CN101472986B

CN101472986B - Liquid phosphite blends as stabilizers

Info

Publication number: CN101472986B
Application number: CN2007800229042A
Authority: CN
Inventors: M·E·盖尔宾; M·鲍尔; J·希尔
Original assignee: Crompton Corp
Current assignee: Shengswiss Group Co ltd
Priority date: 2006-06-20
Filing date: 2007-04-20
Publication date: 2012-04-11
Anticipated expiration: 2027-04-20
Also published as: AR064233A1; ZA200810076B; CN101472986A

Abstract

The invention discloses a composition that comprises a blend of at least two different phosphites of the structure, wherein R1, R2, and R3 are independently selected alkylated aryl groups and wherein said blend is a liquid at ambient conditions. The compositions are useful for stabilizing thermoplastic resins and elastomers.

Description

Liquid phosphite blends as stablizer

I am according to the 35th piece of United States Code (Title 35, United States Code), and that § 119 requires is that on June 20th, 2006 submitted to, name is called the rights and interests as the U.S. Provisional Application of the liquid phosphite blends of stablizer number 60/815,819.

Background of invention

1. invention field

The present invention relates to be used for the model mixture of the phosphite antioxidant of polymer resin composition.The invention still further relates to stabilized resin combination and stablizer enriched material, it comprises the novel aq mixture of said phosphite antioxidant.

2. description of related art

Known organophosphite in this area (aka SULPHOSUCCINIC ACID ESTER) is as being used for polyolefine, SE and elastomeric auxiliary antioxidant.The instance of known phosphorous acid ester like this is at H.Zweifel (Ed), Plastics Additives Handbook, and the 5th edition, HanserPublishers provides among the Munich 2000.One of the most widely used organophosphite is Wytox 312 (TNPP), and it at room temperature is a liquid.But, because the so-called estrogenicity of nonylphenol needs to substitute TNPP.And because TNPP is liquid under envrionment conditions, need be used under the envrionment conditions also is that the phosphorous acid ester of liquid replaces it.

Liquid and solid phosphite ester stabilizer blend are as known in the art.

U.S. Patent number 3,948,801 disclose stabilized composition; It comprises at least a triaryl phosphites; The xylogen of trialkyl phosphite or their mixture and at least a modification, the weight ratio of the xylogen of phosphorous acid ester and modification are 97/3 to 10/90.The xylogen of said modification makes the original guaiacyl structure of a part be converted into catechol through demethylation reaction and produces through thermal treatment xylogen in the presence of nucleophilic reagent.It is said and to prevent said elastomerics atmosphere degraded through in elastomerics, adding 0.01 to 5.0 weight part/100 a part elastomeric said stabilized composition.

The number of patent application 2003/0001136 and the U.S. Patent number 6,824,711 of u. s. published disclose the liquid polymers compositions of additives; It comprises at least a phosphorous acid ester that is selected from down group: aryl phosphite; Alkyl phosphite, aryl phosphite/alkyl ester, phosphorous acid biphenol-A ester; Two aklylene glycol phosphorous acid esters with gather two aklylene glycol phosphorous acid esters; The phosphorous acid pentaerythritol ester, phosphorous acid is to cumyl phenol ester and their blend and the zinc/100 part resin of about 50 to 800ppm (comprising end points).Said stablizer is as the surrogate wholly or in part of the antioxidant stabilizers additive that contains toxic metal.

The number of patent application 2004/0183054 of u. s. published discloses the liquid polymers compositions of additives, and it comprises the blend of the zinc/100 part resin of phosphorous acid ester and 50 to 800ppm (comprising end points), and said phosphorous acid ester is selected from down group: aryl phosphite; Alkyl phosphite; Aryl phosphite/alkyl ester, phosphorous acid biphenol-A ester, two aklylene glycol phosphorous acid esters with gather two aklylene glycol phosphorous acid esters; Pentaerythritol phosphite, phosphorous acid is to the cumyl phenol ester.Said stablizer is as the surrogate wholly or in part of the antioxidant stabilizers additive that contains toxic metal.

The number of patent application 2007/0021537 of u. s. published discloses the polyolefin compositions stabilization with antagonism melt, thermal ageing be exposed to the method for the harmful effect of combustion of natural gas product; This method comprises tricresyl phosphite (monoalkyl) phenylester of in polyolefine, introducing or apply the formula I of effective stabilization amount

Or the mixture of the phosphorous acid ester of formula I, wherein each R is identical or different, and is the straight or branched alkyl of 1 to 8 carbon atom, and wherein said phosphorous acid ester or phosphite mixture are liquid under 25 ℃ of pressure with 1atm.Also disclose stabilized compsn, said composition comprises some mixture of polyolefine and this phosphorous acid ester or phosphite mixture and tricresyl phosphite (monoalkyl) phenylester.These liquid phosphite stablizers it is said compatible especially with new LDPE (film grade).

CA 2,464, and 551 disclose each solid mixture of solid phosphorous acid ester component naturally, and it is used for the stabilization of the no phenol of polyvinylidene film.

CZ 280072 discloses as the phosphorous acid ester of the stablizer that is used for propene polymer and the mixture of phosphonic acid ester.

DE 90-4,001,397 discloses as the phosphonic acid ester and the phosphorous acid ester that are used for the thermo-stabilizer of polymkeric substance.

JP 05202236 discloses and allegedly can be used for the blend production of heat resistant poly compositions of olefines, that comprise phosphorous acid ester and phosphonic acid ester.

JP 59030842 discloses solid phosphorous acid ester blend stabilization, that comprise the solid phosphorous acid ester that allegedly can be used for polyolefin compositions.

RO 112871 discloses formula (RR ¹R ²C ₆H ₂O) ₃The compound of P, wherein (R, R ¹, R ²=CMe ₂Ph; Or R=H, R ¹, R ²=CMe ₂Ph; Or R=R ¹=H, R ²=CMe ₂Ph), for phenol with single, two and the mixture of the GW-540 of triaryl alkylated phenol, it is made up of flowable yellow liquid, contains 4 ± 0.3%P and 0.5%Cl, and has 1.5992 refractive index and 1.1400g/cm ³Density, allegedly can be used as and be used for polymkeric substance and elastomeric stablizer (n.d.).Said mixture passes through PCl ₃With molecular-weight average be 300 phenol with single, two and the mixture of triaryl alkylated phenol with arylalkyl phenol and the mol ratio of phenol and arylalkyl phenol+phenol and the PCl of 1:0.3-0.4 of 1:1-1.5 ₃The esterification preparation of mol ratio; Do not adopt solvent or catalyzer; Stirred 0.5-1.5 hour at 25-40 ° at anhydrous condition, then gradually elevated temperature to 90-150 °, at 150-180 ° of holding temperature 2-6 hour; Through 150-180 ° make nitrogen bubble through removed in reactant 2-5 hour the HCl that in reaction, forms and then through in inert nitrogen atmosphere 10mm Hg and 175 ° down distillation remove unreacted raw material.In the embodiment that provides, 989 grams restrain phenol under agitation 25 ° of fusions through (1-methyl isophthalic acid-phenylethyl) phenol of the alkylation production of phenol and the mixture and 475 of alpha-methyl styrene, and with 1 hour time dropping, 383 gram PCl ₃, then mixture is heated to 90 ° gradually, kept 1 hour at 90 °; Be heated to then 150 ° with remained on this temperature following 5 hours, afterwards through making nitrogen blow out the HCl of formation in 5 hours through mixture at 150 ° of following bubblings, afterwards with unreacted phenol through under nitrogen atmosphere; 175 ° with 10mm Hg pressure distillation down remove, provide 1460 and restrain product mixtures, it is a yellow liquid; Contain 4.14%P and 0.5%Cl, have 1.5992 refractive index and 1.1400g/cm ³Density, it contains tricresyl phosphite phenylester and 2-(α, α-Er Jiajibianji) phenol, 4-(α, α-Er Jiajibianji) phenol, 2, two (α, the α-Er Jiajibianji) phenol and 2,4 of 6-, the tris phosphite of 6-three (α, α-Er Jiajibianji) phenol.

WO 02070625 discloses the liquid phosphite mixture as compositions of additives.

WO 2001/062832 discloses and has added stabilizer additive to be used for rotational molding polymer beads.

WO 2001062833 discloses the mixture of organophosphite and phosphonic acid ester, and it can be used for adding the stabilizer additive that the polymer beads that is used for rotational molding is used.

WO 9303092 discloses each solid mixture purposes in heat-resistance polyester-polycarbonate moulding compound of solid phosphorous acid ester component naturally.

The disclosed content of above-mentioned file all is incorporated among the application by reference.

Summary of the invention

, resin needs liquid phosphite oxidation inhibitor in using always.The present invention relates to phosphite blends, preferred aryl phosphite ester blend, they have antioxidant property, and under envrionment conditions, promptly under environmental stress and room temperature, exist with the liquid physical form.

The various aryl phosphite components that constitute said novel aq phosphite blends at room temperature are solids.Therefore, the present invention relates to non-obvious and surprising discovery, that is, when these each solid-state aryl phosphite components constituted phosphite blends of the present invention, said blend was the physical form of liquid under envrionment conditions.

The invention still further relates to a kind of method, can prepare the aforesaid liquid phosphite blends through making the phosphorus trihalide and the blend direct reaction of corresponding alkylating phenol through this method.

The invention still further relates to these liquid phosphite blends as the purposes that is used for thermoplastic resin and elastomeric stablizer/oxidation inhibitor.

More specifically, the present invention relates to a kind of compsn, it comprises the blend of the phosphorous acid ester of at least two kinds of different following structures

R wherein ₁, R ₂And R ₃Be the alkylated aryl of selecting independently, and wherein said blend is a liquid under envrionment conditions.

In yet another aspect, the present invention relates to stabilized compsn, said composition comprises:

(A) fluoropolymer resin and

(B) blend of the phosphorous acid ester of at least two kinds of the stabilization amount different following structures

In yet another aspect, the present invention relates to comprise the goods of stabilized compsn, said stabilized compsn comprises:

(A) fluoropolymer resin and

Aspect another, the present invention relates to stablized thermoplastic resin or elastomeric method, this method comprises the step of the blend of the phosphorous acid ester of at least two kinds of different following structures of interpolation stabilization amount in said thermoplastic resin or elastomerics

Aspect another, the present invention relates to the method for liquid mixture of the liquid phosphite of synthetic at least two kinds of following structures

R wherein ₁, R ₂And R ₃Be the alkylated aryl of selecting independently, said method comprises makes wherein that Z is the PZ of halogen ₃Adjacent with the solid that comprises the about 95 weight % of about 5-to the solid of alkylating phenol and the about 5 weight % of correspondingly about 95-, the mixture reaction of right-dialkylated phenol.Preferably, Z is a chlorine or bromine, said phenol mixture and said PZ ₃Mol ratio be 3:1, and the alkyl of said alkylating phenol is the straight or branched alkyl of 1 to 6 carbon atom.More preferably, the alkyl of said alkylating phenol is the straight or branched alkyl of 4 to 5 carbon atoms; Most preferably, they are the tertiary butyl or tert-pentyl.

The description of embodiment preferred

As stated, the present invention relates to a kind of compsn, said composition comprises the blend of the phosphorous acid ester of at least two kinds of different following structures

Be present in the aryl moiety aromatics part of 6-18 carbon atom preferably in the The compounds of this invention, phenyl for example, naphthyl, phenanthryl, anthryl, xenyl, terphenyl etc., preferred phenyl.Such aromatics part is replaced by at least one alkyl, and can further can be influenced the physics of The compounds of this invention and any substituting group replacement of stabilization performance basically sharply.

One or more alkyl substituents of said aryl moiety are selected from down the moieties of group: a 1-18 carbon atom, methyl for example, ethyl, propyl group, butyl; Amyl group, hexyl, heptyl, octyl group, nonyl; Decyl, undecyl, dodecyl, tridecyl, tetradecyl; Pentadecyl, hexadecyl, heptadecyl, octadecyl, the isomer of aforementioned group etc.Preferably, such moieties comprises 1 to 6 carbon atom, and it can be straight chain or branching; More preferably comprise 4 or 5 carbon atoms.Most preferably butyl, the particularly tertiary butyl, and amyl group, particularly tert-pentyl.

In a preferred embodiment, R ₁, R ₂And R ₃Be the alkylated aryl of the following structure selected independently:

R wherein ₄, R ₅And R ₆Be independently selected from down group: hydrogen and C ₁-C ₆Alkyl, methyl for example, ethyl, propyl group, butyl, amyl group, hexyl and their isomer, sec.-propyl for example, the tertiary butyl, neo-pentyl etc., prerequisite is R ₄, R ₅And R ₆In at least one is not a hydrogen.Preferably, R ₄, R ₅And R ₆Be selected from down group: hydrogen, methyl, ethyl, propyl group, butyl, amyl group and their isomer, prerequisite also is R ₄, R ₅And R ₆In at least one is not a hydrogen.More preferably, R ₄, R ₅And/or R ₆Be C ₄Or C ₅Alkyl, the most preferably tertiary butyl or tert-pentyl.

Therefore, in a preferred embodiment, the present invention relates to a kind of compsn, it comprises the blend of the phosphorous acid ester of at least two kinds of different following structures

R wherein ₁, R ₂And R ₃Be the alkylated aryl of the following structure selected independently:

R wherein ₄, R ₅And R ₆Be independently selected from hydrogen and C ₁-C ₆Alkyl, prerequisite are R ₄, R ₅And R ₆In at least one is not a hydrogen; With

Wherein said blend is a liquid under envrionment conditions.

Similarly, in another preferred embodiment, the present invention relates to stabilized compsn, it comprises:

(A) fluoropolymer resin and

Wherein said blend is a liquid under envrionment conditions.

In still another preferred embodiment, the present invention relates to comprise the goods of stabilized compsn, said stabilized compsn comprises:

(A) fluoropolymer resin and

R wherein ₁, R ₂And R ₃It is the alkylated aryl of selecting independently;

The aryl moiety that wherein is present in the alkylated aryl in the phosphorous acid ester is independently selected from the aromatics part of 6-18 carbon atom;

Each aryl of wherein said alkylated aryl is replaced by the alkyl of at least one 1-18 carbon atom; With

Wherein said blend is a liquid under envrionment conditions.

In still another preferred embodiment; The present invention relates to stablized thermoplastic resin or elastomeric method; This method comprises the step of in said thermoplastic resin or elastomerics, adding a kind of compsn of stabilization amount, and said compsn comprises the blend of the phosphorous acid ester of at least two kinds of different following structures

Wherein said blend is a liquid under envrionment conditions.

In above-mentioned embodiment, preferred said blend comprises at least three kinds of phosphorous acid esters different, said structure, even more preferably, they comprise at least four kinds of so different phosphorous acid esters.

The invention still further relates to a kind of method, through this method can be in the direct reaction of the phosphorus trihalide and the mixture of corresponding alkyl-substituted phenols the said liquid phosphite mixture of preparation, with or without catalyzer.Reaction product as the result of this method obtains can former state be used, and replaces mixing liquid phosphite blends of the present invention, does not need further modification.In a preferred embodiment, the present invention relates to the method for liquid mixture of the liquid phosphite of synthetic at least two kinds of following structures:

R wherein ₁, R ₂And R ₃It is the alkylated aryl of selecting independently; Wherein this method comprises:

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

The alkylating phenol and the catalyst separating that (B) will obtain; With

(C) making wherein, Z is the PZ of halogen ₃With the mixture reaction that obtains, the said mixture that obtains comprises the solid neighbour of the solid of the about 95 weight % of about 5-to alkylating phenol and the about 5 weight % of correspondingly about 95-, and is right-dialkylated phenol.So-called " phenolic compound " is meant to have at least one OH group and randomly further by one or more substituted aryl moieties of other group that can influence the performance of its hope sharply; Phenyl for example; The instance of phenolic compound is a cresylol, xylenol etc.

Therefore, can be used for preferred means the present invention practice, that be used to prepare said aryl phosphite ester stabilizer is through making phosphorus trihalide PZ ₃, for example phosphorus trichloride or phosphorus tribromide are with the mixture reaction of suitable alkylating phenol.

The mixture of alkylating phenol and PZ ₃Between reaction can under the situation of using or do not use solvent, carry out.Typically, can be with said PZ ₃Add in the mixture of alkylating phenol, perhaps can add the mixture of alkylating phenol to PZ ₃In.Preferably, with said PZ ₃Add in the mixture of alkylating phenol, keep about 5 to 150 ℃ temperature simultaneously.Kept reaction mixture then 1 to 10 hour.During this period of time, HZ gas will be discharged, said HZ gas can be helped to remove through reducing pressure or making rare gas element such as nitrogen sweep cross reaction mixture.Typical decompression is 50 millibars.For example for HCl, this step will proceed to total Cl content and be lower than 50ppm.Typically, can preferably, keep 5 millibars vacuum simultaneously through further elevated temperature to the highest 230 ℃ then, any unreacted alkylating phenol is removed from reaction mixture to about 200 ℃.

The solvent of operable hope is a neutral solvent.Typical solvent is a toluene, heptane, YLENE, methylene dichloride, chloroform and benzene.Preferred solvent is a methylene dichloride, heptane, or YLENE.

Therefore, preferably, liquid phosphite blends of the present invention is directly obtaining in the chemical reaction, is correspondingly regulated in the ratio of the substituted phenol of alkyl described in the said reaction.The route of reaction method is following.

Wherein m=3 and n=2.

In an embodiment preferred of the present invention, all above-mentioned R groups are the tertiary butyl or tert-pentyl, and therefore, the compound of such blend is selected from down group: tricresyl phosphite (4-tert-butyl-phenyl) ester; Tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (the 4-tert-butyl-phenyls)-2 of phosphorous acid, 4-di-tert-butyl-phenyl ester; Two (2, the 4-the di-tert-butyl-phenyl)-4-tert-butyl-phenyl esters of phosphorous acid, tricresyl phosphite (4-tert-pentyl phenyl) ester; Tricresyl phosphite (2, the 4-di-tert-pentyl-phenyl) ester, two (the 4-tert-pentyl phenyl)-2 of phosphorous acid; Two (2, the 4-the di-tert-pentyl-phenyl)-4-tert-pentyl phenyl esters of 4-di-tert-pentyl-phenyl ester and phosphorous acid.

As stated, a characteristic of the present invention is that the mixture of said phosphite antioxidant at room temperature is the liquid physical form.Consider that it wherein itself is that the mixture of solid phosphite ester stabilizer at room temperature also is that several instances of solid are (referring to JP59030842 that prior art has been instructed; WO 9303092; CA 2,464, and 551), this obviously is surprising.In the present invention, the blend of said phosphite ester stabilizer forms liquid, even known each component is a solid.

Therefore, in the route that shows in the above, liquid phosphite blends can be by four kinds of main phosphorous acid ester components; It is tricresyl phosphite (4-tert-butyl-phenyl) ester; Tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (the 4-tert-butyl-phenyls)-2 of phosphorous acid; Two (2, the 4-the di-tert-butyl-phenyl)-4-tert-butyl-phenyl esters of 4-di-tert-butyl-phenyl ester and phosphorous acid are formed.But, in this area known for example component tricresyl phosphite tert-butyl-phenyl ester have 75-76 ℃ fusing point (Kosa lopoff, Organic Phosphorus Compounds, Wiley Interscience, Vol.5, pg163).Similarly, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is a solid as known in the art, and its fusing point is 181-184 ℃ (an Aldrich catalog number (Cat.No.) 441791).Similarly, two (the 4-tert-butyl-phenyls)-2 of phosphorous acid, 4-di-tert-butyl-phenyl ester has 63-65 ℃ fusing point.Similarly, two (2, the 4-the di-tert-butyl-phenyl)-4-tert-butyl-phenyl esters of phosphorous acid have 100-103 ℃ fusing point.

Ester exchange method, for example 3,056, No. 823 (this patent combines in this article by reference) the middle those disclosed methods of USP people such as Hechenbleikner also can be used.Particularly, the method described of people such as Hechenbleikner comprises and makes triaryl phosphites and monohydroxy hydrocarbon in the presence of the metal alkoxide of a small amount of but catalytically effective amount or metal phenates, carry out transesterification reaction.

For fear of pollution, use will be by the alkoxide of the certain alcohols of transesterify.Replace using preformed alkoxide, said alkoxide can come original position to form through in alcohol, adding metal such as sodium, potassium or lithium before in the interpolation triaryl phosphites.The pure and mild triaryl phosphites of said list is with the molar ratio reaction of three mol of alcohol than one mole of triaryl phosphites.

The invention still further relates to the method for the suitable alkylating phenol mixture of preparation.Therefore, phenol (or cresols or alkylating phenol such as p-tert-butylphenol) preferably with light alkene (C ₂-C ₆, more preferably C ₄-C ₅), use many known catalysts (acid clay, Zeo-karb, Br such as sulfuric acid, Lewis acid such as BF ₃) in any reaction, provide the blended alkylating phenol, the composition of this blended alkylating phenol can be through changing the alkylation degree, temperature waits and changes.

And; The invention still further relates to provides blended alkylating phenol raw material (be used for synthetic said phosphite blends), wherein with a kind of phenol with the mixture alkylation abreast (while feed olefin A and B) of light alkene or alkylation one after the other (promptly with alkene A alkylation and use alkene B alkylation subsequently).

The invention still further relates to stabilized thermoplasticity or elastomer resin, wherein a kind of component comprises liquid aryl phosphite ester blend and another kind of component comprises polymkeric substance such as polyolefine, SE etc.

By the said polymkeric substance of phosphorous acid alkylated aryl ester blend stabilization of the present invention can be any thermoplastics known in the art, for example polyolefin homopolymer and multipolymer, polyester, urethane; Polyalkylene terephthalates, polysulfones, polyimide; Ppe, styrenic and multipolymer, polycarbonate; Acrylic acid polymer, polymeric amide, polyacetal and halogen containing polymers.The mixture of various polymerization thing; Ppe/phenylethylene resin series blend for example; SE/ABS or other impact modified polymkeric substance be as containing the ABS of methacrylonitrile and alpha-methyl styrene, and the mixture that polyester/ABS or polycarbonate/ABS and polyester add some other impact modifying agent also can use.Such polymkeric substance is available commercially, perhaps can be through method preparation well known in the art.But because thermoplastic polymer is often processed and/or the extreme temperature when using, stabiliser compsn of the present invention is at thermoplastic polymer such as polyolefine, polycarbonate, and polyester is useful especially in ppe and the styrenic.

Can use the polymkeric substance of monoolefine and diolefine, Vestolen PP 7052 for example, polyisobutene; Poly-1-butylene, polymethylpentene-1, TR 301; Or polyhutadiene, and the polymkeric substance of cycloolefin, the for example polymkeric substance of cyclopentenes or norbornylene; Vilaterm (its optional can being crosslinked), for example high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE) and linear low density polyethylene (LLDPE).Also can use these mixture of polymers, the mixture of Vestolen PP 7052 and polyisobutene for example, (PP/HDPE for example is PP/LDPE) with dissimilar poly mixtures (for example LDPE/HDPE) for Vestolen PP 7052 and poly mixture.Following material also is useful: monoolefine and diolefine each other or with the multipolymer of other vinyl monomer, ethylene/propene copolymer for example, the mixture of LLDPE and itself and LDPE; Propene/but-1-ene-1 multipolymer, ethylene/hexene multipolymer, ethene/ethypentene multipolymer; Ethene/heptene multipolymer, ethylene/octene, propylene/isobutylene copolymers; Ethene/butane-1 multipolymer, propylene/butadienecopolymer, iso-butylene; Isoprene, ethylene/alkyl acrylate copolymer, ethylene/methacrylic acid alkyl ester copolymer; Ethylene (EVA) or ethylene/acrylic acid copolymer (EAA) and their salt (ionomer) and ethene and propylene and diolefine such as hexadiene, the terpolymer of Dicyclopentadiene (DCPD) or ethylidene-norbornylene; And such multipolymer and their mixture and above-mentioned mixture of polymers, polypropylene/ethylene propylene copolymer for example, LDPE/EVA, LDPE/EAA, LLDPE/EVA, and LLDPE/EAA.

Said olefin polymer can (it be optionally supported at carrier such as MgCl at Ziegler-Natta catalyst through alkene for example ₂, chromic salts and complex compound thereof, silicon-dioxide is on the silica-alumina etc.) and polymerization under existing produces.Said olefin polymer can also use chrome catalysts or single-site catalysts such as metalloscene catalyst (the for example cyclopentadiene complex of metal such as Ti and Zr) to produce.Easily understand like those skilled in the art, the polyethylene polymer that uses among this paper, for example LLDPE can contain various comonomers such as 1-butylene, 1-hexene and 1-octene copolymer monomer.

Polymkeric substance can also comprise styrenic, and for example PS gathers (p-methylstyrene); Gather (alpha-methyl styrene), the multipolymer of vinylbenzene or alpha-methyl styrene and diolefine or acrylic acid series verivate, for example styrene/butadiene copolymers; Styrene/acrylonitrile copolymer; The styrene/methacrylic acid alkyl ester copolymer, phenylethylene/maleic anhydride copolymer, vinylbenzene/maleimide copolymer; Phenylethylene/butadiene/ethyl acrylate copolymer; Styrene/acrylonitrile/methyl acrylate copolymer derives from the mixture of the high impact of styrol copolymer and another kind of polymkeric substance (for example being selected from polyacrylic ester, diene polymer or ethylene/propylene/diene terpolymers); With cinnamic segmented copolymer, styrene/butadiene/styrene for example, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/acrylonitrile/styrene alkene block copolymer.

Styrenic can comprise or comprise the graft copolymer of vinylbenzene or alpha-methyl styrene in addition, for example styrene-grafted polyhutadiene, styrene-grafted Polybutadiene-styrene or Polybutadiene-acrylonitrile; Vinylbenzene and vinyl cyanide (or methacrylonitrile) grafted polyhutadiene and its multipolymer; Vinylbenzene and maleic anhydride or maleimide grafted polyhutadiene; Vinylbenzene, vinyl cyanide and maleic anhydride or maleimide grafted polyhutadiene; Vinylbenzene; The polyhutadiene of vinyl cyanide and methyl methacrylate-grafted; Vinylbenzene and alkyl acrylate or alkyl methacrylate grafted polyhutadiene, the ethylene-propylene-diene terpolymer of vinylbenzene and acrylonitrile grafting, the polyacrylic ester of vinylbenzene and acrylonitrile grafting or Rohm tech inc; The acrylate/butadiene copolymers of vinylbenzene and acrylonitrile grafting, and the mixture of they and above-mentioned styrene based copolymer.

Nitrile polymer also can be used for polymer compsn of the present invention.These polymkeric substance comprise the homopolymer and the multipolymer of vinyl cyanide and its analogue; Polymethacrylonitrile for example; Polyacrylonitrile, acrylonitrile/butadiene polymkeric substance, vinyl cyanide/acrylic acid alkyl ester polymer; Vinyl cyanide/alkyl methacrylate/butadiene polymer and the top various ABS compsns of when styrenic is discussed, being mentioned.

Based on acrylic acid or the like such as vinylformic acid, methylacrylic acid, the polymkeric substance of methyl vinylformic acid and ethylacrylic acid and their ester also can use.Such polymkeric substance comprises that polymethylmethacrylate and wherein all or part of vinyl cyanide type monomer are by propenoate or acrylic amide alternate ABS-type graft copolymer.Also can use and comprise other acrylic type monomer such as propenal, Methylacrylaldehyde, the polymkeric substance of acrylic amide and USAF RH-1.

Halogen-containing polymkeric substance also is useful.These polymkeric substance comprise such as following resin: sovprene, Epicholorohydrin homopolymer and multipolymer, SE, polyvinyl bromide; PVF, polyvinylidene chloride, chlorinatedpolyethylene, Chlorinated Polypropylene III; Pvdf, bromination Vilaterm, chlorinated rubber, vinyl chloride vinyl acetate copolymer; Vinyl chloride-ethylene copolymer, VCP, vinylchlorid-styrol copolymer, vinylchlorid-isobutylene copolymers; Vinyl chloride-vinylidene chloride copolymer, vinylchlorid-phenylethylene-maleic anhydride terpolymer, vinylchlorid-styrene-acrylonitrile copolymer, vinylchlorid-butadienecopolymer; The vinylchlorid isoprene copolymer, vinylchlorid-propylene dichloride multipolymer, vinylchlorid-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylate copolymer; Vinylchlorid-maleate copolymer, vinylchlorid-alkylmethacrylate polymer, vinyl chloride-acrylonitrile copolymer and internally plasticized SE.

Other useful polymkeric substance comprises the homopolymer and the multipolymer of cyclic ethers, polyalkylene glycol for example, polyethylene oxide, the multipolymer of polypropyleneoxide or itself and bisglycidyl base ether; Polyacetals, for example polyoxymethylene with contain oxyethane those polyoxymethylene as comonomer; With thermoplastic polyurethane, propenoate or contain the polyacetals of the ABS modification of methacrylonitrile; The mixture of ppe and polyphenylene sulfide and ppe and PS or polymeric amide; Polycarbonate and polyester-carbonic ether; Polysulfones, polyethersulfone and polyetherketone; With derived from dicarboxylicacid and glycol and/or derived from the polyester of hydroxycarboxylic acid or corresponding lactone; Polyethylene terephthalate for example, polybutylene terephthalate, poly terephthalic acid hexanaphthene-1; 4-diformazan alcohol ester; Poly terephthalic acid-2 (2,2,4 (4-hydroxy phenyl)-propane) ester with gather hydroxybenzoate and derived from the block copolyether ester of polyethers with hydroxyl end groups.

Can use derived from diamines and dicarboxylicacid and/or derived from the polymeric amide and the copolyamide of aminocarboxylic acid or corresponding lactan, for example polymeric amide 4, polyamide 6; Polyamide 6/6,6/10,6/9; 6/12 and 4/6; Polymeric amide 11, polymeric amide 12, the aromatic poly that the condensation through m-xylene diamine and hexanodioic acid obtains; From 1,6-hexanediamine and m-phthalic acid be or/and the polymeric amide of terephthalic acid and optional elastomer production as properties-correcting agent for example gathers-2,4,4-trimethylammonium-hexamethylene terephthalamide or gather metaphenylene isophthaloyl amine.In addition; Can use above-mentioned polymeric amide and polyolefine, olefin copolymer, the elastomeric multipolymer of ionomer or chemically bonded or grafted; Or with the multipolymer of polyethers; For example with polyoxyethylene glycol, the multipolymer of W 166 or polytetramethylene glycol and with the polymeric amide or the copolyamide of EPDM or ABS modification.

Polyolefine, polyalkylene terephthalates, ppe and phenylethylene resin series and their mixture are preferred; Vilaterm wherein, Vestolen PP 7052, polyethylene terephthalate; Ppe homopolymer and multipolymer; PS, high-impact polystyrene, polycarbonate and ABS-type graft copolymer and their mixture are preferred especially.

When using in this article; " stabilization amount " or " significant quantity " of so-called phosphite blends of the present invention be meant, the amount when containing the polymer compsn of phosphorous acid ester of the present invention and comparing what physics in office or color characteristics aspect with the similar polymer compsn that does not comprise phosphorous acid ester of the present invention and show improved stability.The instance of improved stability comprises that antagonism is because of for example melt, weathering and/or the long-term exposure improved stability in the for example molecular weight degradation hot, that light and/or other factors caused, color degradation etc.In an example, improved stability is meant a kind of in priming color lower when comparing with the compsn that does not contain stabilizer additive or the additional weather proofing or the two, for example measures by initial yellowness index (YI) or by anti-flavescence and colour-change.

The invention still further relates to stabilized thermoplastic resin; Wherein a kind of component comprises liquid aryl phosphite ester blend, and other component comprises polymkeric substance such as polyolefine, and wherein said liquid phosphite blends and co-stabilizer such as phenol; Aromatic amine; Oxyamine, alkylamine-N-oxide compound, lactone and thioether use together.

Therefore, by the thermoplastic resin of phosphite blends stabilization of the present invention can choose wantonly contain be selected from down the group additional stabilizers or stabilizer blend: phenolic antioxidant, hindered amine stabilizer, UV light absorber; Phosphorous acid ester, phosphonic acid ester, an alkali metal salt of lipid acid, hydrotalcite; MOX, epoxidised soybean oil, oxyamine, tertiary amino oxides; Lactone, the thermal response product of tertiary amino oxides and sulfo-synergist (thiosynergists).

Therefore, the optional additive that also contains various routines of the polymer resin composition of the stabilization that obtains, for example following:

Oxidation inhibitor: oxidation inhibitor can comprise alkylating single phenols, for example: 2,6 di tert butyl 4 methyl phenol, the 2-tertiary butyl-4,6-xylenol; 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2; 6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4; The 6-xylenol, 2,6-two (octadecyl)-4-methylphenol, 2; 4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxymethyl phenol.Alkylating quinhydrones, for example 2,6-di-t-butyl-4-methoxyphenol, DBH 2,5 di tert butylhydroquinone, 2,5-two tert-pentyls-quinhydrones, 2,6-phenylbenzene-4-octadecane oxygen base phenol also can be used as oxidation inhibitor.

The oxidation inhibitor that uses can also comprise hydroxylated sulfo-diphenyl ether, for example 2, and 2 '-sulfo--two (the 6-tertiary butyl-4-methylphenol); 2; 2 '-sulfo--two (4-octyl phenol), 4,4 '-sulfo--two (the 6-tertiary butyl-3-methylphenol); With 4,4 '-sulfo--two (the 6-tertiary butyl-2-methylphenol).

Alkylidene bisphenols also can be used as oxidation inhibitor, and for example 2,2 '-methylene radical-two (the 6-tertiary butyl-4-methylphenol), 2; 2 '-methylene radical-two (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene radical-two (4-methyl-6-(Alpha-Methyl cyclohexyl) phenol), 2; 2 '-methylene radical-two (4-methyl-6-cyclohexylphenol), 2,2 '-methylene radical-two (6-nonyl-4-methylphenol), 2; 2 '-methylene radical-two (6-(α-Jia Jibianji)-4-nonylphenol), 2,2 '-methylene radical-two (6-(α, α-Er Jiajibianji)-4-nonylphenol); 2,2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds), 2; 2 '-ethylidene-two (the 6-tertiary butyl-4-isobutyl-phenol), 4,4 '-methylene radical-two (2,6 di t butyl phenol); 4,4 '-methylene radical-two (the 6-tertiary butyl-2-methylphenol), 1, two (5-tertiary butyl-4-hydroxy-2-methylphenol) butane of 1-; 2,6-two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1; 3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-3-dodecyl-sulfydryl butane of 1-, terepthaloyl moietie-two (3; Two (3 '-tertiary butyl-4 '-the hydroxy phenyl)-butyric esters of 3-)-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-Dicyclopentadiene (DCPD), terephthalic acid two (2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-the methyl-benzyl)-6-tertiary butyl-4-aminomethyl phenyl) ester and other phenol, the for example mono acrylic ester of bisphenols; Ethylenebis-2 for example, 4-DI-tert-butylphenol compounds mono acrylic ester and 3, the ester of 5-dibutyl hydroxy phenyl propionic acid.Make us interested phenolic antioxidant especially and be selected from down group: 3,5-di-t-butyl-4-hydroxyl phenylpropionic acid Octadecane base ester, four (3,5-di-t-butyl-4-hydroxyl phenylpropionic acid) pentaerythritol ester, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids two Octadecane base esters; 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, sulfo-di ethylene bis (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate); 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; 3,6-dioxa eight methylene-biss (3-methyl-5-tertiary butyl-4-hydroxy hydrogenated cinnamate), 2,6-di-t-butyl-p-cresol, 2,2 '-ethylidene-two (4; The 6-DI-tert-butylphenol compounds), 1,3,5-three (2, the 6-dimethyl--4-tertiary butyl-3-hydroxybenzyl) isocyanuric acid ester, 1; 1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3, [2-(3 for 5-three; 5-di-t-butyl-4-cinnamoyloxy hydroxy hydride) ethyl] isocyanuric acid ester, 3,5-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4; The 6-pseudocuminol, hexa-methylene two (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate), 1-(3,5-di-t-butyl-4-hydroxybenzene amido)-3; 5-two (octyl group sulfenyl)-s-triazine, N, N '-hexa-methylene-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), two (3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) calcium, ethylenebis [3,3-two (3-tert-butyl-hydroxy phenyl) butyric ester], 3,5-di-tert-butyl-4-hydroxyl benzyl Thiovanic acid monooctyl ester; Two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide) hydrazine, and N, N '-two [2-(3,5-di-t-butyl-4-cinnamoyloxy hydroxy hydride) ethyl]-oxamide.

Operable other oxidation inhibitor comprises benzyl compounds, for example 1,3, and 5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2; 4,6-Three methyl Benzene, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether, 3; 5-di-tert-butyl-4-hydroxyl benzyl-isooctyl mercaptoacetate, two (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) two mercaptan-terephthalate, 1,3; 5-three (3,5-di-t-butyl-4,10-hydroxybenzyl) isocyanuric acid ester, 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 3, the two stearyl of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids, 3; The calcium salt and 1,3 of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids list ethyl ester, 5-three (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanuric acid ester.

Acyl amino phenol can be used as oxidation inhibitor, 4-hydroxyl-lauryl aniline for example, 4-hydroxyl-stearanilide; 2,4-pair-octyl group sulfenyl-6-(3,5-tertiary butyl-4-hydroxy anilino)-s-triazine; And N-(3, the 5-di-tert-butyl-hydroxy phenyl)-carboxylamine monooctyl ester.

Also can use β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl)-propionic acid and monohydroxy-alcohol or polyvalent alcohol such as methyl alcohol, Diethylene Glycol, Stearyl alcohol; Triethylene glycol, 1, the 6-pinakon; Tetramethylolmethane; NSC 6366, isocyanuric acid trihydroxyethyl ester, the ester of thio-diethylene glycol and dihydroxy ethyl oxalic acid diamide is as oxidation inhibitor.

Oxidation inhibitor can also comprise the acid amides of β-(3,5-di-t-butyl-4 hydroxyl phenol)-propionic acid, N for example, N '-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl group)-1,6-hexanediamine, N; N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl group)-1, the 3-tn; And N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl group)-hydrazine.

UV absorption agent and photostabilizer can comprise 2-(2 '-hydroxy phenyl)-benzotriazole, for example, 5 '-methyl-, 3 ', 5 '-di-t-butyl-; 5 '-tertiary butyl-, 5 '-(1,1,3, the 3-tetramethyl butyl)-; 5-chloro-3 ', 5 '-di-t-butyl-, 5-chloro-3 '-tertiary butyl-5 '-methyl-3 '-sec.-butyl-5 '-tertiary butyl-, 4 '-octyloxy; 3 ', 5 '-two tert-pentyls-3 ', 5 '-two (α, α-Er Jiajibianji)-verivates.Also can use 2-hydroxyl-UVNUL MS-40, for example 4-hydroxyl-4-methoxyl group-, the 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base-; The 4-dodecyloxy-, 4-benzyloxy, 4; 2 ', 4 '-trihydroxy--and 2 '-hydroxyl-4,4 '-dimethoxy verivate is as UV absorption agent and photostabilizer.UV absorption agent and photostabilizer can also comprise and replacing and unsubstituted benzoic ester, Whitfield's ointment phenylester for example, Whitfield's ointment 4-tert-butyl-phenyl ester; Whitfield's ointment octyl phenyl ester, dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical)-Resorcinols; The benzoyl-Resorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2; 4-di-tert-butyl-phenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester.

Esters of acrylic acid; Alpha-cyano-β for example; β-diphenylacrylate ethyl ester or isooctyl acrylate, α-methoxycarbonyl base-cinnamic acid methyl ester, alpha-cyano-Beta-methyl-to methoxyl group-cinnamic acid methyl ester or butyl ester; α-methoxycarbonyl base-to methoxyl group-cinnamic acid methyl ester, and N-(beta-methoxy-formyl radical-beta-cyano-vinyl)-2-methyl-indoline can be used as UV absorption agent and photostabilizer.

Other instance of UV absorption agent and photostabilizer comprises nickel compound, for example 2, and (4-(1,1 for 2 '-sulfo--two; 1,3-tetramethyl butyl)-phenol) nickel complex, for example 1:1 or 1:2 complex compound; Optional additional part such as n-butylamine, trolamine or N-cyclohexyl diethylolamine, the nickel dibutyl dithiocarbamate of containing; 4-hydroxyl-3, the nickel salt of 5-di-t-butyl benzylphosphonic acid mono alkyl ester (like methyl, ethyl or butyl ester); The nickel complex of ketoxime such as 2-hydroxy-4-methyl-phenyl undecyl ketoxime, the nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazoles is chosen wantonly and is contained additional part.

Hindered amine can be used as UV absorption agent and photostabilizer, two (2,2,6, the 6-tetramethyl-piperidyl) esters of sebacic acid for example, sebacic acid two-5 (1,2,2; 6,6-pentamethyl-piperidyl) ester, normal-butyl-3, two (1,2,2,6, the 6-pentamethyl-piperidyl) esters of 5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid; 1-hydroxyethyl-2,2,6, the condensation product of 6-tetramethyl--4-hydroxy-piperdine and succsinic acid, N, N '-(2,2,6; The 6-tetramethyl-piperidyl)-1,6-hexanediamine and uncle's 4-octyl group amino-2,6-two chloro-1,3, the condensation product of 5-s-triazine, NTA three (2,2,6; The 6-tetramethyl-piperidyl) ester, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3; 4-ethylene-dimalonic acid (arbonicacid), 1,1 '-(ethylene)-two (3,3,5,5-tetramethyl-piperazine ketone).These amine that are commonly called HALS (hindered amine as light stabilizer) comprise ethylene-dimalonic acid 2,2,6,6-tetramethyl piperidine alcohol ester.Such amine comprises the oxyamine derived from hindered amine, for example sebacic acid two (1-hydroxyl-2,2,6,6-tetramethyl piperidine-4-yl) ester; 1-hydroxyl-2,2,6,6-tetramethyl--4-benzyloxy piperidines; 1-hydroxyl-2,2,6,6-tetramethyl--4-(3,5-di-t-butyl-4-cinnamoyloxy hydroxy hydride)-piperidines; And N-(1-hydroxyl-2,2,6,6-tetramethyl--piperidin-4-yl)-ε-Ji Neixianan.

UV absorption agent and photostabilizer can also comprise the oxalic acid diamide, for example 4, and 4 '-two octyloxies-oxalyl pentanoic, 2; 2 '-two octyloxies-5 ', 5 '-di-t-butyl oxalyl pentanoic, 2; 2 '-two (dodecyloxies)-5 ', 5 '-di-t-butyl-oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl-oxalyl pentanoic; N, N '-two (3-dimethylaminopropyl)-oxamide, the 2-oxyethyl group-5-tertiary butyl-2 '-ethyl oxalyl pentanoic and with 2-oxyethyl group-2 '-ethyl-5; The mixture of 4-di-t-butyl oxalyl pentanoic and adjacent and to the mixture of the dibasic oxalyl pentanoic of methoxyl group, and adjacent and to the mixture of the dibasic oxalyl pentanoic of oxyethyl group.

UV absorption agent and photostabilizer also comprise hydroxy phenyl-s-triazine, for example 2, and two (2, the 4-the 3,5-dimethylphenyl)-4-(2-hydroxyl-4-octyloxyphenyl) of 6--s-triazine, 2, two (2, the 4-the 3,5-dimethylphenyl)-4-(2, the 4-dihydroxy phenyl) of 6--s-triazine; 52, two (2, the 4-the dihydroxy phenyl)-6-(4-chloro-phenyl-) of 4--s-triazine; 2, two (2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-6-(4-the chloro-phenyl-)-s-triazines of 4-; 2, two (2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-6-phenyl-s-triazines of 4-; 2, two (2-hydroxyl-4-(2-hydroxyl-oxethyl)-the phenyl)-6-(2, the 4-3,5-dimethylphenyl) of 4--s-triazine; 2, two (2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-6-(4-the bromophenyl)-s-triazines of 4-; 2, two (2-hydroxyl-4-(2-acetyl oxygen (acetory) oxyethyl group) phenyl)-6-(4-the chloro-phenyl-)-s-triazines of 4-, 2, two (2, the 4-the dihydroxy phenyl)-6-(2, the 4-3,5-dimethylphenyl) of 4--1-s-triazine.

Also can use metal passivator, N for example, N '-phenylbenzene oxalic acid diamide, N-water sun aldehyde-N '-salicyloyl hydrazine; N, N '-salicil base hydrazine, N; N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl group)-2-hydrazine, salicyloyl amino-1; 2,4-triazole and two tolylene oxalic acid two hydrazides.

Except that phosphorous acid ester of the present invention, can use phosphorous acid ester and phosphonic acid ester in certain embodiments of the invention, tricresyl phosphite phenylester for example, phosphorous acid diphenyl alkyl ester; Phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite Lauryl Ester, tricresyl phosphite (octadecyl) ester; Distearyl pentaerythrityl diphosphite, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, diiso decyl pentaerythritol diphosphites; 2,4,6-tri-tert phenyl-2-butyl-2-ethyl-1, ammediol phosphorous acid ester; Two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, the 4-dicumyl) pentaerythritol diphosphites; Three stearyl Sorbitol Powder GW-540s and four (2, the 4-di-tert-butyl-phenyl) 4,4 '-biphenyl, two basic bisphosphonates.

Can use peroxide scavenger, the ester of β-propane thioic acid for example is like lauryl; Stearyl; Tetradecyl or tridecyl ester, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate; Two octadecyl disulphide and tetramethylolmethane four-(β-dodecyl sulfenyl)-propionic ester.

Oxyamine, N for example, N-dibenzyl oxyamine, N, N-diethylammonium oxyamine; N, N-dioctyl oxyamine, N, N-dilauryl oxyamine, N; N-two (tetradecyl) oxyamine, N, N-two (hexadecyl) oxyamine, N, N-two (octadecyl) oxyamine; N-hexadecyl-N-octadecyl oxyamine, N-heptadecyl-N-octadecyl oxyamine and derived from the N of hydrogenant tallow amine, N-dialkyl group oxyamine also can use in certain embodiments of the invention.

Also can use nitrone, N-benzyl-alpha-phenyl nitrone for example, N-ethyl-Alpha-Methyl nitrone; N-octyl group-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone; N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone; N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone; With derived from N, the nitrone of N-dialkyl group oxyamine (this N, N-dialkyl group oxyamine is derived from the hydrogenant tallow amine).

The polymeric amide stablizer, for example with the mantoquita of iodide and/or phosphorus compound combination, and the salt of bivalent manganese.

The alkalescence co-stabilizer, trimeric cyanamide for example, PVP K120, Dyhard RU 100, triallyl cyanurate; Urea derivatives, hydrazine derivative, amine, polymeric amide, urethane; An alkali metal salt of higher fatty acid and alkaline earth salt, calcium stearate for example, stearyl calcium laurate, lactic acid ca, Zinic stearas; Magnesium Stearate, for example sodium ricinoleate and potassium palmitate, pyrocatechol antimony or pyrocatechol zinc comprise neutralizing agent, for example hydrotalcite and synthetic hydrotalcite; And Li, Na, Mg, Ca and Al hydroxyl carbonate can be used in other embodiment of the present invention, and the MgZn hydroxyl carbonate; MgAl hydroxyl carbonate and AlZn hydroxyl carbonate, and MOX, for example ZnO, MgO and CaO.

Nucleator, 4-p t butylbenzoic acid for example, hexanodioic acid; Diphenyl acetic acid, methylene-bis-2, the sodium salt of 4-dibutyl phenyl; Annular phosphate, Sorbitol Powder three phenyl aldehydes and the phosphoric acid two (2 that contracts; The 4-di-tert-butyl-phenyl) sodium salt of the sodium salt of ester or phosphoric acid ethylenebis (2, the 4-di-tert-butyl-phenyl) ester also can be used in some embodiment.

Filler and toughener can comprise for example lime carbonate, silicate, spun glass, asbestos, talcum, kaolin, mica, permanent white, MOX and oxyhydroxide, carbon black and graphite.

Other additive can be a softening agent for example, the epoxidised vegetables oil such as epoxidised soybean oil, lubricant; Emulsifying agent; Pigment, white dyes, fire retardant; Static inhibitor, whipping agent and the sulfo-synergist such as thiodipropionate dilauryl or thio-2 acid distearyl ester etc.

Additive described here and stablizer preferably exist with the amount of effective improvement composition stable property.During a kind of in using above-mentioned additive and stablizer, measure usually less than about 5 weight %, based on the weight meter of resin, and preferably at least about 50ppm, based on the weight meter of resin.Combination of stabilizers of the present invention makes stable resin, and particularly in the high temperature process process, melting index and/or colour-change are relatively little, extrude even said polymkeric substance possibly experience repeatedly.Stablizer of the present invention can easily introduced in the resin by any stage easily before the resins moulded products through the technology of routine.For example, said stablizer can mix with the dry powder form with said resin, and perhaps the suspension-s of stablizer or emulsion can be mixed with solution, suspension-s or the emulsion of polymkeric substance.The compsn of said stabilization of the present invention can randomly also contain has an appointment 0.001 to about 5% weight; Preferred about 2% weight of about 0.0025-; Particularly about 0.005% various conventional additives to about 1% weight, for example foregoing those, or their mixture.

Stablizer of the present invention advantageously helps the stabilization of polymer resin composition, and particularly in high temperature process, the change of antagonism melting index and/or color is extruded even said fluoropolymer resin possibly experience repeatedly.Stablizer of the present invention can easily be introduced in the resin combination through any easily stage of technology before preparing moulded products by resin combination of routine.For example, said stablizer can mix with the dry powder form with said resin, and perhaps the suspension-s of stablizer or emulsion can be mixed with solution, suspension-s or the emulsion of polymkeric substance.

Compsn of the present invention can be through the whole bag of tricks (mixed uniformly those methods of any additional materials of hoping in for example comprising said composition and filling a prescription) preparation.Suitable method comprises solution blending and melt blended.Because melt blended equipment is in the availability of industrial copolymer processing factory, melt processing method is normally preferred.The instance that is used for the equipment of such melt-mixing method comprises: rotate and the reverse rotation forcing machine single screw extrusion machine, the extrusion equipment of collar plate shape processing machine (disc-pack processor) and various other types in the same way.In some cases, said mixed material leaves said forcing machine through the little outlet in the die head, and through making the molten resin strip that obtains cool off said bar through water-bath.The said bar that is cooled can be cut into little pill, so that packing and further processing.

Can at the very start all said compositions be joined in the system of processing, perhaps additionally, some additive each other pre-mixing or with a part of fluoropolymer resin pre-mixing with preparation stablizer enriched material.And adopting at least one air outlet sometimes also is favourable with the venting (normal pressure or vacuum) that allows melt.Those skilled in the art can regulate blend time and temperature, and the position of component interpolation and order, and not need too much other test.

Although can before fluoropolymer resin is manufactured moulded products, stablizer of the present invention be incorporated in the fluoropolymer resin technology through routine easily, also be possible through stablizer topical application of the present invention is used said stablizer to the goods of accomplishing.Goods can comprise stabilizer compounds of the present invention and resin, and can be made into for example illuminating lamp shade, roof cover sheets, Telephone cover, and aircraft is inner, interior of building, computingmachine and business machine housings, trolley part and home appliances.Said goods can through extrude, injection moulding, rotational molding, compression moulding and other method manufacturing.For the fiber applications that wherein stablizer of the present invention part is applied on the fiber (for example in melt spinning method put in order apply) through spinning, this possibly be useful especially.

Need not further elaboration, believe that those skilled in the art use the description among this paper can utilize the present invention fullest.Following examples are included among this paper, to those skilled in the art extra guidance to be provided in putting into practice invention required for protection.The embodiment that is provided only is the representative of the work that contributes of the instruction to the application.Therefore, these embodiment do not plan to limit by any way the present invention who is limited appended claims.

Embodiment

Embodiment 1

Synthesizing of butylated alkylation of phenol thing

Phenol (188.4 grams, 2.00 moles) and Fulcat22B catalyzer (1.41 gram) are joined in the flask of band oil bath chuck, and under nitrogen atmosphere, be heated to 110 ℃.With 4.5 hour time iso-butylene (180.5 grams, 3.21 moles) being passed through agglomerating glass adds with uniform speed under the phenol surface.After adding end, reactant was kept 1 hour under 110 ℃ jacket temperature.Reactant is filtered, and collect phenolic compound filtrating.Said butylated alkylation of phenol thing is carried out vacuum distilling, with reduce phenol content to be lower than 0.25% with reduce water-content to being lower than 50ppm.Yield=290.3 grams.

Embodiment 2

By like the embodiment 1 said butylated alkylation of phenol thing synthesizing phosphorous acid ester that obtains

Butylated alkylation of phenol thing (152.4 grams, 0.971 mole) is joined in the flask of band oil bath chuck, and under nitrogen atmosphere, be heated to 85 ℃.Under the phenolic compound surface, added PCl with uniform speed with 3 hour time ₃(40.4 grams, 0.294 mole).In the interpolation process, temperature is increased to 150 ℃.Reactant is remained on 150 ℃, stop, and use 1 hour then, simultaneously pressure is reduced to 50 millibars from 1000 millibars reaction mass heated to 200 ℃ up to the effusion of HCl.Reaction is remained on 200 ℃/50 millibars, be lower than 50ppm up to total Cl content.Excessive phenol is removed in distillation through under the interior temperature (145 ℃ of vapour temperatures) of 1 millibar of pressure and 250 ℃.Yield=115.9 grams.

According to the temperature of the embodiment 2 said phosphite mixture that obtain to viscograph

Temperature (℃)	Viscosity (cSt)
		30	3662
40	1662
		50	494

Embodiment 3

From 4-tert.-butyl phenol/2 of the 2:1 that processes by the phenol component, 4-di-tert-butyl phenol mixture synthesizing phosphorous acid ester

With 4-tert.-butyl phenol (176.6 grams, 1.18 moles) and 2,4-DI-tert-butylphenol compounds (121.3 grams, 0.59 mole) joins in the flask of band oil bath chuck, and under nitrogen atmosphere, is heated to 80 ℃.Under the phenolic compound surface, added PCl with uniform speed with 2 hour time ₃(73.4 grams, 0.53 mole).In the interpolation process, temperature is increased to 150 ℃.Reactant is remained on 150 ℃, stop, and use 1 hour then, simultaneously pressure is reduced to 70 millibars from 1000 millibars reaction mass heated to 200 ℃ up to the effusion of HCl.Reaction is remained on 200 ℃/70 millibars, be lower than 50ppm up to total Cl content.Remove excessive phenol through the distillation under the interior temperature of 8 millibars of pressure and 200 ℃ then.Yield=279.3 grams.This product will be called as liquid phosphite P-2 below.

According to the temperature of the embodiment 3 said phosphite mixture that obtain to viscograph

Temperature (℃)	Viscosity (cSt)
		40	8300
50	1776
		60	530
70	218
		80	120

Embodiment 4

Synthesizing of blended amyl group/butylphenol

Phenol (105 grams, 1.12 moles) and Fulcat 22B catalyzer (2.25 gram) are joined in the flask of band oil bath chuck, and under nitrogen atmosphere, be heated to 130 ℃.With 30 fens clock times iso-butylene (64.6 grams, 1.15 moles) is added under the surface of phenol through sintered glass with uniform speed.In the interpolation process, internal temperature is increased to 140 ℃.Accomplish in case add, reactant was kept 1 hour under 130 ℃ jacket temperature.Use 1.25 hours time that amylene (39.2 grams, 0.56 mole) is added under the surface of phenolic compound with uniform speed then.After adding end, reactant was kept 2 hours under 130 ℃ jacket temperature.Then reactant is filtered, and collect phenolic compound filtrating.Said blended butylation/amyl group alkylation of phenol thing is carried out vacuum distilling handle, be lower than 0.25% and water-content is reduced to is lower than 50ppm so that phenol content is reduced to.Yield=161.8 grams.

Embodiment 5

Change into phosphorous acid ester according to the embodiment 4 said alkynylene that obtain

Blended butylation/amyl group alkylation of phenol thing (148.7 grams, 0.86 mole) is joined in the flask of band oil bath chuck, and under nitrogen atmosphere, be heated to 80 ℃.Under the phenolic compound surface, added PCl with uniform speed with 3 hour time ₃(35.8 grams, 0.26 mole).In the interpolation process, temperature is increased to 150 ℃.Reactant is remained on 150 ℃, stop up to the effusion of HCl, and then reactant was heated to 200 ℃ with 1 hour, simultaneously pressure is reduced to 50 millibars from 1000 millibars.Reaction is remained on 200 ℃/50 millibars, be lower than 50ppm up to total Cl content.Remove excessive phenol through the distillation under the interior temperature (140 ℃ of vapour temperatures) of 1 millibar of pressure and 240 ℃ then.Yield=123.1 grams.

According to the temperature of the embodiment 5 said phosphite mixture that obtain to viscograph

Temperature (℃)	Viscosity (cSt)
		30	7481
40	3198
		50	763

Embodiment 6

Synthesizing of amyl group alkynylene

Phenol (150 grams, 1.59 moles) and Fulcat 22B catalyzer (3.36 gram) are joined in the flask of band oil bath chuck, and under nitrogen atmosphere, be heated to 130 ℃.Use 4 hours time that amylene (167.7 grams, 2.39 moles) is added under the surface of phenol with uniform speed then.After adding end, reactant was kept 2 hours under 130 ℃ jacket temperature.Then reactant is filtered, and collect phenolic compound filtrating.Alkylation of phenol thing to said amyl groupization carries out purifying through distillation, is collected in the main distillate fraction between 120 to 146 ℃ (vapour temperature=120 are to 140 ℃) under the 5-7 millibar pressure.Yield=227.3 grams.

Embodiment 7

Alkylation of phenol thing by amyl groupization prepares phosphorous acid ester

With the alkylation of phenol thing (214.7 gram) and the N of amyl groupization, N-dimethyl-lauryl amine (0.65mL) joins in the flask of being with the oil bath chuck and under nitrogen atmosphere, is heated to 80 ℃.Under the phenolic compound surface, added PCl with uniform speed with 3 hour time ₃(51.9 grams, 0.38 mole).In the interpolation process, temperature is increased to 150 ℃.Reactant is remained on 150 ℃, stop up to the effusion of HCl, and then reactant was heated to 200 ℃ with 1 hour, simultaneously pressure is reduced to 130 millibars from 1000 millibars.Reaction is remained on 200 ℃/130 millibars, be lower than 50ppm up to total Cl content.Remove excessive phenol through the distillation under the interior temperature of 3 millibars of pressure and 195 ℃ then.Yield=223.7 grams.This product will be called as liquid phosphite P-4 below.

According to the temperature of the embodiment 7 said phosphite mixture that obtain to viscograph

Temperature (℃)	Viscosity (cSt)
		40	1270
50	513
		60	238
70	132
		80	75

Embodiment 8

Through the polyacrylic performance evaluation of carrying out of repeatedly extruding

Present embodiment explains that liquid phosphite mixture of the present invention is at polyacrylic stabilization effect in repeatedly extruding.

Base polymer is a Basell HF 500N Spheripol HPP homopolymer polypropylene powder, and its melt flow index (MFI) is 12 grams/10 minutes.The calcium stearate that the basis compound also contains 500ppm is as acid scavenger.All compounds prepare in base polymer through adding Anox 20 (four [methylene radical { 3,5-di-t-butyl-4-hydroxyl meat silicon ester }] methane) and corresponding each 500ppm of liquid phosphite mixture of the present invention.The resin formulations of stabilization like this is extruded from the Brabender single screw extrusion machine with the 19mm diameter of the speed running of 60rpm under oxygen atmosphere, and four heating zone of said forcing machine are set at following temperature: 200 ℃; 225 ℃; 250 ℃ and 270 ℃.

Through making extrudate through ice-water bath and with its cooling, and then with its granulation.These pills are extruded once more.After extruding for the third time, under 230 ℃/2.16kg, measure melt flow rate(MFR) (unit is g/10min).The quite little increase of melt flow index means that significant polymer degradation does not take place perhaps means good stability.The result is presented in the table 1.

Table 1

MFI result

Stablizer (ppm)	Extrude MFI (g/10min) for the third time
		The basis	32.0
Liquid phosphite P-2 (500)+Anox 20 (500)	14.7
		Liquid phosphite P-3 (500)+Anox 20 (500)	13.8
Liquid phosphite P-4 (500)+Anox 20 (500)	14.6

Liquid phosphite P-2: shown in embodiment 3, obtain;

Liquid phosphite P-3:, use butylated p-cresol alkynylene to replace butylated alkylation of phenol thing synthetic shown in this phosphite mixture such as the embodiment 2 by the phosphite mixture that butylated p-cresol alkynylene obtains.

Liquid phosphite P-4: shown in embodiment 7, obtain.

The result of this research shows that when comparing with control samples, liquid phosphite mixture P-2 to P-4 of the present invention provides superior melt stability.Therefore, compare with control samples, the compound that contains the liquid phosphite mixture only produces relatively little melt flow rate(MFR) to be increased.

Embodiment 9

Performance evaluation in high density polyethylene(HDPE)

Present embodiment is explained the stabilization effect of liquid phosphite mixture of the present invention in the plasti-corder test.

The basis compound comprises the Anox 20 (four [methylene radical { 3,5-di-t-butyl-4-hydroxyl meat silicon ester }] methane) of Solvay HP-54-60 high density polyethylene polyethylene polymers sheet and 300ppm.The test compound joins in the basic compound through the liquid phosphite mixture corresponding of the present invention with 1000ppm and prepares.

In order to carry out the test of said plasti-corder, each compound that will comprise basic control samples joins to be furnished with in the Brabender plastometer 60cc mixing head, that under 220 ℃/60rpm condition, move.When in said mixing head, mediating said test compound, continuously measured and record moment of torsion.After inductive phase, said polymkeric substance begins crosslinked, and this can significantly increase from moment of torsion finds out.Table 2 listed before moment of torsion begins to increase in minute time inductive phase.Long relatively induction time is the indication of excellent stability.

The result of this test shows, compares with control samples, and liquid phosphite blends P-2 to P-4 provides superior melt stability for the HDPE polymkeric substance.Therefore, compare with the control samples that does not contain phosphorous acid ester, the compound that contains P-2 to P-4 provides long relatively induction time in the plasti-corder test.

Consider many variations and the change that under the situation that does not deviate from principle of the present invention, can make, should understand protection scope of the present invention with reference to appended claims.

Claims

1. compsn, it comprises the blend of the phosphorous acid ester of at least two kinds of different following structures

R wherein ₄, R ₅And R ₆Be independently selected from down group: hydrogen and C ₁-C ₆Alkyl, prerequisite are R ₄, R ₅And R ₆In be not hydrogen one of at least, the R in every kind of phosphorous acid ester wherein ₄, R ₅And R ₆In be selected from down one of at least group: the tertiary butyl and tert-pentyl; With

Wherein said blend is a liquid under envrionment conditions.

2. the compsn of claim 1, wherein said compsn comprise the blend of the phosphorous acid ester of at least three kinds of said different following structures

3. the compsn of claim 1, wherein said compsn comprise the blend of the phosphorous acid ester of at least four kinds of said different following structures

4. each compsn among the claim 1-3, wherein said phosphorous acid ester is independently selected from down group: tricresyl phosphite (4-tert-butyl-phenyl) ester, tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, two (the 4-tert-butyl-phenyls)-2 of phosphorous acid, 4-di-tert-butyl-phenyl ester; Two (2, the 4-the di-tert-butyl-phenyl)-4-tert-butyl-phenyl esters of phosphorous acid, tricresyl phosphite (4-tert-pentyl phenyl) ester; Tricresyl phosphite (2, the 4-di-tert-pentyl-phenyl) ester, two (the 4-tert-pentyl phenyl)-2 of phosphorous acid; Two (2, the 4-the di-tert-pentyl-phenyl)-4-tert-pentyl phenyl esters of 4-di-tert-pentyl-phenyl ester and phosphorous acid.

5. stabilized compsn, it comprises:

(A) fluoropolymer resin and

(B) each compsn among the claim 1-4 of stabilization amount.

6. goods that comprise stabilized compsn, said stabilized compsn comprises:

(A) fluoropolymer resin and

(B) each compsn among the claim 1-4 of stabilization amount.

7. a stablized thermoplastic resin or elastomeric method, this method comprise the step of each compsn among the claim 1-4 that in said thermoplastic resin or elastomerics, adds the stabilization amount.

8. each method for compositions among the synthetic claim 1-4, this method comprises:

The alkylating phenol and the catalyst separating that (B) will obtain; With

(C) making wherein, Z is the PZ of halogen ₃With the mixture reaction that obtains, the solid that the said mixture that obtains comprises 5-95 weight % is to alkylating phenol and correspondingly the solid of 95-5 weight % is adjacent, right-dialkylated phenol.