GB2215727A - Stabilisers for polymers - Google Patents
Stabilisers for polymers Download PDFInfo
- Publication number
- GB2215727A GB2215727A GB8903148A GB8903148A GB2215727A GB 2215727 A GB2215727 A GB 2215727A GB 8903148 A GB8903148 A GB 8903148A GB 8903148 A GB8903148 A GB 8903148A GB 2215727 A GB2215727 A GB 2215727A
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- United Kingdom
- Prior art keywords
- composition according
- butyl
- weight
- component
- composition
- Prior art date
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- Granted
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- 239000003381 stabilizer Substances 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 51
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 235000006708 antioxidants Nutrition 0.000 claims description 14
- 230000003019 stabilising effect Effects 0.000 claims description 13
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- -1 phosphite compound Chemical class 0.000 claims description 9
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 8
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 8
- 229930003427 Vitamin E Natural products 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011709 vitamin E Substances 0.000 claims description 6
- 235000019165 vitamin E Nutrition 0.000 claims description 6
- 229940046009 vitamin E Drugs 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 229940087168 alpha tocopherol Drugs 0.000 claims description 4
- 125000005001 aminoaryl group Chemical group 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229960000984 tocofersolan Drugs 0.000 claims description 4
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002076 α-tocopherol Substances 0.000 claims description 4
- 235000004835 α-tocopherol Nutrition 0.000 claims description 4
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 claims description 3
- MQQKTNDBASEZSD-UHFFFAOYSA-N 1-(octadecyldisulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCCCCC MQQKTNDBASEZSD-UHFFFAOYSA-N 0.000 claims description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- KXZXLEYRSHQNCR-UHFFFAOYSA-N methane 2-methylidenenonanethioic S-acid Chemical compound C.CCCCCCCC(=C)C(O)=S.CCCCCCCC(=C)C(O)=S.CCCCCCCC(=C)C(O)=S.CCCCCCCC(=C)C(O)=S KXZXLEYRSHQNCR-UHFFFAOYSA-N 0.000 claims description 2
- 229940080818 propionamide Drugs 0.000 claims description 2
- 230000000063 preceeding effect Effects 0.000 claims 3
- 241001122767 Theaceae Species 0.000 claims 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- URPFLJMILYVJPZ-UHFFFAOYSA-N benzene;2-hydroxybenzoic acid Chemical class C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O URPFLJMILYVJPZ-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical class OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KDBYJAXRGTUGSC-UHFFFAOYSA-N diphenoxyphosphane Chemical compound C=1C=CC=CC=1OPOC1=CC=CC=C1 KDBYJAXRGTUGSC-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Description
22 15727 Case 153-5237 IMPROVEM M S IN OR RELATING TO ORGANIC COMPOUNDS
The invention relates to a mixture of a phosphonite and a phosphite stabiliser for polymeric substrates.
According to the invention, there is provided a composition for use as a processing stabiliser (herein defined as a stabilising composition), comprising a) 30-80% by weight of a compound of formula I t.butyl HC-C HC-CH (t. bu tyl-C 0 C -0-) 2 P-C 0 C-R, (I) HC-CH HC-CH in which R, is hydrogen, methyl, unsubstituted phenyl or a group of formula a,) t.butyl HC-C (0), HC-CH (t.butyl-C 0 C-O-)2- P -C 0 C- (a,) HC-CH HC-CH 2 Case 153-5237 in which n is 0 or 1 or mixtures thereof; (herein defined to as component a); and b) 20-70% by weight of an organic phosphite compound ( herein defined as component b). and Usually component a) will be a mixture of a mono di-phosphonite.
Compounds of formula I and component b) are antioxidants. i Preferably a composition according to the invention contains one or more additional antioxidants (for example sterically hindered j phenolic antioxidants, aminoaryl antioxidants or sulphur containing antioxidants).
Preferred phosphites are those of formula II or III P(-O-R)3 (II) O-CH2 CH2-0 ROP c P-O-R (III) O-CH2 CH2-0 in which each R, independently, is a linear or branched Cl-22 alkyl or phenyl,unsubstituted or substituted by 1 to 3 linear or branched Cl-12alkyl groups (preferably methyl or t.butyl).
More preferred phosphites of a stabilising composition according 5 to the invention are selected from tris-(2,4-di t.butylphenyl) phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, bis 3 - Case 153-5237 (2,6-di-t.butyl-4- methylphenyl) pentaerythrityldiphosphite, bis (2,4-dit.butyl phenyl) pentaerythrityl-diphosphite and distearylpentaerythrityl diphosphite.
Preferred phenolic antioxidants are selected from octadecyl-3-(31,51ditert.butyl-41-hydroxyphenyl)-propionate, pentaerythrityl-tetrakis-3-(31, 51-ditert.butyl-41-hydroxyphenyl) -propionate, 1,3,5-tris-(31,51-ditbutyl-41-hydroxy-phenyl) -isocyanurate, 1,1,3,tris-(51-tert.butyl-41hydroxy-21-methylphenyl) -butane, 1,3,5-tris-(31,51-ditert.butyl-41hydroxybenzyl)-mesitylene and ethylene glycol-bis-(3,3-bis-(31-tert.butyl41-hydroxyphenyl) -butyrate).
Preferred aminoaryl antioxidants are selected from N,NI-dinaphthyl-pphenylene diamine and N,N1-hexamethylene bis-3-(3,5-ditert.butyl-4hydroxyphenyl)-propionamide.
Preferred sulphur containing antioxidants are selected from di-tridecyl-3, 3- thiodipropionate, di-lauryl-3,31-thiodipropionate, distearyl3,31 thiodipropionate, methane tetrakis- (methylene -3-hexyl thiopropionate) and dioctadecyl-disulphide.
A further preferred additive to a stabilising composition according to the invention is alpha tocopherol (Vitamin E).
Preferably, in a composition according to the invention, the amount of component a) present is from 70 to 40% by weight and the amount of component b) present is from 30 to 60%, by weight of the composition. More preferably in a composition according to the invention, the amount of component a) present is 40-60% by weight and the amount of component b is 60-40% by weight of the composition.
Preferably, if an antioxidant (or Vitamin E) is present, it is present in an amount of 50 to 200%, by weight of components a) and b) of a composition according to the invention.
4 - Case 153-5237 Further, according to the invention, there is provided a polymeric composition comprising a polymeric material and a stabilising amount of a stabilising composition according to the invention.
Preferably the total amount of components a) and b) present in such a polymeric composition is from 0.01 to 1 X; more preferably 0.05 to 0.3 % by weight based on the polymeric material.
It has been found that a combination of a) and b) in a stabilising composition according to the invention produces a 1 synergistic effect on the stability of a polymeric composition to which it is applied. Properties such as yellowing (as measured using the yellowness index) and the melt flow index (MFI) of such polymeric compositions are significantly improved over those in which only component a) or b) is present.
Preferred polymeric materials to be stabilised are polyolefins such as polypropylene, polyethylene (e.g. high density polyethylene, low density polyethylene, linear low density polyethylene or medium density polyethylene), polyisobutylene, poly-4-methylpentene and copolymers thereof (such as EVA-ethylene vinyl acetate).
Further polymeric materials that can be stabilised by a stabilising composition according to the invention include polystyrene and copolymers and blends thereof, ABS, polyvinyl acetate, polyvinylalcohol, polyacetate (POM), polyacrylate and polymethacrylate, polyacrylonitrile, polyacrylamide, PVC, polyvinylidene chloride, polyamide, polyester (for example polybutylene terephthalate and polyethylene terephthalate), polyether (e.g. polyphenylene oxide - PPO), polythioether and thioplast, polycarbonate, polyurethane, cellulose derivatives, maleinate resins, melamine resins, phenolic resins, aniline resins, furane resins, carbamide resins, epoxide resins and silicon resins.
Further additives that can be added to a stabilising or a Case 153-5237 polymeric composition according to the invention include flame retardants, antistatic agents, U.V. stabilisers such as hindered light amine stabilisers and U.V. absorbers (e.g. 2-(21-hydroxyphenyl) -benztriazoles, 2-hydroxybenzophenones, 1,3-bis-(21-hydroxybenzoyl-) benzene salicylates, cinnamates and oxalic acid diamides;), U-.V.quenchers such as benzoates and substituted benzoates, sterically hindered amines (for example Nunsubstituted, N-alkyl or N-acyl substituted 2,2,6,6-tetramethylpiperidine compounds), softeners, nucleating agents, metal deactivators, biocides, impact modifiers, fillers, pigments and fungicides.
Stabilising compositions according to the invention may be added to the polymeric material before, during or after the polymerization step and may be added in solid or molten form, in solution preferably as a liquid concentrate containing from 10 to 80 % by weight of the composition and 90 to 20 % by weight of solvent or as a solid masterbatch composition containing 10 to 80 % (more preferably 40 to 70 X) by weight of the composition and 90 to 20 % (more preferably 60 to 30 X) by weight of a solid polymeric material which is identical with or compatible with the material to be stabilized.
The compositions according to the invention may be incorporated by known methods into the polymeric material to be stabilized. Of particular importance is blending of the compounds with thermoplastic polymers in the melt, for example in a melt blender or during the formation of shaped articles, including foils, tubes, fibres and foams by extrusion, injection moulding, blow moulding, spinning or wire coating. The compositions according to the invention are particularly useful for polypropylene fibres or foils.
Further, in this specification, where a range is given, the figures defining the range are included therein. Any group capable of being linear or branched is linear or branched unless indicated to the contrary.
For the avoidance of doubt, in this specification t-butyl means
6 Case 153-5237 tertiary butyl.
The invention will now be illustrated by the following Examples in which all parts and percentages are by weight and all temperatures are in C unless indicated to the contrary.
i - I i I i 1 EXAMPLE 1
A solution is made up as follows:
1 g. of calcium stearate, 1 g. of pentaerythrityl-tetrakis-3-(31,51-di-t.butyl-41-hydroxy -phenyl)propionate, 0.4 g. of tetrakis-(2,4di-t.butyl-phenyl)-4,41biphenylene -diphosphonite, and 0.4 g. of tris (2,4-di-t.butyl-phenyl)-phosphite, and 0.2 g. of bis(2,4 di-t.butylphenyl) diphenyl phosphonite (=0,01-bis(2,4ditertiarybutyl)biphenylphosphonite) dissolved in 25 mls of acetone.
This solution is added to 1000 g of polypropylene powder and is mixed for 5 minutes at 400 revs per minute. The powder is dried for 30 minutes at 50'C in an oven and subsequently compounded in a G8ttfert extrusiometer having a 20 mm screw (compression 1:3, diameter to length [d:l] = 1:20) at 2701C. Multiple extrusions are carried out under the same conditions. The Melt Flow Index (MFI) is determined at 2301C/2.16kp and is used to characterise the stabilisation efficiency.
EXAMPLES 2 to 4 Example 1 is repeated using, instead of 0.4 g. of the tris (2,4-di-t. butyl- phenyl) phosphite, 0.2 g of the tris (2,4-di-t.butylphenyl) phosphite and 0.2 g. of one of the f ollowing:
Example 2: tris-(nonylphenyl)phosphite; Example 3: a 40:60 mixture of alpha tocopherol (Vitamin E) and tris- (nonylphenyl)-phosphite; and Example 4: a 20:40:40 mixture of alpha tocopherol (Vitamin E), ditridecyl3,31-thiodipropionate and tri-lauryl-phosphite.
Claims (16)
1. A composition for use as a processing stabiliser (herein defined as a stabilising composition), comprising a) 30-80X. by weight of a compound of formula I t.butyl HC-C HC-CH 1 \ (t.butyl-C 0 C-O-)2 P-C 0 C-R, (I) HC-CH HC-CH in which R, is hydrogen, methyl, unsubstituted phenyl or a group of formula a,) t.butyl HC-C (0),, HC-CH (t. butyl-C 0 CO-) 2 P -C 0 C- (a,) HC-CH HC-CH in which n is 0 or 1; (herein defined to as component a); and b) 20-70% by weight of a phosphite compound ( herein defined as component b).
2. A composition according to Claim 1 in which component b is selected from one or more compounds of formula II or III P(-O-R)3 O-CH2 CH2-0 R-0-P c P-O-R (III) O-CH2 CH2-0 in which each R, independently, is a linear or branched Cl-22 alkyl or phenyl,unsubstituted or substituted by 1 to 3 linear or branched Cl- 12alkyl groups.
3. A composition according to Claim 2 in which component b) is selected from tris-(2,4-di t.butylphenyl) phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, bis (2,6-di-t.butyl-4methylphenyl) pentaerythrityldiphosphite, bis (2,4-dit.butyl phenyl) pentaerythrityl-diphosphite and distearyl- pentaerythrityl diphosphite.
4. A composition according to any one of the preceding claims which contains one or more additional antioxidants.
5. A composition according to Claim 4 in which the additional antioxidants are selected from sterically hindered phenolic antioxidants, aminoaryl antioxidants or sulphur containing antioxidants.
6. A composition according to Claim 5 in which the phenolic antioxidants are selected from octadecyl-3-(31,51-ditert.- - 10 Case153-5237 butyl-41-hydroxyphenyl)propionate, pentaerythrityl-tetrakis-3(3f,51ditert.butyl41-hydroxyphenyl) -propionate, 1,3,5-tris(31,51-di-t-butyl-41hydroxy-phenyl) -isocyanurate, 1,1,3,tris(51-tert.butyl-41-hydroxy-21methylphenyl) -butane, 1,3,5-tris-(31,51-ditert.butyl41-hydroxybenzyl)mesitylene and ethylene glycol-bis-(3,3-bis-(31-tert.butyl-41hydroxyphenyl) -butyrate).
7. A composition according to Claim 5 in which the aminoaryl antioxidants are selected from N,NI-dinaphthyl-p- phenylene diamine and N,N1hexamethylene bis-3-(3,5-ditert.butyl-4- hydroxyphenyl)-propionamide.
8. A composition according to Claim 5 in which the sulphur containing antioxidants are selected from di-tridecyl-3,3- i:
thiodipropionate, di-lauryl-3,31-thiodipropionate, distearyl-3,31 thiodipropionate, methane tetrakis- (methylene -3-hexyl thiopropionate) and dioctadecyl-disulphide
9. A composition according to any one of the preceeding claims containing as a further additive alpha tocopherol (Vitamin E).
10. A composition according to any one of the preceeding claims in which the amount of component a) present is from 70 to 40% by weight and the amount of component b) present is from 30 to 60%, by weight of the composition.
11. A composition according to Claim 10 in which the amount of component a) present is 40-60% by weight and the amount of component b is 60-40% by weight of the composition.
12. A composition according to Claim 4 or any one of Claims 5 to 11 when appendant to Claim 4 in which the additional antioxidant (or Vitamin E) is present in an amount of 50 to 200%, by weight of components a) and b) of the composition.
Case 153-5237
13. A polymeric composition comprising a polymeric material and a stabilising amount of a stabilising composition according to any one of the preceeding claims.
14. A polymeric composition according to Claim 13 in which the amounts of components a) and b) present are from 0.01 to 1 % by weight based on the polymeric material.
15. A stabilising composition according to Claim 1 substantially as herein described with reference to the any one of Examples 1 to 4.
16. A polymeric composition according to Claim 4 substantially as herein described with reference to the any one of Examples 1 to 4.
1 C Publiabbd IW9atThe Patent Offtce,State House, 66171 High HoIbornLondoIXWC1R4TP. Purther copies maybe obtainedfrom TheP&tentO:Moe.
Sales Branch, St Mary Cray, Orpington, Kent BRB 3P.D. Printed by Multiplex techniques ltd, St Mary Cray, Kent, Con. 1187 --,a- zrancD, ut mary uway, urpmgron, jLent bliz 41W. k=tea DY MUMPlax techniques Itd, St Merv Cray, Kent, Con. 1187
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB888803439A GB8803439D0 (en) | 1988-02-15 | 1988-02-15 | Improvements in/relating to organic compounds |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8903148D0 GB8903148D0 (en) | 1989-03-30 |
| GB2215727A true GB2215727A (en) | 1989-09-27 |
| GB2215727B GB2215727B (en) | 1992-06-03 |
Family
ID=10631714
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB888803439A Pending GB8803439D0 (en) | 1988-02-15 | 1988-02-15 | Improvements in/relating to organic compounds |
| GB8903148A Expired GB2215727B (en) | 1988-02-15 | 1989-02-13 | Stabilizers for polymers |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB888803439A Pending GB8803439D0 (en) | 1988-02-15 | 1988-02-15 | Improvements in/relating to organic compounds |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH01254744A (en) |
| CH (1) | CH678331A5 (en) |
| DE (1) | DE3903218A1 (en) |
| FR (1) | FR2627185B1 (en) |
| GB (2) | GB8803439D0 (en) |
| HK (1) | HK70395A (en) |
| IT (1) | IT1230465B (en) |
| SG (1) | SG25295G (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2227490A (en) * | 1989-01-24 | 1990-08-01 | Sandoz Ltd | Polymer stabilisers |
| GB2247241A (en) * | 1990-08-22 | 1992-02-26 | Sandoz Ltd | Stabilising composition for filled polymeric materials |
| GB2261667A (en) * | 1991-11-20 | 1993-05-26 | Sandoz Ltd | Stabilized polymeric compositions |
| US5300257A (en) * | 1991-05-27 | 1994-04-05 | Yoshitomi Pharmaceutical Industries, Ltd. | 4,4'-biphenylenediphosphonite compound and use thereof |
| US5308549A (en) * | 1991-11-12 | 1994-05-03 | Hoffmann-La Roche Inc. | Stabilizers for thermo plastic materials |
| GB2263280B (en) * | 1992-01-17 | 1996-07-31 | Sandoz Ltd | Use of a phosphonite and optionally a phosphite for clarifying propylene polymers |
| US5703150A (en) * | 1994-12-28 | 1997-12-30 | Yoshitomi Pharmaceutical Industries, Ltd. | Phosphonite or phosphonate compounds and use thereof |
| EP0842985A1 (en) * | 1996-11-15 | 1998-05-20 | Basf Aktiengesellschaft | Thermooxidation resistant thermoplastic moulding masses |
| EP1024165A1 (en) * | 1997-10-02 | 2000-08-02 | Yoshitomi Fine Chemicals, Ltd. | Stabilizer composition for organic polymeric materials containing 6-hydroxychroman compounds and organic polymeric material compositions |
| US6465548B1 (en) | 1997-10-02 | 2002-10-15 | Yoshitomi Fine Chemicals, Ltd. | Stabilizer for organic polymer material and organic polymer material composition |
| WO2014074596A1 (en) | 2012-11-08 | 2014-05-15 | Equistar Chemicals, Lp | Stabilized high-density polyethylene composition with improved resistance to deterioration and stabilzer system |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2525319B2 (en) * | 1992-04-08 | 1996-08-21 | チッソ株式会社 | Crystalline polyolefin composition |
| US5468895A (en) * | 1994-10-19 | 1995-11-21 | General Electric Company | Amine stabilized amorphous phosphite |
| WO1997045483A1 (en) * | 1996-05-31 | 1997-12-04 | Kanebo, Limited | Polyester resin composition and film made therefrom, polyester composite film and metal laminate made by using the same, and process for decreasing the content of low-molecular compounds present in polyester |
| GB9613515D0 (en) * | 1996-06-27 | 1996-08-28 | Clariant Int Ltd | Stabilizer compositions |
| JP2000290503A (en) * | 1999-04-08 | 2000-10-17 | Tosoh Corp | Polyphenylene sulfied resin composition |
| JP2008222817A (en) * | 2007-03-12 | 2008-09-25 | Furukawa Electric Co Ltd:The | Resin composition and molded article using it |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427814A (en) * | 1980-03-10 | 1984-01-24 | Mitsubishi Gas Chemical Company, Inc. | Polyphenylene ether resin composition having improved heat stability |
| EP0151327A1 (en) * | 1984-01-06 | 1985-08-14 | SOLVAY & Cie (Société Anonyme) | Stabilized compositions based on alpha-olefin polymers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0005447B1 (en) * | 1978-04-20 | 1982-05-05 | Ciba-Geigy Ag | Ortho-alkylated phenylphosphonites, process for their preparation and stabilized compositions |
| DE3170981D1 (en) * | 1980-03-10 | 1985-07-25 | Mitsubishi Gas Chemical Co | Polyphenylene ether resin composition of improved heat stability and shaped articles thereof |
| JPS57158254A (en) * | 1981-03-24 | 1982-09-30 | Teijin Chem Ltd | Stabilized polycarbonate resin composition |
-
1988
- 1988-02-15 GB GB888803439A patent/GB8803439D0/en active Pending
-
1989
- 1989-02-03 DE DE3903218A patent/DE3903218A1/en not_active Withdrawn
- 1989-02-09 FR FR8901798A patent/FR2627185B1/en not_active Expired - Fee Related
- 1989-02-10 CH CH474/89A patent/CH678331A5/de not_active IP Right Cessation
- 1989-02-13 GB GB8903148A patent/GB2215727B/en not_active Expired
- 1989-02-14 IT IT8947641A patent/IT1230465B/en active
- 1989-02-14 JP JP1032904A patent/JPH01254744A/en active Pending
-
1995
- 1995-02-16 SG SG25295A patent/SG25295G/en unknown
- 1995-05-11 HK HK70395A patent/HK70395A/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427814A (en) * | 1980-03-10 | 1984-01-24 | Mitsubishi Gas Chemical Company, Inc. | Polyphenylene ether resin composition having improved heat stability |
| EP0151327A1 (en) * | 1984-01-06 | 1985-08-14 | SOLVAY & Cie (Société Anonyme) | Stabilized compositions based on alpha-olefin polymers |
| US4670493A (en) * | 1984-01-06 | 1987-06-02 | Solvay & Cie (Societe Anonyme) | Stabilized compositions based on alpha-olefin polymers |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2227490A (en) * | 1989-01-24 | 1990-08-01 | Sandoz Ltd | Polymer stabilisers |
| GB2227490B (en) * | 1989-01-24 | 1993-01-06 | Sandoz Ltd | New phosphonite compounds |
| GB2247241A (en) * | 1990-08-22 | 1992-02-26 | Sandoz Ltd | Stabilising composition for filled polymeric materials |
| US5300257A (en) * | 1991-05-27 | 1994-04-05 | Yoshitomi Pharmaceutical Industries, Ltd. | 4,4'-biphenylenediphosphonite compound and use thereof |
| US5308549A (en) * | 1991-11-12 | 1994-05-03 | Hoffmann-La Roche Inc. | Stabilizers for thermo plastic materials |
| GB2261667A (en) * | 1991-11-20 | 1993-05-26 | Sandoz Ltd | Stabilized polymeric compositions |
| GB2263280B (en) * | 1992-01-17 | 1996-07-31 | Sandoz Ltd | Use of a phosphonite and optionally a phosphite for clarifying propylene polymers |
| US5703150A (en) * | 1994-12-28 | 1997-12-30 | Yoshitomi Pharmaceutical Industries, Ltd. | Phosphonite or phosphonate compounds and use thereof |
| EP0842985A1 (en) * | 1996-11-15 | 1998-05-20 | Basf Aktiengesellschaft | Thermooxidation resistant thermoplastic moulding masses |
| US6479572B1 (en) | 1996-11-15 | 2002-11-12 | Basf Aktiengesellschaft | Thermoplastic molding materials stable to thermal oxidation |
| EP1024165A1 (en) * | 1997-10-02 | 2000-08-02 | Yoshitomi Fine Chemicals, Ltd. | Stabilizer composition for organic polymeric materials containing 6-hydroxychroman compounds and organic polymeric material compositions |
| EP1024165A4 (en) * | 1997-10-02 | 2001-01-24 | Yoshitomi Fine Chemicals Ltd | Stabilizer composition for organic polymeric materials containing 6-hydroxychroman compounds and organic polymeric material compositions |
| US6465548B1 (en) | 1997-10-02 | 2002-10-15 | Yoshitomi Fine Chemicals, Ltd. | Stabilizer for organic polymer material and organic polymer material composition |
| WO2014074596A1 (en) | 2012-11-08 | 2014-05-15 | Equistar Chemicals, Lp | Stabilized high-density polyethylene composition with improved resistance to deterioration and stabilzer system |
Also Published As
| Publication number | Publication date |
|---|---|
| SG25295G (en) | 1995-06-16 |
| GB8903148D0 (en) | 1989-03-30 |
| FR2627185A1 (en) | 1989-08-18 |
| FR2627185B1 (en) | 1993-05-14 |
| JPH01254744A (en) | 1989-10-11 |
| DE3903218A1 (en) | 1989-08-24 |
| GB8803439D0 (en) | 1988-03-16 |
| IT8947641A0 (en) | 1989-02-14 |
| IT1230465B (en) | 1991-10-23 |
| HK70395A (en) | 1995-05-19 |
| CH678331A5 (en) | 1991-08-30 |
| GB2215727B (en) | 1992-06-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970213 |