CN101595172B - Method for stabilization of polymers with styrenated-p-cresols - Google Patents
Method for stabilization of polymers with styrenated-p-cresols Download PDFInfo
- Publication number
- CN101595172B CN101595172B CN200880003611.4A CN200880003611A CN101595172B CN 101595172 B CN101595172 B CN 101595172B CN 200880003611 A CN200880003611 A CN 200880003611A CN 101595172 B CN101595172 B CN 101595172B
- Authority
- CN
- China
- Prior art keywords
- cresol
- acid
- styrenated
- compsn
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed herein is a process for the preparation of a mixture of styrenated p-cresol species that is liquid at room temperature and has a viscosity of less than 40,000 cps at 25 DEG C, wherein the process affords 2, 6-distyrenated p-cresol assaying at 70% minimum by GC area percent, comprising reacting styrene with p-cresol at a molar ratio of 1.85 to 2.1:1, respectively, in the presence of an acid catalyst at elevated temperature, wherein the mixture comprises monostyrenated-p-cresol, distyrenated-p-cresol, and tristyrenated-p-cresol and exhibits an acid number of less than 0.1 mg KOH/gram.
Description
I am according to the 35th piece of United States Code (Title 35, United States Code), and the title that § 119 requires to submit on February 26th, 2007 is the U.S. Provisional Application of " comprising 2, the stabiliser compsn of 6-toluylene p-cresol " number 60/903,725; The title of submitting on May 24th, 2007 is the U.S. Provisional Application of " the ground fog phenolic antioxidant that is used for polyurethane foam products " number 60/931; The title of submitting on June 21st, 954 and 2007 is the interests of the U.S. Provisional Application number 60/936,918 of " at room temperature being the light styrenated p-cresol compsn of liquid ".
Background of invention
1. invention field
The present invention relates to the stabilization of polymkeric substance.More particularly, the present invention relates to the styrenated p-cresol and make polymer compsn, preferably comprise the stable purposes of thermoplastic polymer or elastomer compositions.
2. description of related art
Still need be in many polymkeric substance market, the phenolic antioxidant that for example has liquid outward appearance in thermoplastics, thermoplastic elastomer, rubber and the oil additive.For many phenolic antioxidants, liquid outward appearance can only reach through they being heated to its temperature more than fusing point.Instance comprises octadecyl-3, and 5-two-tertiary butyl-4-hydroxy laurate, its fusing point are in 48 ℃-58 ℃ scope and 2, and 6-two-Butylated Hydroxytoluene, its fusing point are approximately 69 ℃.
With the main drawback that at room temperature interrelates for the solid compound that molten state is provided is to continue heating for the liquid appearance requirement that keeps it.Yet this area is heated always not continuablely, and therefore, molten product possibly cool off and form solid.In case solidify, with compound shift leave its holder become hardly maybe, and this possibly be it to be transported to treat that in addition the polymkeric substance of stabilization is necessary.On the other hand, make it return to liquid appearance requirement reheat, but in encloses container, make solid material again fusion possibly be effort and the process that prolongs.Therefore, this situation possibly cause process lag, thereby increases unnecessary cost.
When the polymkeric substance that is adopted is a urethane, particularly during foamed polyurethane (they are processed by polyether glycol (polyvalent alcohol) and vulcabond usually), additional problem possibly appear.The polyol component that adopts in the manufacturing of this type of polyurethane foam contains inhibitor usually to reach improved stability and low color.
The polyurethane-type froth product is usually used in automotive interior application, for example seat or test board, and the level of the additive of the plastics discharging that possibly from these are used, use of worry day by day.Additive is sometimes referred to as fog from the phenomenon of automotive interior plastics discharging, because the evaporable additive is known they oneself is deposited on the window inboard in automobile main cabin.In case deposition, they just possibly cause that windshield glass or other window blur.Yet, be not only owing to the safety issue that harms visibility to the worry of automotive interior fog, and pay close attention to the healthy problem of automobile occupant especially.
Therefore; Still need develop the inhibitor with two key features or the stablizer that are used for stabilization of polyols: first; They are compared with the industrial standards control sample and must show low fog characteristic, and the second, they must be quite or surpass the stablizer efficient of industrial standards sample.
U.S. Patent number 3; 956; 247 disclose EPDM (the rubber-like terpolymer of ethene, α monoolefine and non-conjugated diene) at epoxy compounds, and for example epoxidised soybean oil exists down in the solution halogenation that has or do not gather under the situation of (alkylene ether) glycol and produces the halogenation EPDM with excellent viscosity stability and limited gel content.The mixture of two parts of nonylated phenyl phosphites and a styrenated p-cresol can be used as inhibitor.
U.S. Patent number 5; 140; 055 discloses imidazolium compounds or the imidazolinium compounds that contains special restriction; Or the rubber combination of the verivate of the special restriction of benzoglyoxaline or its has big tan in high TR, and has the tire of the tyre surface that uses this kind rubber combination owing to be stopped in the reduction aspect the tan value and during high-speed cruising, have improved earth-catching property in the temperature rising of run duration.Br and being used in combination of imidazoles, tetrahydroglyoxaline or benzoglyoxaline can be eliminated the shortcoming of the anti-incipient scorch property difference of the rubber combination that only contains imidazoles, tetrahydroglyoxaline or benzoglyoxaline.Br to be used comprise amphyl, carboxylic acid, sulfonic acid, sulfuric acid and verivate, phosphoric acid and verivate thereof, cyanuric acid and verivate thereof,-sulfinic acid, nitric acid and verivate thereof, phosphorous acid and carbonic acid and verivate thereof.Classify useful compound as and comprise 2; 6-two-Butylated Hydroxytoluene, 2; 2 '-methylene-bis-4-methyl-6-tert butyl phenol, 4,4 '-thiobis-3 methy 6 tert butyl phenol, styrenated p-cresol, phosphoric acid, SULPHOSUCCINIC ACID ESTER, phosphorous acid and phosphorous acid ester and other are many.
U.S. Patent number 5; 466; 740 disclose through introducing following material and have become to the halogen-containing resin composition of light and thermally stable: (a) calcium based composite metal oxyhydroxide and calcium based composite metal oxidate, (b) organic acid salt of beta-diketone compound or its metal-salt and non-essential (c) zinc.This halogen-containing resin composition can contain conventional additives, organotin stabilizer for example, epoxy stabilizer, phosphorous acid ester; The sulfocompound stablizer, phenol stabilizer and inhibitor, for example styrenated p-cresol, 2; 6-two-tertiary butyl-4-methylphenol, butylation methyl-phenoxide, 4,4 '-methylene-bis (the 6-tertiary butyl-3-methylphenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol), 1; 3,5-trimethylammonium-2,4; 6-three (3,5-two-tertiary butyl-4-acrinyl) benzene and four [3-(4-hydroxyl-3,5-two-tert-butyl-phenyl) propionyloxy methylene radical] methane.
U.S. Patent number 6,242,562 disclose the preparation method of vinyl chloride-base polymer, may further comprise the steps: the monomer mixture suspension polymerization that (A) in water medium, makes vinylchlorid or vinyl-chloride-containing is to obtain polymer paste; (B) with remaining unreacted monomer stripping in this polymer paste; (C) let the polymer paste of process step (B) under 80 ℃-95 ℃ temperature, dewater, preferably behind this stripping, carry out in 60 minutes.More particularly, at first, with monomer mixture, water medium, polymerization starter and the dispersion agent adding aggregation container of vinylchlorid or vinyl-chloride-containing, the polymerization temperature (30-75 ℃ usually) of under agitation keeping regulation is so that this vinylchlorid or monomer mixture polymerization.When polymerization reaches specified degree (usually 60-98%), through for example having the inhibitor of polymerization retardation effect, phenol antioxidant for example, for example styrenated p-cresol etc. adds in this reaction mixture and stops polymerization.
U.S. Patent number 6,339,132 disclose and have made unreacted vinyl chloride monomer regenerated method, may further comprise the steps: the unreacted vinyl chloride monomer that utilizes compressor compresses to reclaim from the vinyl chloride-base polymer production technique; And with this reacted vinyl chloride monomer compression that contacts with the lubricating oil that infeeds compressor.In this method, lubricating oil contains the stopper that vinyl chloride monomer is had polymerization retardation effect.This kind stopper can be by the phenols suppressor factor, for example styrenated p-cresol etc.; The amine suppressor factor; Sulphur class suppressor factor and Phosphorus suppressor factor example, they can use separately or two kinds or more kinds of use in combination.
U.S. Patent number 6,391,065 discloses water-dilutable UV light absorber compsn and the method for improving the DYED FABRICS light fastness.This compsn is applied to fabric and comprises ultraviolet absorbers and the organic solvent that is suitable for dissolving this ultraviolet absorbers.The embodiment 5 of this patent discloses 10.0g benzyl-benzoic ether has been added in 20.0g " Naugard 529 " liquid antioxidant/solvent (alkylated styrenes p-cresol) to reduce viscosity.
Summary of the invention
The purpose of this invention is to provide the phenolic antioxidant that at room temperature has liquid outward appearance.
Another object of the present invention provides when being used for the polyurethane-type foam formulations can serve as the ground fog additive, also gives the phenolic antioxidant of favorable and stableization simultaneously.
Another object of the present invention provide analyze minimum 75%, 2 of the analyst coverage of preferred 80-90%, the method for manufacture of 6-toluylene p-cresol.
Another object of the present invention provides 25 ℃ of following viscosity less than 40,2 of 000cps, the method for manufacture of 6-toluylene p-cresol.
These and other purpose is reached by the present invention; The present invention relates at room temperature for liquid and 25 ℃ of following viscosity less than 40; The preparation process of mixture of the styrenated p-cresol material of 000cps; Wherein said method provide by the GC area percentage analyze minimum 70% 2; 6-toluylene p-cresol, comprise making vinylbenzene and p-cresol by 1.85-2.1 separately: 1 mol ratio is reaction at elevated temperatures in the presence of acid catalyst, and wherein said mixture comprises single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol and shows the acid number less than the 0.1mgKOH/ gram.
In one aspect of the method; The present invention relates to the method that makes polymer compsn stable; Be included in the said compsn add significant quantity at room temperature for liquid and 25 ℃ of following viscosity less than 40; The mixture of the styrenated p-cresol material of 000cps; Wherein said mixture prepares through following method: this method produces by 2 of GC areal analysis minimum 70%; 6-diphenylethyllene p-cresol and comprising makes vinylbenzene and p-cresol by 1.85-2.1 separately: 1 mol ratio is reaction at elevated temperatures in the presence of acid catalyst, and wherein said mixture comprises single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol and shows the acid number less than the 0.1mgKOH/ gram.
In aspect another; The present invention relates to compsn; It comprises at room temperature for liquid and 25 ℃ of following viscosity less than 40; The mixture of the styrenated p-cresol material of 000cps, comprise through the preparation of following method by the GC area percentage analyze minimum 70% 2,6-toluylene p-cresol; This method comprises makes vinylbenzene and p-cresol by 1.85-2.1 separately: 1 mol ratio is reaction at elevated temperatures in the presence of acid catalyst, and wherein said mixture comprises single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol and shows the acid number less than the 0.1mgKOH/ gram.
The description of preferred embodiment
As stated, the present invention relates at room temperature be liquid styrenated p-cresol material the preparation method with it as the purposes of the stablizer of polymer compsn.
The styrenated p-cresol compsn that adopts in the present invention practice is prepared as follows: make vinylbenzene and p-cresol with separately about 1.85: about 2.1: 1 mol ratio of 1-is reacted in the presence of acid catalyst under heating up and the mixture of styrenated p-cresol material is provided.Preferred vinylbenzene: the p-cresol mol ratio is 1.85-1.98: 1, and more preferably 1.9-1.98: 1, for example 1.95: 1.Following flow process 1 has been described typical reaction.Primary product in the mixture is 2, and 6-two-styrenated p-cresol (Di) is through gc (GC) areal analysis minimum 70%, preferred 75%.The preferred GC area percentage of Di in mixture is about 80-about 95%.In addition, through with two kinds of additional reaction product, promptly single styrenated p-cresol (Mono is referring to flow process 1) and triphenylethylene p-cresol (Tri is referring to flow process 1) are combined in the liquid outward appearance that reaches mixture in the gained styrenated p-cresol compsn.In order to reach required liquid outward appearance, said Mono and Tri component should be separately exist to be no less than about 1% level by the GC planimeter.Typical Mono composition level is counted about 1-about 15% by the GC area.The levels typical of Tri component is similarly about 1-about 15% by the GC planimeter.Preferably, the per-cent of the combination of Mono and Tri component is pressed the GC planimeter will be about 30% for about 5-, based on the total area of Mono, Di and Tri component.
Flow process 1
The typical case who at room temperature is the styrenated p-cresol compsn of liquid prepares the path
In above-mentioned reaction, require to exist catalyzer.The catalyzer that is fit to has acid performance usually, for example Br or Lewis acid.Yet, the known styrenated p-cresol compsn yellow color that causes of number acid catalyzer, this possibly make them be not suitable for wherein color is some application of major criterion.The instance of this type of catalyzer includes but not limited to, boron trifluoride etherate and sulfuric acid.For example, the known generation of boron trifluoride etherate catalyzer APHA (APHA) color index value is greater than 150 product.
On the other hand, some catalyzer makes and has basically no color.Therefore, another preferred feature of the present invention is if necessary, can prepare the liquid styrene p-cresol compsn with very low color.The typical preferred APHA value of liquid styrene p-cresol compsn of the present invention is the APHA value less than 150, preferably less than 100 APHA value.In this article, the instance of the catalyzer of the low color of generation includes but not limited to trifluoromethayl sulfonic acid and Zeo-karb.
Preferably, be reflected at about 40 ℃-about 150 ℃, more preferably approximately carry out under the about 80 ℃ temperature of 60-.Reaction times will be about 7 hours of about 1-, about 4 hours of preferably approximately 3-usually.If necessary, reaction can be carried out in that reaction is in the inert solvent, and they preferably will be hydrocarbon, for example toluene, benzene, heptane, hexane etc.
Embodiment 1
2, the synthetic-typical program of 6-diphenylethyllene p-cresol
In the 1 liter of round-bottomed flask that is equipped with whisking appliance, TM and feed hopper, add 151.3 gram (1.4 moles) p-cresol.With this mixture heating up to 70 ℃, then add the 5L trifluoromethayl sulfonic acid via the 100L syringe.Under blanket of nitrogen, 284.5 gram (2.73 moles) vinylbenzene are put into funnel, dropwise add in then under agitation during three hours.During vinylbenzene added, pot temperature was no more than 80 ℃.After adding all vinylbenzene, under 70 ℃ pot temperature, continue to stir 1.5 hours.
The analysis of gained styrenated p-cresol compsn is following
Table 1
APHA value=50
Acid number=0.01mg KOH/g
Brookfield viscosity=29900cps (25 ℃)
Weight yield=94%
Hereinafter, for simplicity, the stablizer that adopts in the present invention's practice will abbreviate 2 as, 6-diphenylethyllene p-cresol; Yet, should be appreciated that employed actual product is the mixture of above-mentioned Mono, Di and Tri.
The invention further relates to the thermoplasticity or the elastic resin of stabilization, wherein a kind of component comprises 2,6-diphenylethyllene p-cresol, and other component comprises thermoplasticity and/or elastomeric polymer, for example polyolefine, SE, SBR, nitrile rubber etc.
Can be through the present invention 2, the thermoplastic polymer of 6-diphenylethyllene p-cresol stabilization can be any thermoplastic material as 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 polyester/ABS or polycarbonate/ABS and polyester add some other impact modifying agent and also can use.Such polymkeric substance is available commercially, perhaps can be through method preparation well known in the art.Stablizer of the present invention especially can be used for polyolefine, urethane and halogen containing polymers.
Can use the polymkeric substance of monoolefine and diolefine, Vestolen PP 7052 for example, polyisobutene; Polybutene-1, 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 (ionic polymer) and ethene and propylene and diolefine such as hexadiene, the terpolymer of Dicyclopentadiene (DCPD) or ethidine-norbornylene; And these multipolymers and their mixture and above-mentioned mixture of polymers, polypropylene/ethylene propylene copolymer for example, LDPE/EVA, LDPE/EAA, LLDPE/EVA and LLDPE/EAA.
Halogen containing polymers, for example PVC also possibly be useful.The term that this paper adopts " gathers (vinylchlorid) " and " PVC " is intended to comprise simultaneously the homopolymer and the multipolymer of vinylchlorid, the i.e. unitary ethenoid resin of vinyl-chloride-containing, the for example multipolymer of the vinyl ester of vinylchlorid and aliphatic acid, especially vinyl-acetic ester in the structure; The ester of vinylchlorid and vinylformic acid and methylacrylic acid and with the multipolymer of vinyl cyanide; The multipolymer of vinylchlorid and diolefin and unsaturated dicarboxylic acid or its acid anhydrides, the for example multipolymer of vinylchlorid and ethyl maleate, DEF or maleic anhydride; The post chlorization polymkeric substance and the multipolymer of vinylchlorid; Vinylchlorid and vinylidene chloride and unsaturated aldehyde, ketone and other, the for example multipolymer of propenal, crotonic aldehyde, ethenyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether etc.
The term that this paper adopts " gathers (vinylchlorid) " and " PVC " also is intended to comprise the graftomer of PVC and EVA, ABS and MBS.Preferred substrate still is the mixture of above-mentioned homopolymer and multipolymer; Especially the mixture of ryuron and other thermoplasticity and/or elastomeric polymer is especially with the blend of ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactone.
The ester of vinyl-acetic ester, vinylidene chloride, vinyl cyanide, chlorine vinyl fluoride and/or vinylformic acid, fumaric acid, toxilic acid and/or methylene-succinic acid can be mentioned as the monomeric preferred embodiment that can close with chloroethylene copolymer.In addition, SE can chlorination arrive the chlorinity of 70wt% at the most.The present invention is particularly useful for ryuron.
Within the scope of the present invention, PVC also will be interpreted as and comprise owing to the recycled matter of processing, use or store the halogen containing polymers that suffers damage.Said 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.
Also can use 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.These polymkeric substance comprise 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.
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 diamine 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 hexa-methylene diamine and m-phthalic acid or/and the polymeric amide of terephthalic acid and optional elastomer production as properties-correcting agent for example gathers-2,4,4-trimethylammonium-hexa-methylene terephthalamide or gather metaphenylene isophthaloyl amine.In addition; Can use above-mentioned polymeric amide and polyolefine, olefin copolymer, the elastomeric multipolymer of ionic polymer 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.
The representative example of the elastomeric polymer that is fit to comprises solution styrene butadiene rubber (SSBR), styrene-butadiene rubber(SBR) (SBR), tree elastomer (NR), polyhutadiene (BR), ethylene-propylene copolymer-and terpolymer (EP, EPDM) and acrylonitrile-butadiene rubber (NBR).Rubber combination is by at least a diene based elastomer, or rubber is formed.The conjugated diolefine that is fit to is isoprene and 1,3-butadiene, and suitable vinyl aromatic compounds is vinylbenzene and alpha-methyl styrene.Therefore, rubber is the sulphur curable rubber.This type of diene based elastomer, or rubber can for example be selected from the following material at least a: cis-1; 4-polyisoprene rubber (natural and/or viton, preferred tree elastomer), the styrene/butadiene copolymers rubber of emulsion polymerization prepared; The styrene/butadiene rubbers of organic solution polymerization preparation, 3, the 4-polyisoprene rubber; Isoprene/butadiene rubber, styrene/isoprene/butadiene tri-component copolymer rubber, cis-1; The 4-polyhutadiene, medium vinyl polybutadiene rubber (35%-50% vinyl), high vinyl polybutadiene rubber (50%-75% vinyl); The styrene/isoprene multipolymer, the phenylethylene/butadiene of emulsion polymerization prepared/acrylonitrile terpolymer rubber and butadiene/acrylonitrile copolymer rubber.Possibly use phenylethylene/butadiene (e-SBR) that the letex polymerization of the conventional relatively styrene content with 20%-28% combined styrene obtains or; For some application; Possibly use have in to higher combined styrene content, the i.e. e-SBR of the combined styrene content of 30%-45%.Phenylethylene/butadiene/acrylonitrile terpolymer the rubber that in terpolymer, contains the emulsion polymerization prepared of 2-40wt% bound acrylonitrile also is considered as and is used for diene rubber of the present invention.
The SBR of solution polymerization (S-SBR) has 5-50% usually, the combined styrene content of preferred 9-36%.Polybutadiene elastomer can be aptly for example, and by having 90wt% cis-1 at least, 4-content characterizes.
When using in this article; " stabilization amount " or " significant quantity " of stablizer of the present invention be meant, the amount when containing the polymer compsn of this type of stablizer 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, variable color 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 variable color.
The invention further relates to the thermoplasticity and/or the elastic resin of stabilization, wherein a kind of component comprises 2,6-diphenylethyllene p-cresol, other component comprise polymkeric substance for example above-mentioned those; With wherein said 2,6-diphenylethyllene p-cresol and co-stabilizer such as phenoplast, aromatic amine; Phosphorous acid ester and phosphinate, oxyamine, alkylamine-N-oxide compound; Lactone, thioether, epoxidized vegetable oil for example epoxidised soybean oil etc. use together.
Therefore, by of the present invention 2, the thermoplastic resin of 6-diphenylethyllene p-cresol stabilization can be chosen wantonly and contain additional stabilizers or the stabilizer blend that is selected from down group: phenolic antioxidant, hindered amine stabilizer; UV light absorber, phosphorous acid ester, phosphinate, 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).Phenolic cpd, diarylamine and organophosphite are especially preferred.
Can include, but are not limited to as the phenolic cpd of the optional co-stabilizer in the present invention's practice:
1. 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)-4,6-xylenol, 2,6-two (octadecyl)-4-methylphenol; 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxymethyl phenol.
2. 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.
3. hydroxylated sulfo-diphenyl ether, for example 2,2 '-sulfo--two (the 6-tertiary butyls-4-methylphenol), 2,2 '-sulfo--two (4-octyl phenols), 4,4 '-sulfo--two (the 6-tertiary butyls-3-methylphenol), 4,4 '-sulfo--two (the 6-tertiary butyls-2-methylphenol).
4. alkylidene bis-phenol, for example 2,2 '-methylene radical-two (the 6-tertiary butyls-4-methylphenol), 2,2 '-methylene radical-two (the 6-tertiary butyls-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-nonyls-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 butyls-4-isobutyl-phenol), 4; 4 '-methylene radical-two (2,6 di t butyl phenols), 4,4 '-methylene radical-two (the 6-tertiary butyls-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 (3,3-pair (3 '-tertiary butyl-4 '-hydroxy phenyl)-butyric ester)-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-Dicyclopentadiene (DCPD), terephthalic acid two (2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-methyl-benzyl)-the 6-tertiary butyl-4-aminomethyl phenyl) ester; With other phenolic cpd, the mono acrylic ester of bisphenols for example, for example ethidine is two-2,4-DI-tert-butylphenol compounds mono acrylic ester.
5. benzyl compounds, 1,3,5-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, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2; The 6-dimethyl benzyl) isocyanuric acid ester, 3, the two stearyl of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids, 3, the calcium salt of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids list ethyl ester; 1,3,5-three (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanuric acid ester.
6. acyl amino phenol, 4-hydroxyl-bay anilide for example, 4-hydroxyl-stearic anilide, 2,4-is two-octyl group sulfydryl-6-(3,5-tertiary butyl-4-hydroxy anilino)-s-triazine, and N-(3, the 5-di-tert-butyl-hydroxy phenyl) carboxylamine monooctyl ester.
7. β-(3,5-two-tert-butyl-hydroxy phenyl)-propionic acid and monohydroxy-alcohol or polyvalent alcohol such as methyl alcohol, Diethylene Glycol, Stearyl alcohol; Triethylene glycol, 1,6-pinakon, tetramethylolmethane; NSC 6366, tris(2-hydroxy ethyl)isocyanurate, thio-diethylene glycol, the ester of dihydroxy ethyl oxalic acid diamide.
8. 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; 1,6-pinakon, tetramethylolmethane, NSC 6366; Tris(2-hydroxy ethyl)isocyanurate, thio-diethylene glycol, the ester of dihydroxy ethyl oxalic acid diamide.
9. β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and list or polyvalent alcohol, for example with methyl alcohol, Diethylene Glycol, Stearyl alcohol; Triethylene glycol, 1, the 6-pinakon; Tetramethylolmethane, NSC 6366, three (hydroxyethyl) isocyanuric acid ester; Thio-diethylene glycol, N, the ester of two (hydroxyethyl) oxalic acid diamide of N-.
10. the acid amides of β-(3,5-di-t-butyl-4-hydroxyl phenol)-propionic acid, for example N; N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl group)-hexamethylene-diamine, N; N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl group)-trimethylene diamines, N; N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl group)-hydrazine.
The aromatic amine that can be used for the present invention's practice can be represented by following general formula
R
1NHR
2
R wherein
1And R
2Of course, but not necessarily, identical.Therefore, in a preferred embodiment, R
1And R
2Can be independently selected from (i) aromatics carbon, (ii) aliphatic R
1With aromatics R
2Carbon atom produces the aromatics carbon of phenylenediamine with (iii) being connected with second nitrogen-atoms.
Work as R
1Be aliphatic series the time, it can be straight or branched and can have 1-12 carbon atom, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their isomer.Preferably, work as R
1Be aliphatic series the time, it is the aliphatic group that straight or branched contains 1-8 carbon atom, more preferably it contains 1-4 carbon atom.
Amine antioxidants can be the substituted diarylamine of hydrocarbon, for example the substituted pentanoic antioxidant materials of aryl, alkyl, alkaryl and aralkyl.The non-limiting detail of the substituted pentanoic of commercially available hydrocarbon comprises the styrenated or the alpha-methyl styrene diphenylamines of substituted octyl groupization, nonylated and heptyl diphenylamines and para-orientation.The substituted pentanoic of sulfur-bearing hydrocarbon, for example to (right-tolylsulfonyl is amino)-pentanoic, that is,
Also be regarded as the part of this kind.
The substituted diarylamine of hydrocarbon of the present invention's practice can be represented by following general formula
Ar-NH-Ar′
Wherein Ar and Ar ' are the independent aryl of selecting, and wherein at least one preferably is substituted with at least one alkyl.Said aryl for example can be, phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl etc.Said alkyl substituent for example can be, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, their isomer etc.
The preferred substituted diarylamine of hydrocarbon is a U.S. Patent number 3,452, those disclosed in 056 and 3,505,225, and the disclosure of said document is hereby incorporated by.The preferred substituted diarylamine of hydrocarbon can be represented by following general formula:
Wherein
R
11Be selected from phenyl and p-methylphenyl;
R
12And R
13Be independently selected from methyl, phenyl and p-methylphenyl;
R
14Be selected from methyl, phenyl, p-methylphenyl and neo-pentyl;
R
15Be selected from methyl, phenyl, p-methylphenyl and 2-phenyl isobutyl-; With
R
16It is methyl.
Wherein
R
11To R
15Be independently selected from the group shown in the general formula I, R
17Be selected from methyl, phenyl and p-methylphenyl;
X is selected from methyl, ethyl, C
3-C
10Secondary alkyl, α, the group of the metal-salt of α-Er Jiajibianji, α-Jia Jibianji, chlorine, bromine, carboxyl and carboxylic acid, said metal is selected from zinc, cadmium, nickel, lead, tin, magnesium and copper; With
Y is selected from hydrogen, methyl, ethyl, C
3-C
10The group of secondary alkyl, chlorine and bromine.
Wherein
R
11Be selected from phenyl or p-methylphenyl;
R
12And R
13Be independently selected from methyl, phenyl and p-methylphenyl;
R
14Be to be selected from hydrogen, C
3-C
10The primary, the second month in a season and tertiary alkyl and can be the C of straight or branched
3-C
10The group of alkoxyl group; With
Y is selected from hydrogen, methyl, ethyl, C
3-C
10The group of secondary alkyl, chlorine and bromine.
Wherein
R
18Be selected from phenyl and p-methylphenyl;
R
19It is the group that is selected from methyl, phenyl, p-methylphenyl and 2-phenyl isobutyl-; With
R
20It is the group that is selected from methyl, phenyl and p-methylphenyl.
Wherein
R
21Be selected from hydrogen, α, α-Er Jiajibianji, Alpha-Methyl diphenyl-methyl, trityl and to trimethyl benzyl;
R
22Be selected from phenyl or p-methylphenyl;
R
23Be selected from methyl, phenyl and p-methylphenyl; With
R
24Be selected from methyl, phenyl, p-methylphenyl and 2-phenyl isobutyl-.
It is following to can be used for typical chemical substance of the present invention:
Second type of amine antioxidants comprises the reaction product of diarylamine and aliphatic ketone.In this useful diarylamine aliphatic ketone reaction product in U.S. Patent number 1,906,935; 1,975,167; Disclose in 2,002,642 and 2,562,802.In brief, obtain these products as follows: make diarylamine, preferred pentanoic (they can have one or more substituting groups if necessary on aryl) and aliphatic ketone, the reaction in the presence of the catalyzer that is fit to of preferred acetone.Except pentanoic, other diarylamine reactant that is fit to comprises dinaphthyl amine; P-nitrodiphenylamine; 2, the 4-dinitro diphenylamine; Mutual-amido two polyaniline; P-hydroxydiphenylamine etc.Except acetone, other useful reactive ketone thing comprises methylethylketone, diethyl ketone, Mono Chloro acetone, Dichloro acetone etc.
Preferred diarylamine-aliphatic ketone reaction product is by pentanoic and acetone (NAUGARD A, Chemtura Corporation), and for example, according to U.S. Patent number 2,562, the condition of describing in 802 is carried out the condensation reaction acquisition.Commerical prod is as khaki-green powder or as the breen feeding sheets and have 85-95 ℃ melting range.
The 3rd type of suitable amine comprises N, the substituted P-pHENYLENE dI AMINE of N ' hydrocarbon.Hydrocarbon substituent can be an alkyl or aryl, and they can be replacements or unsubstituted.Only if special in addition the description, term as used herein " alkyl " is intended to comprise naphthenic base.Representational material is:
N-phenyl-N '-cyclohexyl-P-pHENYLENE dI AMINE;
N-phenyl-N '-sec.-butyl-P-pHENYLENE dI AMINE;
N-phenyl-N '-sec.-propyl-P-pHENYLENE dI AMINE;
N-phenyl-N '-(1, the 3-dimethylbutyl)-P-pHENYLENE dI AMINE;
N, N '-two-(1,4-dimethyl-amyl group)-P-pHENYLENE dI AMINE;
N, N '-phenylbenzene-P-pHENYLENE dI AMINE;
N, N '-two-β naphthyl-P-pHENYLENE dI AMINE;
Mixed diaryl-right-N, N '-two-(1-ethyl-3-methyl amyl)-P-pHENYLENE dI AMINE; With
N, N '-two-(1-methylheptyl)-P-pHENYLENE dI AMINE.
The 4th type of amine antioxidants comprises the material based on quinoline, and particularly polymeric 1,2-dihydro-2,2,4-trimethylquinoline (Naugard Super Q, Chemtura Corporation).Representational material also comprises 6-dodecyl-2,2,4-trimethylammonium-1,2-EEDQ; 6-oxyethyl group-2,2,4-trimethylammonium-1-2-EEDQ etc.
The secondary amine that is particularly preferred for the present invention practice is 4,4 '-(Naugard 445 for two (α, α-Er Jiajibianji) pentanoic; Chemtura Corporation), octylated diphenylamine (NaugardOctamine, Chemtura Corporation); Polymeric 1,2-dihydro-2,2; 4-trimethylquinoline (Naugard Super Q, Chemtura Corporation) and to (tolysulfonyl amino)-diphenylamine (Naugard SA, Chemtura Corporation).
The phosphorous acid ester and the phosphinate that can be used as the co-stabilizer in the present invention's practice for example comprise; Triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, trilauryl phosphite, tricresyl phosphite (octadecyl) ester, distearyl pentaerythrityl diphosphite, tricresyl phosphite (2; 4-two-tert-butyl-phenyl) ester, diiso decyl pentaerythritol diphosphites, two (2; 4-two-tert-butyl-phenyl) pentaerythritol diphosphites, three stearyl sorbyl alcohol GW-540s and four (2; 4-two-tert-butyl-phenyl) 4,4 '-biphenylene two phosphinates.
The lactone of the co-stabilizer in can putting into practice as the present invention comprise those of following structure
Wherein
R
1And R
2Be independently selected from hydrogen; Chlorine; Hydroxyl; C
1-C
25Alkyl; C
7-C
9-phenylalkyl; Unsubstituted or C
1-C
4Alkyl-substituted phenyl; Unsubstituted or C
1-C
4Alkyl-substituted C
5-C
8Naphthenic base; C
1-C
18Alkoxyl group; C
1-C
18Alkylthio; C
1-C
4Alkylamino; Two-(C
1-C
4Alkyl) amino; C
1-C
25Alkanoyloxy, C
1-C
25Alkyl amido; C
3-C
25The alkene acyloxy; By oxygen, sulphur or＞NR
8The C that is interrupted
3-C
25Alkanoyloxy; C
6-C
9Naphthenic base carbonyl oxygen base; Benzoyloxy or C
1-C
12Alkyl-substituted benzoyloxy,
R
8Be hydrogen or C
1-C
8Alkyl; With
R
3And R
4Be independently selected from hydrogen, C
1-C
8Alkyl, C
1-C
4Alkoxyl group, halogen, group
Wherein n is 1 or 2, or group
Wherein group A is independently selected from C
1-C
8Alkyl and C
1-C
8Alkoxyl group.
A kind of useful representative of these lactones is 5,7-two-tertiary butyl-3-(3, the 4-3,5-dimethylphenyl)-3H-benzofuran-2-ones, and it has following structure
This compound can be purchased as HP 136 from Ciba Specialties.
The thioether that can be used as the co-stabilizer in the present invention's practice can have following structure:
Wherein p is 1 or 2, and q is 0 or 1, p+q=2, R
18Be the straight or branched alkyl structure part that contains 1-20 carbon atom, and R
19It is the straight or branched alkylidene group structure division that contains 1-8 carbon atom.Therefore, R
18For example can be, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their isomer; And R
19Can be for example, be methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene and their isomer.Preferred R
18Be the straight or branched alkyl structure part that contains 8-18 carbon atom, R
19It is the straight or branched alkylidene group structure division that contains 1-4 carbon atom.More preferably R
19Be ethylidene, promptly-CH
2-CH
2-.
Other thioether that can be used for the present invention's practice can have following structure:
Wherein a is 0-3, and b is 1-4, a+b=4, R
18As stated, and R
19And R
20It is the independent straight or branched alkylidene group structure division of selecting that contains 1-8 carbon atom.Preferred R
19And R
20It is the independent straight or branched alkylidene group structure division of selecting that contains 1-4 carbon atom.More preferably R
20Be methylene radical, promptly-CH
2-, R
19Be ethylidene, promptly-CH
2-CH
2-.
The preferred thioether that can be used for the present invention practice is by product distearylthiodi-propionate (Naugard DSTDP for example; Chemtura Corporation); Tyox B (Naugard DLTDP, Chemtura Corporation), tetramethylolmethane four (lauryl thiopropionate) (Naugard 412S; Chemtura Corporation) and propane thioic acid tetramethylolmethane monooctyl ester (Naugard 2140, Chemtura Corporation).
Optional co-stabilizer of the present invention can also be the oxidation trialkylamine, for example, and GENOX
TMEP (can be purchased) and in U.S. Patent number 6,103,798 from Chemtura Corporation; 5,922,794; Be described in 5,880,191 and 5,844,029.
Another kind of co-stabilizer can be an azanol, for example, and N, N-dibenzyl hydroxylamine, N, N-diethyl hydroxylamine, N; N-dioctyl azanol, N, N-dilauryl azanol, N, N-two (tetradecyl) azanol, N, N-cerylic azanol; N, N-two (octadecyl) azanol, N-hexadecyl-N-octadecyl azanol, N-heptadecyl-N-octadecyl azanol, N, N-dioctyl azanol; N, N-two-tertiary butyl azanol, N-cyclohexyl azanol, N-cyclo-dodecyl azanol, N, N-dicyclohexyl azanol; N, N-didecyl azanol, N, N-two (cocoyl alkyl) azanol, N, N-two (C
20-C
22Alkyl) azanol and derived from the N of hydrogenated tallow amine, N-dialkyl group azanol (that is, N, N-two (tallow alkyl) azanol) and the mixture that contains any above-mentioned substance.
The stabilization of polymers compsn of gained of the present invention can randomly also contain various conventional additives, for example below:
1.UV absorption agent and photostabilizer.
1.1 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.
1.2 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-, the 4-benzyloxy, 4,2 ', 4 '-trihydroxy--with 2 '-decyl hydroxyl-4,4 '-the dimethoxy verivate.
1.3 replace 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.
1.4 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, N-(beta-methoxy-formyl radical-beta-cyano-vinyl)-2-methyl-indoline.
1.5 nickel compound, for example 2,2 '-(4-(1,1 for thiobis; 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.
1.6 the space hindered amine, two (2,2,6, the 6-tetramethyl-piperidyl) esters of sebacic acid for example, sebacic acid two-(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)-and 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 (arbonic acid), 1,1 '-(1,2-ethane two bases)-two (3,3,5,5-tetramethyl-piperazine ketone).These amine of so-called HALS comprise BTCA 2,2,6,6-tetramethyl piperidine alcohol ester.This type of 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.
1.7 the oxalic acid diamide, 4,4 '-two octyloxies-oxanilide for example, 2; 2 '-two octyloxies-5 ', 5 '-the di-t-butyl oxanilide, 2; 2 '-two (dodecyloxy)-5 ', 5 '-di-t-butyl-oxanilide, 2-oxyethyl group-2 '-ethyl-oxanilide; N, N '-two (3-dimethylaminopropyl)-oxamide, the 2-oxyethyl group-5-tertiary butyl-2 '-the ethyl oxanilide and with 2-oxyethyl group-2 '-ethyl-5; The mixture of 4-di-t-butyl oxanilide and adjacent and to the mixture of the dibasic oxanilide of methoxyl group, and adjacent and to the mixture of the dibasic oxalyl pentanoic of oxyethyl group.
2. metal passivator, N for example, N '-phenylbenzene oxalic acid diamide, N-salicylic aldehyde-N '-salicyloyl hydrazine, N; N '-salicil base hydrazine, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl group)-hydrazine; Salicylyl amino-1,2,4-triazole, two benzal base oxalic acid two hydrazides.
3. peroxide scavenger; The ester of β-propane thioic acid for example; Like lauryl, stearyl, myristyl or tridecyl ester, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate; Two octadecyl disulphide, tetramethylolmethane four-(β-dodecyl sulfydryl)-propionic ester.
4. polymeric amide stablizer, for example with the mantoquita of iodide and/or phosphorus compound combination, and the salt of bivalent manganese.
5. alkaline co-stabilizer, melamine 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, CSL, lactic acid ca, Zinic stearas, Magnesium Stearate; Sodium ricinoleate and potassium palmitate, burnt basic tea phenol antimony or pyrocatechol zinc comprise neutralizing agent, for example hydrotalcite and synthetic hydrotalcite and Li, Na, Mg, Ca and A1 hydroxyl carbonate.
6. the contract sodium salt of three phenyl aldehydes and two (2, the 4-di-tert-butyl-phenyl) esters of phosphoric acid of 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.
7. filler and toughener, lime carbonate for example, silicate, spun glass, asbestos, talcum, kaolin, mica, permanent white, MOX and oxyhydroxide, carbon black and graphite.
8. compound of the present invention can also use with the aminooxy propanoate ester derivatives is collaborative, for example methyl-3-(N, N-dibenzyl aminooxy) propionic ester; Ethyl-3-(N, N-dibenzyl aminooxy) propionic ester; 1,6-hexa-methylene-two (3-N, N-dibenzyl aminooxy) propionic ester; Methyl-(2-(methyl)-3 (N, N-dibenzyl aminooxy) propionic ester; Octadecyl-3-(N, N-dibenzyl aminooxy) propionic acid; Four (N, N-dibenzyl aminooxy) ethyl ketonic oxygen methyl) methane; Octadecyl-3-(N, N-diethylammonium aminooxy)-propionic ester; 3-(N, N-dibenzyl aminooxy) propionic acid sylvite and 1, two (3-(N-allyl group-N-dodecyl aminooxy) propionic esters of 6-hexa-methylene.
9. other additive that can combine with The compounds of this invention to adopt for example comprises softening agent, epoxidized vegetable oil, for example epoxidised VT 18, lubricant, emulsifying agent, pigment, azanol, for example R
2NOH, wherein R is C
1-C
30Alkyl, for example propyl group or stearyl, optical whitening agent, fireproofing agent, static inhibitor, whipping agent and sulfo-synergist.
10. 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).
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, consumption is usually less than about 5wt%, based on the weight of resin, and preferably about at least 50ppm, based on the weight 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.The compsn of said stabilization of the present invention can randomly also contain about 0.001 to about 5wt%; The about 2wt% of preferably approximately 0.0025-; Particularly about 0.005% to about 1wt% various conventional additives, for example foregoing those, or their mixture.
In following examples, use Mettler Universal V2.5H TA instrument that pure material is carried out thermogravimetric analysis (TGA).Through under 160 ℃ under nitrogen thermostatically heating sample record weight loss.
The polyurethane foam sample that is fit to is carried out the test of called after Windscreen FoggingCharacteristics of Trim Materials in Motor Vehicles and collect the fog data.TP is also claimed DIN 75 201 method B.Di Iso Decyl Phthalate (DIDP) is as authentic specimen.Usually, TR kept 16 hours under sample is exposed to 100 ℃.
Be surprisingly found out that of the present invention 2 when being used for the polyurethane-type foam formulation, 6-diphenylethyllene p-cresol comprises two key features: it serves as low fog additive (1), and satisfactory stability property is also given in (2) simultaneously.The term that this paper adopts " low fog " be defined as 100 ℃ down after the heating 160 hours the mist settling be the about 0.4mg of about 0.01-, the about 0.1mg of preferably approximately 0.02-.
The reason of above-mentioned unexpected situation is following:
Pure 2, the volatility of 6-diphenylethyllene p-cresol and its molar mass (MM) are linear; And the empirical rule in this area thinks that the molar mass of molecule is low more, and its volatility is high more.
Therefore, pure 2,6-diphenylethyllene p-cresol (MM=316) is not as pure 2,6-di-t-butyl-p-cresol (MM=220) volatilization.Simultaneously, as their corresponding molecular weight show, 2,6-diphenylethyllene p-cresol is than 3, and 5-two-tertiary butyl-4-hydroxy phenylpropionic acid stearyl (MM=531) has more volatility.
Yet in the polyurethane-type froth product, this empirical rule is inapplicable.Therefore, contain 2, the prescription of 6-diphenylethyllene p-cresol with contain the corresponding prescription of high-molecular weight additive (3,5-two-tertiary butyl-4-hydroxy phenylpropionic acid stearyl) more and compare and produce much lower mist (being volatility).
Use following formulation polyurethane-type foam specimen:
On Mettler Toledo instrument, carry out dsc (DSC) analysis.The heating rate of using 8 ℃/min under oxygen with sample when 30 ℃ are heated to 300 ℃, write down the oxidation inducing temperature (OIT) of temperature to start with.
Embodiment 2
It is pure 2 that this embodiment explains, the volatility of being measured by TGA of 6-diphenylethyllene p-cresol.The TGA result data is summarised in the table 3.
* estimate
These results show that pure additive volatility and the additive molar mass measured by TGA are linear.
Embodiment 3
This embodiment explanation is added with 2 by the mist sedimentation measurement, the volatile matter discharging of the polyurethane foam of 6-diphenylethyllene p-cresol.Fog test-results data are summarised in the table 4.
* estimate
These results' demonstrations are added with 2, the wondrous low discharging of the polyurethane-type foam sample of 6-diphenylethyllene p-cresol.Therefore, 2, it is suitable that the total mist deposition value and the nothing of 6-diphenylethyllene-p-cresol prescription added control sample.In other words, the mist of this prescription deposition is markedly inferior to and has more two kinds of control materials of high molecular weight separately.In addition, astoundingly, the mist deposition is not linear with the order that the additive molar mass is represented.
Embodiment 4
This embodiment explanation is by 2 of oxidation inducing temperature measurement, the polyol stabilizer usefulness of 6-two-styryl p-cresol.Result data is summarised in the table 5.
These results of this test show that 6-diphenylethyllene p-cresol is to the favorable and stable performance of polyvalent alcohol prescription by 2 of OIT measurement.Several phenolic antioxidant control samples are used for this test.
Embodiment 5
2, the performance evaluation of 6-toluylene p-cresol in LLDPE
Extrude the maintenance of back melt flow index at multipass
This embodiment explains and comprises 3 that the control sample of the blend of 5-two-tertiary butyl-4-hydroxy phenylpropionic acid stearyl and phosphite ester stabilizer compares 2, the stablizer usefulness of 6-diphenylethyllene p-cresol in the presence of phosphite ester stabilizer.
Base polymer is C
4-linear low density copolymer polyethylene powders has 1 melt index (MI), has 0.918g/cm
3Density.This basic components also contains the 500ppm Zinic stearas as acid scavenger.All prescriptions are following to be constituted: will be with 2, and 6-diphenylethyllene p-cresol or 3,5-two-tertiary butyl-4-hydroxy phenylpropionic acid stearyl bonded tricresyl phosphite (nonyl phenyl) ester adds (for more details, referring to table 6) in this basic components to.Be set to the resin formula of extruding stabilization like this under 230 ℃ the temperature from 19mm diameter Bradley Bender single screw extrusion machine with 60rpm then.Under inert atmosphere, carrying out first pass extrudes.It is cooled off granulation then through letting extrudate pass ice-water bath.Use and under air, extrude these pellets again five times at the most with aforementioned identical RPM, temperature and granulation condition.The result of this test is shown in the table 6.
P1 is tricresyl phosphite (nonyl phenyl) ester
The less reduction of melt flow index aspect means higher stablizer usefulness.Therefore, the result of this test shows and phosphorous acid ester P1 bonded 2 that 6-diphenylethyllene p-cresol is compared with control sample and obtained winning melt stabilization.
Embodiment 6
This embodiment explanation is through measuring 2 of tint retention mensuration, the stablizer usefulness of 6-diphenylethyllene p-cresol in the presence of phosphite ester stabilizer.With the result with contain 3, the control sample of the blend of 5-two-tertiary butyl-4-hydroxy phenylpropionic acid stearyl and identical phosphite ester stabilizer is compared.
Base polymer is C
4-linear low density copolymer polyethylene powders has 1 melt index (MI), has 0.918g/cm
3Density.This basic components also contains the 500ppm Zinic stearas as acid scavenger.All prescriptions are processed as follows: will be with 2, and 6-diphenylethyllene p-cresol or 3,5-two-tertiary butyl-4-hydroxy phenylpropionic acid stearyl bonded tricresyl phosphite (nonyl phenyl) ester adds (for more details, referring to table 7) in this basic components to.Be set to the resin formula of extruding stabilization like this under 230 ℃ the temperature from 19mm diameter Bradley Bender single screw extrusion machine with 60rpm then.Under inert atmosphere, carrying out first pass extrudes.It is cooled off granulation then through letting extrudate pass ice-water bath.Use and under air, extrude these pellets again five times at the most with aforementioned identical RPM, temperature and granulation condition.The result of this test is as shown in table 7.
P1 is tricresyl phosphite (nonyl phenyl) ester
The less raising of yellowness index aspect means outstanding stablizer usefulness.Therefore, the result of this test shows and phosphorous acid ester P1 bonded 2 that 6-diphenylethyllene p-cresol is compared with control sample and obtained winning tint retention.
Embodiment 7
2, the performance evaluation of 6-diphenylethyllene p-cresol in styrene-butadiene rubber(SBR)
Under 100 ℃ during oven ageing mooney viscosity along with the change of time
This embodiment explains 2,6-diphenylethyllene p-cresol individually with the stablizer usefulness of comparing with loose material (control sample) with phosphite ester stabilizer with combining.
Use e-SBR 1502 type resins.Condensing agent is following: 7.5 moles of %H in water
2SO
4With 5 moles of %Al
2(SO
4)
3Preparation contains the e-SBR sample of the stablizer shown in the table 8, and the baking oven of putting into 100 ℃ then carries out the oven ageing experiment.
On the viscTech mooney's viscosimeter, restrain sample measurement mooney viscosity (temperature: 100 ℃ by 30; 1min does not have rotation warm up time; The clock Measuring Time is 4 minutes after preheating).Every kind of prescription is measured mooney viscosity before the oven ageing, in case the SBR sample is exposed in 100 ℃ the baking oven, with regard to periodic measurement then.The result of this test is illustrated in the table 8.
P1 is tricresyl phosphite (nonyl phenyl) ester
The less raising of mooney viscosity aspect means outstanding stablizer usefulness.Therefore, the result of this test shows 2, and 6-diphenylethyllene p-cresol (combining separately and with phosphorous acid ester P1) obtains than has the winning stabilization of the control sample of interpolation.
Consider many changes and the modification that under not breaking away from, can make, should understand protection domain provided by the invention with reference to appended claims based on the situation of principle of the present invention.
Claims (20)
1. the compsn that contains the mixture of styrenated p-cresol material; This mixture at room temperature is a liquid; Under 25 ℃, have less than 40; The viscosity of 000cps, comprise by the GC area percentage analyze minimum 70% 2,6-toluylene p-cresol; Wherein said mixture comprises single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol and shows the acid number less than the 0.1mgKOH/ gram, and said preparation process of mixture comprises makes vinylbenzene and p-cresol by 1.85-2.1 separately: 1 mol ratio is reacted in the presence of acid catalyst at elevated temperatures.
2. the compsn of claim 1, wherein said mixture has the APHA value less than 150.
3. the compsn of claim 1; Wherein said single styrenated p-cresol and triphenylethylene p-cresol exist with the concentration of 1-15% by the GC planimeter separately; Based on the total area of single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol, and acid number restrains less than 0.01mgKOH/.
4. the compsn of claim 1, wherein said 2,6-toluylene p-cresol exists with minimum 75% concentration by the GC planimeter, based on the total area of single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol.
5. the compsn of claim 1, wherein said 2,6-toluylene p-cresol exists by the concentration of GC planimeter with 80-95%, based on the total area of single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol.
6. the compsn of claim 1; The GC area percentage of the combination of wherein said single styrenated p-cresol and triphenylethylene p-cresol component is pressed planimeter will be 5-30%, based on the total area of single styrenated p-cresol, toluylene p-cresol and triphenylethylene p-cresol.
7. according to the preparation process of mixture of the styrenated p-cresol material of claim 1-5 in each.
8. the method for claim 7, it is 2 of 80-90% that wherein said method provides by the analysis of GC area percentage, 6-toluylene p-cresol.
9. the method for claim 7, wherein said acid catalyst is Br or Lewis acid.
10. the method for claim 7, wherein said acid catalyst is a trifluoromethayl sulfonic acid.
11. make the stable method of polymer compsn, be included in the said compsn mixture of the styrenated p-cresol material of claim 1-6 in each that adds significant quantity.
12. the method for claim 11, wherein said polymer compsn also comprises co-stabilizer.
13. the method for claim 11, wherein said polymkeric substance is selected from polyolefine, PVC, urethane, polyvalent alcohol and elastomerics.
14. the method for claim 13, wherein said elastomerics is a styrene-butadiene rubber(SBR).
15. the method for claim 12, wherein said co-stabilizer is selected from phenolic cpd, phosphorous acid ester, diarylamine, and epoxidized vegetable oil.
16. the method for claim 15, wherein said phosphorous acid ester is an organophosphite.
17. the method for claim 16, wherein said organophosphite are tricresyl phosphite (nonyl phenyl) ester.
18. the method for claim 15, wherein said diarylamine is a dialkylated diphenylamine.
19. the method for claim 15, wherein said epoxidized vegetable oil are epoxidised soybean oil.
20. the method for claim 11, wherein said polymer compsn comprise the composition exhibiting ground fog of polyvalent alcohol or urethane and stabilization.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US93195407P | 2007-05-24 | 2007-05-24 | |
| US60/931,954 | 2007-05-24 | ||
| US93691807P | 2007-06-21 | 2007-06-21 | |
| US60/936,918 | 2007-06-21 | ||
| US12/069,631 US8193260B2 (en) | 2007-02-26 | 2008-02-11 | Stabilization of polymers with styrenated-p-cresols |
| US12/069,631 | 2008-02-11 | ||
| PCT/US2008/053979 WO2008144086A1 (en) | 2007-05-24 | 2008-02-14 | Stabilization of polymers with styrenated-p-cresols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101595172A CN101595172A (en) | 2009-12-02 |
| CN101595172B true CN101595172B (en) | 2012-12-26 |
Family
ID=41409156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880003611.4A Expired - Fee Related CN101595172B (en) | 2007-05-24 | 2008-02-14 | Method for stabilization of polymers with styrenated-p-cresols |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101595172B (en) |
| ES (1) | ES2365795T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267876B (en) * | 2011-06-20 | 2014-06-18 | 常州大学 | Preparation method of styrenated hindered phenol or styrenated phenol antioxidant product |
| CN102633921B (en) * | 2012-04-06 | 2014-06-18 | 常州大学 | Preparation method of aqueous emulsion type polyvinyl chloride resin non-toxic terminator |
| KR101638871B1 (en) * | 2013-09-26 | 2016-07-12 | 금호석유화학 주식회사 | Styrenated phenol adduct and manufacturing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0623555B1 (en) * | 1993-05-06 | 1998-07-15 | Kabushiki Kaisha Kaisui Kagaku Kenkyujo | Stabilized, halogen-containing resin composition, and composite metal oxide and process for the production thereof |
| US6242562B1 (en) * | 1998-12-28 | 2001-06-05 | Shin-Etsu Chemical Co., Ltd. | Process for producing vinyl chloride polymer |
-
2008
- 2008-02-14 CN CN200880003611.4A patent/CN101595172B/en not_active Expired - Fee Related
- 2008-02-14 ES ES08729877T patent/ES2365795T3/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0623555B1 (en) * | 1993-05-06 | 1998-07-15 | Kabushiki Kaisha Kaisui Kagaku Kenkyujo | Stabilized, halogen-containing resin composition, and composite metal oxide and process for the production thereof |
| US6242562B1 (en) * | 1998-12-28 | 2001-06-05 | Shin-Etsu Chemical Co., Ltd. | Process for producing vinyl chloride polymer |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-52421A 2006.02.23 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101595172A (en) | 2009-12-02 |
| ES2365795T3 (en) | 2011-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101688143A (en) | Liquid styrene phenols composition and forming method thereof | |
| CN1229427C (en) | Polymer composition containing amine oxide stabilizing agent composition | |
| CN1048019C (en) | Hydrolytically stable pentaerythritol diphosphites | |
| US7902280B2 (en) | Liquid styrenated phenolic compositions and processes for forming same | |
| CN101472986B (en) | Liquid phosphite blends as stabilizers | |
| US10683409B2 (en) | Additive mixture for stabilization of polyol and polyurethane | |
| US20080161454A1 (en) | Stabilization Of Polyol Or Polyurethane Compositions Against Thermal Oxidation | |
| CA1295619C (en) | 1,3,2-oxazaphospholidine stabilizers | |
| CN101903456A (en) | Olefin elastic resin composition | |
| US9550886B2 (en) | Stabilizer and composition including the same | |
| CN101595172B (en) | Method for stabilization of polymers with styrenated-p-cresols | |
| JP5379023B2 (en) | Styrene-P-cresol polymer stabilizer and process for producing the same | |
| CN104262678B (en) | A kind of additive for polymkeric substance | |
| CN1036275C (en) | N-methylate bis-4-piperidyl phosphite | |
| CN101437886B (en) | Derivatives of pyrimidines as flame retardants | |
| KR102011678B1 (en) | Cycloaliphatic polyphosphite polymer stabilizers | |
| CN1250623C (en) | Antioxidants for polyamides | |
| CN100387579C (en) | Graftable hindered amine light stabilizers | |
| TWI438233B (en) | Stabilization of polymers with styrenated-p-cresols | |
| EP0252003B1 (en) | Substituted aminoxy succinates and their application as stabilisers | |
| WO2017140170A1 (en) | Phosphorus-containing additive for polymer | |
| AU644867B2 (en) | Hydrolytically stable phosphites | |
| US7442732B2 (en) | Hindered amine light stabilizers comprising neoalkanediol phosphites | |
| WO2017152684A1 (en) | Additive for polymer | |
| JPH05306255A (en) | Diphenyl acetic acid derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121226 Termination date: 20150214 |
|
| EXPY | Termination of patent right or utility model |