45 coal F. 0.7 parts calcium very yellow dehydroacetate cloudy, very Pale ver Weak Pale yellow carbonates yellow yellow G 0.6 parts magnesium easy yellow dehydroacetate cloudy, 0.25 parts of dehydrating colorless acetic acid

Table VIII

sample Ketoacetic acid component
of the stabilizer Initial
clarity
and coloring Discoloration
after a
15th yellow yellow ng in the heat
Heating time from ..
30th i 191 ° C
. Minutes
45 A. 0.5 part of magnesium benzoate cloudy yellow charred B. 0.5 part of magnesium benzoate clear white yellow charred 0.25 part of dehydroacetic acid yellow C. 0.6 parts of magnesium dehydroacetate , very cloudy Dark yellow Pale yellow charred D. 0.6 parts calcium benzoate yellow very dark charred 1 yellow with Points E. 0.6 parts calcium benzoate very clear, Dark yellow black 0.25 part of dehydroacetic acid White F. 0.7 parts calcium dehydroacetate very cloudy, charred Pale yellow G 0.6 parts of magnesium dehydroacetate slightly cloudy, charred 0.25 part of dehydroacetic acid colorless

These tests clearly show that the coloration and clarity of the compositions containing the dehydroacetic acid and containing the calcium and magnesium salt mixture according to the invention are by far the best and which Heat resistance is at least as good and in most cases slightly better than the masses, which do not contain the clarity-enhancing additive according to the invention. The masses that Magnesium or calcium salt of dehydroacetic acid, but not containing dehydroacetic acid, show in comparison with the polymers, which contain a mixture of the salts and the acid, as well as with the control mass a drop in heat resistance and clarity.

Examples

The base material from Example 5 is made with sodium and potassium benzoate in each case individually and in each case Mixture mixed with dehydroacetic acid. The amounts used and the results are shown in Table IX compiled. . .

Table IX. - ■■ ./. ·.-.-

Per
be Ketoacetic acid component
of the stabilizer Initial
clarity 15th Discoloration when heated at 177 ° C
after a heating time of ... minutes 30th 45 60 75 ^: 90 105 and coloring Bright orange orange Bright Bright Bright- ; black orange orange orange orange A. 0.25 part sodium yellowish, nearly very Pale Pale yellow black benzoate weak
cloudy clear Pale yellow yellow B. 0.25 part sodium clear, yellow benzoate; '.-- _; colorless 0.25 parts of dehydro Bright very Pale yellow yellow black acetic acid orange Pale yellow C. 0.25 part potassium yellowish, yellow benzoate weak cloudy

27

ί boil 4U7

continuation

28

Ketoacetic acid component
of the stabilizer

Initial

clarity
and coloring

Discoloration in the warmth at 177 ° C after one. heating up of ... minutes

30th

60

75

90

0.25 parts potassium

benzoate
0.25 parts of dehydrating

acetic acid

clear,
colorless

nearly
clear

very pale yellow

Pale yellow

yellow

yellow

black

The results of this test show the effectiveness of the clarity-promoting additive with the alkali salts omitted in the stabilizer according to the invention.

Example 7

A series of compositions is produced, each of which has 150 parts of vinyl chloride homopolymer in a mixture with mixed salts of barium and cadmium myristate (4.5 parts) and 0.1 part of 2,6-di-tert-butyl-4-methylphenol as well as the other stabilizers according to Tables X and XI, the mixing on a two-roll grinder takes place at temperatures up to 199 ° C. For each sample, the initial clarity will be on of a press-polished film obtained by pressing at 199 ° C. for 3 minutes. Every sample will then divided into 2 parts, one heated to 177 ° C and the other to 199 ° C in an air oven to keep it warm to determine. Check for discoloration (Tables X and XI). - -

Ketoacetic acid Initial 15th Table X - 30th Discoloration in the Warmth at 60 - 75 177 ° C 105 120 component clarity Bright orange after a heating time of ... Dark 1
Dark Minutes Dark very- 1 ΓΟ-
U of the stabilizer and coloring orange orange orange orange Dark- Ut 45 90 orange Control weak orange Dark A. sample I pink orange Colours, Bright Bright Bright Bright Dark Dark weak yellow yellow orange orange orange orange cloudy Control weak Bright orange B. sample II pink very Bright orange Bright orange Dark Dark (9.75 parts cloudy Bright orange orange orange orange Glycerine) as a orange 0.75 parts clear, very Bright . Bright orange orange orange Dark Dark C. 2-ethyl-hexyl- colorless Bright orange orange orange orange acetoacetate orange 0.75 parts clear, Bright orange D. Glyce'ryl-tri- weak orange acetoacetate pink

Table XI

Ketoacetic acid Initial - Discoloration in the Heat at 191 ° C 45 60 75 90 sample component clarity _t _ - after a heating time of ... minutes orange orange charred of the stabilizer and coloring 15th Bright 30th A. Control sample I weak orange orange pink Colours, Bright orange Dark charred weak orange orange cloudy Salvation- B. ■ Control sample II weak - orange Bright (0.75 parts pink,. orange orange orange Dark charred 'Glycerine) cloudy orange, - as a very With C. 0.75 part 2-ethyl clear, - Bright orange black -hexyl acetoacetate colorless orange zen fleck - '"^ V"''' ¹ - ■ ■ ken ™ "'.

29 .......:, ketoacetic acid
component
of the stabilizer Initial
clarity
and coloring 1 569 407
continuation Ver
nache
30th coloring in the
heating
45 30th rc
inutcn
75 .. 90 sample 0.75 parts glyceryl
triacetoacetate clear,
weak
pink 15th orange orange Heat at 19
»Time from ... M
60 fjünkel-
. .orange
niit. ■:
black
zen ^ Flelc-
ken ·, £ ·: * « charred D. very
Hell-: '■■:
orange Orange; I.

This example shows the effectiveness of the clarity-promoting additive according to the invention, the ketoacetic acid ester, on a new recipe and further explains the comparatively ineffectiveness of pure glycerine regarding an improvement in the clarity of this mass. The use of an additive in which glycerin and a metal salt of a fatty acid are incorporated in U.S. Patent 2,711,401. If glycerine is added to the control mass, which contains the metal salt, in the present example the stabilizer composition obtained according to this patent without any noticeable Improves clarity.

• Example 8

It is a series of materials using 150 parts of vinyl chloride homopolymer in a mixture with a stabilizer of (based on the resin weight) 4.5 parts of the mixed salts barium and cadmium myristate, 0.1 part 2,6-di-tert. -butyl-4-methyl-phenol and the corresponding component according to Tables XII and XIII. Mixing and the heat test are carried out as in Example 7. . _; ''.; ■:., ...: .'-. . . ". '".

.Ketoacetic acid Initial 15; ^: · ■ Table XII 30th I. 60 75 . Minutes 105 120 component clarity Bright · - ■ '■ orange Dark Dark Dark very Per- of the stabilizer and coloring orange Discoloration when heated at 177 ° C orange orange 90 orange Dark be after a heating time of .. Dark orange Control weak- orange ■ A ,; sample I pink 45 Colours, Yellow v yellow orange yellow yellow yellow yellow weak cloudy yellow Control weak, "• ■ Bf sample II Cloudiness (1.5 parts Bright yellow yellow Dark Bright orange orange Octyl diphenyl yellow yellow orange phosphite) orange Control black C. sample III cher (0.76 parts yellow, very Bright yellow yellow yellow yellow Dark- Octyl diphenyl fewer Bright yellow yellow phosphite) cloudy yellow yellow 0.75 parts octyl clear, D. diphenyl colorless phosphite, yellow 0.75 parts Glyceryl tri- - acetoacetate

Ketoacetic acid
. component
of the stabilizer Initial
clarity
and coloring 15th Table XIII Discoloration
after a
45. ing in the λ
Heating rate
60 Värme at 191
«It by ... 'me
75 " ° c
lute
90 105?, sample Control sample I. weak
pink
Colours,
weak
cloudy ■ Bright
orange : 30: orange orange charred A; orange

continuation

sample Ketoacetic acid
component Initial
clarity 15th 30th Discoloration in the heat at 19 Γ C
after a heating time of ... minutes 60 75 90 105 of the stabilizer and coloring yellow yellow 45 yellow Dark charred B. Control sample II weak yellow yellow, (1.5 parts octyl cloudy Ver diphenyl carbonization phosphite) Bright yellow yellow Dark Dark charred C. Control sample III black yellow yellow yellow. yellow, on (0.7-5 parts octyl cher Margins diphenyl yellow charred phosphite) black cher cloudy very Bright yellow Dark Dark charred D. 0.75 parts octyl clear, Bright yellow yellow yellow yellow, diphenyl colorless yellow begins phosphite, to ver 0.75 parts coal Glyceryl tri- acetoacetate

This example of the invention shows the greater effectiveness of the compounds according compared with the use of Phosphitzusätze alone at 177 as well as 191 ° C, particularly during the first hour at 177 ⁰ C and the first 15 minutes at 191 ° C. A comparison of the samples shows that the addition of a small amount of the glyceryl triacetoacetate to the tested phosphite mixtures improves the heat resistance of the composition compared to the use of the pure phosphite. As the table shows, when using the same total amount by weight of the pure phosphite additive on the one hand and a mixture of the phosphite and the ketoacetic acid compound on the other hand, the polymer containing the mixture gives the best properties.

Example9

A series of samples is prepared, each of which has 100 parts of vinyl chloride homopolymer in a mixture with a stabilizer made from (based on the polymer weight) 2 parts of a mixture of magnesium benzoate, Zinc tallow fatty acid salts and mannitol (ratio 3: 4: 5) plus the additives according to the tables XIV and XV contains. Mixing and heat testing are carried out as in Example 7.

Table XIV

Per- . Ketoacetic acid
component Initial
clarity 15th 30th Discoloration in the heat
after a heating time of .. 60 75 177 ° C
Minutes i05 120 oe of the stabilizer and
coloring Pale yellow 45 yellow yellow 90 charred A. Control sample I. cloudy, yellow yellow yellow pale yellow very Pale yellow yellow black B. 0.25 parts DE clear Pale yellow Pale yellow yellow yellow Pale yellow yellow yellow C. Control sample II clear yellow yellow black (1 part TP) ^: very Bright yellow yellow black D. 0.25 parts DE, - clear i Pale yellow Bright Dark 0.5 TeUeTP colorless yellow yellow yellow nearly very yellow yellow black F. 0.25 parts DE, clear, colorless Bright Bright begins 1 part TP colorless yellow yellow to ver nearly very Pale yellow coal F. 0.25 part DE, clear colorless Bright Bright yellow black 0.5 parts GIy- yellow yellow ceryltriaceto- ■; acetate ■ - ^: - ~. , ^ nearly very yellow begins G 0.25 parts DE, i ■ clear; .. ■ / ■ colorless Bright Bright to ver Black λ ; 0.5 parts of GIy-; s: yellow yellow:> coal ceryltriaceto- acetate, 1 part TP;

DE = dehydroacetic acid. TP = tris (nonyl phenyl) phosphite.

Table XV

F. Ketoacetic acid component
of the stabilizer Initial
clarity
and coloring Discoloration when heated at 191 ° C yellow heating time from ..
30th . Minutes
45 sample Control sample I. cloudy, after a
15th Dark yellow black A. G Pale yellow Pale yellow 0.25 part of dehydroacetic acid clear will black B. yellow black Control sample II clear darkened black C. (1 part tris (nonyl-phenyl) - yellow phosphite very 0.25 part of dehydroacetic acid, clear, Pale yellow darkened. black D. 0.5 parts tris (nonyl-phenyl) - colorless yellow phosphite very 0.25 part of dehydroacetic acid, clear, Pale yellow nearly black , E 1 part tris (nonyl-phenyl) - . colorless black ; phosphite Pale yellow 0.25 part of dehydroacetic acid, clear Black ¹ 0.5 part glyceryl triacetoacetate very 0.25 part of dehydroacetic acid, clear, Pale yellow black 0.5 part of glyceryl triacetoacetate, colorless 1 part tris (nonyl-phenyl) - phosphite

This example complements Example 8 in that it demonstrates the effectiveness of blending another ketoacetic acid compound with a different phosphite compared to using the pure phosphite indicates. '

B e i s ρ i e 1 10

A series of samples is made, each containing 100 parts of vinyl chloride homopolymer. Each sample is mixed according to the procedure of Example 7 with the additives shown in Table XVI. Man checks for discoloration and clarity using the same test method (results in Table XVI).

Table XVI

, i stabilizer Initial 15th 30th Discoloration in the heat at 177 ° C. 60 75 90 105 120 sample * D clarity very Pale after a heating time of ... minutes yellow yellow yellow yellow easy , i 0.67 part of Mg benzoate, and coloring Pale yellow 45 carbonization A. 0.67 parts ZS, weak yellow yellow at the edges 0.67 parts of mannitol cloudy Hell- ■ orange Dark very very very very "E. 0.5 parts CA, orange orange Dark Dark Dark Dark B. 0.67 part of Mg benzoate, yellowish, Dark orange orange orange black 0.67 parts ZS, almost un- orange orange F. 0.67 parts of mannitol through orange orange orange orange Light orange Light orange Orange with 0.67 parts Ca stearate, sighted black C. 0.67 parts ZS, + Orange, orange Specks 0.67 parts of sorbitol weak orange Dark very very Dark Dark charred 0.67 parts CA, cloudy orange Dark Dark orange with orange with 0.67 parts ZS, Dark Dark orange orange black black 0.67 parts of sorbitol orange, orange Specks Specks very cloudy orange orange Dark- Dark Orange with charred black 0.33 parts CA, orange orange black 0.67 parts ZS, Dark orange Specks 0.67 parts of sorbitol orange, Bright Bright Bright- ' Bright- Light orange, black 0.22 parts CA, cloudy orange orange orange orange orange, 0.67 parts ZS, Light orange Bright black 0.67 parts of sorbitol easy orange . > Spot: V> \ '. ·' ■ cloudy

ZS = zinc stearate. CA = calcium ethyl acetoacetate. ,. ·. · _. . . '·'; ·

This example shows the adverse results obtained by the addition of the calcium ethylacetoacetate salt described in US Pat. No. 2,307,075. The addition of this salt leads, like the table in connection with two of the heat stabilizer compositions of earlier examples; phhe. the. Composition according to the invention shows a reduction in heat resistance and poor initial clarity and coloration. In addition, has dift ^ asse) the beim'Ersatz de? Calcium stearate, of the heat stabilizer mixture of sample C, is obtained by calcium ethyl acetoacetate salt, poorer heat resistance than when the stearate salt is used. and furthermore the initial clarity and coloration is the better, the lower the amount of Ätttylacetoacetats used. . '■ * ■'''"

B e i s ρ i e 1 11

It is prepared a number of compositions, each of 100 parts of vinyl chloride homopolymer and contains on a two-roll mill at temperatures up to 199 ⁰ C with 0.5 part of magnesium benzoate, 0.7 parts of zinc stearate, 0.8 parts of mannitol plus other stabilizers is mixed according to Table XVII. Each sample is then heated to 177 ° C in an air oven to determine its heat resistance. Check for discoloration (Table XVII).

Table XVII

sample Ketoacetic acid component
of the stabilizer Initial
clarity
and coloring 15th 30th Avail
after one
45 rbung in d
he Erhitzui
60 he warmth
ig time from
75 at 177 ° C
... minute
90 sn
105 120 A. Control sample I. Pale yellow, Light yellow yellow yellow yellow yellow Light yellow darkened charred cloudy yellow B. 0.25 part benzoic acid weak very Pale- yellow yellow yellow yellow Dark charred (Control sample II) cloudy, very Pale yellow yellow, Pale yellow black Specks C. 0.5 parts of benzoic acid weak very Pale yellow yellow yellow yellow Dark charred (Control sample III) cloudy, Pale yellow yellow very Pale yellow D. 0.125 parts of dehydroacetic very very Pale yellow Pale yellow yellow yellow yellow darkened black acid weak Pale yellow yellow cloudy, very Pale yellow E. 0.25 parts of dehydroacetic clear, very very very Pale yellow yellow yellow yellow black acid Pale yellow Pale yellow Pale yellow F. 0.25 part of benzoic acid, weak Pale yellow Pale yellow yellow yellow yellow yellow yellow 3.0 parts epoxidized soy cloudy, very bean oil (control
nrobe IVl Pale yellow I. G LH \ J KJ w L V β
0.5 parts benzoic acid, weak very Pale yellow yellow yellow yellow yellow yellow 3.0 parts epoxidized cloudy, very Pale yellow Soybean oil. (Control Pale yellow sample V) H 0.125 parts of dehydroacetic all very · Pale yellow Pale yellow yellow yellow yellow yellow acid, 3.0 parts epoxy weak Pale yellow dated soybean oil cloudy, very Pale yellow

In this example, the effectiveness of the clarity-enhancing additive, dehydroacetic acid, is compared with the Effectiveness compared that a benzoic acid has higher concentration on clarity. Like the results show, is obtained with as well as without the addition of an epoxidized UI to the dehydroacetic acid stabilizer a superior coloration of the resin without affecting the heat resistance compared to the control composition (sample A) is significantly impaired, and one compared to the benzoic acid stabilizer (especially without the epoxidized oil) improved heat resistance.

Example 12

A series of compounds is produced, each of which contains 100 parts of vinyl chloride homopolymer, on a two-roll grinder at temperatures up to 191 ° C with 2 parts of a mixture of magnesium benzoate, Zinc stearate and mannitol (ratio 3: 4: 5), 2 parts epoxidized soybean oil, 1 part Glyceryl monoricinoleate, 15 parts of acrylonitrile butadiene styrene terpolymer (to modify the impact strength) and the other stabilizers according to Tables XVIII and XIX is mixed. Each sample is then divided into 2 parts, one of which is heated to 177 ° C and the other to 191 ° C in an air oven to obtain the Determine heat resistance. Check for discoloration (Tables XVIII and ΧΓΧ).

Ketoacetic acid
component Initial
clarity , 15 Table XVIII Discoloration in heat
after a heating time of 60 . 75. at 177 ° C
.. minutes ι 105 :: 120 Per
be of the stabilizer and coloring Pale- Dark- Bright orange Dark · ■ · ^./-: ■ yellow 45 yellow orange 90 orange Control sample I. . ■. ■■■ i ^J ! R "·. '
all :., 30th yellow orange '7a weak yellow ·. Pale yellow, very Hefi-7 yellow Dark Salvation- cloudy Bright '■■' .- · ■ ·. yellow... yellow . ... ,orange 0.25 parts: / 7 '' schwaüi " yellow Bright yellow B. Dehydrated cloudy Bright-" yellow . acid yellow.

continuation

Per- Ketoacetic acid
component Initial
clarity 15th 30th Discoloration in heat
after a heating time of 60 75 at 177 ° C
... minutes 105 120 OC of the stabilizer and coloring very Bright yellow yellow Bright orange Bright yellow 45 90 orange C. 0.5 parts glyceryl Pale yellow, yellow yellow Bright triacetoacetate weak Bright Bright yellow Bright orange orange Dark ester cloudy yellow yellow orange orange D. 1 part tris- (nonyl- very Bright orange phenyl) phosphite Pale yellow, very Bright yellow Bright Bright Bright orange Control sample II cloudy Bright yellow yellow yellow orange E. 1 part tris- (nonyl- weak yellow Bright Bright phenyl) phosphite, cloudy, yellow yellow 0.25 parts colorless Dehydrated very very Bright Yellow . Bright orange acid Bright Bright yellow orange F. 1 part tris- (nonyl- colorless, yellow yellow' Bright yellow phenyl) phosphite, weak yellow 0.5 parts cloudy Glyceryl triaceto acetate

Table XEK

sample Ketoacetic acid component
of the stabilizer Initial
clarity
and coloring Discoloration in the heat
after a heating time of ... 15th 30th 45 191-C
Minutes 60 Light orange orange Dark charred A. 'Control sample I. Pale yellow, orange cloudy Pale yellow yellow Dark black B. 0.25 part of dehydroacetic acid weak orange cloudy, very Pale yellow Light yellow yellow Dark charred C. 0.5 parts glyceryl triaceto weak orange acetate ester cloudy, Pale yellow Light yellow yellow Dark charred D. . 1 part tris (nonyl-phenyl) - very orange phosphite Pale yellow, Control sample II cloudy Light yellow yellow Dark black E. 1 part tris (nonyl-phenyl) - weak orange phosphite, 0.25 part cloudy, Dehydroacetic acid colorless Light yellow yellow orange black F. 1 part tris (nonyl-phenyl) - weak phosphite, 0.5 part cloudy, Glyceryl triacetoacetate colorless

This example shows the effectiveness of the clarity-enhancing additives according to the invention in use together with the additive which improves the impact strength (acrylonitrile-butadiene-styrene terpolymer). This improvement is a most valuable property as there are many polymers, especially those for packaging purposes valuable rigid mass, need an impact modifier. Like the exam shows, the stabilizer according to the invention provides an effective improvement in initial clarity and Color of the mass as well as the resistance at the processing temperatures compared to only one Compositions containing phosphite clarity improvers.

, Example 13,

As in Example 2, a series of compositions is made using a post-chlorinated polyvinyl chloride produced using the additives in the same proportions and carrying out the same tests. With this polymer, similar advantages are obtained with the additives according to the invention.

Example 14 '

There are two sets of compositions using 100 parts by weight of vinyl chloride homopolymer and 3.0 parts of epoxidized soybean oil, 2 parts of calcium benzoate and 1.1 parts of zinc stearate as well as the other ingredients according to Tables XX and XXI. Substituting 1.2 parts of calcium benzoate

A third pair of samples is prepared by adding 1.2 parts of calcium ethyl acetoacetate. Mixing the earth and the heat tests are carried out as in Example 7. The results of the test for discoloration in the heat are summarized in Tables XX and XXI.

Ketoacetic acid
component Initial
clarity sample Ketoacetic acid component
of the stabilizer Table XX 15th 30th Discoloration in the heat
after a heating time of ... 60 75 Table XXI in Initial
clarity
and coloring Discoloration in the
after heating 15th 30th 177 ° C
vlinuten 105 120 191 ° C
Minutes 60 Per- of the stabilizer and coloring yellow yellow yellow Bern Place of calcium benzoate) Light yellow charred ver be A. Control sample I. 45 stone Pale yellow, 90 carbonates Control sample I. Pale yellow, yellow Colours cloudy Light yellow charred Brown A. weak B. 1.0 part glyceryl triaceto Pale Pale yellow deep- very ver cloudy acetate yellow yellow Bern- Pale yellow, carbonates. 1.0 part glyceryl very yellow stone- very Brown B. triacetoacetate Pale yellow, Colours weak very cloudy Light yellow deep bern weak C. Control sample II very very Pale yellow very stone Brown ver charred cloudy (Calcium ethyl acetoacetate Pale Pale yellow Pale yellow, Colours carbonates Control sample II very yellow yellow Pale milky deep- C. (Calcium ethyl Pale yellow, yellow Bern- acetoacetate milky stone- Position of the CaI Colours ciumbenzoates) Warmth at
time of ... 45

This example demonstrates the effectiveness with which the ketoacetic acid compounds according to the invention, in conjunction with yet another heat stabilizer mixture, improve clarity. The results further show the unsuitability of the calcium salt of the ketoacetic acid compounds for improving the clarity. _: ·. . ■.,:. ... .. _;

■ Example 15 _:. ■::

A series of compositions is prepared, each of which contains 150 parts of vinyl chloride homopolymer mixed with 3 parts of a mixture of magnesium benzoate, zinc stearate and mannitol (ratio 3: 4: 5) plus the additives shown in Table XXII. The production and testing are carried out as in Example 7. ;: - ■ c ^; - -. ■,

Ketoacetic acid
: ■;.;.: Component
of the stabilizer Initial
clarity
and coloring ■ .15 Table XXII Ver
nache
45 coloring in de
ner heating
60 r heat
time of '..
75 : i 177 ⁰ C
. Minutes
90 105 120 Per
be Control sample ':: weak
cloudy,
very
Bright
orange very
Bright
orange 30th Bright
orange Bright
orange Bright
orange Bright- .
orange Bright
orange Bright
orange A. Bright
orange;

1 569 4UEV

continuation

Per
be Ketoacetic acid
component Initial
clarity 15th 30th Discoloration when heated at 177 ° C
after a heating time of. . . Minutes 60 75 90 105 120 of the stabilizer and coloring very Bright 45 yellow yellow yellow yellow yellow B. 0375 parts very Bright yellow yellow Dehydrated weak yellow acid cloudy, colorless very Bright yellow yellow yellow yellow Dark C. 0.75 parts Pale yellow, Bright yellow Bright yellow Ethylene glycol weak yellow · yellow 3-aminocrotonate cloudy (Control sample II) very Pale Pale Pale Pale Pale yellow D. N-phenylindole, colorless, Pale yellow Pale yellow yellow yellow yellow 0.75 parts weak yellow yellow (Control cloudy sample III) yellow yellow dark Red ver E. 0.75 parts canaries orange leres carbonates Diphenylthio bird orange urea yellow, (Control weak sample IV) cloudy

In this series of tests, the use of the ketoacetic acid compounds according to the invention is used Improved clarity compared to the use of other systems previously studied. As the Table XXII shows the initial clarity and coloration of the ketoacetic acid compound according to FIG Invention containing system versus the corresponding properties in the other three, one Clarity-improving additive-containing systems significantly improved. Those with the addition according to the The heat resistance obtained according to the invention is at least as good and in one case better than that of the additive According to the state of the art.

Example 16
A number of compounds are made from chlorinated polyethylene with a chlorine content of 44% as follows:

A. B. C. D. E. Chlorinated polyethylene (44% chlorine) ...
Zinc stearate 100
0.67
0.67
0.05
0.67 100
0.67
0.67
0.05
0.67 100
0.67
0.67
0.05
0.67
0.25 100
0.67
0.67
0.05
0.67
0.25 100
0.67
0.67
0.05 Mannitol 0.25 2,6-di-tert-butyl-4-methyl-phenol
Magnesium benzoate Magnesium dehydroacetate
Dehydroacetic acid

The mixture of the magnesium salts with the dehydroacetic acid results in a clarity and stabilizer additive similar advantages as in Example 5. The uselessness of the magnesium salt of the dehydroacetate for improvement shows the clarity in comparison with the mixture of dehydroacetic acid with a magnesium salt also in this case a chlorinated polyethylene.

Example 17 A series of compositions are made as follows:

Mixed polymer made of 90% vinyl chloride,

10% vinyl acetate

Zinc stearate .......;

Mannitol

2,6-di-tert-butyl-4-methyl-phenol

Magnesium benzoate

Magnesium dehydroacetate

Dehydroacetic acid

100 0.67 0.67 0.05 0.67

100
0.67
0.67
0.05
0.67

0.25

100
0.67
0.67
0.05

0.67

.100.; .... 0.67 0.67 0.05

0.67 0.25

43 44

In tests similar to those in Example 5, the effectiveness of the mixtures according to the table in terms of stabilization and clarity improvement compared. One obtains with the additive according to the invention in the Vinyl chloride-vinyl acetate copolymer in comparison with the addition of the salt of the dehydroacetate alone similar advantages as with the vinyl chloride homopolymer and the chlorinated polyethylene resin in the Examples 5 and 16.,

Example 18

A series of compositions is produced which contain 100 parts of vinyl chloride homopolymer, 45 parts of dioctyl phthalate, 0.75 part of barium nonylphenate, 0.375 part of cadmium 2-ethyl-hexanoate and the other additives according to Table XXIII. The mixtures are mixed as above and checked for discoloration heated to 177 ° C in an air oven. The results are shown in Table XXIII.

Ketoacetic acid
component Initial
clarity 15th table XXIII 60 . ' 75 177 ° C
Minutes 105 120 Per
be of the stabilizer and coloring nearly very very 90 very Pale Control sample colorless, colorless 30th Pale Pale very Pale yellow A. very nearly Discoloration in the heat
after a heating time of .. yellow yellow Pale yellow weak colorless 45 yellow cloudy nearly very nearly Light Light Light 0.15 parts colorless,- colorless Pale colorless tend- Light tend- tend- B. Dehydrated clear nearly yellow yellow tend- yellow yellow · acid very colorless Bright Bright yellow' yellow yellow 0.75 parts clear, Bright nearly yellow yellow yellow C. Amylbenzoyl colorless yellow Bright colorless acetate. yellow Bright yellow

Table XXIII shows the effectiveness of the stabilizers according to the invention on a vinyl chloride polymer, which contains phenate additives. As the results show, the stabilizers improve the initial one Clarity considerable ", without the heat resistance during the long, for the processing of some vinyl chloride polymers required periods of time is somehow substantially damaged.

Example 19

There are masses using 100 parts of vinyl chloride homopolymer and a heat stabilizer from (based on the polymer weight) 1.2 parts of calcium benzoate, 1.1 parts of zinc stearate and 1.0 part of sorbitol and 0.17 part of dehydroacetic acid in the second sample. The mixing and the Thermal tests are carried out as in Example 7. The discoloration obtained from the heat test is compiled in Tables XXIV and XXV.

Ketoacetic acid Initial .15 Table XXIV 30th in a hurry
45 lerErhitzuri
60 gszeitvon.
75 . ■. Minutes
90 105 120 component
of the stabilizer clarity
and
coloring Bright orange orange orange orange orange orange orange Per
be Control sample Pink, orange With With ' With A- weak Discoloration when heated at 177 ° C Points Points Points cloudy yellow yellow Bern Bern Bern Bern Bern Bern 0.17 parts Pale stone stone stone stone stone stone ^B. Dehydro pink, - Colours Colours Colours Colours Colours Colours acetic acid clear With With With Points Points Points

¹ ketoacetic acid
component
'- of the stabilizer, j χ ,. ■ · - ■: Initial
clarity
and coloring Table XXV 15th Author
after egg
30. ''"^; coloring in the
nerheating
■: .-. ₄₅ Heat at 19
time from ... M
60 rc
to mute
■■ ... ₇₅ ..;:, :: ■■■ -: 90 sample Control sample Pale pink,
weak
cloudy orange Amber
Colours
With
Points Amber
Colours
With
Points Amber
Colours
With
Points strength
Point
education charred A.

continuation

Ketoacetic acid

component

of the stabilizer

Initial

clarity
and coloring

Discoloration when heated at 191 ° C
after a heating time of. . . Minutes

15th

45

60

75

90

0.17 parts
Dehydroacetic acid

Pale pink,
clear

yellow

Yellow amber
With
Points

amber
With
Points

amber
With
Points

charred

This example shows the effectiveness with which the ketoacetic acid compound improves clarity, in conjunction with the heat stabilizer of U.S. Patent 3,004,000.

example

A series of compositions is made using 100 parts of vinyl chloride homopolymer and 3 parts, based on the weight of the polymer, of a heat stabilizer made from a mixture of magnesium benzoate, zinc stearate and mannitol (ratio 3: 4: 5) plus the compound according to Table XXVI. Mixing and heat test at 177 ⁰ C are carried out as in Example 7. FIG. The discoloration during the heat test is summarized in Table XXVI.

Table XXVI

Ketoacetic acid Initial 15th 30th Discoloration when heated at 177 ° C 60 75 90 ■ 105 120 Per component clarity Pale Bright after a heating time of ... minutes yellow Ge _- Ib Margins ver be of the stabilizer and coloring yellow yellow charred carbonates 45 A. Control sample Pale pink, Pale Bright yellow yellow yellow yellow Bern ver weak yellow yellow stone carbonates cloudy Colours B. 0.2 parts. colorless, Bright Isodehydro clear yellow acetic acid

This example shows the effectiveness of the isodehydroacetic acid compound as a clarity enhancing agent.

Example 21

There are two samples made from 100 parts of vinyl chloride homopolymer manufactured. A heat stabilizer mixture is added to the first sample which, based on the weight of the polymer, is 1.8 parts Contains glycerine, 0.75 part calcium benzoate and 0.45 part zinc stearate (according to USA. Patent 3 003 998). The stabilizer for the second sample is made from the material used for the first sample plus 0.33 parts of dehydroacetic acid. Mix as in Example 7 and exhibit each mass by pressing for 3 minutes at 191 ° C a press-polished foil to the initial clarity and color to determine.

The first sample, which does not contain dehydroacetic acid, is slightly cloudy and yellow in color, while the second sample containing dehydroacetic acid is clear and only slightly yellow in color.

6o

Claims (8)

Patent claims: 1. Stabilizer mixtures for vinyl chloride polymers to improve the initial clarity and heat resistance consisting of a nitrogen-free ketoacetic acid compound with at least 8 carbon atoms and a metal salt of an organic acid and / or a metal phenate. 2. Stabilizer mixtures according to claim 1, characterized by a content of alkali or alkaline earth salt as a metal salt. 3. Stabilizer mixtures according to claim 2, characterized by a content of a second Salt of a polyvalent metal and an organic acid. 4. Stabilizer mixtures according to claim 1, characterized by a content of a ketoacetic acid ester of a monohydric or polyhydric alcohol as a ketoacetic acid compound. 5. Stabilizer mixtures according to claim 1, characterized by a content of dehydroacetic acid as a ketoacetic acid compound. 6. Stabilizer mixtures according to claim 1, characterized by a content of a non-toxic ketoacetic acid compound and one non-toxic metal salt. ■ 7. Stabilizer mixtures according to claim 1, characterized by an additional content on an organic phosphite, a phenol and / or a. Epoxy esters with 22 to 150 carbon atoms. . 1 '; «=' 8. Vinyl chloride polymer composition containing a stabilizer mixture according to Claims 1 to 7.