MXPA99005989A

MXPA99005989A - 6-aminouraciles replaced in position 5 as stabilizers for halogenic polymers

Info

Publication number: MXPA99005989A
Application number: MXPA/A/1999/005989A
Authority: MX
Inventors: Friedrich Hanshelmut; Wehner Wolfgang
Original assignee: Witco Vinyl Additives Gmbh
Priority date: 1998-06-26
Filing date: 1999-06-24
Publication date: 2000-12-06

Abstract

A description is given of compounds of the general formula I, in which n is 1 or 2, and is oxygen or sulfur and R 1, R 2, R 3 and R 4 are as defined in claim 1, which are suitable for stabilizing chlorinated polymers, especially P

Description

6-AMINOURACILES REPLACED IN POSITION AS STABILIZERS FOR HALOGENATED POLYMERS Description The invention relates to 6-aminouracils, substituted in position 5, which correspond to formula I represented below and are intended for the stabilization of chlorinated polymers, especially PVC.

PVC can be stabilized by a variety of additives. Lead, barium and cadmium compounds are particularly suitable for this purpose, but are currently controversial for ecological reasons or because of their heavy metal content (see "Kunststoffadditive", R. Gachter / H. Müller, Carl Hanser Verlag , 3"Edition, 1989, pages 303-311, and" Kunststoff Handbuch PVC ", volume 2/1, W. Becker / D. Braun, Cari Hanser Verlag, 2nd Edition, 1985, pages 531-538, as well as Kirk- Othmer: "Encyclopedia of Chemical Technology", 4th Edition, 1994, Vol 12, Heat Stabilizers, pp. 1071-1091) Therefore, research continues on the search for stabilizers and combinations of effective stabilizers that are exempt from lead, barium and cadmium Disubstituted aminouracils in positions 1,3 have already been described in US 3,436,362, US 4,656,209, US 4,352,903 and EP-A-0 768 336, and can be prepared by known methods in one (or more) process steps. It has now been found that the 6-aminourac ilos substituted in position 5 of the general formula I n is 1 or 2, - - Y is oxygen or sulfur, Ri and R2 / independently of one another, are Cx-Ciß alkyl unsubstituted or substituted by C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl, -OH and / or Cl, alkenyl C3-C6, C5-C8 cycloalkyl, phenyl or phenylalkyl C-C9 which is unsubstituted or substituted in the phenyl ring with CJ.sub.12 alkyl, C1-C4 alkoxy, C5-C8 cycloalkyl, -OH and / or Cl, R3 is H, C? -C? 8 alkyl unsubstituted or substituted with -OH, C1-C4 alkoxy, -C = 0 (OR6) and / or -0-COR6, C3-C6 alkenyl, C5-C8 cycloalkyl, C7-C9 phenylalkyl unsubstituted or substituted by -OH, C1-C4 alkyl, C3-C4 alkoxy, -C = 0 (OR6) and / or -0-COR6, or phenyl or naphthyl, R6 is C1-C12 alkyl or alkenyl C2-C? 2, and, if n is 1, R4 is - (C = 0) -alkyl C? -C12, - (C = 0) -O-C3-C12 alkyl, - (C = 0) -C0-C alkylene 2- (C = 0) OZ, where Z is H or C? -Cfi alkyl, - (C = 0) -phenyl, phenyl unsubstituted or substituted with -OH, alkyl C? -C4 / C1-C4 alkoxy, -C = 0 (ORs) and / or -0-CORs, or C? -C? 8 alkyl substituted with halogen and / or -C = 0 (OH) or and, if n is 2, R4 is the group -CHR5-, in which R5 is H, C1-C12 alkyl, unsubstituted phenyl or mono- to penta-substituted with -OH, C1-C4 alkyl, alkoxy 0.-C4 , -C = 0 (ORs) and / or -0-C0R6, are particularly suitable for stabilization of chlorinated polymers such as PVC, for example. For the compounds of the formula I, C 1 -C alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-, i-, sec- or t-butyl. Cs-C8 alkyl is, for example, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, i-octyl, decyl, nonyl, undecyl, dodecyl, pentadecyl, hexadecyl, etc. Preference is given to methyl, ethyl, propyl and butyl, especially methyl and n-butyl.

C3-C3 alkenyl is allyl, 1-butenyl, 2-butenyl, 3-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, -hexenyl, 5-hexenyl and its isomers. Preference is given to alilo. Alkoxy C? -C4 is, for example, methoxy, ethoxy, n-propoxy and n-butoxy and also isopropoxy, isobutoxy and tert-butoxy. C5-C8 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cyclohexyl. C 7 -C 10 phenylalkyl is, for example, benzyl, 1- or 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, or 2-phenylisopropyl, preferably benzyl and 2-phenethyl, especially benzyl. If the aromatic radical is substituted, then it is preferably substituted with three, two or, in particular, a single substituent, and the substituents are, in particular, hydroxyl, chloro, methyl, ethyl, tere-butyl, methoxy or ethoxy. Particular preference is given to hydroxyl, methoxy and tere-butyl. C 0 -C 2 alkylene is a direct bond or, for example, methylene, ethylene, propylene, butylene, octylene or dodecenylene, and all its possible isomers. Preference is given to compounds of the formula I in which Y is oxygen and to those in which n is 1 or 2. Additional advantageous compounds are those in which Y is sulfur. Preference is also given to compounds of the general formula I in which Y is oxygen and n is 1 and Ri and R2, independently of one another, are Ci-C8 alkyl, C7-C9 allyl or phenylalkyl and R3 is H, C alquilo alkyl? -C 8 unsubstituted or substituted with -OH or C 1 -C 4 alkoxy, C 3 -C 6 alkenyl, C 5 -C 3 cycloalkyl or phenyl substituted with -OH, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, C 7 -C 9 phenylalkyl substituted with - OH, C 1 -C 4 alkyl or Q 1 -C 4 alkoxy, or naphthyl, and R 4 is - (C = 0) -C x C 6 alkyl, - (C = 0) -O-C 1 -C 3 alkyl, - (C = 0) -C0-C3 alkylene- (C = 0) OZ, in which formula Z is H or C1-C4 alkyl, - (C = 0) -phenyl, phenyl unsubstituted or substituted with -OH or C? -C4 alkyl / or C 1 -alkyl substituted with halogen and / or -C = 0 (OH), or p <; Similarly, preference is given to compounds of the general formula I in which Y is oxygen and n is 2 and y 2 independently of one another, are C 8 -C 8 alkyl, allyl or C 7 -C 9 phenylalkyl and R 3 is H, unsubstituted Ci-Ciß alkyl or substituted with -OH or C1-C4 alkoxy, C3-C6 alkenyl, C5-C8 cycloalkyl or phenyl substituted with -OH, CX-C4 alkyl or C1-C4 alkoxy, C7-C9 phenylalkyl substituted with -OH, alkyl O.- C4 or C1-C4 alkoxy, or naphthyl, and R4 is the group -CHR5- in which Rs is H, alkyl CL-CS, phenyl unsubstituted or substituted with -OH, C alquilo-C4 alkyl and / or C alco-alkoxy C4 In order to achieve stabilization in the chlorinated polymer, the compounds of the formula I have to be used in a proportion conveniently between 0.01 and 10% by weight, preferably between 0.05 and 5% by weight, and in particular, from 0.1 to 3% by weight. It is also possible to use combinations of compounds of the general formula I with other conventional additives and stabilizers, for example with disaccharide polyols and alcohols and / or perchlorate compounds and / or glycidyl compounds and / or zeolitic compounds and / or layered lattice compounds. (hydrotalcites) as well as, for example, photostabilizers. Examples of such additional components are listed and illustrated below.

-Polyoles and disaccharide alcohols Examples of suitable compounds of this type are: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bis-rimethylolpropane, inositol (cyclitol), polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol (hexitols), maltitol, isomaltitol, cellobiitol, lactitol, licasine, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, palatinitol, tetramethylol-cyclohexanol, tetramethylolcyclopentanol, tetramethylolcycloparanol, xylitol, arabinitol (pentitoles), tetritols, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-O-a-D-glycopyranosyl-D-mannitol dihydrate. Of these, preference is given to disaccharide alcohols. It is also possible to use polyol syrups, such as sorbitol syrup, mannitol syrup and maltitol syrup. The polyols can be used in an amount of, for example, 0.01 to 20, conveniently 0.1 to 20 and, in particular, 0.1 to 10 parts by weight per 100 parts by weight of PVC. Perchlorate Compounds Examples are those of the formula M (C104) n, in which M is Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La or Ce. Depending on the valence of M, the index n is 1, 2 or 3. The perchlorate salts can be present as solutions or they can be complexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols. The ester alcohols also include the partial polyol esters. In the case of polyhydric alcohols or polyols, their dimers, trimers, oligomers and polymers are also suitable, such as di-, tri-, tetra- and polyglycols and likewise di-, tri- and tetrapentaerythritol or poly (vinyl alcohol) in various degrees of polymerization. Other suitable solvents are phosphate esters and also cyclic and acyclic carbonates.

In this context, perchlorate salts can be used in various common forms of presentation; for example, as a salt or solution in water or in an organic solvent as such, or adsorbed on a support material such as PVC, Ca silicate, zeolites or hydrotalcites, or fixed by chemical reaction in a hydrotalcite or other layered reticular compound . As partial ethers of polyols, preference is given to glycerol monoethers and glycerol monothioethers. Further embodiments are described in EP 0 394 547, EP 0 457 471 and WO 94/24200. The perchlorates can be used in an amount of, for example, 0.001 to 5, conveniently 0.01 to 3, and, with particular preference, 0.01 to 2 parts by weight per 100 parts by weight of PVC. Glycidyl compounds These contain the glycidyl group • attached directly to carbon atoms, oxygen, nitrogen or sulfur, and in such compounds Rx and R3 are both hydrogen, in which case R is hydrogen or methyl and n is 0, or Rx and R3 together are -CH2-CH2- or -CH2-CH2-CH2-, in which case R2 is hydrogen and n is 0 or 1. I) Glycidyl esters and b-methylglycidyl esters, which can be obtained by reaction of a compound having at least one carboxyl group in the molecule with epichlorohydrin or glycerol dichlorohydrin or b-methylepichlorohydrin. The reaction conveniently takes place in the presence of bases. As compounds having at least one carboxyl group in the molecule, it is possible to use aliphatic carboxylic acids. Examples of these carboxylic acids are glutaric, adipic, pimelic, suberic, azelaic and sebacic acids, or dimerized or trimerized linoleic acid, acrylic and methacrylic acid, caproic, caprylic, lauric, myristic, palmitic, stearic and pelargonic acids, as well as acids mentioned in connection with organic zinc compounds. However, it is also possible to use cycloaliphatic carboxylic acids such as, for example, cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid. Aromatic carboxylic acids can also be used, examples being benzoic, italic, isophthalic, trimellitic and pyromellitic acids. Analogously, it is possible to make use of carboxyl-terminated adducts of, for example, trimellitic acid with polyols, such as glycerol or 2,2-bis (4-hydroxycyclohexyl) propane. Other epoxy compounds which can be used in the context of this invention are given in EP 0 506 617. ir) Glycidyl ethers or b-methyl glycidyl ethers obtainable by reaction of a compound having at least one alcoholic hydroxyl group and / or free phenolic hydroxyl group with an appropriately substituted epichlorohydrin under alkaline conditions or in the presence of an acid catalyst with subsequent alkaline treatment.

Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol, or poly (oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and of polyepichlorohydrins, butanol, amyl alcohol, pentanol, and of monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol, as well as mixtures of C7-C9 alkanols and C9-Cn alkanols. They are, however, also derived, for example, from cycloaliphatic alcohols, such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis- (4-hydroxycyclohexyl) propane or , 1-bis (hydroxymethyl) cyclohex-3-ene, or possess aromatic nuclei, such as N, N-bis (2-hydroxyethyl) aniline op, p'-bis (2-hydroxyethylamino) diphenylmethane. The epoxy compounds can also be derived from mononuclear phenols such as, for example, phenol, resorcinol or hydroquinone; or they are based on polynuclear phenols, such as, for example, on bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) ) propane, in 4,4 '-dihydroxydiphenyl-sulfone or in condensates of phenols with formaldehyde obtained under acidic conditions, such as phenolic novolaks. Examples of other possible terminal epoxides are: glycidyl-1-naphthyl ether, glycidyl-2-phenylphenyl ether, 2-biphenylyl-glycidyl ether, N- (2,3-epoxypropyl) phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether. . III) N-glycidyl compounds which can be obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least one amino hydrogen atom. These amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane, as well as N, N, 0-triglycidyl-m. -aminophenol or N, N, O-triglycidyl-p-aminophenol. However, the N-glycidyl compounds also include derivatives of N, N'-di-, N, N ', N "-tri- and N, N', N", N '' '-tetraglycidyl of cycloalkyleneureas , such as ethyleneurea or 1,3-propyleneurea and N, N'-diglycidyl derivatives of hydantoins, for example 5,5-dimethylhydantoin or -glycoluril and triglycidyl isocyanurate. IV) S-glycidyl compounds, such as di-S-glycidyl derivatives, which are derived from dithiols, such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether, for example. V) Epoxy compounds having a radical of the above formula in which R x and R 3 together are -CH 2 -CH 2 - and n is O, are bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether or 1, 2 bis (2,3-epoxycyclopentyloxy) ethane. An epoxy resin having a radical of the above formula in which Rx and R3 together are -CH2-CH2- and n is 1 is, for example, 3,4-epoxy-6-methylcyclohexanecarboxylate of (3 ', 4'-epoxy) -6'-methylcyclohexyl) methyl. Examples of suitable terminal epoxides are: a) liquid diglycidyl ethers of bisphenol A, such as Araldit®GY 240, Araldit®GY 250, Araldit®GY 260, Araldit®GY 266, Araldit®GY 2600 and Araldit®MY 790; b) diglycidyl solid ethers of bisphenol A, such as Araldit®GT 6071, Araldit®GT 7071, Araldit®GT 7072, Aral-dit®GT 6063, Araldit®GT 7203, Araldit®GT 6064, Araldit®GT 7304, Araldit® GT 7004, Araldit®GT 6084, Araldit®GT 1999, Araldit®GT 7077, Araldit®GT 6097, Araldit®GT 7097, Araldit®GT 7008, Araldit®GT 6099, Araldit®GT 6608, Araldit®GT 6609 and Araldit® GT 6610; c) liquid diglycidyl ethers of bisphenol F, such as Araldit®GY 281, Araldit®PY 302 and Araldit®PY 306; d) solid polyglycidyl ethers of tetraphenylethane, such as the Epoxy Resin CG® 0163; e) polyglycidyl ether solid and liquid novolac phenol-formaldehyde, such as EPN 1138, EPN 1139, GY 1180 and PY 307; f) o-cresol-formaldehyde novolac solid and liquid polyglycid ethers, such as ECN 1235, ECN 1273, ECN 1280 and ECN 1299; g) liquid glycidyl ethers of alcohols, such as glycidyl ether Shell® 162, Araldit® DY 0390 and Araldit® DY 0391; h) liquid glycidyl ethers of carboxylic acids, such as Shell® Cardura E terephthalic acid ester, trimellitic acid ester and Araldit® PY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as Araldit®PT 810; j) liquid cycloaliphatic epoxy resins such as Araldit®CY 179; k) Liquid N, N, 0-triglycidyl ethers of p-aminophenol, such as Araldit® MY 0510; and 1) tetraglycidyl-4,4'-methylenebenzamine or N, N, N ', N'-tetraglidicildia inofenylmethane, such as Araldit®MY 720 and Araldit®MY 721. Preference is given to the use of epoxy compounds having two functional groups. In principle, however, it is also possible to employ epoxy compounds having one, three or more functional groups. It is predominantly used epoxy compounds, especially diglycidyl compounds, which have aromatic groups. If desired, it is also possible to employ a mixture of different epoxy compounds. Particular preference is given as terminal epoxide compounds to diglycidyl ethers based on bisphenols, for example in 2,2-bis (4-hydroxyphenyl) -panoene (bisphenol A), bis (4-hydroxyphenyl) methane or mixtures of bis (ortho / para- hydroxyphenyl) methane (bisphenol F), for example. The terminal epoxide compounds can be used in an amount of preferably at least 0.1 part, for example from 0.1 to 50, conveniently from 1 to 30 and in particular from 1 to 25 parts by weight, per 100 parts by weight of PVC Hydrotalcites The chemical composition of these compounds is known to those skilled in the art, for example, by DE 3 843 581, US 4,000,100, EP 0 062 813 and WO 93/20135. The compounds of the series of the hydrotalcites can be described by the following general formula M2 + 1-XM3 + X (OH) 2 (Ab ") xb • d H20 in which M '2+ = one or more metals of the Mg group, Ca, Sr, Zn and Sn, An is an anion having the valence n, b is a number of 1-2, 0 <x <0.5, m is a number from 0 to 20. Preferably, An = OH ', C104", HC03", CH3COO "CgHsCOO" CO, (CHOHCOO) 22 ~, (CH2COO) 22 ~, CH3CH0HC00", HP03" or HP04 Examples of hydrotalcites are Al203.6MgO.C02.12H20 (i), Mg4,5Al2 (OH) 13. C03.3, 5H20 (ii) , 4MgO.Al203.C02.9H20 (iii), 4MgO. Al203. C02.6H20, Zn0.3MgO.Al203.C02.8-9H20 and ZnO.3MgO.Al203.C02.5-6H20. Particular preference is given to types i, ii and iii. Zeolites (alkali metal and alkaline earth metal aluminosilicates) These compounds can be described by the following general formula Mx / n [(Al02) x (SiO2) y]. H20 in which n is the charge of the cation M; M is an element of the first or second major group, such as Li, Na, K, Mg, Ca, Sr or Ba; and: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.

Examples of zeolites are sodium aluminosilicates of the formulas Na12Al12Si12048.27 H20 [zeolite A], Na6AlsSi6024.2NaX.7, 5H20, X = OH, halogen, C104 [sodalite]; Na6Al6Si3o072.24 H20; Na8Al8Si4o096.24 H20; Na16Al? SSi2408o .16 H20; Na16Al16Si32096.16 H20; Na56 l5ßSi? 36? 384,250 H20 [zeolite Y], Na86Al86Si? O6? 384.264 H20 [zeolite X]; or the zeolites that can be prepared by complete or partial replacement of the Na atoms by Li, K atoms, Mg, Ca, Sr or Zn, such as (Na, K)? Or Al10 Si22? 64.20 H20; Ca4.5Na3 [(Al02) 12 (SiO2) 12] .30 H20; K9Na3 [(Al02) 12 (SiO2)? 2] .27 H20. Preferred zeolites are those of the formulas Na? 2 Al12Si12? 48.27 H20 [zeolite A], NasAl6Sis024.2NaX.7.5H20, X = OH, Cl, Cl04, l / 2C03 [sodalite], Na6AleSi3o072.24 H20, Na8Al8Si40O96.24 H20, - - Na16Al? 6Si24O80. 16 H20, Na? EAl16Si32? 96. 16 H20, Na56Al5sSi? 3sO384 .250 H20 [zeolite Y], Na8SAl86Si? Oß0384. 264 H20 [zeolite X] and those X and Y zeolites having an Al / Si ratio of about 1: 1, or the zeolites that can be prepared by complete or partial replacement of the Na atoms by Li, K atoms, Mg, Ca, Sr, Ba or Zn, such as (Na, K)? 0Al10Si22O64.20 H20, Ca4.5Na3 [(A102) 12 (Si02) i2] • 30 H20, K9Na3 [(Al02)? 2 (SiO2) i2] -27 H20. The indicated zeolites may also have lower water content, or be anhydrous. Other suitable zeolites are: Na2O.Al203. (2 to 5) Si02. (3.5 to 10) H2O [zeolite P], Na2O.Al203.2Si02. (3.5-10) H2O (zeolite MAP) or the zeolites that can be prepared by complete or partial replacement of the Na atoms by Li, K or H atoms, such as (Li, Na, K, H)? 0Al10SÍ22? 64 .20H2O, K9Na3 [(Al02)? 2 (S02)? 2] .27H20, K4Al4Si4Oi6. 6H20 [zeolite K-F), Na8Al8Si4o096.24H20 [zeolite D], as described in Barrer et al. , J. Chem. Soc. 1952, 1561-71, and in the document US 2 950 952 The following zeolites are also suitable: Kettite K, as described in EP-A-400,961; R zeolite, as described in GB 841,812; zeolite LZ-217, as described in the US document 4. 503,023; LZ-218 zeolite free from Ca, as described in US 4,333,859; zeolite T and zeolite LZ-220, as described in US 4,503,023; Na3K6Al9Si27? 72 .21 H20 [zeolite L]; zeolite LZ-211, as described in the US document 4,503. 023; zeolite LZ-212, as described in US 4,503,023; zeolite O and zeolite LZ-217, as described in US 4,503,023; zeolite LZ-219, as described in US 4,503,023; Rho zeolite and zeolite LZ-214, as described in US 4,503,023; zeolite ZK-19, as described in Am. Mineral. 54 1607 (1969); zeolite W (K-M), as described in the paper by Barrer et al., J. Chem. Soc. 1956, 2882, and Na30Al30SiS6 ?? 92.98 H20 [zeolite ZK-5, zeolite Q]. Particular preference is given to the zeolite P grades of the above formula wherein x is from 2 to 5 and y is from 3.5 to 10, and very particular preference is given to the zeolite MAP of the formula indicated in which x is 2 and y is from 3.5 to 10. In particular, the zeolite referred to is Na-P zeolite, that is, M is Na. This zeolite exists generally in the variants Na-P-1, Na-P-2 and Na-P-3, which differ in their cubic, tetragonal or orthorhombic structure (RM Barrer, BM Munday, J. Chem. Soc. A 1971 , 2909-14). The reference of last quoted bibliography also describes the preparation of zeolites P-1 and P-2. According to said reference, zeolite P-3 is very rare and therefore has virtually no interest in practice. The structure of zeolite P-l corresponds to the structure of gismondite known from the Atlas of Zeolite Structures, mentioned above. In the recent literature (EP-A-384 070) a distinction is made between cubic zeolites (zeolite B or Pc) and tetragonal zeolites (zeolite Px) of type P. Relatively new zeolites of the P type which have Relationships Yes: At lower than 1.07: 1. In this case, they are zeolites having the designation MAP or MA-P, corresponding to "Maximum Aluminum P". Depending on the preparation process, the zeolite P may also include small fractions of other zeolites. A high purity zeolite P has been described in WO 94/26662. Within the scope of the invention it is also possible to use those water-insoluble and finely divided sodium aluminosilicates which have been precipitated and crystallized in the presence of water-soluble organic or inorganic dispersants. These may be introduced into the reaction mixture in any desired manner, before or during precipitation and crystallization. Particular preference is given to sodium zeolite A and sodium P zeolite. The hydrotalcites and / or zeolites can be used in amounts, for example, from 0.1 to 20, suitably from 0.1 to 10 and, in particular, from 0.1 to 5 parts by weight per 100 parts by weight of polymer halogenated Other conventional additives, such as stabilizers, auxiliary materials and processing aids, can also be added to the compositions of the invention, examples being alkali metal compounds and alkaline earth metal compounds, lubricants, plasticizers, pigments, fillers, phosphites, thiophosphites and thiophosphates, 'mercaptocarboxylic esters, esters of epoxidized fatty acids, antioxidants, UV absorbers and photostabilizers, optical brighteners, impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal passivators, flame retardants and propellants, antifog agents, compatibility lizers and anti-plating agents (see "Handbook of PVC Formulating" by EJ Wickson, John Wiley &Sons, New York, 1993). Examples of said additives are the following: I. Loads: Loads (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley &; Sons, Inc., 1993, pp. 393-449) and reinforcing agents (TASCHENBUCH der KUNSTSTOFFADDITIVE, R. Gachter &H. Müller, Carl Hanser, 1990, pp. 549-615) are, for example, calcium carbonate, dolomite, wollastonite, magnesium oxide, hydroxide magnesium, silicates, porcelain earth, talc, glass fibers, glass beads, sawdust, mica, metal oxides, or metal hydroxides, carbon black, graphite, rock dust, heavy spar, glass fibers, talc, kaolin and chalk. Crete is preferred. The fillers can be used in an amount of preferably at least 1 part, for example from 5 to 200, conveniently from 10 to 150 and, in particular, from 15 to 100 parts by weight per 100 parts by weight of PVC. II. Metal soaps: Metal soaps are primarily metal carboxylates of carboxylic acids preferably having a relatively long chain. Familiar examples are stearates and laurates, as well as oleates and salts of shorter chain alkanecarboxylic acids. It is also said that alkylbenzoic acids are included under the expression metal soaps. Metals that may be mentioned are Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce, and rare earth metals. It is often used what are known as synergistic mixtures, such as barium / zinc, magnesium / zinc, calcium / zinc or calcium / magnesium / zinc stabilizers. The metal soaps can be used individually or in mixtures. A review of common metallic soaps is given in the Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A16 (1985), p. 361 and following). It is convenient to use organic metal soaps of the series of the saturated aliphatic C2-C22 carbsxylates, the unsaturated C3-C22 aliphatic carboxylates, the C2-C2 aliphatic carboxylates substituted with at least one OH group, the cyclic and bicyclic carboxylates having 5-22 carbon atoms, unsubstituted benzenecarboxylates substituted with at least one OH group and / or with alkyl 0.-0.6, the unsubstituted naphthalenecarboxylates substituted with at least one OH group and / or with 0-06 alkyl, the phenyl-alkyl-C? ß-carboxylates, the naphthyl-alkyl Ci-Cie-carboxylates or the phenolates, talates and resinates unsubstituted or substituted by C? -C12 alkyl. Specified examples that may be mentioned are the zinc, calcium, magnesium or barium salts of monobasic carboxylic acids such as acetic, propionic, butyric, valeric, hexanoic, enanthic, octanoic, neodecanoic, 2-ethylhexanoic, pelargonic, decanoic, undecanoic, dodecanoic, tridecanoic, myristic, palmitic, isostearic, stearic, 12-hydroxystearic, behenic, benzoic, p-tert-butylbenzoic, N, N-dimethylhydroxybenzoic, 3,5-di-tert-butyl-4-hydroxybenzoic, toluic, dimethylbenzoic, ethylbenzoic, n-propylbenzoic, salicylic, p-tert-octylsalicylic and sorbic; salts of calcium, magnesium and zinc of the monoesters of bivalent carboxylic acids such as oxalic, malonic, succinic, glutaric, adipic, fumaric, pentane-1,5-dicarboxylic, hexane-1,6-dicarboxylic, heptane-1, 7-dicarboxylic, octane-1, 8-dicarboxylic, italic, isophthalic, terephthalic and hydroxy-phthalic; and di- or tri-esters of tri- or tetra-basic carboxylic acids such as hemimelitic, trimellitic, picromellitic and citric acids. Preference is given to the calcium, magnesium and zinc carboxylates of carboxylic acids having 7 to 18 carbon atoms (metal soaps in the strict sense), such as, for example, benzoates or alkanoates, preferably stearate, oleate, laurate, palmitate , behenate, hydroxystearates, dihydroxystearates or 2-ethylhexanoate. Particular preference is given to stearate, oleate and p-tert-butylbenzoate. Also preferred are carboxylates with excess base, such as zinc octoate with excess base. Analogously, preference is given to calcium soaps with excess base. If desired, it is also possible to employ a mixture of carboxylates of different structures. Preference is given to compositions such as those described, which comprise an organic zinc compound and / or an organic calcium compound.

In addition to the compounds mentioned, organic aluminum compounds are also suitable, which are compounds analogous to those mentioned above, especially aluminum tristearate, aluminum distearate and aluminum monostearate, as well as aluminum acetate and basic derivatives thereof. Additional information about the aluminum compounds that can be used and which are preferred is given in US 4,060,512 and US 3,243,394. Also suitable are, in addition to the aforementioned compounds, organic rare earth compounds, especially compounds analogous to those mentioned above. The expression compound of rare earths means especially compounds of the elements cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum and yttrium, the mixtures being preferred - especially with cerium. Other preferred rare earth compounds can be found in EP-A-0 108 023. It is possible, if desired, to employ a mixture of zinc, alkali metal, alkaline earth metal, aluminum, cerium, lanthanum or structure lanthanide compounds different. It is also possible to coat organic zinc compounds, organic aluminum compounds, organic cerium compounds, organic alkali metal compounds, organic alkaline earth metal compounds, organic lanthanum compounds or organic compounds of lanthanide elements on an aluminosal compound; in connection with this see also DE-A-4 031 818. The metallic soaps and / or their mixtures can be used in an amount of, for example, 0.001 to 10 parts by weight, conveniently 0.01 to 8 parts by weight. and, with particular preference, from 0.05 to 5 parts by weight per 100 parts by weight of PVC. The same applies to additional metal stabilizers: III. Additional metal stabilizers: Here mention can be made in particular of organic tin stabilizers. These can be the carboxylates, mercaptides and sulfides, in particular. Examples of suitable compounds are described in US 4,743,640. XV Alkali metal and alkaline earth metal compounds: These compounds are primarily understood as the carboxylates of the acids described above, but also the corresponding oxides and / or hydroxides or carbonates. Mixtures thereof with organic acids are also suitable. Examples are LiOH, NaOH, KOH, CaO, Ca (OH) 2, MgO, Mg (OH) 2, Sr (OH) 2, Al (OH) 3, CaCO 3 and MgCO 3 (as well as basic carbonates, such as magnesia alba and huntita), and also salts of Na and K of fatty acids. In the case of alkaline earth metal carboxylates and Zn it is also possible to use their adducts with MO or M (OH) 2 (M = Ca, Mg, Sr or Zn), known as "base excess" compounds. In addition to the combination of stabilizers of the invention, it is preferred to employ alkali metal carboxylates, alkaline earth metal carboxylates and / or aluminum carboxylates. V. Lubricants: Examples of suitable lubricants are mountain wax, fatty acid esters, PE waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earth metal soaps. Lubricants that can be used are also described in "Kunststoff dditive", R. Gáchter / H. Müller, Cari Hanser Verlag, 3rd edition, 1989, pages 478-488. Mention may also be made of fatty ketones (such as those described in DE 4 204 887) and lubricants based on silicones (such as those described in EP 0 225 261) or combinations thereof, such as those indicated in EP 0 259 783. Calcium stearate is preferred. The lubricants can also be applied to an aluminosal compound; see also DE-A-4 031 818 in this regard. VI. Plasticizers: Examples of suitable organic plasticizers are those of the following groups: A) Phthalates: Examples of such plasticizers are dimethyl phthalates, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutylglycol, benzyl-butyl and diphenyl, as well as mixtures of phthalates, such as phthalates of C7-C9 alkyl and C9-Cn, obtained from predominantly linear alcohols, n-C3-0 alkyl phthalates and n-C8-Oo alkyl phthalates. Of these, preference is given to the dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl and benzyl-butyl phthalates, as well as the mixtures of alkyl phthalates indicated. Particular preference is given to the di-2-ethylhexyl, diisononyl and diisodecyl phthalates, which are also known by the common DOP abbreviations (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate) and DIDP (diisodecyl phthalate). B) Esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid: examples of said plasticizers are di-2-ethylhexyl adipate, diisooctyl adipate • (mixture), diisononyl adipate (mixture), diisodecyl adipate ( mixture), benzyl-butyl adipate, benzyl-octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate (mixture). Di-2-ethylhexyl adipate and diisooctyl adipate are preferred. C) TrimelitATES, examples of which are tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) as well as tri-C3-C8 alkyl trimellitate, tri-C6 alkyl x0, tri-C7-C9 alkyl and tri-C9-Cn alkyl. The last trimellitATES are formed by esterification of trimellitic acid with the corresponding alkanol mixtures. Preferred trimelliths are tri-2-ethylhexyl trimellitate and the trimellitates of alkanole mixtures mentioned above.

Conventional abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate) and TITD ™ (triisotridecyl trimellitate). D) Epoxy plasticizers: these are essentially epoxidized unsaturated fatty acids, such as epoxidized soybean oil. E) Polymer plasticizers: a definition of these plasticizers and examples of them are given in "Kunst-stóffadditive", R. Gáchter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, section 5.9.6, pages 412-415, as well as in "PVC Technology", W.V. Titow, 4th edition, Elsevier Publ., 1984, pages 165-170. The most common starting materials for preparing the polyester plasticizers are dicarboxylic acids, such as adipic, phthalic, azelaic and sebacic acids; diols, such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol. F) Phosphoric esters: a definition of these esters is given in the work mentioned above "Taschenbuch der Kunststoffadditive", section 5.9.5, pp. 408-412. Examples of said phosphoric esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl phosphate and diphenyl, cresyl phosphate and diphenyl, triphenyl phosphate, phosphate tricresyl and trixilenyl phosphate. Preference is given to tri-2-ethylhexyl phosphate and to ®Reofos 50 and 95 (Ciba Spezialit tenchemie). G) Chlorinated hydrocarbons (paraffins). H) Hydrocarbons. I) Monoesters, e.g., butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkylsulphonic esters. J) Glycol esters, e.g., diglycol benzoates. Definitions and examples of plasticizers of groups G) to J) are given in the following manuals: "Kunststoffadditive", R. Gáchter / H. Müller, Cari Hanser Verlag, 3rd edition, 1989, section 5.9.14.2., Pp. 422-425 (group G), and section 5.9.14.1., P. 422, (group H). "PVC Technology", W.V. Titow, 4th edition, Elsevier Publishers, 1984, section 6.10.2, pages 171-173 (group G), section 6.10.5, page 174 (group H), section 6.10.3, page 173 (group I) and section 6.10 .4, pages 173-174 (group J). It is also possible to use mixtures of different plasticizers. The plasticizers can be used in an amount of, for example, 5 to 20 parts by weight, conveniently 10 to 20 parts by weight, per 100 parts by weight of PVC. The rigid or semi-rigid PVC preferably contains up to 10%, particularly preferably up to 5%, or does not contain any amount of plasticizer. VII. Pigments: Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are Ti02, pigments based on zirconium oxide, BaS04, zinc oxide (zinc white) and lithopones (zinc sulphide / barium sulfate), carbon black, black carbon / titanium dioxide mixtures, iron oxide pigments, Sb203, (Ti, Ba, Sb) 02, Cr203, spinels, such as cobalt blue and cobalt green, Cd (S, Se ), and ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolpyrrole pigments and anthraquinone pigments. Preference is also given to Ti0 in micronized form. A definition and additional descriptions are given in the work "Handbook of PVC Formulating", E.J. Wickson, John Wiley &; Sons, New York, 1993. VIII. Phosphites (phosphorous triesters): Examples are triphenyl phosphite, diphenyl-alkyl phosphites, phenyl-dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, -di-tert-butylphenyl), diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diphosphite of bisisodecyloxytentaerythritol, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl tristebityl triphosphite, bis ( 2,4-di-tert-butyl-6-methylphenyl) -methyl, and bis (2,4-di-tert-butyl-6-methylphenyl) -ethyl ester. Particularly suitable are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite and, with particular preference, the aryl dialkyl and alkyl diaryl phosphites, examples being phenyl-didecyl phosphite , 2,4-di-tert-butylphenyl-didodecyl phosphite, 2,6-di-tert-butylphenyl-didodecyl phosphite and the dialkyl and diaryl pentaerythritol diphosphites, such as distearyl pentaerythritol diphosphite, as well as triaryl phosphites do not stoichiometric, whose composition is, for example, (H19C9-C6H4) 01.5P (OC? 2.13H25.27) ?, 5 or (H8Ci7-C6H4) 02P (i-C8H170) or (H19C9-C6H4)?!, 5P (OC9, ?? H19.23) 1.5 or (-C 10 H 21 O) 2 P-O O-P (Oi-C 10 H 21), CH 3 CH 3 Preferred organic phosphites are distearyl pentaerythritol diphosphite, trisnonylphenyl phosphite and phenyl didecyl phosphite. Other suitable phosphites are phosphorous diesters (with the radicals mentioned above) and phosphorous monoesters (with the radicals mentioned above), possibly in the form of their alkali metal, alkaline earth metal, zinc or aluminum salts. It is also possible that these phosphorous esters have been applied to an aluminosal compound; in this regard, see also DE-A-4 031 818. The organic phosphites can be used in an amount of, for example, 0.01 to 10, conveniently of -0.05 to 5 and, in particular, 0.1 to 3 parts by weight per 100 parts by weight of PVC. IX. Thiophosphites and thiophosphates: Thiophosphites and thiophosphates are compounds of the general type (RS) 3P, (RS) 3P = 0 and (RS) 3P = S, respectively, as described, for example, in DE 2 809 492, EP 0 090 770 and EP 0 573 394. Examples of these compounds are trithiohexyl phosphite, tritiooctyl phosphite, trithiolauryl phosphite, trithiobenzyl phosphite, tris (carbo-isooctyloxy) methyl ester of trithiophosphorous acid, tris (carbotrimethyl-cyclohexyloxy) ester. methyl trithiophosphorous acid, S, S, S-tris (carbo-isooctyloxy) -methyl ester of trithiophosphoric acid, S, S, S-tris- (carbo-2-ethylhexy-loxy) methyl ester of trithiophosphoric acid, ester S, S, S-tris-1- (carbohexyloxy) ethyl of trithiophosphoric acid, S, S, S-tris-l- (carbo-2-ethylhexyloxy) ethyl ester of trithiophosphoric acid and ester S, S, S-tris- 2- (carbo-2-ethylhexyloxy) ethyl of trithiophosphoric acid. X. Mercaptocarboxylic esters: Examples of these compounds are esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic acids and thiolactic acid, mercaptoethyl stearate and mercaptoethyl oleate, as described in patents FR 2 459 816, EP 0 090 748, FR 2 552 440 and EP 0 365 483. The generic mercaptocarboxylic esters also include polyol esters and their partial esters, as well as thioethers derived therefrom. XI. Esters of epoxidized fatty acids and other epoxy compounds: The combination of stabilizers of the invention may additionally preferably comprise at least one epoxidized fatty acid ester. Esters of this type particularly suitable are those of fatty acids from natural sources (glycerides of fatty acids), such as soybean oil or rapeseed oil. However, it is also possible to use synthetic products such as epoxidized butyl oleate. Epoxidized polybutadiene and polyisoprene can also be used, as such or in partially hydroxylated form, or glycidyl acrylate and glycidyl methacrylate homo- or copolymers can be used. These epoxy compounds may also have been applied to an aluminosal compound; in this regard see also DE-A-4 031 818. XII. Antioxidants: Examples of suitable compounds of this type are: alkylated monophenols, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-dihydrogen tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4- methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxy- methylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1 '-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1' - il) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol, octylphenol, nonylphenol, dodecylphenol, and mixtures thereof. Alkyltiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-didodecylthiomethyl-4-nonylphenol. Alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4- stearate hydroxyphenyl, and bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate. Hydroxylated thiodiphenyl ethers, for example, 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl- 3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amylphenol), and 4,4'-disulfide - bis (2,6-dimethyl-4-hydroxyphenyl). Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl] -6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'- methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-iso-butylphenol) , 2, 2'-methylenebis [6- (a-methylbenzyl) -4-nonyl-phenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphene-nol], 4, 4 '-methylenebis (2,6-di-tert-butylphenol), 4,' -methyl-lenobis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy) 2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2) -methyl-phenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, bis [3, 3-bis- (3'-ester) butyl-4 '-hydroxyphenyl) butyrate] of ethylene glycol, bis (3-tert-butyl-4-hydroxy) 5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl], 1,1-bis (terephthalate) terephthalate. 3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-buty1-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-phenyl) propane, 2, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane and 1, 1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane . Benzyl compounds, for example, 3,5, 3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3, 5-dimethylbenzyl mercaptoacetate, tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl) sulfide 4-hydroxybenzyl) and isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate. Hydroxybenzylated malonates, for example diocta-decyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) - dioctadecyl malonate, mercaptoethyl-2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate of didodecyl and 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) di [4- (1,1,3,3-tetramethyl-butyl) -phenyl] malonate].

Hydroxybenzyl aromatic compounds, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) 2,4,6-trimethylbenzene, 1,4-bis (3,5-dihydro), tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol. Triazine compounds, for example 2,4-bisoctylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- (3 , 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-hydroxyphenoxy) - 1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, isocyanurate of 1, 3, 5-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl), isocyanurate of 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2, 4, 6-tris (3 , 5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hexahydro-1, 3, 5-triazine and 1,3,4-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate. Phosphonates and phosphonites, for example, dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, 3,5-di-tert-butyl Dioctadecyl-4-hydroxybenzylphosphonate, 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate dioctadecyl, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 4,4'-biphenylenediphosphonate tetrakis (2,4-di-tert-butylphenyl), 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1, 3, 2-dioxaphosphocin and 6- fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocin. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide and N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate octyl. Esters of b- (3,5-di-tert-butyl-4-hydroxyphenyl) ropionic acid with mono- or polyvalent alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, dipentaerythritol, isocyanurate of tris (hydroxyethyl), N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, ditrimethylolpropane and 4-hydroxymethyl-l-phospha-2,6,6-trioxabicyclo [2.2 .2] octane. Esters of b- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyvalent alcohols, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1, 9- nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Esters of b- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3 -thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent alcohols, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, , 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-aethylene glycol decanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-l-phospha-2,6,6-trioxabicyclo [2.2.2] octane. Amides of b- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, and N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine. Vitamin E (tocopherol) and its derivatives. Preference is given to antioxidants of groups 1-5, 10 and 12, especially 2,2-bis (4-hydroxyphenyl) propane, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid esters with octanol, octadecanol or pentaerythritol or tris (2,4-di-tert-butylphenyl) phosphite. It is also possible, if desired, to use a mixture of antioxidants of different structures. The antioxidants can be used in an amount of, for example, 0.01 to 10 parts by weight, conveniently 0.1 to 10 parts by weight, and in particular 0.1 to 5 parts by weight per 100 parts by weight. PVC weight. XIII. UV Absorbers and Photostabilizers: Examples of these are: 2- (2'-Hydroxyphenyl) benzotr azoles, such as, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5' -di-tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5' - (1,1,3, 3 - etrame ilbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' -methylphenyl) -5-chloro-benzotriazole, 2- (3 '-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, - (3 ', 5' -di-tert-amyl-2 '-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, mixtures of 2- (3 '-tert -butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) ) carbonylethyl] -2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonyl-ethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 '-hi-droxy-5' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3 '- tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl ) benzotriazole, 2- (3 '-dodecyl-2' -hi-droxy-5 '-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5' - (2-isooctyloxycarbonylethyl) -phenylbenzotriazole , 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -benzotriazole with polyethylene glycol 300; and [R-CH2CH2-COO-CH2CH2-] 2-, where R 3 '-tert -butyl-4' -hydroxy-5'-2H-benzotriazol-2-yl-phenyl. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4' -trihydroxy and 2'-hydroxy-4, 4 derivative '-dimetoxi. Esters of substituted or unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl- 2,4-di-tert-butylphenyl 4-hydroxybenzoate, hexa-decyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate and 3, 2-Methyl-4,6-di-tert-butylphenyl-5-di-tert-butyl-4-hydroxy-benzoate. Acrylates, for example a-cyano-b, ethyl b-diphenylacrylate or a-cyano-b, isooctyl-ethyl biphenylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-b-methyl-p-methoxycinnamate or butyl a-cyano-b-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (b-carbomethoxy-b-cyanovinyl) -2-methy1indoline. Nickel compounds, for example nickel complexes with 2, 2'-thiobis [4- (1, 1, 3, 3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi-ethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters such as methyl or ethyl ester, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes with ketoximes, such as 2-hydroxy-4-methylphenyl-undecyl ketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands. Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyl-oxanilide , 2-ethoxy-2'-ethyl-oxa-nilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2 '-ethyl-5, 4' -di-tert-butyl-oxanilide, and mixtures of oxanilides disubstituted with o- and p-methoxy and o- and p-ethoxy. 2- (2-Hydroxyphenyl) -1,3,5-triazines, for example 2, 4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4) -propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5 -triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy) 3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazine. Sterically hindered amines, for example bis (2, 2, 6,6-tetramethyl-piperidin-4-yl) sebacate, bis (2, 2, 6,6-tetramethylpiperidin-4-yl) succinate, bis-bacca-sebacate (1, 2, 2, 6, 6-pentamethylpiperidin-4-yl), bis (l-octyloxy-2, 2,6,6,6-tetramethylpiperidin-4-yl) sebacate, n-butyl-3, 5-di -tert-butyl-4-hydroxybenzymalonate bis (1, 2, 2, 6, 6-pentamethylpiperidyl), the condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear condensates or cyclic of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, nitrilotriacetate of tris (2, 2, 6, 6-tetramethyl-4-piperidyl), 1, 2, 3, 4-butanetetratoate tetrakis (2,2,6,6-tetramethyl-4-piperidyl), 1,1 '- ( 1,2-ethanediyl) -bis (3,3, 5, 5-tetramethylpiperazinone), 4-benzoyl-2, 2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 2- n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) m bis (1, 2, 2, 6, 6-pentamethylpiperidyl) allonate, 3-n-octyl-7, 7, 9, 9-tetramethyl-1,3,8-triazaspiro- [4.5] decane-2, 4- dione, bis (1-octyloxy) -2, 2,6,6,6-tetramethylpiperidyl sebacate), bis (l-octyloxy-2,6,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensates of N, N ' bis (2, 2, 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-dihydro- (4-n-butylamino-2, 2,6,6-tetramethylpiperi-dil) -1,3,5-triazine and 1,2-bis (3-aminopro-phenylamino) ethane, the 2-chloro-4 condensate , 6-di (4-n-butylamino-1,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-amino-propylamino) ethane, 8-acetyl- 3-dodecyl-7,7,9,9-tetramethyl-l, 3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl) 4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione, mixtures of 4-hexadecyloxy- and 4-stearyl-oxy-2, 2,6,6-tetramethylpiperidin a, the condensate of N, N'-bis- (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and also 4-butylamino-2, 2,6,6-tetramethylpiperidine (CAS Reg. No. [136504 -96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecyl succinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2-undecyl- 7, 7,9, 9-tetramethyl-l-oxa-3,8-diaza-4-oxospiro [4.5] decane, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-oxa -3,8-diaza-4-oxospiro [4.5] decane and epichlorohydrin, 1,1-bis- (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N '-bisformyl-N, N' -bis (2,2,6,6- -tetramethyl-4-piperidyl) hexamethylenediamine, the diester of 4-methoxymethylene-malonic acid with 1,2,2,6,6- pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2, 2, 6, 6-tetramethyl-4-piperidyl)] siloxane, the reaction product of maleic anhydride-α-olefin copolymer and 2, 2 , 6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine. XIV. Propellants: Examples of propellants are organic compounds of the azo and hydrazo type, tetrazoles, oxazines, isatoic anhydride, as well as sodium carbonate and sodium bicarbonate. Preference is given to azodicarboxamide and sodium bicarbonate and their mixtures. Definitions and examples of impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal passivators, optical brighteners, flame retardants, antifog agents and compatibilizers are described in "Kunststoffadditive", R. Gachter / H. Müller, Cari Hanser Verlag, 3rd edition, 1989, in the "Handbook of Polyvinyl Chloride Formulating", E.J. Wickson, J. Wiley & Sons, 1993, and "Plastics Additives", G. Pritchard, Chapman & Hall, London, edition, 1988. Impact modifiers are also described in detail in "Impact Modifiers for PVC", J.T. Lutz / D.L. Dunkelberger, John Wiley & Sons, 1992. XV. b-Dicetones, b-ketoesters: 1,3-dicarbonyl compounds that can be used can be linear or cyclic dicarbonyl compounds. Preference is given to the use of dicarbonyl compounds of the following formula: R '? CO-CHR'2-COR'3 / in which R'i is alkyl 0-C22, C5-C? 0 hydroxyalkyl, C2-C? 8 alkenyl, phenyl, phenyl substituted with OH, d-C4 alkyl, 0-C4 alkoxy or halogen, phenyl C7-0 alkyl, C5-C12 cycloalkyl, C5 cycloalkyl 02 substituted with 0-C4 alkyl or a group -R's-S-R'ß or -R'5-0-R'6, R'2 is hydrogen, C? -C8 alkyl, C2-C12 alkenyl, phenyl, alkylphenyl C7-02, phenylalkyl C-C10 or a group -CO-R '/ R'3 is as defined for R'x or is alkoxy -Cia, R'4 is 0-C4 alkyl or phenyl, R'5 is alkylene - or - and R'6 is O-C12 alkyl, phenyl, C7-C8 alkylphenyl or C7-0 phenylalkyl. These include the hydroxyl-containing diketones of EP 0 346 279 and the oxa- and thia-diketones of the invention. EP 0 307 358, as well as keto esters based on isocyanic acid of the US document 4. 339,383. R'i R * 3 as alkyl, may be in particular C -C 8 alkyl, such as for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tere-butyl, pentyl, hexyl, heptyl, octyl, decyl , dodecyl or octadecyl.

R'i and '3 as hydroxyalkyl are in particular a group - (CH 2) n-OH in which n is 5, 6 or 7. R'i and R 3 as alkenyl can be, for example, vinyl, allyl, methallyl, -butenyl, 1-hexenyl or oleyl, preferably allyl. R'i and R'3 as phenyl substituted with OH, alkyl, alkoxy or halogen can be for example tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl. R'i and! 3 as phenylalkyl are in particular benzyl. R'2 and R'3 as cycloalkyl or alkylcycloalkyl are, in particular, cyclohexyl or methylcyclohexyl. R'2 as alkyl can be in particular 0-C alkyl. R'2 as C2-C12 alkenyl can be in particular allyl. R'2 as alkylphenyl may be in particular tolyl. R'2 as phenylalkyl can be in particular benzyl. Preferably, R'2 is hydrogen. R'3 as alkoxy may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R'5 as alkylene - or is, in particular, C2-C4 alkylene. R's as alkyl is, in particular, C4-d2 alkyl, such as, for example, butyl, hexyl, octyl, decyl or dodecyl. R'6 as alkylphenyl is in particular tolyl. R's as phenylalkyl in particular is benzyl. Examples of 1,3-dicarbonyl compounds of the above formula and their chelates with alkali metal, alkaline earth metal and zinc are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-2,4-heptanedione, benzoyl. -acetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) ) methane, 1-benzoyl-l-acetylnonano, benz-oylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis- (4-tert-butylbenzoyl) methane, benzoylformylmethane, benz-o-phenylacetylmethane, bis-cyclohexanoylmethane, di-pival-oil-methane, 2-acetylcyclopentanone, 2-benzoylcyclopentane, methyl, ethyl and allyl diacetoacetate, methyl and ethyl benzoyl-, propionyl- and butyrylacetoacetate, triacetylmethane, acetoacetate methyl, ethyl, hexyl, octyl, dodecyl or octadecyl, methyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl benzoylacetate, and also alkyl-8-propionylacetates and butyrylacetates; ethyl, propyl, butyl, hexyl or octyl stearoylacetate, as well as polycyclic b-ketoesters, as described in EP 0 433 230, and dehydractic acid, and its zinc, magnesium or alkali metal salts. Preference is given to 1,3-diketone compounds of the above formula in which R'i is alkyl O-s, phenyl, phenyl substituted with OH, methyl or methoxy, phenylalkyl C7-0 or cyclohexyl, R'2 is hydrogen and R'3 is as defined for R'i. The 1,3-diketone compounds can be used in an amount of, for example, 0.01 to 10, conveniently 0.01 to 3 and, in particular, 0.01 to 2 parts by weight per 100 parts in PVC weight. Examples of the chlorinated polymers to be stabilized are: polymers of vinyl chloride and vinylidene chloride, vinyl resins comprising vinyl chloride units in their structure, such as vinyl chloride copolymers, and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, fumarate diethyl or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with aldehydes, ketones and other unsaturated compounds, such as acrolein, crotonic aldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; vinylidene chloride polymers and their copolymers with vinyl chloride and other polymerizable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and acrylic acid substituted on a; chlorinated styrene polymers, for example dichlorostyrene; chlorinated rubbers; chlorinated ethylene polymers; polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, natural and synthetic chlorinated rubbers, as well as mixtures of these polymers with each other or with other polymerizable compounds. In the context of this invention, PVC also encompasses copolymers with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers. Preference is given to a PVC homopolymer, alone or in combination with polyacrylates. Also included are PVC graft polymers with EVA, ABS and MBS. Preferred substrates are also mixtures of the aforementioned homo- and copolymers, especially vinyl chloride homopolymers, with other thermoplastic polymers and / or elastomers, especially mixtures with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA , EPDM and polylactones. Examples of such components are compositions of (i) 20-80 parts by weight of a vinyl chloride homopolymer (PVC) and (ii) 80-20 parts by weight of at least one thermoplastic copolymer based on styrene and acrylonitrile, in particular of the group ABS, NBR, NAR, SAN and EVA. The abbreviations used for the copolymers are familiar to those skilled in the art and have the following meanings: ABS: acrylonitrile-butadiene-styrene; SAN: styrene-acrylonitrile; NBR: acrylonitrile-butadiene; NAR: acrylonitrile-acrylate; EVA: ethylene-vinyl acetate. Particularly suitable are styrene-acrylonitrile copolymers based on acrylate (ASA). Preferred components in this context are polymer compositions comprising as components (i) and (ii) a mixture of 25-75% by weight of PVC and 75-25% by weight of the aforementioned copolymers. Examples of such compositions are: 25-50% by weight of PVC and 75-50% by weight of copolymers or 40-75% by weight of PVC and 60-25% by weight of copolymers. Preferred copolymers are ABS, SAN and modified EVA, especially ABS. NBR, NAR and EVA are also particularly suitable. In the composition of the invention it is possible that one or more of the aforementioned copolymers are present. Particularly important components are compositions comprising (i) 100 parts by weight of PVC and (ii) 0-300 parts by weight of ABS and / or SAN-modified ABS, and 0-80 parts by weight of the copolymers NBR, NAR and / or EVA, but especially EVA. For stabilization in the context of this invention, additionally suitable polymers are, in particular, recycled chlorinated polymer materials, these polymers being the polymers described in greater detail above which have also suffered deterioration throughout their processing, use or storage. A recycled PVC material is particularly preferred. The recycled materials can also include small amounts of foreign substances, such as, for example, paper, pigments, adhesives, which are often difficult to separate. These foreign substances - may also come from contact with various materials in the course of their use or reprocessing, examples being fuel residues, coating material fractions, metal traces and initiator residues. The stabilization according to the invention is particularly advantageous in the context of PVC formulations such as those which are conventional for pipes and profiles. The stabilization can be carried out without heavy metal compounds (Sn, Pb, Cd, Zn stabilizers). This feature offers advantages in certain fields, since heavy metals - with the exception of zinc at best - are often undesirable both during the production and during the use of certain PVC articles., for ecological reasons. The production of stabilizers containing heavy metals also often causes problems from the point of view of industrial hygiene. Similarly, the processing of minerals containing heavy metals is frequently associated with serious effects on the environment, including in this case the environment, the biosystem of mankind, animals (fish), plants, air and soil. For these reasons, the incineration and burial in landfills of plastic materials containing heavy metals is also challenged. The invention also relates to a PVC stabilization method, which comprises adding thereto at least one of the stabilizer combinations mentioned above. The stabilizers can be conveniently incorporated by the following methods: as an emulsion or dispersion (one possibility, for example, is the form of a paste-like mixture) One advantage of the combination of the invention in the case of this form is the stability of the pasta.); as a dry mixture in the course of mixing additional components or polymer blends; by direct addition - to the processing apparatus (eg calenders, mixers of various types, extruders and the like), or as a solution or melt or in the form of flakes or nodules in a powder-free form as a product consisting of a single package . The stabilized PVC according to the invention, to which the invention refers analogously, can be prepared in a manner known per se using devices known per se such as the aforementioned processing apparatus for mixing the combination of stabilizers of the invention and any other additives with PVC. In this case, the stabilizers can be added individually or in the form of a mixture, or otherwise in the form of so-called masterbatches. The stabilized PVC according to the present invention can be put into the desired shape by known methods. Examples of such methods are grinding, calendering, extrusion, injection molding or spinning, as well as extrusion-blow molding. Stabilized PVC can also be transformed into alveolar materials. A stabilized PVC according to the invention is suitable, for example, for hollow articles (bottles), packaging films (thermoformed sheets), blown films, pipes, honeycomb materials, heavy profiles (window frames), transparent wall profiles, profiles for construction, wall panels, accessories, office films and case covers (computers, household appliances). Preference is given to rigid PVC foam articles and PVC pipes for drinking water or wastewater, pressure pipes, gas pipes, pipes for cable routing and cable protection pipes, pipes for industrial pipelines, exhaust pipes, Exit pipes, gutter pipes and drainage pipes. For additional details on this subject see "Kunststoffhandbuch PVC", Vol. 2/2, W. Becker / H. Braun, 2nd edition, 1985, Cari Hanser Verlag, pages 1236-1277.

The 6-aminouracils are prepared by known methods [e.g., U.S. Pat. 2,598,936, WO 96/04280, J. Org. Chem. 16, 1879-1890 (1951), J. Org. Chem. 30, 656 (1965), JACS 82, 3973 (1960) and Synthesis 1996, page 459 et seq., Berichte 99, 3530 (1966) and CA 70 87727J (1969)]. The compounds 1 to 22 prepared are summarized in Table 1. As in the rest of the text, the parts and percentages are by weight unless otherwise indicated.

Table 1 42 Table 1 (continued) 43 -. 43 - - 44 - Preparation Examples Example 1 A mixture of 31.0 g (0.2 mole) of 6-amino-1,3-dimethyluracil, 8.1 g (0.11 mole) of formaldehyde solution with 37% strength. The concentration, 120 ml of toluene and 100 ml of glacial acetic acid is heated to reflux until 15 ml of water / acetic acid mixture have been collected in a water separator. The mixture is subsequently cooled to 20 ° C and the precipitate obtained is filtered off with suction, washed with toluene and dried under reduced pressure at 100 ° C. Yield: 30.6 g = 95% of the theory. Example 15 15.5 g (0.1 mol) of 6-amino-1,3-dimethyluracil, 14.0 g (0.1 mol) of benzoyl chloride and 16 g of pyridine are heated at 116 ° C with stirring During 4 hours. After cooling to 20 ° C, the reaction mixture is stirred in 250 ml of water and the resulting precipitate is filtered off with suction after 2 hours, washed with water and dried in a vacuum drying oven at 100 ° C. 100 ° C. Performance: 21.7 g = 84% of the theory. EXAMPLE 18 In a 500 ml two-neck flask, fitted with a magnetic stirrer, thermometer, water separator and reflux condenser, 34 g (0.22 mol) of 6-amino-1,3-dimethyluracil, 45 g (0.degree. , 3 moles) of methyl 4-chloroacetoacetate, 80 ml of acetic acid and 100 ml of toluene are heated to reflux with stirring for 3.5 hours. During this time, 10.2 ml of water / acetic acid mixture are separated. Then, the reaction mixture is cooled to 30 ° C (precipitate formation) and then to 0 ° C. The precipitate is isolated, washed with water and dried. Yield: 18.7 g = 35.8% of the theory.

- Example 18 15.5 g (0.1 mol) of 6-amino-l, 3-dimethyluracil, 26.4 g (0.1 mol) of 4- (dimethylaminoethylene) -2,6-di-tert- Butylphenol and 100 ml of acetic acid are heated at 121 ° C with stirring for 2.5 hours. After cooling to 20 ° C, the reaction mixture is stirred in 500 ml of water and the resulting precipitate is filtered off with suction, washed with water and dried in a vacuum drying oven at 100 ° C. Yield: 37.3 g = 100% of the theory. Example 20 31.0 g (0.2 mol) of 6-amino-1,3-dimethyluracil, 25.0 g (0.22 mol) of glutaric anhydride and 100 ml of acetic acid are heated at 120 ° C for 90 minutes. minutes and then cooled to 20 ° C. The reaction mixture is stirred in 500 ml of water and the white precipitate is filtered off with suction, washed with water and dried to constant weight. Performance: 31.2 g = 57.9% of the theory. Example 21 18.8 g (0.07 mole) of the compound of Example 20 are stirred under reflux with 100 ml of ethanol and 2 ml of concentrated sulfuric acid for 3 hours, after which the reaction solution is cooled to 20 °. C and then stirred in 500 ml of water. It is neutralized with sodium carbonate and the precipitated reaction product is filtered off with suction, washed with water and dried. Yield: 16.0 g = 76.9% of the theory. Example 22 A melt of 15.4 g (0.06 moles) of 6-amino-1,3-di-n-butyluracil and 29.4 g (0.13 moles) of benzoic anhydride is stirred at 110-120. C for 4 hours, after which it is cooled and dissolved in 20 ml of methanol. This solution is stirred in a solution of 250 ml of water / 8 g of sodium hydroxide. The reddish brown solid is filtered off with suction, dried and recrystallized from 30 ml of ethyl acetate. Yield: 8.3 g = 40.3% of the theory. Static heating test A dry mixture consisting of 100.0 parts of Evipol SH 6030 = PVC, K value 60 5, O parts of ESO = epoxidized soybean oil 0.4 parts of Loxiol G 71 S = high molecular weight multi-component ester 0.8 parts of Irgastab CH 300 = liquid diaryl-dialkyl phosphite and in each case one of the stabilizers indicated in Tables 2 and 3 (corresponding to the examples in Table 1) is laminated in a set of mixing rollers to 180 ° C for five minutes. Pieces of the 0.3 mm thick test film are taken from the resulting laminated sheet. The film samples are subjected to thermal fatigue at 190 ° C in an oven. The Yellowness Index (AI) is determined according to the ASTM method D-1925-70 at 5 minute intervals. The results can be read in Table 2 [1.0 parts by weight of stabilizer] and Table 3 [0.6 parts by weight of stabilizer] below. Low AI values denote satisfactory stabilization.

A dry mix consisting of 100.0 parts of Evipol SH 6030 = PVC, K value 60 5.0 parts of ESO = epoxidized soybean oil 0,4 parts of Loxiol G 71 S = high molecular weight multi-component ester 0.8 parts of Irgastab CH 300 = liquid diaryl-dialkyl phosphite and in each case one of the stabilizers indicated in Tables 2 and 3 (corresponding to the examples in Table 1) is rolled in a set of roller mixers at 180 ° C for five minutes Pieces of the 0.3 mm thick test film are taken from the resulting laminated sheet. The film samples are subjected to thermal fatigue at 190 ° C in an oven. The Yellowness Index (AI) is determined according to the ASTM D-1925-70 method at 5 minute intervals. The results can be read in Table 2 [1.0 parts by weight of stabilizer] and Table 3 [0.6 parts by weight of stabilizer] below. Low IA values denote satisfactory stabilization.

Table 2 (1 part by weight of stabilizer in each case) Table 2 (continued) (one part by weight of stabilizer in each case) Table 3 (0.6 parts by weight of stabilizer) The examples clearly demonstrate that the stabilizers of the invention give results in terms of initial color, color maintenance (intermediate color) and long-term stability - IA measures - which constitute an improvement over the prior art.

Claims

CLAIMS A compound of the general formula I n is 1 or 2, Y is oxygen or sulfur, Ri and R2 / independently of each other, are Ci-Cis unsubstituted or substituted with C?-C4 alkoxy, C5-C8 cycloalkyl, -OH and / or Cl, C3 alkenyl -C6, C5-C8 cycloalkyl, phenyl or C7-C9 phenylalkyl which is unsubstituted or substituted on the phenyl ring with C? -C4 alkyl, C? -C4 alkoxy, C5-C8 cycloalkyl, -OH and / or Cl, R3 is H, C? -C? 8 alkyl unsubstituted or substituted by -OH, C? -C4 alkoxy, -C? 0 (OR6) and / or -0-COR6, C3-C6 alkenyl, C5-C8 cycloalkyl, C7 phenylalkyl -C9 unsubstituted or substituted with -OH, C? -C4 alkyl, C? -C alkoxy, -C? 0 (OR6) and / or -0-COR6, or phenyl or naphthyl, R6 is C1-C12 alkyl or C2 alkenyl -C12, and, if n is 1, R4 is - (C = 0) -alkyl C? -C12, - (C = 0) -O-C1-C? 2alkyl,

- (C = 0) -C0-C alkylene 2- (C = 0) OZ, where Z is H or C? -C6 alkyl, - (C = 0) -phenyl, phenyl unsubstituted or substituted with -OH, alkyl C? -C4, C? -C4 alkoxy, -C? 0 (0R6) and / or -0-C0R6 or phenylcarbamoyl or C? -C? 8 alkyl substituted with halogen and, if n is 2, R4 is the group -CHR5-, in which R5 is H, C? -C12 alkyl, or phenyl unsubstituted or substituted with -OH, C? -C alkyl, C? -C4 alkoxy,? C = 0 (0R6) and / or -O-CORg.
- - 2. A compound of the general formula 1 according to claim 1, wherein Y is oxygen.
3. A compound of the general formula 1 according to claim 1, wherein n is 1.
4. A compound of the general formula 1 according to claim 1, wherein Y is oxygen and n is 1 and Ri and 2, independently of one another, are d.-C8 alkyl, allyl or phenylalkyl C7-C9 and R3 is H, C? -C? 8 alkyl unsubstituted or substituted with -OH or C? -C4 alkoxy, C3-C6 alkenyl? , C5-C8 cycloalkyl or phenyl substituted with -OH, C? -C4 alkyl or C? -C alkoxy, C7-C9 phenylalkyl substituted with -OH, d-C4 alkyl or C? -C alkoxy, or naphthyl, and R4 is - (C = 0) -alkyl C? -C6, - (C = 0) -O-C? -C6 alkyl, or - (C = 0) -C0-C3alkylene- (C = 0) OZ, in which formula Z is H or C?-C4 alkyl / - (C = 0) -phenyl, phenyl insulfided or substituted with -OH or C C-C 4 alkyl, or C alquilo-alkyl
5. A compound of the general formula I according to claim 1, wherein Y is oxygen and n is 2 and Ri and R2 > independently of one another, they are alkyl d-C8, allyl or phenylalkyl C7-C9 and R3 is H, C? -C18 alkyl unsubstituted or substituted with -OH or C? -C alkoxy, C3-C6 alkenyl, C5-C8 cycloalkyl or phenyl substituted with -OH, C? -C4 alkyl or C-C4 alkyloxy C7-C9 phenyl substituted with -OH, C? -C4 alkyl or C? -C4 alkoxy, or naphthyl, and R is the group -CHR5- in which R5 is H, C? -C8 alkyl, phenyl unsubstituted or substituted with -OH, C? -C4 alkyl and / or C-alkoxy? -C4. -
6. A composition comprising a chlorinated polymer and at least one compound of the general formula I according to claim 1.
7. A composition according to claim 6, comprising at least one epoxidized fatty acid ester.
8. A composition according to claim 6, comprising at least one zinc carboxylate and / or alkali metal carboxylate and / or alkaline earth metal carboxylate and / or aluminum carboxylate.
9. A composition according to claim 6, comprising at least one additional substance of the phosphite groups, antioxidants, b-dicarbonyl compounds, plasticizers, fillers, lubricants or pigments.
10. A composition according to claim 6, comprising chalk as filler.
11. A composition according to claim 6, comprising calcium stearate as a lubricant.
12. A composition according to claim 6, comprising titanium dioxide and / or zirconium oxide and / or barium sulfate as a pigment.
13. A composition according to claim 6, comprising at least one polyol and / or a disaccharide alcohol.
14. A composition according to claim 6, comprising at least one glycidyl compound.
15. A composition according to claim 6, comprising at least one perchlorate compound.
16. A composition according to claim 6, which comprises at least one zeolitic compound.
17. A composition according to claim 6, comprising at least one layered reticular compound.
18. A composition according to claim 6, comprising at least one hydrotalcite.
19. A method for stabilizing chlorinated polymers, comprising incorporating into said polymers at least one compound of the formula I according to claim 1.
20. The use of a compound of the general formula 1 according to claim 1, as a stabilizer for halogenated polymers.
21. The use of a compound of the general formula 1 according to claim 1, as a stabilizer for recycled halogenated polymers.