Liquid mixtures of phosphites as stabilizers

The present invention relates to a phosphite composition for stabilizing thermoplastic resins and elastomers, and a polymer composition stabilized using such a phosphite composition as antioxidants. In the present description, the terms phosphite composition, mixture of phosphites and phosphite stabilizers are used interchangeably to define the subject matter of the invention.

Organic phosphites (also known as phosphorous acid esters) are known as secondary antioxidants for polyolefins, polyvinyl chloride, and elastomers. Examples of such known phosphites are given in H. Zweifel, Plastics Additives Handbook, 5th Edition, Hanser Publishers, Munich 2000. One of the most widely used organic phosphites is tris (nonylphenyl) phosphite (TNPP), which is a liquid at room temperature. However, there is a need to replace TNPP due to the estrogenicity attributed to nonylphenol. Moreover, since TNPP is a liquid under normal conditions, there is a need to replace it with a phosphite which is also a liquid under normal conditions.

Mixtures of phosphite stabilizers, both liquid and solid, are known.

US Patent No. 3,948,801 describes stabilizing compositions comprising at least one triaryl phosphite, trialkyl phosphite, or mixtures thereof with at least one modified lignin, the weight ratio of phosphite to modified lignin being from 97/3 to 10/90. Modified lignins are prepared by heat treating lignins in the presence of a nucleophile so that some of the starting guaiacyl structures are converted to catechins by a demethylation reaction. The elastomers are protected against atmospheric degradation by adding 0.01 to 5.0 parts by weight of the stabilizer composition per 100 parts of elastomer.

U.S. Published Patent Application No. 2003/0001136 and U.S. Patent No. 6,824,711 describe a liquid polymeric additive composition containing at least one phosphite ester selected from the group consisting of aryl phosphites, alkyl phosphites, aryl / alkyl phosphites, bisphenol-A phosphites, phosphites of glycol and dialkylene glycol. polydialkylene glycol, pentaerythritol phosphites, p-cumylphenol phosphites, and mixtures thereof, and about 50 to 800 ppm zinc per 100 parts resin. The stabilizer is used as a complete or partial replacement for stabilizing antioxidant additives containing toxic metals.

Published US Patent Application No. 2004/0183054 discusses liquid polymeric additive compositions containing mixtures of phosphite esters selected from the group consisting of aryl phosphites, alkyl phosphites, aryl / alkyl phosphites, bisphenol-A phosphites, dialkylene glycol and phosphites of perythialylphosphites, perythialkyl phosphites. -cumylphenol with a content of 50 to 800 ppm of zinc per 100 parts of resin. The stabilizer is used as a complete or partial replacement for stabilizing antioxidant additives containing toxic metals.

U.S. Published Patent Application No. 2007/0021537 discloses a method of stabilizing polyolefin compositions against the deleterious effects of melting, heat, and exposure to natural gas combustion products, the method comprising incorporating or applying to a polyolefin an effective stabilizing amount of a tris (monoalkylphenyl) phosphite ester of formula AND

<img file="PL216865B1_D0001.tif" />

Or mixtures of phosphite esters of formula I, in which each R has the same or different meaning and represents a straight or branched chain alkyl containing from 1 to 8 carbon atoms, said phosphite ester or mixture of phosphite esters being in the state of liquid at a temperature of 25 ° C and a pressure of 1 atm (101.325 kPa). Also described is a stabilizing composition comprising a polyolefin and the present phosphite ester or a mixture of phosphite esters and certain mixtures of tris (monoalkyl) phenyl phosphites. These liquid phosphite ester stabilizers are especially suitable for low density polyethylene.

CA 2464551 discloses solid mixtures of individual solid phosphite components for a phenol free stabilization of a polyethylene film.

CZ 280072 describes mixtures of phosphites and phosphonites as stabilizers for propylene polymers.

DE 90-4001397 describes phosphonite and phosphite esters as heat stabilizers for polymers.

JP 05202236 discloses mixtures containing phosphites and phosphonites suitable for use in the production of heat resistant polyolefin compositions.

JP 59030842 describes solid phosphite mixtures containing solid phosphites suitable for use in stabilizing polyolefin compositions.

RO 112871 discusses compounds of formula (RR¹R²C6H2O) 3P where (R, R¹, R² = CMe2Ph;

or R = H, R.¹, R² = CMe2Ph or R = R¹ = H, R.² = CMe2Ph), as a mixture of phenol triphosphites and mono-, di- and triarylalkylated phenols, which exists as a mobile yellow liquid containing ₃ ± 0.3% P and 0.5% Cl and showing a refractive index of 1.5992 and d 1.1400 g / cm³and are suitable for use as stabilizers for polymers and elastomers (no data available). The mixture is prepared by esterifying PCl3 with a mixture of phenol and mono-, di- and triarylalkylated phenols with an average molecular weight of 300 in a molar ratio of aralkylphenols to phenol 1: 1-1.5 and aralkylphenols + phenol to PCl3 1: 0.3-0 , 4 in the absence of a solvent or catalyst under anhydrous conditions, under agitation, at a temperature of 25-40 ° C for 0.5-1.5 hours, then the temperature is gradually increased to 90-150 ° C, the temperature is maintained at 150- 180 ° C in 2-6 hours, HCl formed during the reaction is removed by bubbling nitrogen through the reaction mass at 150-180 ° C for 2-5 hours, followed by removal of unreacted starting materials by distillation under an inert nitrogen atmosphere at 10 mm Hg at 175 ° C. In the given example, 989 g of a mixture of (1-methyl-1-phenylethyl) -phenols obtained by alkylation of phenol with α-methylstyrene and 475 g of phenol are melted with stirring at 25 ° C and 383 g of PCl 3 are added dropwise over 1 hour. the mixture is then gradually heated to 90 ° C, kept for 1 hour at 90 ° C, then heated to 150 ° C and kept there for 5 hours, the HCl formed is then stripped off by bubbling nitrogen through the mixture at 150 ° C for 5 hours, then the unreacted phenol is removed by distillation under nitrogen at 175 ° C and 10 mm Hg to give

1460 g product mixture which is a yellow liquid containing 4.14% P and 0.5% Cl, ₃ with a refractive index of 1.5992 and 1.1400 g / cm³which contains triphenyl phosphite and triphosphite 2- (α, α-dimethylbenzyl) -phenol, 4- (α, α-dimethylbenzyl) -phenol, 2,6-bis- (α, α-dimethylbenzyl) -phenol and 2,4 , 6-tris (α, α-dimethylbenzyl) phenol.

WO 02070625 discloses liquid phosphite mixtures as additive compositions.

WO 2001/062832 describes the addition of stabilizing additives to polymer particles in rotomoulding.

WO 2001062833 describes mixtures of organic phosphites and phosphonates suitable for addition as stabilizing additives for polymer molecules in rotomoulding.

WO 9303092 discloses the use of solid mixtures of individual solid phosphite components as forming compositions for heat resistant polyester-polycarbonates.

The above disclosures are incorporated herein by reference in their entirety.

There is a continuing need for liquid phosphite antioxidants used in resins.

The present invention generally relates to aryl phosphite mixtures which exhibit antioxidant properties and are in a liquid physical form under normal conditions, i.e. at atmospheric pressure and at room temperature.

The individual components of the aryl phosphites that make up the new liquid phosphite mixtures are solid at room temperature. The present invention relates to the non-obvious and unexpected finding that when these constants, the individual components of the aryl phosphites degrade

As they are suitable for the phosphite mixtures according to the invention, these mixtures are normally in the liquid state.

It is further described that said liquid phosphite mixtures can be prepared by direct reaction of phosphorus trihalide and the corresponding mixture of alkylated phenols.

These liquid phosphite mixtures find use as stabilizers / antioxidants for thermoplastic resins and elastomers.

Specifically, the invention relates to a phosphite composition for stabilizing thermoplastic resins and elastomers which comprises a mixture of at least two, preferably at least three, most preferably at least four different phosphites of the formula

R, O_{Xp /}° R₂ or₃ wherein R1, R2 and R3 are independently selected from alkylated aryl groups of the formula

<img file="PL216865B1_D0002.tif" />

wherein R4, R5 and R6 are independently selected from the group consisting of hydrogen and C1-C6-alkyl with at least one of R4, R5 and R6 different from hydrogen; wherein at least one of the substituents R4, R5 and R6 in each phosphite is selected from the group consisting of tert-butyl and tert-pentyl, furthermore said mixture of phosphites is normally a liquid.

The method of stabilizing a thermoplastic resin or elastomer comprises the step of adding to the thermoplastic resin or elastomer a stabilizing amount of the phosphite mixture of the invention as defined above.

The present invention involves reacting PZ3, where Z is halogen, with a mixture containing from about 5 to about 95% by weight of solid p-alkylated phenol and from about 95 to about 5% by weight of solid p-alkylated phenol, respectively. , p-dialkylated phenol. Preferably, Z is chlorine or bromine, the molar ratio of the mixture of phenols to PZ3 is 3: 1 and the alkyl groups of the alkylated phenols are straight or branched chain alkyl groups of one to six carbon atoms, most preferably tert-butyl or tert-pentyl. .

As described above, the present invention relates to a composition comprising a mixture of at least two different phosphites of the formula

<img file="PL216865B1_D0003.tif" />

or₃ wherein R1, R2 and R3 are independently selected from alkylated aryl groups, and the mixture is a liquid under standard conditions.

PL 216 865 B1

The aryl group present in the compounds of the present invention is a substituted phenyl group. Such phenyl groups are substituted with at least one alkyl group and may be further substituted with substituents which substantially do not adversely affect the physical and stabilizing properties of the compounds of the invention.

The alkyl substituent or substituents of the aryl group are selected from the group consisting of alkyl groups having one to six carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of the foregoing groups.

In the above-described embodiments, it is preferred that these mixtures contain at least three different phosphites of the described structure, even more preferably that they contain at least four such different phosphites.

Liquid phosphite mixtures can be prepared by the direct reaction of phosphorus trihalide and a suitable mixture of alkyl substituted phenols, with or without a catalyst. The reaction products obtained from this process can be used as such, instead of mixing liquid phosphite mixtures, without the need for further modification. Liquid mixtures of at least two liquid phosphites of the formula:

R «0

<img file="PL216865B1_D0004.tif" />

0R₃ wherein R1, R2 and R3 are independently selected alkylated aryl groups; is produced by a method that includes:

(A) alkylation of a phenolic compound with an alkene in the presence of an acid catalyst;

(B) separating the resulting alkylated phenol from the catalyst; and (C) reacting PZ3, where Z is halogen, with the resulting mixture that contains from about 5 to about 95% by weight of solid p-alkylated phenol and, respectively, from about 95 to about 5% by weight of solid o, p-dialkylated phenol . By "phenolic compound" is meant an aryl moiety, e.g. phenyl containing at least one OH group, and optionally further substituted with one or more additional groups which would not adversely affect their desired properties, e.g. cresol, xylenol and the like.

Thus, a preferred method of preparing the aryl phosphite stabilizers which are used in the practice of the present invention is by reacting phosphorus trihalide, PZ3, e.g., phosphorus trichloride or phosphorus tribromide, with a mixture of the appropriate alkylated phenols.

The reaction between the mixture of alkylated phenols and PZ3 can be carried out with or without the use of a solvent. Typically, PZ3 may be added to a mixture of alkylated phenols or a mixture of alkylated phenols may be added to PZ3. Preferably PZ3 is added to the mixture of alkylated phenols while maintaining the temperature around 5 to 150 ° C. The reaction mixture is then held for 1 to 10 hours. During this time, HZ gas is evolved, the removal of which may be assisted by reducing the pressure or by bubbling an inert gas such as nitrogen through the reaction mixture. Generally the reduced pressure is 50 mbar (5 kPa). In the case of HCl, for example, this step is carried out until the total Cl content is less than 50 ppm. Typically, unreacted alkylated phenol can then be removed from the reaction mixture by further increasing the temperature to 230 ° C, preferably around 200 ° C, while maintaining a vacuum of 5 mbar (500 Pa).

The preferred solvents that can be used are inert solvents. Typical solvents are toluene, heptane, xylene, methylene chloride, chloroform, and benzene. Preferred solvents are methylene chloride, heptane, or xylene.

Thus, preferably the inventive liquid phosphite mixtures are obtained by a direct chemical reaction in which appropriately alkyl substituted phenols are used. Mon iżej given scheme of this reaction.

PL 216 865 B1

<img file="PL216865B1_D0005.tif" />

where m = 3, an = 2.

In a preferred embodiment of the invention, all of the above R groups are tert-butyl or tert-pentyl. Exemplary phosphites in such a mixture are independently selected from the group consisting of tris-4-tert-butylphenyl phosphite, tris-2,4-di-tert-butylphenyl phosphite, bis (4-tert-butylphenyl) -2,4-di-tert phosphite. -butylphenyl, bis (2,4-di-tert-butylphenyl) -4-tert-butylphenyl phosphite, tris-4-tert-pentylphenyl phosphite, tris-2,4-di-tert-pentylphenyl phosphite, bis (4- tert-pentylphenyl) -2,4-di-tert-pentylphenyl and bis (2,4-di-tert-pentylphenyl) -4-tert-pentylphenyl phosphite.

In a preferred embodiment of the phosphite compositions of the invention, at least one of R4, R5 and R6 in each phosphite is tert-pentyl.

In this embodiment, exemplary phosphites are independently selected from the group consisting of tris-4-tert-pentylphenyl phosphite, tris-2,4-di-tert-pentylphenyl phosphite, bis (4-tert-pentylphenyl) -2,4-di-tert phosphite. -pentylphenyl and bis (2,4-di-tert-pentylphenyl) -4-tert-pentylphenyl phosphite.

In another preferred embodiment of the phosphite composition of the invention, at least one of R4, R5 and R6 in each phosphite is tert-butyl.

In this embodiment, exemplary phosphites are independently selected from the group consisting of tris-4-tert-butylphenyl phosphite, tris-2,4-di-tert-butylphenyl phosphite, bis (4-tert-butylphenyl) -2,4-di-tert phosphite. -butylphenyl, bis (2,4-di-tert-butylphenyl) -4-tert-butylphenyl phosphite.

As mentioned above, it is a feature of the present invention that the mixture of phosphite antioxidants is in a liquid physical form at room temperature. This is completely unexpected, since the known art states in several examples that a mixture of phosphite stabilizers, which are themselves solid, is also solid at room temperature (see JP

PL 216 865 B1

59030842; WO 9303092; CA 2464551). In contrast, the phosphite composition of the present invention forms a liquid, even though the individual components are known as solids.

Thus, in the above scheme, the liquid phosphite mixture may be composed of the four main phosphites, tris-4-tert-butylphenyl phosphite, tris-2,4-di-tert-butylphenyl phosphite, bis (4-tert-butylphenyl) -2 phosphite , 4-di-tert-butylphenyl and bis (2,4-di-tert-butylphenyl) -4-tert-butylphenyl phosphite. However, it is known in the art, for example, that the tris-tert-butylphenyl phosphite component has a melting point of 75-76 ° C (Kosalopoff, Organic Phosphorus Compounds, Wiley Interscience, Vol. 5, p. 163). Similarly, tris-2,4-di-tert-butylphenyl phosphite is a solid substance known in the art with a melting point of 181-184 ° C (Aldrich catalog # 441791). Similarly, bis (4-tert-butylphenyl) -2,4-di-tert-butylphenyl phosphite has a melting point of 63-65 ° C. Also bis (2,4-di-tert-butylphenyl) -4-tert-butylphenyl phosphite has a melting point of 100-103 ° C.

Transesterification processes, such as those disclosed in Hechenbleikner et al., US Patent No. 3,056,823, which is hereby incorporated by reference, may also be used. In particular, the process described by Hechenbleikner et al. Comprises the transesterification of a triaryl phosphite with a monohydroxy hydrocarbon in the presence of a small but catalytically effective amount of a metal alkoxide or metal phenate.

In order to prevent contamination, the alcoholate of the transesterified alcohol is used. Instead of using a preformed alkoxide, the alkoxide can be generated in situ by adding a metal, e.g. sodium, potassium or lithium to the alcohol, prior to the addition of the triaryl phosphite. The monoalcohol and the triaryl phosphite are reacted in a molar ratio of three moles of alcohol to one mole of triaryl phosphite.

The embodiment described herein also relates to a process for the preparation of a corresponding mixture of alkylated phenols. Thus, reacting a phenol (either cresol or an already alkylated phenol, e.g. p-tert-butylphenol) with, preferably, a lower alkene (C2-C6, more preferably C4-C5) using any of a number of known catalysts (acid clays, cationic ion exchange resins, Bronsted acids, e.g. sulfuric acid, Lewis acids, e.g. BF₃) mixed alkylated phenols are obtained, the composition of which can be modified by changing the degree of alkylation, temperature, etc.

Moreover, the embodiment described herein relates to the preparation of a feed stream of mixed alkylated phenols (for the synthesis of these phosphite mixtures) wherein the phenol is alkylated with a mixture of lower alkenes either in parallel (feed with alkene A and B at the same time) or sequentially (i.e. alkylation with alkene A) and then alkene B).

The invention also includes a stabilized thermoplastic or elastomeric resin where one component comprises liquid mixtures of aryl phosphites and the other component comprises a polymer such as polyolefin, polyvinyl chloride, etc.

Specifically, the invention relates to a stabilized polymer composition comprising a polymeric resin and a stabilizing amount of the phosphite composition, wherein:

(A) the polymeric resin is selected from the group consisting of thermoplastic polymers such as homopolymers and olefin copolymers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, poly (phenylene ethers), homopolymers and copolymers of styrene, polycarbonates, acrylic polymers, polyamides, polyacetals and halide-containing polymers, and (B) the phosphite composition comprises a mixture of at least two, preferably at least three, most preferably at least four different phosphites of formula

R "O

<img file="PL216865B1_D0006.tif" />

OR '3

Wherein R1, R2 and R3 are independently selected from alkylated aryl groups of the formula

<img file="PL216865B1_D0007.tif" />

wherein R4, R5 and R6 are independently selected from the group consisting of hydrogen and C1-C6-alkyl with at least one of R4, R5 and R6 different from hydrogen; wherein at least one of R4, R5 and R6 in each phosphite is selected from the group consisting of tert-butyl and tert-pentyl and this mixture is normally a liquid.

The polymers stabilized by the mixtures of alkylaryl phosphites according to the invention may be known thermoplastic polymers such as homopolymers and olefin copolymers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, poly (phenylene ethers), styrene acrylic homopolymers and copolymers, polymers , polyamides, polyacetals and halide-containing polymers. Mixtures of different polymers can also be used, such as polyphenylene ether / styrene resin mixtures, polyvinyl chloride / ABS, or other impact modified polymers such as methacrylonitrile and ABS containing alpha-methylstyrene, and polyester / ABS or polycarbonate / ABS and polyester plus some other impact modifiers. Such polymers are commercially available or can be made in a known manner. However, the stabilizer compositions of the invention are particularly suitable for use in thermoplastic polymers such as polyolefins, polycarbonates, polyesters, poly (phenylene ethers) and styrene polymers, due to the extreme temperatures at which thermoplastic polymers are often processed and / or used.

Polymers of monoolefins and diolefins, e.g. polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, e.g. cyclopentene or norbornene, polyethylene (which may optionally be cross-linked), e.g. high polyethylene, may be used. Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), and Linear Low Density Polyethylene (LLDPE). Mixtures of these polymers can also be used, for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE). Copolymers of monolefins and diolefins are also used with each other or with other vinyl monomers, such as, for example, ethylene / propylene, LLDPE and its mixtures with LDPE, propylene / butene-1, ethylene / hexene, ethylene / ethyl-pentene, ethylene / heptene, ethylene / octene, propylene / isobutylene, ethylene / butane-1, propylene / butadiene, isobutylene, isoprene, ethylene / alkyl acrylates, ethylene / alkyl methacrylates, ethylene / vinyl acetate (EVA) or ethylene / acrylic acid copolymers (EAA) and their salts (ionomers) and terpolymers of ethylene with propylene and diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; as well as mixtures of such copolymers and mixtures thereof with the above-mentioned polymers, for example polypropylene / ethylene copolymers of propylene, LDPE / EVA, LDPE / EAA, LLDPE / EVA and LLDPE / EAA.

The olefin polymers can be prepared, for example, by polymerization of olefins in the presence of Ziegler-Natta catalysts optionally on a support such as, for example, MgCl2, chromium salts and complexes thereof, silica, silica-alumina and the like. The olefinic polymers can also be prepared using chromium catalysts or single-sided catalysts, e.g. metallocene catalysts such as, for example, cyclopentadiene metal complexes such as Ti and Zr. As is known to those skilled in the art, the polyethylene polymers used herein, e.g. LLDPE, may contain various comonomers, such as, for example, butene-1, hexene-1 and octene-1 comonomers.

The polymers can also include styrene polymers such as polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene. / alkyl methacrylate, styrene / maleic anhydride, styrene / maleimide, styrene / butadiene / ethyl acrylate, styrene / acrylonitrile / methyl acrylate, high impact mixtures of styrene copolymers and other polymers, such as, for example, polyacrylate, diene polymer or ethylene / propylene / diene terpolymer; and styrene block copolymers such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

PL 216 865 B1

The styrenic polymers may additionally or alternatively contain styrene or α-methylstyrene graft copolymers, such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene and their copolymers; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on copolymers / but acrylates with the above-mentioned styrene copolymers.

Nitrile polymers are also used in the polymer compositions of the invention. These include homopolymers and copolymers of acrylonitrile and its analogs such as polymethacrylonitrile, polyacrylonitrile, acrylonitrile / butadiene polymers, acrylonitrile / alkyl acrylate polymers, acrylonitrile / alkyl methacrylate / butadiene polymers, and various ABS compositions as mentioned above in connection with styrene compounds.

Polymers based on acrylic acids, such as acrylic acid, methacrylic acid, methyl methacrylic acid, and methacrylic acid, and their esters can also be used. Such polymers include polymethyl methacrylate and ABS graft copolymers wherein all or some of the acrylonitrile type monomers have been replaced with acrylic acid ester or acrylic acid amide. Polymers containing other acrylic type monomers such as acrolein, methacrolein, acrylamide and methacrylamide can also be used.

Halogen-containing polymers can also be used. These include resins such as polychloroprene, epichlorohydrin homo- and copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, fluorinated polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride copolymer, vinyl acetate copolymer, vinyl-ethylene, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic acid anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinyl chloride-vinyl chloride terpolymer - vinyl acetate, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymer and internally plasticized polyvinyl chloride.

Other suitable polymers include homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxides, polypropylene oxides, or copolymers thereof with bis-glycidyl ethers; polyacetals such as polyoxymethylene and such polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or methacrylonitriles containing ABS; poly-phenylene oxides and sulphides, and mixtures of polyphenylene oxides with polystyrene or polyamides; polycarbonates and polyester carbonates; polysulfones, polyethersulfones and polyetherketones; and polyesters which are derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or suitable lactones such as poly (ethylene terephthalate), poly (butylene terephthalate), poly (1,4-dimethylcyclohexane terephthalate), poly (2-terephthalate) [ 2,2,4- (4-hydroxyphenyl) propane]} and polyhydroxybenzoates as well as block copolyether esters derived from polyethers containing hydroxyl end groups.

It is also possible to use polyamides and copolyamides which are derived from bisamines and dicarboxylic acids and / or from aminocarboxylic acids or suitable lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylene bisamine and adipic acid; polyamides obtained from hexamethylene bisamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. It is also possible to use further copolymers of the abovementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycols, and polyamides or copolyamides modified with EPDM or ABS.

Polyolefins, polyalkylene terephthalates, poly phenylene ethers, and styrene resins, and mixtures thereof are preferred, with polyethylene, polypropylene, polyethylene terephthalate, homopolymers and copolymers of polyphenylene ethers, polystyrene, high impact polystyrene, particularly preferred, polycarbonates and ABS graft copolymers and mixtures thereof.

PL 216 865 B1

As used herein, the terms "stabilizing amount" or "effective amount" of a phosphite mixture of the invention mean that the phosphite-containing polymer composition of the invention exhibits improved physical or color stability compared to an analogous polymer composition that does not contain phosphite of the invention. Examples of the improved stability are improved stabilization against, for example, molecular weight degradation, color degradation and the like in the case of, for example, melting processes, weathering and / or prolonged exposure to heat, light and / or other factors. In one example, improved durability is considered to be either or both of lowering initial color or additional weathering resistance as measured by, for example, Initial Yellowing Index (YI) or resistance to yellowing and discoloration compared to the composition. without stabilizing additives.

The invention further relates to stabilized thermoplastic resins, where one component comprises aryl phosphite liquid mixtures and the other component comprises a polymer such as a polyolefin, and wherein said liquid phosphite mixture is used with a co-stabilizer, e.g., phenolic compounds, aromatic amines, hydroxylamines, N- alkylamine oxides, lactones and thioethers.

Thus, the thermoplastic resins stabilized with the phosphite mixtures according to the invention may optionally contain an additional stabilizer or a stabilizer mixture selected from the group consisting of phenolic antioxidants, hindered amine stabilizers, UV absorbers, phosphites, phosphonines, alkali metal salts of fatty acids, hydrotalcites, oxides. metals, epoxidized soybean oils, hydroxylamines, tertiary amine oxides, lactones, thermal reaction products of tertiary amine oxides and thiosynergetics.

Thus, the resulting stabilized polymeric resin compositions optionally also contain various conventional additives, such as the following:

Antioxidants: Antioxidants can include alkylated monophenols, for example

2.6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4- n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4- methylphenol, 2,4,6-tricyclohexylphenol,

2.6-di-tert-butyl-4-methoxymethylphenol. Alkylated hydroquinones can also be used as antioxidants, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl- 4-octadecyloxyphenol.

Antioxidants used may also include hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'- thio-bis (6-tert-butyl-3-methylphenol) and 4,4'-thio-bis (6-tert-butyl-2-methylphenol).

Alkylidenebisphenols can also be used as antioxidants, for example 2,2'-methylene bis (6-tert-butyl-4-methylphenol), 2,2'-methylene bis (6-tert-butyl-4-ethylphenol), 2 , 2'-methylene-bis (4-methyl-6- (α-methylcyclohexyl) -phenol), 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis ( 6-nonyl-4-methylphenol), 2,2'-methylene-bis (6- (a-methylbenzyl) -4-nonylphenol), 2,2'-methylene-bis (6- (a, a-dimethylbenzyl) - 4-nonylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-iso-butylphenol), 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-methylene-bis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenol) -butane, 2,6-di- (3-tert-butyl-5- methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 1,1-bis (5-tert-butyl-4- hydroxy-2-methylphenyl) -3-dodecyl mercaptobutane, ethylene glycol di- (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene bis (3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate), 6-tert-butyl Di- (2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -4-methylphenyl) terephthalate and other phenolic compounds such as bisphenol monoacrylate esters such as ethylidiene bis-2 monoacrylate ester , 4-di-t-butylphenol and 3,5-dibutylhydroxyphenylpropionic acid esters. Phenolic antioxidants of particular interest are selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, n-octadecyl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) neopentanetetrayl, 3,5-di- di-n-octadecyl tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, bis (3,5-di-tert-butyl-4) -hydroxyhydrocinnamate) thiodiethylene, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -benzene, 3,6-dioxaoctamethylene bis (3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis (4,6-di -tert-butylphenol), 1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5- tert-butylphenyl) -butane, 1,3,5-tris- [2- (3,5-di-tert-buPL 216 865 B1-yl-4-hydroxyhydrocinnamoyloxy) -ethyl], 3,5-di- (3) , 5-di-tert-butyl-4-hydroxybenzyl) -mesitol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3,5-di-tert-butyl-4-hydroxyanilino) -3,5-di- (octylthio) -s-triazine, N, N'-hexamethylene bis (3,5-di-tert-butyl -4-hydroxyhydrocinnamamide), calcium bis (ethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate), bis- [3,3-di- (3-tert-butyl-4-hydroxyphenyl) butyrate] ethylene , 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate octyl, bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) -hydrazide and N, N'-bis- [2- (3,5-di- tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] oxamide.

Other antioxidants that can be used include benzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, bis (3,5 -di-tert-butyl-4-hydroxybenzyl), isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioloterephthalate, isocyanurate 1, 3,5-tris (3,5-di-tert-butyl-4,10-hydroxybenzyl), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, Dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate calcium salt and 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl isocyanurate) ).

Acylaminophenols can also be used as antioxidants, for example 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine and N Octyl - (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example, methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6- hexanediol, pentaerythritol, neopentyl glycol, tris-hydroxyethyl isocyanurate, thiodiethylene glycol and dihydroxyethyl oxalic acid diamide.

Antioxidants may also include β- (3,5-di-tert-butyl-4-hydroxyphenol) propionic acid amides such as, for example, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylenediamine, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine and N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine.

The UV absorbers and light stabilizers may include 2- (2'-hydroxyphenyl) benzotriazoles, for example 5'-methyl-, 3'5'-di-tert-butyl-, 5'-tert-butyl-, 5 'derivatives - (1,1,3,3-tetramethylbutyl) -, 5-chloro-3 ', 5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-3'- sec-butyl-5'-tert-butyl-4'-octoxy-, 3 ', 5'-di-tert-amyl-3', 5'-bis (α, α-dimethylbenzyl). 2-hydroxybenzophenones, for example 4-hydroxy-4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'- trihydroxy and 2'-hydroxy-4,4'-dimethoxy. UV absorbers and light stabilizers may also include esters of substituted or unsubstituted benzoic acids, such as phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

Acrylates can also be used as UV absorbers and light stabilizers, for example α-cyano-β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxycinnamic acid methyl ester, methyl ester or α-cyano-β-acid butyl ester. methyl-p-methoxycinnamic acid, α-carbomethoxy-p-methoxycinnamic acid methyl ester and N - 4 - carbomethoxy-β-cyanovinyl) -2-methylindoline.

Other examples of UV absorbers and light stabilizers include nickel compounds, for example nickel 2,2'-thio-bis (4- (1,1,1,3-tetramethylbutyl) -phenol complexes) such as a 1: 1 complex or 1: 2, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as methyl, ethyl or butyl, nickel complexes of ketoximes such as 2-hydroxy-4-methylphenyloundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.

Also, hindered amines, such as, for example, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis-5- sebacate (1,2,2,6,6- pentamethylpiperidyl), n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis (1,2,2,6,6, -pentamethylpiperidyl) ester, 1-hydroxyethyl-2,2,6 condensation product, 6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N, N '- (2,2,6,6-tetramethylpiperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris nitrilotriacetate (2, 2,6,6-tetramethylpiperidyl), tetrakis acid (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetra12

Arbonic, 1,1 '- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone). These amines, usually called HALS (Hindered Amine Light Stabilizers), include 2,2,6,6-tetramethylpiperidinol esters of butane tetracarboxylic acid. Such amines include hydroxylamines derived from hindered amines such as di- (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 1-hydroxy-2,2,6,6-tetramethyl-4-benzoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4- (3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyloxy) -piperidine and N- (1-hydroxy-2,2,6,6 -tetramethyl-piperidin-4-yl) -epsilone-caprolactam.

UV absorbers and light stabilizers may also include oxalic acid diamides, for example 4,4'-di-octyloxyoxanilide, 2,2'-di-octyloxy-5 ', 5'-di-tert-butyloxanilide, 2,2' -di-dodecyloxy-5 ', 5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl- 2'-ethyloxanilide and its mixtures with 2-ethoxy-2'-ethyl-5,4-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as o- and p-ethoxy-, disubstituted oxanilides.

UV absorbers and light stabilizers also include hydroxyphenyl-s-triazines, such as, for example, 2,6-bis (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,6-bis (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) -s-triazine; 5-2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) s-triazine; 2,4-bis (2-hydroxy-4- (2-hydroxyethoxy) -phenyl) -6- (4-chlorophenyl) -s-triazine; 2,4-bis (2-hydroxy-4- (2-hydroxyethoxy) -phenyl) -6-phenyl-s-triazine; 2,4-bis (2-hydroxy-4- (2-hydroxyethoxy) -phenyl) -6- (2,4-dimethylphenyl) -s-triazine; 2,4-bis (2-hydroxy-4- (2-hydroxyethoxy) -phenyl) -6- (4-bromophenyl) -s-triazine; 2,4-bis (2-hydroxy-4- (2-acetoxyethoxy) -phenyl) -6- (4-chlorophenyl) -s-triazine, 2,4-bis- (2,4-dihydroxyphenyl) -6- ( 2,4-dimethylphenyl) -1-s-triazine.

Metal deactivators can also be used, such as, for example, Ν, Ν'-diphenyldiamide of oxalic acid, N-salicylal-N-salicyloylhydrazine, N, N'-bis-salicyloylhydrazine, N, N'-bis (3,5-di-tert) -butyl-4-hydrophenylpropionyl) -2-hydrazine, salicyloylamino-1,2,4-triazole and bis-benzylidene tachalic acid dihydrazide.

In some embodiments, phosphites and phosphonites such as, for example, triphenylphosphite, diphenylalkyl phosphites, phenyldialkylphosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctorythritol diphosphite, trioctadhethritol diphosphite, -tert-butylphenyl), di-isodecylpentaerythritol diphosphite, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) pentaerythritol diphosphite, tristearyl sorbitan triphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4'- diphosphite biphenylene.

Peroxide scavengers, such as, for example, beta-thiodipropionic acid esters, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazoles or zinc salts of 2-mercaptobenzimidazoles, zinc dibutyl dithiocarbamate, penta dioctentoctentecyl disulfide, penta diacetyl disulfide, can also be used.

In some embodiments, hydroxylamines such as, for example, N, N-dibenzylhydroxylamine, Ν, Ν-diethylhydroxylamine, N, N-dioctylhydroxylamine, Ν, Ν-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-ditetradecylhydroxylamine, Nyladecylhydroxylamine, Nyladecylhydroxylamine, Nyladecylhydroxylamine, Ν-Dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine and Ν, Ν-dialkylhydroxylamine derived from hydrogenated tallow amines.

Nitrons can also be used, e.g. -a-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-evolving nitrone and hexadecyl-a-nitrone , Ν-dialkylhydroxylamines derived from hydrogenated tallow amines.

Polyamide stabilizers are also used, for example copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts.

In other embodiments, basic co-stabilizers may be used, such as, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, e.g. calcium, calcium lactate, Zn stearate, Mg stearate, e.g. Na ricinoleate and K palmitate, salt of pyrocatechin and antimony, or salt of pyrocatechin and zinc, including neutralizing agents such as hydrotalcites and synthetic talcites, and Li, Na, Mg, Ca and Al hydroxycarbonates, and MgZn hydroxycarbonates, MgAl hydroxycarbonates and AlZ hydroxycarbonates, and oxides metals such as ZnO, MgO and CaO.

In some embodiments, nucleating agents may also be used, such as, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium methylene bis-2,4-dibutylphenyl, cyclic phosphate esters, sorbitan tris-benzaldehyde acetal, and sodium phosphate salt. bis (2,4-di-t-butylphenyl) or ethylidene bis (2,4-di-t-butylphenyl) phosphate Na salt.

Fillers and reinforcements may include, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, and graphite.

Other additives include, for example, plasticizers, epoxidized vegetable oils such as epoxidized soybean oils, lubricants, emulsifiers, pigments, optical brighteners, fire retardants, antistatic agents, blowing agents and thiosynergics, such as dilauryl thiodipropionate or thiodipropionate thi. similar.

The additives and stabilizers described herein are preferably present in an amount effective to improve the stability of the composition. When one of the aforementioned additives and stabilizers is used, the amount is generally less than about 5% by weight, based on the weight of the resin, and is preferably at least about 50 ppm, based on the weight of the resin. The stabilizer combinations of the invention stabilize the resins especially during high temperature processes with relatively little variation in melt index and / or color, even though the polymer may be subjected to multiple extrusions. These stabilizers can be readily incorporated into the resins by conventional techniques at any appropriate stage prior to the manufacture of molded articles therefrom. For example, the stabilizers may be mixed with the resin in a dry, powdered form, or the stabilizer suspension or emulsion may be mixed with a solution, suspension, or emulsion of the polymer. The stabilized compositions of the invention may also optionally contain from about 0.001 to about 5%, preferably from about 0.0025 to about 2%, and more preferably from about 0.005% to about 1% by weight of various conventional additives such as those described above or mixtures thereof. .

The stabilizers of the invention preferably help to stabilize the polymer resin compositions, especially in high temperature processes, relative to changes in melt index and / or color, even though the polymeric resin may undergo multiple extrusions. The stabilizers of the invention can be readily incorporated into the resin composition by conventional techniques, at any appropriate stage prior to manufacturing a shaped article therefrom. For example, the stabilizer may be mixed with the resin in a dry, powdered form, or the stabilizer suspension or emulsion may be mixed with a solution, suspension, or emulsion of the polymer.

The compositions of the invention can be prepared by a variety of methods, such as by intimately mixing the ingredients with any additional substances desired in the formulations. Suitable procedures include solution blending and melt blending. Due to the availability of melt-blending equipment in commercial polymer processing media, melt-processing methods are generally selected. Examples of equipment used in such melt-blending methods include: co-rotating and counter-rotating extruders, single screw extruder, disc packet processors, and various other types of extrusion equipment. In some cases, the mixed material exits the extruder through the small exit holes in the die and the resulting molten resin strands are cooled by passing the strands through a water bath. The cooled strands can be cut into small granules for packaging and further handling.

All ingredients may be added initially to the processing system, or some additives may be pre-mixed with each other or with part of the polymeric resin to form a stabilizer concentrate. Furthermore, it is also sometimes advantageous to use at least one venting outlet to allow venting (atmospheric or vacuum) of the melt. It is known to those skilled in the art to determine the time and temperature of mixing, as well as the location and sequence of adding ingredients, without additional experimentation.

While the stabilizers of the invention can advantageously be incorporated into polymeric resins by conventional techniques before being processed into shaped articles, it is also possible to apply finished stabilizers by topical application to finished articles. The articles can contain ready-made stabilizer compounds and resins, and can be processed into, for example, headlamp covers, roofing, telephone covers, aircraft interiors, building interiors, computer and office equipment housings, automotive parts and household utensils. These products can be manufactured by extrusion, injection molding, and flap molding14

By ironing, pressing and other methods. This may be particularly useful in the case of fibers where the finished stabilizers are applied topically to the fibers, for example by spin finish during melt spinning.

Examples

Example 1

Preparation of butylated alkylphenols

Phenol (188.4 g, 2.00 mol) and Fulcat 22B catalyst (1.41 g) were charged to a jacketed oil flask and heated to 110 ° C under a nitrogen atmosphere. Isobutylene (180.5 g, 3.21 mol) is introduced under the sintered glass frit at a constant rate for 4.5 hours under the phenol surface. After the addition was complete, the reaction mixture was kept at a jacket temperature of 110 ° C for one hour. The reaction mixture is filtered and the phenol filtrate is collected. The butylated alkylphenol is subjected to vacuum distillation to reduce the phenol content to less than 0.25% and the water content to less than 50 ppm. Yield = 290.3 g.

Example 2

Preparation of phosphite from butylated alkylphenol obtained according to example 1

The butylated alkylphenol (152.4 g, 0.971 mol) was charged to a jacketed oil flask and heated to 85 ° C under a nitrogen atmosphere. PCl3 (40.4 g, 0.294 mol) is added under the surface of the phenolic compound at a constant rate for three hours. The temperature rises to 150 ° C during the addition. The reaction mixture is kept at 150 ° C until the evolution of HCl has ceased, then it is heated at 200 ° C for one hour, the pressure being released from 1000 to 50 mbar (100 to 5 kPa). The reaction mixture is kept at 200 ° C / 50 mbar (5 kPa) until the total Cl content is less than 50 ppm. The excess phenolic compounds are removed by distillation at 1 mbar (100 Pa) and an internal temperature of 250 ° C (steam temperature 145 ° C). Yield = 115.9 g.

Temperature vs. viscosity profile for the phosphite mixture obtained according to example 2

<td>Temperature (° C)</td><td>Viscosity (m²/ s)</td>

<td> 30</td><td> 0,003662</td>

<td> 40</td><td> 0,001662</td>

<td> 50</td><td> 0,000494</td>

Example 3

Phosphite preparation from a 2: 1 mixture of 4-tert-butylphenol / 2,4-di-tert-butylphenol made from phenolic components

Charge 4-tert-Butylphenol (176.6 g, 1.18 mol) and 2,4-di-tert-butylphenol (121.3 g, 0.59 mol) to a jacketed oil flask and heat to 80 ° C under nitrogen atmosphere. PCl3 (73.4 g, 0.53 mol) is added under the surface of the phenolic compounds at a constant rate over two hours. The temperature rises to 150 ° C during the addition. The reaction mixture is held at 150 ° C until the evolution of HCl has ceased, then it is heated to 200 ° C in one hour, the pressure being released from 1000 to 70 mbar (100 to 7 kPa). The reaction mixture is kept at 200 ° C / 70 mbar (7 kPa) until the total Cl content is less than 50 ppm. The excess phenolic compounds are then removed by distillation at 8 mbar (800 Pa) and an internal temperature of 200 ° C. Yield = 279.3 g. This product is referred to below as liquid P-2 phosphite.

Temperature vs. viscosity profile for the phosphite mixture obtained according to example 3

<td>Temperature (° C)</td><td>Viscosity (m²/ s)</td>

<td> 40</td><td> 0,008300</td>

<td> 50</td><td> 0,001776</td>

<td> 60</td><td> 0,000530</td>

<td> 70</td><td> 0,000218</td>

<td> 80</td><td> 0,000120</td>

PL 216 865 B1

Example 4

Preparation of mixed amyl / butyl phenols

Phenol (105 g, 1.12 mol) and Fulcat 22B catalyst (2.25 g) were charged to a jacketed oil flask and heated to 130 ° C under a nitrogen atmosphere. Isobutylene (64.6 g, 1.15 mol) is introduced under the sintered glass frit at a constant rate for 30 minutes. The internal temperature rises to 140 ° C during the addition. After the addition was complete, the reaction mixture was kept at a jacket temperature of 130 ° C for one hour. Then amylene (39.2 g, 0.56 mol) was added under the surface of the phenolic compounds at a constant rate over 1.25 hours. After the addition was complete, the reaction mixture was kept at a jacket temperature of 130 ° C for two hours. The reaction mixture is then filtered and the phenol filtrate is collected. Mixed butylated / arylated alkylphenols are subjected to vacuum distillation to reduce the phenol content to less than 0.25% and the water content to less than 50 ppm. Yield = 161.8 g.

Example 5

Conversion to phosphite of the alkyl compound obtained in example 4

The mixed butylated / amylated alkylphenol (148.7 g, 0.86 mol) was charged to the oil jacketed flask and heated to 80 ° C under a nitrogen atmosphere. PCl3 (35.8 g, 0.26 mol) is added under the surface of the phenolic compounds at a constant rate for three hours. The temperature rises to 150 ° C during the addition. The reaction mixture is held at 150 ° C until the evolution of HCl has ceased, then it is heated to 200 ° C in one hour, the pressure being released from 1000 to 50 mbar (100 to 5 kPa). The reaction mixture is kept at 200 ° C / 50 mbar (5 kPa) until the total Cl content is less than 50 ppm. The excess phenolic compounds are then removed by distillation at 1 mbar and an internal temperature of 240 ° C (steam temperature 140 ° C). Yield = 123.1 g.

Temperature vs. viscosity profile for the phosphite mixture obtained according to example 5

<td>Temperature (° C)</td><td>Viscosity (m²/ s)</td>

<td> 30</td><td> 0,007481</td>

<td> 40</td><td> 0,003198</td>

<td> 50</td><td> 0,000763</td>

Example 6

Preparation of an amylalkyl compound

Phenol (150 g, 1.59 mol) and Fulcat 22B catalyst (3.36 g) were added to the oil jacketed flask and heated to 130 ° C under a nitrogen atmosphere. Then amylene (167.7 g, 2.39 mol) was added under the surface of the phenolic compounds at a constant rate over four hours. After the addition was complete, the reaction mixture was kept at a jacket temperature of 130 ° C for two hours. The reaction mixture is then filtered and the phenol filtrate is collected. The amylated alkylphenol compounds are purified by distillation, the main fraction collected at 120 to 146 ° C (vapor temperature = 120 to 140 ° C) at a pressure of 5-7 mbar (500-700 Pa). Yield = 227.3 g.

Example 7

Preparation of phosphite from amylated alkylphenols

The amylated alkylphenols (214.7 g) and N, N-dimethyldodecylamine (0.65 mL) were charged to an oil jacketed flask and heated to 80 ° C under a nitrogen atmosphere. PCl3 (51.9 g, 0.38 mol) is added under the surface of the phenolic compounds at a constant rate over three hours. The temperature rises to 150 ° C during the addition. The reaction mixture is held at 150 ° C until the evolution of HCl has ceased, then it is heated to 200 ° C in one hour, the pressure being released from 1000 to 130 mbar (100 to 13 kPa). The reaction mixture is kept at 200 ° C / 130 mbar (13 kPa) until the total Cl content is less than 50 ppm. Then the excess phenolic compounds are removed by distillation at 3 mbar (300 Pa) and an internal temperature of 195 ° C. Yield = 223.7 g. This product is referred to below as liquid P-4 phosphite.

PL 216 865 B1

Temperature vs. viscosity profile for the phosphite mixture obtained according to example 7

<td>Temperature (° C)</td><td>Viscosity (m²/ s)</td>

<td> 40</td><td> 0,001270</td>

<td> 50</td><td> 0,000513</td>

<td> 60</td><td> 0,000238</td>

<td> 70</td><td> 0,000132</td>

<td> 80</td><td> 0,000075</td>

Example 8

Evaluation of polypropylene behavior in multi-pass extrusion

This example illustrates the stabilizing efficiency of the liquid phosphite mixtures of the invention in the case of multiple pass extrusion into polypropylene.

The base polymer is Basell HF500N Spheripol polypropylene homopolymer powder having a melt flow index (MFI) of 12 g / 10 minutes. The base formulation also contains 500 ppm calcium stearate as an acid scavenger. All formulations are prepared by adding each time 500 ppm of Anox 20 (tetrakis [methylene- {3,5-di-tert-butyl-4-hydroxycinnamate}] methane) and the corresponding liquid phosphite mixture according to the invention to the base polymer. The thus stabilized resin formulations are extruded from a 19 mm diameter Brabender single screw extruder at 60 rpm with four heating zones at the following temperatures: 200 ° C; 225 ° C; 250 ° C and 270 ° C in an oxygen atmosphere.

The extrudate is cooled by passing it through an ice-water bath and then granulated. These granules are extruded again. After the third extrusion, the melt index (in g / 10 minutes) is measured at 230 ° C / 2.16 kg. A relatively small increase in the melt index indicates either negligible polymer degradation or good stabilization. The results are given in Table 1.

Table 1

Melt flow index results

<td>Stabilizer (ppm)</td><td>The melt index (g / 10 minutes) for pass 3 of extrusion</td>

<td>Basis</td><td> 32,0</td>

<td>Liquid Phosphite P-2 (500) + Anox 20 (500)</td><td> 14,7</td>

<td>Liquid Phosphite P-3 (500) + Anox 20 (500)</td><td> 13,8</td>

<td>Liquid Phosphite P-4 (500) + Anox 20 (500)</td><td> 14,6</td>

Liquid P-2 phosphite: prepared according to example 3.

Liquid P-3 Phosphite: a mixture of phosphites obtained from butylated alkyl p-cresol prepared according to example 2 by using butylated alkyl p-cresol in place of butylated alkylphenol.

Liquid P-4 phosphite: prepared according to example 7.

The results of these tests show that the liquid phosphite mixtures P-2 to P-4 according to the invention give higher melt stabilization compared to the control. Thus, formulations containing a liquid phosphite mixture produced only a relatively small increase in the melt index compared to the control.

Example 9

Evaluation of behavior in high-density polyethylene

This example illustrates the stabilizing efficiency of the inventive liquid phosphite mixtures in the Plasticorder test.

The base formulation contains high-density polyethylene polymer flake Solvay HP-54-60 and 300 ppm Anox 20 (tetrakis [methylene- {3,5-di-tert-butyl-4-hydroxycinnamate}] methane). Preparations

Test results are prepared by adding 1000 ppm of the respective liquid phosphite mixtures according to the invention to the stock formulation.

To perform the Plasticorder test, each preparation, including the control sample, is added ₃ for Brabender plastograph equipped with a 60 cm mixing head³ at 220 ° C / 60 rpm. As the test specimens are kneaded in the mixing head, the torque is continuously measured and recorded. After the induction period, the polymer begins to cross-link, which can be seen as a significant increase in momentum. Table 2 shows the time in minutes for the pre-torque induction period. A relatively long induction time indicates greater stabilization.

Table 2 Test Plasticorder

<td colspan="2">Stabilizer (ppm)</td><td>Induction time (minutes)</td>

<td>(AND):</td><td>HDPE + Anox 20 flake (300)</td><td> 10</td>

<td>(B):</td><td>(A) + liquid P-2 phosphite (1000)</td><td> 22</td>

<td>(C):</td><td>(A) + liquid P-3 phosphite (1000)</td><td> 28</td>

<td>(D):</td><td>(A) + liquid P-4 phosphite (1000)</td><td> 24</td>

The results of this test show that the liquid mixtures of P-2 to P-4 phosphites cause higher melt stabilization of HDPE polymer compared to the control. Thus, preparations containing P-2 to P-4 show a relatively long induction time in the Plasticorder test compared to the phosphite free control.