CN106479015A - Modified polymeric materials and composite stabilizer compositions - Google Patents
Modified polymeric materials and composite stabilizer compositions Download PDFInfo
- Publication number
- CN106479015A CN106479015A CN201610674076.1A CN201610674076A CN106479015A CN 106479015 A CN106479015 A CN 106479015A CN 201610674076 A CN201610674076 A CN 201610674076A CN 106479015 A CN106479015 A CN 106479015A
- Authority
- CN
- China
- Prior art keywords
- chemical formula
- represent
- independently
- another
- alkyl
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims description 32
- 239000006084 composite stabilizer Substances 0.000 title abstract 4
- 239000000203 mixture Substances 0.000 title abstract 4
- 239000000126 substance Substances 0.000 claims abstract description 88
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 14
- 229920000098 polyolefin Polymers 0.000 claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005977 Ethylene Substances 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 239000000470 constituent Substances 0.000 claims description 23
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 23
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- -1 polyethylene Polymers 0.000 claims description 20
- 230000006641 stabilisation Effects 0.000 claims description 20
- 238000011105 stabilization Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 16
- 239000003963 antioxidant agent Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 230000003078 antioxidant effect Effects 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract 2
- 229920000307 polymer substrate Polymers 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 description 14
- 238000007493 shaping process Methods 0.000 description 9
- 235000006708 antioxidants Nutrition 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 2
- WAOPGHCXGUXHKF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-1,1-diphenylpropane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.C1(=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=CC=CC=C1 WAOPGHCXGUXHKF-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000001458 anti-acid effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 2
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 description 1
- AADSABAIOWQMDI-UHFFFAOYSA-N (4-tert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C=C1 AADSABAIOWQMDI-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- JWOWIZVDYKUULJ-UHFFFAOYSA-N 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OPOCC11COPOC1 JWOWIZVDYKUULJ-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- MLOBRFXCJDVMED-UHFFFAOYSA-N CC(C(C1)N)=CC=C1N=C Chemical compound CC(C(C1)N)=CC=C1N=C MLOBRFXCJDVMED-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 description 1
- HHOOGTWDCIXRKV-UHFFFAOYSA-N P(O)(O)O.C(C)(C)(C1=CC=CC=C1)C1=C(C=CC(=C1)C(C)(C)C1=CC=CC=C1)C(C(CO)(CC)CCCC)O Chemical compound P(O)(O)O.C(C)(C)(C1=CC=CC=C1)C1=C(C=CC(=C1)C(C)(C)C1=CC=CC=C1)C(C(CO)(CC)CCCC)O HHOOGTWDCIXRKV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical class C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- SAAMKFBWYWFBNY-UHFFFAOYSA-N tris(4-tert-butylphenyl) phosphite Chemical compound C1=CC(C(C)(C)C)=CC=C1OP(OC=1C=CC(=CC=1)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1 SAAMKFBWYWFBNY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
- C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
A modified polymer material comprises a polymer substrate selected from olefin polymers, ethylene/vinyl acetate copolymers or a combination thereof, and a composite stabilizer composition, wherein the composite stabilizer composition comprises a phosphorus-containing organic antioxidant selected from at least one of chemical formulas 1 to 8, and a sulfur-containing carboxylate selected from at least one of chemical formulas 9 to 11. By using the composite stabilizer composition, the modified polymer material has good color stability and processing stability in the processing and forming process.
Description
Technical field
The present invention relates to a kind of modified polymeric material, more particularly to a kind of include specifically phosphorous have by one
The combined type stabilization agent constituent of machine antioxidant and sulfur-containing carboxylate compound is by olefin polymer or ethylene/vinyl acetate
The modified polymeric material of ester copolymer modification.
Background technology
Polymeric substrate, such as olefin polymer, ethylene/vinyl acetate copolymer have good chemically stable
Property, mechanical strength, electric insulating quality and product size stability, and have the advantages that non-toxic and easy to process, thus wide
General application is used as various products.Though polymeric substrate is with above-mentioned advantage, above-mentioned polymeric substrate is easy under heat energy effect
Oxidized degraded, causes xanthochromia and engineering properties to decline.
Therefore, in order to prevent the oxidative degradation of above-mentioned polymeric substrate, antioxidant can be added in machine-shaping processing procedure
To reduce the oxidative degradation of polymeric substrate, to strengthen engineering properties and the heat resistance of polymeric substrate；However, anti-oxidant
Agent itself may cause polymeric substrate colored and processing stability declines.Additionally, typically can add again in machine-shaping processing procedure
Enter antiacid, be in order to suppress acidic materials cause polymeric substrate degrade, however, the species of some antiacids or addition
When more, also result in the colored and processing stability of polymeric substrate and decline.
Content of the invention
The first object of the present invention is to provide a kind of modified polymeric material, its in machine-shaping processing procedure, energy
Enough maintenances preferably colour stability and processing stability.
The modified polymeric material of the present invention includes：
One polymeric substrate, be selected from olefin polymer, ethylene/vinyl acetate copolymer or above-mentioned group
Close；And
One combined type stabilization agent constituent, including：
A kind of phosphorous organic oxidation-resistant agent selected from least one in chemical formula 1 to chemical formula 8, and
A kind of sulfur-containing carboxylate selected from chemical formula 9 to chemical formula 11 shown at least one,
【Chemical formula 1】
【Chemical formula 2】
【Chemical formula 3】
【Chemical formula 4】
【Chemical formula 5】
【Chemical formula 6】
【Chemical formula 7】
【Chemical formula 8】
【Chemical formula 9】
【Chemical formula 10】
【Chemical formula 11】
In chemical formula 1 to chemical formula 7, R11To R13、R21To R26、R31To R35、R41To R48、R51To R56、R61To R64, and
R71To R78Represent hydrogen, the tert-butyl group, cumenyl or C independently of one another1To C8Straight chained alkyl；T represents C1To C18Alkyl orR65To R67Represent hydrogen, the tert-butyl group, cumenyl or C independently of one another1To C8Straight chained alkyl；Z41、
Z42、Z51And Z61Represent O, S or C independently of one another1To C4Stretch alkyl,
In chemical formula 9, X11And X12Represent Ca independently of one another2+、Ba2+、Mg2+Or Zn2+, Y11And Y12Table independently of one another
Show C1To C30Alkyl or C6To C18Aryl, a and b represent 1 to 6 integer independently of one another,
In chemical formula 10, p represents 1 to 9 integer, X21Represent Ca2+、Ba2+、Mg2+Or Zn2+, G1And G2Table independently of one another
ShowC and d represent 1 to 6 integer independently of one another, and when p >=2, many
Individual G1Can be identical or different, multiple X21Can for identical or different,
In chemical formula 11, X31Represent Ca2+、Ba2+、Mg2+、Zn2+, Y31Represent C1To C30Alkyl, C6To C18Aryl or
R93OOC-(CH2)k-, R93Represent C1To C30Alkyl or C6To C18Aryl, k represent 1 to 5 integer.
The modified polymeric material of the present invention, with the weight of the polymeric substrate as 100 weight portions, the combined type
The content range of stabilization agent constituent is 0.01 to 2.2 weight portion.
The modified polymeric material of the present invention, the olefin polymer be selected from polyethylene, polypropylene or above-mentioned
One combination.
The second object of the present invention is to provide a kind of combined type stabilization agent constituent, be for modifying above-mentioned polymer
Base material.
Combined type stabilization agent constituent of the present invention includes：A kind of selected from least one contain in chemical formula 1 to chemical formula 8
Phosphorus organic oxidation-resistant agent, and a kind of sulfur-containing carboxylate selected from chemical formula 9 to chemical formula 11 shown at least one.Its
In, the chemical formula 1 to 11 be as described above, therefore repeating no more.
The beneficial effects of the present invention is：By adding containing specifically phosphorous organic antioxygen in the polymeric substrate
Agent and the combined type stabilization agent constituent of sulfur-containing carboxylate so that the modified polymeric material is in procedure for processing
Middle energy maintains good colour stability and processing stability, and high-quality products formed is obtained then.
Specific embodiment
Hereinafter will be described in detail with regard to present invention：
[polymeric substrate]
The polymeric substrate be selected from olefin polymer, ethylene/vinyl acetate copolymer or above-mentioned one
Combination.It is preferred that the olefin polymer is selected from polyethylene, polypropylene or above-mentioned combination.
[combined type stabilization agent constituent]
Phosphorous organic oxidation-resistant agent shown in the chemical formula 1 is such as, but not limited to：Three (2,4- di-t-butyl) phosphorous acid
Phenyl ester [tris (2,4-ditert-butylphenyl) phosphite, abbreviation antioxidant 168], triphenyl phosphite
(triphenyl phosphite), three (4- tert-butyl-phenyl) phosphite ester [tris (4-tert-butylphenyl)
Phosphite], three (nonyl phenyl) phosphite ester [tris (nonylphenyl) phosphite], or three (p- cumenyls
Phenyl) phosphite ester [tris (p-cumylphenyl) phosphite].
Phosphorous organic oxidation-resistant agent shown in the chemical formula 2 is such as, but not limited to：Double (2,4- di-tert-butyl-phenyl) seasons
Double (2,4- diisopropylbenzene (DIPB) phenoxyl) -2,4,8,10- tetra- oxygen of penta tetrol diphosphites (abbreviation antioxidant 626), 3,9-
Miscellaneous -3,9-, bis- phospha spiral shell [5.5] hendecane (abbreviation antioxidant 9228), diphenyl pentaerythritol diphosphites
(diphenyl pentaerythritol diphosphite), or 2,4,8,10- tetra- oxa- -3, bis- phospha spiral shell [5.5] ten of 9-
One alkane { 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane }.
Phosphorous organic oxidation-resistant agent shown in the chemical formula 3 is such as, but not limited to：
(cas number is 161717-32-4), 2- [2,4- double (1,1- dimethyl ethyl) phenoxy groups] -5,5- dimethyl -1,3,2- dioxies
Phospha cyclohexane { 2- [2,4-bis (1,1-dimethylethyl) phenoxy] -5,5-dimethyl-1,3,2-
Dioxaphosphorinane }, 2,4- diisopropylbenzyl phenyl -2- butyl -2- ethyl -1,3-PD phosphite ester (2,4-
Dicumylphenyl 2-butyl-2-ethyl-1,3-propanediol phosphite), 2- [2,4- double (1,1- dimethyl
Ethyl) phenoxy group] -5- butyl -5- ethyl -1,3,2- dioxaphosphorinanes { 2- [2,4-bis (1,1-dimethylethyl)
Phenoxy] -5-butyl-5-ethyl-1,3,2-dioxaphosphorinane }.
Phosphorous organic oxidation-resistant agent shown in the chemical formula 4 is such as, but not limited to：
(cas number is 1601458-04-1).
Phosphorous organic oxidation-resistant agent shown in the chemical formula 5 is such as, but not limited to：
(cas number is 205518-79-2).
Phosphorous organic oxidation-resistant agent shown in the chemical formula 6 is such as, but not limited to：2,4,8,10- tetra-tert -6-
[(2- second hexyl) oxygen] eight ring (abbreviation HP-10) of -12H- diphenyl [d, g] [1,3,2] dioxy phospha, 2,2 '-thio two [tertiary fourth
Base-paracresol] ring-type list phenyl phosphites { 2,2 '-thiobis [6-tert-butyl-p-cresol] cyclic
Monophenyl phosphite }, 2,2 '-stretch double (4,6- di-tert-butyl-phenyl) (2, the 4- di-tert-butyl-phenyl) phosphorous acid of methyl
Ester [2,2 '-methylene bis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl)
phosphite].
Phosphorous organic oxidation-resistant agent shown in chemical formula 7 is such as, but not limited to：Antioxidant P-EPQ, phosphonic acids [1,1 '-connection
Benzene] -4,4 '-diyl double-four [2- (1,1- dimethyl ethyl) phenyl] esters phosphonous acid, [1,1 ' -
Biphenyl] -4,4 '-diylbis-tetrakis [2- (1,1-dimethylethyl) phenyl] ester }, phosphonic acids [1,1 ' -
Biphenyl] -4,4 '-diyl pair-triphen base ester phosphonous acid, [1,1 '-biphenyl] -4,4 '-diylbis-,
tetraphenyl ester}.
It is preferred that in the chemical formula 9, X11And X12Represent Ca or Zn, Y independently of one another11And Y12Each solely
On the spot expression-C7H15Or-C17H35.Sulfur-containing carboxylate shown in the chemical formula 9 is such as, but not limited to： Or
It is preferred that in the chemical formula 10, X21Represent Ca or Zn, G1And G2Represent independently of one anotherWherein c and d represent 1 or 2 independently of one another.Shown in the chemical formula 10
Sulfur-containing carboxylate is such as, but not limited to：
OrWherein, p represent 1 to
9 integer.
Sulfur-containing carboxylate shown in the chemical formula 11 is such as, but not limited to：Or
The phosphorous organic oxidation-resistant agent is 1: 99 to 99: 1 with the usage ratio scope of the sulfur-containing carboxylate.
[modified polymeric material]
It is preferred that with the weight of the polymeric substrate as 100 weight portions, the content of the combined type stabilization agent constituent
Scope is 0.01 to 2.2 weight portion.
There is no particular restriction for the preparation method of the modified polymeric material, such as but not limited to by the polymer
Base material is mixed with the combined type stabilization agent constituent.
There is no particular restriction for the machine-shaping mode of the modified polymeric material, can need according to follow-up product
Ask, using the machine-shaping mode that olefin polymer, ethylene/vinyl acetate copolymer are conventional.The machine-shaping
Mode be such as, but not limited to extrusion molding, ejection formation etc..
【Embodiment】
The present invention will be described further with regard to following examples, however, it should be noted that the embodiment is only to illustrate saying
Bright be used, and be not necessarily to be construed as the restriction of present invention enforcement.
[experimental drug]
1. polypropylene：Purchased from Tai Hua company, the name of an article is B8001, abbreviation PP in table 1 and table 2.
2. polyethylene：Purchased from Tai Su company, the name of an article is LL120, abbreviation PE in table 1 and table 2.
3. three (2,4- di-t-butyl) phenyl-phosphite：Phosphorous organic oxidation-resistant agent shown in chemical formula 1, abbreviation antioxygen
Abbreviation A1 in agent 168, table 1 and table 2.
4. pair (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites：Phosphorous organic antioxygen shown in chemical formula 2
Abbreviation A2 in agent, abbreviation antioxidant 626, table 1 and table 2.
5. double (2,4- diisopropylbenzene (DIPB) phenoxyl) -2,4,8,10- tetra- oxa- -3 of 3,9-, bis- phospha spiral shell [5.5] of 9- 11
Alkane：Phosphorous organic oxidation-resistant agent shown in chemical formula 2, abbreviation antioxidant 9228, abbreviation A3 in table 1 and table 2.
6. 2,4,8,10- tetra-tert -6- [(2- second hexyl) oxygen] -12H- diphenyl [d, g] [1,3,2] dioxy phospha
Eight rings：Phosphorous organic oxidation-resistant agent shown in chemical formula 6, abbreviation HP-10, abbreviation A4 in table 1 and table 2.
7.For chemistry
Phosphorous organic oxidation-resistant agent shown in formula 7, abbreviation P-EPQ, abbreviation A5 in table 1 and table 2.
8. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide：Phosphorous organic oxidation-resistant shown in chemical formula 8
Abbreviation A6 in agent, abbreviation DOPO, table 1 and table 2.
9.Phosphorous organic oxidation-resistant agent shown in chemical formula 3, CAS
Number is 161717-32-4, abbreviation A7 in table 1 and table 2.
10.Phosphorous organic oxidation-resistant agent shown in chemical formula 5,
Cas number is 205518-79-2, abbreviation A8 in table 1 and table 2.
11.For 4 institute of chemical formula
The phosphorous organic oxidation-resistant agent that shows, cas number are 1601458-04-1, abbreviation A9 in table 1 and table 2.
12.For changing
Abbreviation B1 in sulfur-containing carboxylate shown in formula 9, table 1 and table 2；
13.
Abbreviation B2 in sulfur-containing carboxylate shown in chemical formula 10, table 1 and table 2.
14.Abbreviation B3 in sulfur-containing carboxylate shown in chemical formula 11, table 1 and table 2.
The double octadecyl esters of 15. thio-2 acids：The entitled disteaxyl thiodipropionate of English, hereinafter referred to as
DSTDP.
The modified polymeric material of 1 to 16 ＞ of ＜ embodiment
According to the constituent shown in table 1 and ratio (weight portion), by 100 parts by weight of polypropylene or the poly- second of 100 weight portions
Alkene is uniformly mixed at 25 DEG C with combined type stabilization agent constituent, respectively obtains the modified polymeric material of embodiment 1 to 16
Material E1 ' to E16 '.
The modified polymeric material of 1 to 19 ＞ of ＜ comparative example
According to the constituent shown in table 2 and ratio (weight portion), by 100 parts by weight of polypropylene or the poly- second of 100 weight portions
Alkene is uniformly mixed at 25 DEG C with stabilization agent constituent, respectively obtains the modified polymeric material CE1 ' of comparative example 1 to 19
To CE19 '.
[evaluation test]
By above-mentioned modified polymeric material E1 ' to E16 ' and CE1 ' to CE19 ' respectively with twin-screw extruder (platform
Wan Hong illuminate Mechanology Inc. testing machine PSM20A) (temperature setting is 190 to 230 DEG C, and screw speed is 200 revs/min for mixing extrusion
Clock, charging rate are 6 revs/min), then through supercooling, air-dried, pelletizing, drying, prepare sample E1 to E16 and CE1 extremely
CE19.Sample E1 to E16 and CE1 to CE19 is repeated above-mentioned extrusion, cooling, air-dried, pelletizing, drying steps respectively, with
Evaluate sample in the change of yellow chromaticity and melt index after the program of multiple machine-shaping, the less representative of the change of yellow chromaticity
Colour stability of the modified polymeric material in machine-shaping processing procedure is better, and the change of melt index is less to be represented through changing
Processing stability of the polymeric material of matter in machine-shaping processing procedure is better.
1. yellow aberration (Δ b* value)
Sample E1 to E16 and CE1 is measured respectively extremely using color difference meter (for the ColorQuest XE of HunterLab company)
CE19 after the 3rd time and the 5th extrusion compared to the 1st extrusion value of chromatism (Δ b* value), as a result as shown in table 3 and table 4.
2. melt index (melting index, MI) changes (Δ MI)
Using laboratory fusion index instrument (the Laboratory Melt Indexer LMI for Dynisco company
D4004) sample E1 to E16 and CE1 to CE19 melting compared to the 1st extrusion after the 3rd time and the 5th extrusion is measured respectively
Index variation As a result as shown in table 3 and table 4.
Table 1
Table 2
Note：In table 1 and table 2, "-" represents no added.
Table 3
Table 4
By table 3 and table 4 it is known that obtained in embodiment 1 to 16 sample E1 to E16, the Δ b* value through the 3rd extrusion
Below 2.51, the Δ b* value through the 5th extrusion is below 4.58, however, sample CE1 is extremely obtained in comparative example 1 to 19
CE19, the Δ b* value through the 3rd extrusion more than 3.12, the Δ b* value through the 5th extrusion more than 5.92, show compared to than
Stabilization agent constituent is used compared with example 1 to 19, the modified polymeric material of embodiment 1 to 16 is stable by using the combined type
Agent constituent so that modified polymeric material has preferably colour stability, and then obtained sample is had
Relatively low yellow aberration (Δ b* value), xanthochromia is less obvious.
Change the result of (Δ MI) according to melt index, sample E1 to E16 obtained in embodiment 1 to 16, through the 3rd signature
, below 144.43%, the Δ MI through the 5th extrusion is below 251.33% for the Δ MI for going out；So, obtained in comparative example 1 to 19
Sample CE1 to CE19, the Δ MI through the 3rd extrusion more than 172.51%, Δ MI through the 5th extrusion 315.65% with
On, showing compared to comparative example 1 to 19 and stabilization agent constituent is used, the modified polymeric material of embodiment 1 to 16 is by making
With the combined type stabilization agent constituent so that modified polymeric material has preferably processing stability (physical property), enters
And cause obtained sample to have relatively low melt index change (Δ MI).
In sum, the present invention pass through to add in the polymeric substrate containing specific phosphorous organic oxidation-resistant agent and
The combined type stabilization agent constituent of the sulfur-containing carboxylate so that the modified polymeric material is in procedure for processing
Good colour stability and processing stability can be maintained, therefore the purpose of the present invention can be reached really.
Claims (4)
1. a kind of modified polymeric material, it is characterised in that the modified polymeric material includes：
One polymeric substrate, is combined selected from olefin polymer, ethylene/vinyl acetate copolymer or above-mentioned one；
And
One combined type stabilization agent constituent, including：
A kind of phosphorous organic oxidation-resistant agent selected from least one in chemical formula 1 to chemical formula 8, and
A kind of selected from the sulfur-containing carboxylate of at least one in chemical formula 9 to chemical formula 11,
【Chemical formula 1】
【Chemical formula 2】
【Chemical formula 3】
【Chemical formula 4】
【Chemical formula 5】
【Chemical formula 6】
【Chemical formula 7】
【Chemical formula 8】
【Chemical formula 9】
【Chemical formula 10】
【Chemical formula 11】
In chemical formula 1 to chemical formula 7, R11To R13、R21To R26、R31To R35、R41To R48、R51To R56、R61To R64, and R71Extremely
R78Represent hydrogen, the tert-butyl group, cumenyl or C independently of one another1To C8Straight chained alkyl；T represents C1To C18Alkyl orR65To R67Represent hydrogen, the tert-butyl group, cumenyl or C independently of one another1To C8Straight chained alkyl；Z41、
Z42、Z51And Z61Represent O, S or C independently of one another1To C4Stretch alkyl,
In chemical formula 9, X11And X12Represent Ca independently of one another2+、Ba2+、Mg2+Or Zn2+, Y11And Y12Represent C independently of one another1Extremely
C30Alkyl or C6To C18Aryl, a and b represent 1 to 6 integer independently of one another,
In chemical formula 10, p represents 1 to 9 integer, X21Represent Ca2+、Ba2+、Mg2+Or Zn2+, G1And G2Represent independently of one anotherC and d represent 1 to 6 integer independently of one another, and when p >=2, multiple
G1Can be identical or different, multiple X21Can for identical or different,
In chemical formula 11, X31Represent Ca2+、Ba2+、Mg2+、Zn2+, Y31Represent C1To C30Alkyl, C6To C18Aryl or
R93OOC-(CH2)k-, R93Represent C1To C30Alkyl or C6To C18Aryl, k represent 1 to 5 integer.
2. modified polymeric material according to claim 1, it is characterised in that the weight of the polymeric substrate is
100 weight portions, the content range of the combined type stabilization agent constituent is 0.01 to 2.2 weight portion.
3. modified polymeric material according to claim 1, it is characterised in that the olefin polymer is to be selected from
In polyethylene, polypropylene or above-mentioned combination.
4. a kind of combined type stabilization agent constituent, it is characterised in that the combined type stabilization agent constituent includes：
A kind of phosphorous organic oxidation-resistant agent selected from least one in chemical formula 1 to chemical formula 8；And
A kind of selected from the sulfur-containing carboxylate of at least one in chemical formula 9 to chemical formula 11；
【Chemical formula 1】
【Chemical formula 2】
【Chemical formula 3】
【Chemical formula 4】
【Chemical formula 5】
【Chemical formula 6】
【Chemical formula 7】
【Chemical formula 8】
【Chemical formula 9】
【Chemical formula 10】
【Chemical formula 11】
In chemical formula 1 to chemical formula 7, R11To R13、R21To R26、R31To R35、R41To R48、R51To R56、R61To R64, and R71Extremely
R78Represent hydrogen, the tert-butyl group, cumenyl or C independently of one another1To C8Straight chained alkyl；T represents C1To C18Alkyl orR65To R67Represent hydrogen, the tert-butyl group, cumenyl or C independently of one another1To C8Straight chained alkyl；Z41、
Z42、Z51And Z61Represent O, S or C independently of one another1To C4Stretch alkyl；
In chemical formula 9, X11And X12Represent Ca independently of one another2+、Ba2+、Mg2+Or Zn2+, Y11And Y12Represent C independently of one another1Extremely
C30Alkyl or C6To C18Aryl, a and b represent 1 to 6 integer independently of one another；
In chemical formula 10, p represents 1 to 9 integer, X21Represent Ca2+、Ba2+、Mg2+Or Zn2+, G1And G2Represent independently of one anotherC and d represent 1 to 6 integer independently of one another, and when p >=2, multiple
G1Can be identical or different, multiple X21Can be identical or different；
In chemical formula 11, X31Represent Ca2+、Ba2+、Mg2+、Zn2+, Y31Represent C1To C30Alkyl, C6To C18Aryl or
R93OOC-(CH2)k-, R93Represent C1To C30Alkyl or C6To C18Aryl, k represent 1 to 5 integer.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104128114 | 2015-08-27 | ||
| TW104128114 | 2015-08-27 | ||
| TW105103696 | 2016-02-04 | ||
| TW105103696 | 2016-02-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106479015A true CN106479015A (en) | 2017-03-08 |
Family
ID=58273845
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610674278.6A Active CN106479041B (en) | 2015-08-27 | 2016-08-16 | Modified polymeric materials and composite stabilizer compositions |
| CN201610674076.1A Pending CN106479015A (en) | 2015-08-27 | 2016-08-16 | Modified polymeric materials and composite stabilizer compositions |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610674278.6A Active CN106479041B (en) | 2015-08-27 | 2016-08-16 | Modified polymeric materials and composite stabilizer compositions |
Country Status (6)
| Country | Link |
|---|---|
| KR (1) | KR102003595B1 (en) |
| CN (2) | CN106479041B (en) |
| BR (1) | BR102017017764A2 (en) |
| ES (1) | ES2836703T3 (en) |
| RU (1) | RU2678593C1 (en) |
| TW (2) | TWI650359B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294151B (en) * | 2017-07-24 | 2021-03-09 | 奕益实业股份有限公司 | Modified polymeric materials and mixtures for preparing polymeric materials |
| TWI647273B (en) * | 2017-07-24 | 2019-01-11 | 奕益實業有限公司 | Modified polymeric material and mixture for preparing polymeric materials |
| CN109880347A (en) * | 2019-03-07 | 2019-06-14 | 禾聚实业有限公司 | Polyurethane materials |
| CN115368630B (en) * | 2021-05-17 | 2024-04-09 | 天津利安隆新材料股份有限公司 | Liquid antioxidant composition for raw rubber and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1220602B (en) * | 1960-08-04 | 1966-07-07 | Bergwerksgesellschaft Hibernia | Process for stabilizing polyolefins |
| CN101003643A (en) * | 2006-12-30 | 2007-07-25 | 中国科学院广州化学研究所 | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application |
| CN102432961A (en) * | 2011-11-16 | 2012-05-02 | 山东瑞丰高分子材料股份有限公司 | Composite heat stabilizer for polyvinyl chloride (PVC), and preparation method for composite heat stabilizer |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL265210A (en) * | 1960-05-27 | |||
| SU593451A1 (en) * | 1976-04-21 | 1999-12-27 | В.Н. Забористов | METHOD FOR STABILIZATION |
| ES2144264T3 (en) * | 1995-08-29 | 2000-06-01 | Exxon Chemical Patents Inc | RADIATION TOLERANT POLYPROPYLENE AND ITS USEFUL ITEMS. |
| JPH10101687A (en) * | 1996-08-07 | 1998-04-21 | Sumitomo Chem Co Ltd | Phosphite esters, their production and their use |
| JP3951367B2 (en) * | 1996-11-28 | 2007-08-01 | 住友化学株式会社 | Stabilizer for thermoplastic resin containing pentavalent phosphorus compound as active ingredient, its production method and its use |
| CN101440179B (en) * | 2003-03-28 | 2011-09-21 | 三井化学株式会社 | Polyolefin resin composition |
| US8124702B2 (en) * | 2006-11-24 | 2012-02-28 | Mitsubishi Rayon Co., Ltd. | Stabilizer for polyolefin resin and stabilized polyolefin resin composition |
-
2016
- 2016-08-16 CN CN201610674278.6A patent/CN106479041B/en active Active
- 2016-08-16 CN CN201610674076.1A patent/CN106479015A/en active Pending
- 2016-08-19 TW TW105126496A patent/TWI650359B/en active
- 2016-08-19 TW TW105126497A patent/TWI599604B/en active
-
2017
- 2017-08-14 RU RU2017128892A patent/RU2678593C1/en active
- 2017-08-14 ES ES17186089T patent/ES2836703T3/en active Active
- 2017-08-16 KR KR1020170103454A patent/KR102003595B1/en active IP Right Grant
- 2017-08-18 BR BR102017017764-5A patent/BR102017017764A2/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1220602B (en) * | 1960-08-04 | 1966-07-07 | Bergwerksgesellschaft Hibernia | Process for stabilizing polyolefins |
| CN101003643A (en) * | 2006-12-30 | 2007-07-25 | 中国科学院广州化学研究所 | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application |
| CN102432961A (en) * | 2011-11-16 | 2012-05-02 | 山东瑞丰高分子材料股份有限公司 | Composite heat stabilizer for polyvinyl chloride (PVC), and preparation method for composite heat stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106479041A (en) | 2017-03-08 |
| TWI599604B (en) | 2017-09-21 |
| KR102003595B1 (en) | 2019-07-24 |
| TWI650359B (en) | 2019-02-11 |
| RU2678593C1 (en) | 2019-01-30 |
| ES2836703T3 (en) | 2021-06-28 |
| TW201708347A (en) | 2017-03-01 |
| BR102017017764A2 (en) | 2019-04-16 |
| CN106479041B (en) | 2019-04-26 |
| TW201708357A (en) | 2017-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106479015A (en) | Modified polymeric materials and composite stabilizer compositions | |
| JP5649782B2 (en) | Polyurethane flame retardant composition | |
| CN105745278B (en) | Fire retardant resin composition and solar electrical energy generation module connection structural bodies | |
| US20040227130A1 (en) | Flame retardant and stabilizer combined for thermoplastics polymers | |
| JP5229061B2 (en) | Thermoplastic polymer composition | |
| SG184562A1 (en) | Thermoplastic polymer composition and stabiliser composition | |
| CN105658719A (en) | Composition | |
| TWI503326B (en) | Spiro bisphosphite based compound and uses of the same | |
| CN104066793B (en) | Polycarbonate resin composition and molded article thereof | |
| JP6619670B2 (en) | Resin filament for three-dimensional structure creation by extrusion lamination and its molded article | |
| KR20110078259A (en) | Novel phosphoanate based compound and flame retardant thermoplastic resin composition including the same | |
| KR20190132366A (en) | Efficient Phosphorus Stabilizer Based on Diphenylamine and Heterocyclic Diphenylamine Derivatives | |
| CN111051412A (en) | Composition, thermoplastic resin composition using the same, and molded article thereof | |
| CN106479040A (en) | Combined type tranquilizer constituent and modified polymeric material | |
| CN106133056A (en) | Flame-retardant polyester composition and goods | |
| TW201903134A (en) | Flame retardant composition and flame retardant resin composition containing same | |
| CN106317804B (en) | A kind of high grade of transparency bittern-free flame-proof material | |
| CN104812814B (en) | It is used to prepare the method based on polyacrylic article with increased surface energy | |
| EP3284779B1 (en) | Modified polymer composition and stabilizer mixture for making the same | |
| JP6676591B2 (en) | Modified polymer composition and stabilizer mixture for producing the same | |
| CN111087796B (en) | Phosphorus-containing copolymerized nylon and preparation method and application thereof | |
| TWI537321B (en) | Heat-resistant stabilizer and heat-resistant composition | |
| CN109294151B (en) | Modified polymeric materials and mixtures for preparing polymeric materials | |
| CN106479100A (en) | Heat-resisting stable material and heat-resisting constituent | |
| JP2001310972A (en) | Composition for discoloring inhibitor of organic polymer materials by nitrogen oxide gas and organic polymer materials containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170308 |