GB2584307A - Antidegradant blend - Google Patents
Antidegradant blend Download PDFInfo
- Publication number
- GB2584307A GB2584307A GB1907631.4A GB201907631A GB2584307A GB 2584307 A GB2584307 A GB 2584307A GB 201907631 A GB201907631 A GB 201907631A GB 2584307 A GB2584307 A GB 2584307A
- Authority
- GB
- United Kingdom
- Prior art keywords
- antidegradant blend
- antidegradant
- antioxidant
- blend according
- amount
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 244
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 91
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 84
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005864 Sulphur Substances 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 230000001458 anti-acid effect Effects 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 16
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical group ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 6
- 239000008116 calcium stearate Substances 0.000 claims abstract description 6
- 239000002243 precursor Chemical group 0.000 claims abstract description 4
- 150000007970 thio esters Chemical group 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 58
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- ITUWQZXQRZLLCR-UHFFFAOYSA-N n,n-dioctadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCCCC ITUWQZXQRZLLCR-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 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 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 5
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001204 N-oxides Chemical class 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 150000002443 hydroxylamines Chemical class 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- GXELTROTKVKZBQ-UHFFFAOYSA-N n,n-dibenzylhydroxylamine Chemical compound C=1C=CC=CC=1CN(O)CC1=CC=CC=C1 GXELTROTKVKZBQ-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 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
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000010499 rapseed oil Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 239000000806 elastomer 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 group [H]* 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- DDLNUIWJEDITCB-UHFFFAOYSA-N n,n-di(tetradecyl)hydroxylamine Chemical compound CCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCC DDLNUIWJEDITCB-UHFFFAOYSA-N 0.000 claims description 2
- DHXOCDLHWYUUAG-UHFFFAOYSA-N n,n-didodecylhydroxylamine Chemical compound CCCCCCCCCCCCN(O)CCCCCCCCCCCC DHXOCDLHWYUUAG-UHFFFAOYSA-N 0.000 claims description 2
- OTXXCIYKATWWQI-UHFFFAOYSA-N n,n-dihexadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCC OTXXCIYKATWWQI-UHFFFAOYSA-N 0.000 claims description 2
- WQAJFRSBFZAUPB-UHFFFAOYSA-N n,n-dioctylhydroxylamine Chemical compound CCCCCCCCN(O)CCCCCCCC WQAJFRSBFZAUPB-UHFFFAOYSA-N 0.000 claims description 2
- ZRPOKHXBOZQSOX-UHFFFAOYSA-N n-heptadecyl-n-octadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCCC ZRPOKHXBOZQSOX-UHFFFAOYSA-N 0.000 claims description 2
- WGCBLWIBXXQTAW-UHFFFAOYSA-N n-hexadecyl-n-octadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCC WGCBLWIBXXQTAW-UHFFFAOYSA-N 0.000 claims description 2
- GZNRISJLOXVOSH-UHFFFAOYSA-N n-phenylaniline;propan-2-one Chemical compound CC(C)=O.C=1C=CC=CC=1NC1=CC=CC=C1 GZNRISJLOXVOSH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims 1
- 125000005264 aryl amine group Chemical group 0.000 claims 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims 1
- -1 sodium hypophosphite Chemical compound 0.000 abstract description 17
- 150000004982 aromatic amines Chemical group 0.000 abstract description 3
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 description 66
- 239000002585 base Substances 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 230000003019 stabilising effect Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000002035 prolonged effect Effects 0.000 description 5
- 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 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010094 polymer processing Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ORWQBKPSGDRPPA-UHFFFAOYSA-N 3-[2-[ethyl(methyl)amino]ethyl]-1h-indol-4-ol Chemical compound C1=CC(O)=C2C(CCN(C)CC)=CNC2=C1 ORWQBKPSGDRPPA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 2
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 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 description 2
- YYGNSEHPYQFDLN-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid;ethenylsulfanylethene Chemical compound C=CSC=C.CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O YYGNSEHPYQFDLN-UHFFFAOYSA-N 0.000 description 2
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 2
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000004283 Sodium sorbate Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- 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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/012—Additives improving oxygen scavenging properties
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
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- 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
An antidegradant blend comprises (i) an aminic component, (ii) an inorganic antioxidant/reducing agent, and (iii) a phenolic antioxidant, organic phosphite antioxidant, sulphur-containing antioxidant, and/or anti-acid. The aminic component may be a secondary arylamine or a hydroxylamine or precursor/derivative thereof, such as an amine oxide, which may be present in an amount of 0.1-20 wt.%. The inorganic antioxidant/reducing agent is preferably a metal hypophosphite, such as sodium hypophosphite, which may be present in an amount of 0.1-40 wt.%. The blend may further comprise 1-60 wt.% phenolic antioxidant, 10-90 wt.% organic phosphite antioxidant, 10-90 wt.% sulphur-containing antioxidant having a thioether or thioester group, and/or 1-60 wt.% anti-acid, such as calcium stearate. The use of the blend to stabilise a polymer, such as a polyolefin, is disclosed. A polymer composition containing a polymer with the antidegradant blend is also claimed. The blend may be present in an amount of 0.01-5 wt.% of the composition.
Description
ANTIDEGRADANT BLEND
The present invention relates to antidegradant blends. More specifically, but not exclusively, the present invention relates to antidegradant blends for stabilising polymers, for example polyolefins.
Polymers are used in a wide variety of applications. For many polymer applications, it is desirable for the polymer to retain certain properties during storage, handling and subsequent application. More specifically, it may be desirable for the polymer to retain its melt flow properties (as measured by melt flow rate or MFR), viscosity and have good colour stability, even during prolonged or repeated exposure to heat.
To aid retention of polymer properties such as melt flow, viscosity and colour stability, it is known to add different types of additives to the polymer, for example phenolic antioxidants, organic phosphite antioxidants, acid scavengers, or combinations thereof.
The control of colour is a considerable problem in polymer processing, and especially in polyolefins. Customers desire polymer items, such as food containers, to be white because alternative colouring may insinuate a lack of quality and cleanliness, or an undesirable age of the product. Colour has always been one of the most difficult polymer properties to control at a reasonable cost.
EP0538509 describes an antioxidant resin composition containing a resin, a solution of a hypophosphite compound in an organic solvent, a heat stabilizer and a hindered amine base weathering stabilizer, which has improved heat stability and weather resistance.
CN102503821A describes the use of sodium hypophosphite as an antioxidant in a polymerization process.
US3691131 describes heat stabilized synthetic polyamide compositions prepared by incorporating therein a mixture of a phenolic antioxidant and metal hypophosphite, a copper compound and metal halide. A typical embodiment includes polyamides which are stabilized with 1,2-bis[3,5-di-t-butyl-4-hydroxyphenyI)-propionamido]ethane and sodium hypophosphite, copper acetate and potassium iodide.
W02014152237 describes a polycarbonate composition comprising metallic salts of s phosphoric acid, at least one of which is a potassium salt of phosphoric acid.
W02018202791 describes a stabilising composition comprising: at least one antioxidant comprising one or more of: a phenolic antioxidant; a phosphite antioxidant; a sulphur-containing antioxidant; and an aminic antioxidant; at least one buffering to agent; and a secondary inorganic antioxidant, wherein the buffering agent has the capacity to buffer in aqueous solution at a pH range from 4 to 8. The buffering agent typically comprises one or more metal phosphates and/or metal pyrophosphates. The secondary inorganic antioxidant is said to comprise one or more of a metal hypophosphite, a metal thiosulphate, a metal bisulphite, a metal metabisulphite and/or a metal hydrosulphite. It was found that a stabilising composition with a hydrated metal hypophosphite, for example a monohydrate metal hypophosphite, performs comparably to, and in some instances better than, a stabilising composition with the anhydrous form of the metal hypophosphite at the same phosphorous loading.
GB2567456 describes an antidegradant blend, comprising: a metal carboxylate; an inorganic phosphite; and a phenolic antioxidant. This document describes that the presence of a metal carboxylate and an inorganic phosphite in the antidegradant blend produces a synergistic effect with respect to the colour stability of a variety of polymers. More specifically, it was found that the combination of a metal carboxylate and an inorganic phosphite in the antidegradant blend causes a significant reduction in colour formation. The synergistic effect was said to be particularly apparent where the metal carboxylate is a metal stearate and the inorganic phosphite is a metal hypophosphite.
Unpublished patent application PCTEP2019060914 describes an antidegradant blend, comprising an antioxidant selected from one or more of a phenolic antioxidant; an organic phosphite antioxidant; and an inorganic antioxidant or reducing agent, wherein the blend is absent any metal carboxylate or buffering agent having the capacity to buffer in aqueous solution at a pH range from 4 to 8.
There remains a need for an improved additive blend which provides better performance than has hitherto been realised in connection with polymer properties such as discolouration.
s According to an aspect of the present invention, there is provided an antidegradant blend, comprising: a. an aminic component; b. an inorganic antioxidant or reducing agent; and c. one or more of: i. a phenolic antioxidant; ii. an organic phosphite antioxidant; iii. a sulphur-containing antioxidant; and iv. an anti-acid.
Advantageously, the blend may be absent any buffering agent having the capacity to buffer in aqueous solution at a pH range from 4 to 8.
Also provided in accordance with the invention is an antidegradant blend according to the above which, when added to a polymeric base material, causes the yellowness index (YI) of the polymeric base material (measured by ASTM D1925) to rise less over five passes through an extruder at 260 °C in air, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
For example, the antidegradant blend of the invention, when added to a polymeric base material, may cause the yellowness index of the polymeric base material (measured by ASTM D1925) to rise by at least 20% less, over five passes through an extruder at 260 °C in air, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
The antidegradant blend which, when added to a polymeric base material, may cause the yellowness index of the polymeric base material (measured by ASTM D1925) to rise by less than 2.3, less than 2, less than 1.8, less than 1.5, or less than 1, over five passes through an extruder at 260 °C in air.
The antidegradant blend may comprise either or both of a phenolic antioxidant and an s organic phosphite antioxidant.
It is well known that the use of phenolic or organic phosphite antioxidant additives and especially additive blends corn prising organic phosphite antioxidants in combination with phenolic antioxidants, gives improved heat aging performance in polymers such as polypropylene. However, it has now been surprisingly found that the addition of an aminic component and an inorganic antioxidant or reducing agent to such a blend produces an improvement in the colour protection in multipass thermal aging experiments.
It has been found that the use of such combinations of antidegradant blends is particularly beneficial in polymers and leads to improvements in the processing and long-term heat aging performance of the polymers.
Without wishing to be bound by theory, it is believed that the aminic component of the antidegradant blend is oxidised. For example, where the aminic component is a hydroxylamine, this may be successively oxidised to a nitrone. Subsequently, the inorganic antioxidant or reducing agent is able to reduce the oxidised component back to the original aminic component. This process effectively regenerates the relatively expensive aminic component, and thus permits the use of a low ppm amount of said aminic component, for example less than about 45 ppm, less than about 35 ppm, or less than about 30 ppm in the polymeric composition.
The inventors of the present invention have surprisingly found that the combination of stabilising components in the antidegradant blend significantly improves the colour retention of a wide range of polymers (as measured by yellowness index), especially polyolefins, even during prolonged or repeated exposure to heat and/or shear. Many polymer processing operations are high shear due to the high viscosity of the polymer, for example extrusion is a high shear environment.
Without wishing to be bound by theory, it is believed that the addition of the inventive antidegradant blend to a polymer leads to significantly less derived colour in the polymer (as measured by the multipass thermal aging experiments) compared to stabilising blends of the art.
This antidegradant blend represents an unexpected and previously unachievable level of colour control for a compounded polymeric material and may completely remove the problem of colour formation from polymer processing.
In addition, it has been found that the polymer to which the antidegradant blend is added retains its melt flow properties, even during prolonged or repeated exposure to heat and/or shear.
The improved colour stability and retention of melt flow properties during prolonged or repeated exposure to heat and/or shear is advantageous since polymers are often kept in a molten state for prolonged periods of time during production and prior to use in an application, and shear forces may be present at any point during polymer processing operations.
By 'prolonged heat exposure' it is meant exposure to a temperature of at least about °C, at least about 110 °C, at least about 120 °C, at least about 130 °C, at least about 140 °C, at least about 150 °C, at least about 160 °C, at least about 170 °C, at least about 180 °C, at least about 190 °C, at least about 200 °C, at least about 210 °C, at least about 220 °C, at least about 230 °C, at least about 240 °C or at least about 250 °C, for at least about 1 hour, at least about 2 hours, at least about 4 hours, at least about 6 hours, at least about 12 hours, at least about 24 hours, at least about 36 hours, at least about 48 hours, at least about 3 days, at least about 4 days, at least about 5 days, at least about 6 days, at least about 7 days, at least about 10 days or at least about 14 days.
By 'repeated heat exposure' it is meant exposure to a temperature of at least about 100 °C, at least about 150 °C, at least about 200 °C, at least about 250 °C, or at least about 300 °C, on more than one occasion, for at least about 5 seconds, at least about 10 seconds, at least about 20 seconds, at least about 30 seconds, at least about 1 minute, at least about 5 minutes, or at least about 10 minutes. Repeated heat exposure may be experienced during multiple passes through an extruder. For example, a polymeric composition may be subjected to repeated cycles of exposure to high temperature and high shear forces followed by cooling to ambient conditions. The combination of high shear and heat is a potent force for causing polymer degradation, and the antidegradant blend of the invention is intended to mitigate those effects.
The antidegradant blend may be absent any buffering agent having the capacity to buffer in aqueous solution at a pH range from 4 to 8. In particular, the blend may be Zo absent any metal phosphates and/or metal pyrophosphates as disclosed in W02018202791.
By 'absent' it is meant that the amount of the material in the antidegradant blend is less than about 1% w/w, less than about 0.5% w/w, less than about 0.2% w/w, or completely absent, i.e. 0% w/w.
It is believed that the inorganic antioxidant or reducing agent has a dual function in that it behaves as an antacid and as an inorganic antioxidant or reducing agent.
The inorganic antioxidant or reducing agent may comprise one or more of a metal phosphite, a metal hypophosphite, a metal thiosulphate, a metal bisulphite, a metal metabisulphite and/or a metal hydrosulphite. Mixtures of any two or more thereof may also be used.
The metal of the phosphite, hypophosphite, thiosulphate, bisulphite, metabisulphite and/or hydrosulphite may be an alkali metal and/or an alkaline earth metal. The alkali metal may be selected from lithium (Li), sodium (Na), and potassium (K). The alkaline earth metal may be selected from calcium (Ca) and magnesium (Mg).
The metal phosphite may be selected from compounds with the formula M2HPO3. The metal hypophosphite may be selected from compounds with the formula: MPO2H2. The metal thiosulphate may be selected from compounds with the formula: M2S203. The metal bisulphite may be selected from compounds with the formula: MHSO3. The metal metabisulphite may be selected from compounds with the formula: M2S205. The metal hydrosulphite may be selected from compounds with the formula: M2S204. In each case, M is an alkali metal cation. The alkali metal cation may be selected from lithium (Li), sodium (Na), and potassium (K).
s The inorganic antioxidant or reducing agent may comprise a metal hypophosphite. The metal hypophosphite may comprise sodium hypophosphite.
The metal hypophosphite may be anhydrous. The metal hypophosphite may be hydrated, for example a monohydrate or poly-hydrated metal hypophosphite.
The metal hypophosphite may be provided in mono-hydrated form.
The inorganic antioxidant or reducing agent may be present in an amount of from about 0.1% to about 40%, from about 1% to about 30%, from about 5% to about 25%, 15 from about 10% to about 20%, or from about 14% to about 18%, by weight of the antidegradant blend.
The inorganic antioxidant or reducing agent may be a solid at ambient conditions.
In this context, by 'ambient conditions' it is meant a temperature of about 50 °C or lower, a temperature of about 40 °C or lower, a temperature of about 30 °C or lower, or a temperature of about 25 °C or lower, and about 1 atmosphere pressure i.e. 101.325 kPa.
The inorganic antioxidant or reducing agent may be a solid at a temperature of about 25 °C and about 1 atmosphere pressure i.e. 101.325 kPa.
The inventors of the present invention have surprisingly found that a solid inorganic antioxidant or reducing agent can be used in the antidegradant blend. Inorganic antioxidants or reducing agents of the prior art have often been used as solutions.
Providing the inorganic antioxidant or reducing agent as a solid provides handling benefits during processing as the solid inorganic antioxidant or reducing agent can be more easily compounded into the polymer.
The aminic component may comprise a single compound or a blend of two or more compounds.
The aminic component may be a secondary amine. The aminic component may be an s arylamine. The aminic component may be a secondary arylamine.
The aminic component may have the general formula R-NH-R wherein each R independently denotes a hydrogen, hydrocarbyl or aromatic group, the or each hydrocarbyl and/or aromatic group having at least 1 carbon atom and may or may not The aminic component may comprise at least one aromatic group. The aminic component may comprise at least two aromatic groups.
Unless otherwise indicated herein all compounds designated by tradenames and/or CAS numbers are available from SI Group USA (USAA), LLC, 4 Mountainview Terrace, Suite 200, Danbury, CT 06810.
The aminic component may comprise, for example, 4,4'-bis(a,a-dimethylbenzyl) diphenylamine (NAUGARDTM 445 -CAS 10081-67-1); mixed butylated, octylated diphenylamine (NAUGARDTM PS30 -CAS 68411-46-1); octylated diphenylamine (OCTAMINETm -CAS 101-67-7); nonylated diphenylamine; styrenated diphenylamine (NAUGARDTM 635 -CAS 68442-68-2); diphenylamine (CAS 122-39-4); polymerised 1,2-dihydro-2,2,4-trimethylquinoline (NAUGARDTM Q -CAS 26780-96-1); N,N-bis- (1,4-dimethylpentyI)-p-phenylenediamine (FLEXZONETM 4L -CAS 3081-14-9); acetone diphenylamine (AMINOXTM -CAS 68412-48-6); reaction products of diphenylamine and acetone (BLETM -CAS 112-39-4); 1,4-benzenediamine, N,N'-mixed phenyl and tolyl derivatives (NOVAZONETM AS -CAS 68953-84-4);N-(1,3-dimethylbuty1)-N'-phenyl-p-phenylenediamine (6PPD -CAS 793-24-8); 1,4-Benzenediamine N,N'-mixed phenyl and tolyl derivatives (NOVAZONETM AS); N,N'-diphenyl-p-phenylendiamine (DPPD -CAS 74-31-7); N-isopropyl-N'-pheny1-1,4-phenylenediamine (IPPD -CAS 101-72-4); 2,4,6-tris-(N-1,4-dimethylpentyl-pphenylenediamino)-1,3,5-triazine (DURAZONETTM 37 -CAS 121246-28-4); and/or compatible mixtures of two or more thereof.
The aminic component may comprise 4,4'-bis(a,a-dimethylbenzyl) diphenylamine (NAUGARDTM 445 -CAS 10081-67-1).
s The aminic component may comprise hydroxylamine. The aminic component may comprise one or more hydroxylamine derivatives.
The aminic component may comprise one or more hydroxylamines of general formula RxRyNOH wherein each R independently denotes an optionally branched hydrocarbyl group having from 1 to 25 carbon atoms.
The aminic component may comprise, for example, N,N-dibenzylhydroxylamine; N,Ndiethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N- ditetradecylhydroxylam ine; N, N-dihexadecylhydroxylam ine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine, bis(octadecyl)hydroxylamine; and/or compatible mixtures of two or more thereof.
The aminic component may comprise a precursor such as an amine oxide which, when heated, gives a hydroxylamine. The amine oxide may comprise general formula 20 RxRyR,NO wherein each R independently denotes an optionally branched hydrocarbyl group having from 1 to 25 carbon atoms.
The aminic component may therefore comprise one or more hydroxylamines and/or one or more amine oxides.
The aminic component may comprise bis(octadecyl)hydroxylamine (IRGASTABTm FS042 -CAS 143925-92-2, available from BASF) and/or amines, bis(hydrogenated rape-oil alkyl)methyl, N-oxides (GENOXTM EP -CAS 204933-93-7).
The aminic component may be a solid at ambient conditions (as previously defined). The aminic component may be a solid at a temperature of about 25 °C and about 1 atmosphere pressure i.e. 101.325 kPa.
The aminic component may be present in an amount of from about 0.1% to about 30%, from about 0.1% to about 20%, from about 0.5% to about 15%, from about 1% to about 10%, or from about 2% to about 4%, by weight of the antidegradant blend.
The ratio of inorganic antioxidant or reducing agent to aminic component may be from about 1:15 to about 15:1, from about 1:3 to about 14:1, from about 1:1 to about 13:1, from about 2:1 to about 12:1, or from about 5:1 to about 12:1.
The antidegradant blend may comprise a phenolic antioxidant. The phenolic Zo antioxidant may comprise a single phenolic antioxidant or a blend of two or more phenolic antioxidants.
The phenolic antioxidant may comprise a partially hindered phenolic antioxidant and/or a hindered phenolic antioxidant. In this context, by 'partially hindered' it is preferably meant that the phenolic antioxidant comprises at least one substituent hydrocarbyl group ortho to the phenolic -OH group, where either none or only one of the or each substituent group is branched at the Ci and/or C2 position, preferably at the Ci position, with respect to the aromatic ring. In this context, by 'hindered' it is preferably meant that the phenolic antioxidant comprises substituent hydrocarbyl groups on both positions ortho to the phenolic -OH group, each of those substituent groups being branched at the Ci and/or C2 position, preferably at the Ci position, with respect to the aromatic ring.
The phenolic antioxidant may comprise, for example, 2-(1,1-dimethylethyl)-4,6-dimethyl-phenol (LOWINOXTM 624 -CAS 1879-09-0); 6-tert-butyl-2-methylphenol (CAS 2219-82-1); 4,6-di-tert-butyl-2-methylphenol; 2-tert-butyl 4 methylphenol; 2-tert-butyl-5-methylphenol; 2,4-di-tert-butylphenol; 2,4-di-tert-pentylphenol; triethyleneglycol-bis-[3-(3-t-butyl-4-hydroxy-5-methylphenyppropionate] (LOWINOXTM GP45 -CAS 36443-68-2); 1,3,5-tris(4-t-buty1-3-hydroxyl-2,6- dimethylbenzyI)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione (LOWINOXTM 1790); 2,2'- ethylidenebis[4,6-di-t-butylphenol] (ANOXTM 29 -CAS 35958-30-6); 2,2'methylenebis(6-t-butyl 4 methylphenol) (LOWINOXTM 22M46 -CAS 119-47-1); the butylated reaction product of p-cresol and dicyclopentadiene (LOWINOXTM CPL CAS 68610-51-5); 2,6-xylenol; C13-C15 linear and branched alkyl esters of 3-(3'S'-di-t-butyl-4'-hydroxyphenyl) propionic acid (ANOXTM 1315 -CAS 171090-93-0); octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionate (ANOXTM PP18 -CAS 208279-3); N,N'-hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide] (LOWINOXTM HD98 -CAS 23128-74-7); C9-C11 linear and branched alkyl esters of 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionic acid (NAUGARDTM PS48 -CAS 12564361-0); butylated hydroxytoluene (BHT -CAS 128-37-0, available from Sigma-Aldrich); 2,6-di-tertiary-butyl-4-sec-butylphenol (ISONOXTM 132, available from SI Group Inc. of 2750 Balltown Road, Schenectady, NY 12301, US); 2,6-di-tertiary-buty1-4-nonylphenol (ISONOXTM 232, available from SI Group Inc. of 2750 Balltown Road, Schenectady, NY 12301, US); tetrakismethylene(3,5-di-t-buty1-4- hydroxyhydrocinnamate) methane (ANOXTM 20 -CAS 6683-19-8); 1,3,5-tris(3,5-di-tbuty1-4-hydroxybenzyl) isocyanurate (ANOXTM IC14 -CAS 27676-62-6); 1,2-bis(3,5-di-t-butyl 4 hydroxyhydrocinnamoyl)hydrazine (LOWINOXTM MD24 -CAS 32687-788); 2,2'thiodiethylene bis[3(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (ANOXTM 70 -CAS 41484-35-9); 1,3,5-trimethy1-2,4,6-tris(3,5-di-t-buty1-4-hydroxybenzyl)benzene (ANOXTM 330 -CAS 1709-70-2); butylated hydroxyanisole (BHA -CAS 25013-16-5, available from Sigma-Aldrich); DL a-tocopherol (CAS 10191-41-0, available from 15 Sigma-Aldrich or from BASF as IRGANOXTM E201); and/or compatible mixtures of two or more thereof.
The phenolic antioxidant may comprise tetrakismethylene (3,5-di-t-buty1-4-hydroxyhydrocinnamate) methane (ANOXTM 20 -CAS 6683-19-8).
The phenolic antioxidant may comprise a food additive, for example butylated hydroxytoluene (BHT -CAS 128-37-0, available from Sigma-Aldrich); butylated hydroxyanisole (BHA -CAS 25013-16-5, available from Sigma-Aldrich); tocopherol, tocopherol derivatives, tocotrienol and tocotrienol derivatives (Vitamin E e.g. DL atocopherol -CAS 10191-41-0, available from Sigma-Aldrich or from BASF as IRGANOXTM E201); and/or compatible mixtures of two or more thereof.
The phenolic antioxidant may be a solid at ambient conditions (as previously defined). The phenolic antioxidant may be a solid at a temperature of about 25 °C and about 1 atmosphere pressure i.e. 101.325 kPa.
The phenolic antioxidant may be present in an amount of from about 1% to about 60%, from about 5% to about 55%, from about 10% to about 50%, from about 20% to about 45%, or from about 25% to about 35%, by weight of the antidegradant blend.
The antidegradant blend may comprise an organic phosphite antioxidant. The organic phosphite antioxidant may comprise a single organic phosphite antioxidant or a blend of two or more organic phosphite antioxidants.
The organic phosphite antioxidant may comprise, for example, bis(2,4,di-tbutylphenyl)pentaerythritol diphosphite (ULTRANOXTM 626 -CAS 26741-53-7); 2,4,6-tri-tert-butylpheny1-2-buty1-2-ethyl-1,3-propanediol phosphite (ULTRANOXTm 641 CAS 161717-32-4); tris(2,4-di-t-butylphenyl)phosphite (ALKANOXTM 240 -CAS 31570 04 4); tetrakis (2,4-di-t-butylpheny1)4,4'-biphenylene diphosphonite (ALKANOXTM 24-44 -CAS 38613-77-3); tris(4-n-nonylphenyl)phosphite (WESTONTM TNPP -CAS 26523-78-4); distearylpentaerythritol diphosphite (WESTONTM 618 -CAS 3806-34-6); bis(2,4-dicumylphenyl) pentaerythritol diphosphite (DOVERPHOSTM 9228 -CAS 154862-43-8, available from Dover Chemical Corporation); WESTONTM 705 CAS 939402-02-5; tris(dipropyleneglycol) phosphite, Ci6H3909P (WESTONTM 430 CAS 36788-39-3); poly(dipropylene glycol) phenyl phosphite (WESTONTM DHOP -CAS 80584-86-7); diphenyl isodecyl phosphite, C22H3103P (WESTONTM DPDP -CAS 26544-23-0); phenyl diisodecyl phosphite (WESTONTM PDDP -CAS 25550-98-5); heptakis (dipropyleneglycol) triphosphite (WESTONTM PTP -CAS 13474-96-9); bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP 36 -CAS 8069300-1, available from Adeka Polymer Additives); tris(2-t-butylphenyl)phosphite (CAS 31502-36-0); and/or compatible mixtures of two or more thereof.
The organic phosphite antioxidant may comprise tris(2,4-di-t-butylphenyl)phosphite (ALKANOXTM 240 -CAS 31570-04-4).
The organic phosphite antioxidant may be a solid at ambient conditions (as previously defined). The organic phosphite antioxidant may be a solid at a temperature of about 25 °C and about 1 atmosphere pressure i.e. 101.325 kPa.
The organic phosphite antioxidant may be present in an amount of from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, from about 40% to about 65%, or from about 50% to about 60%, by weight of the antidegradant blend.
The antidegradant blend may comprise a sulphur-containing antioxidant. The sulphur-containing antioxidant may comprise a single sulphur-containing antioxidant or a blend of two or more sulphur-containing antioxidants.
The sulphur-containing antioxidant may comprise one or more thioether groups. The sulphur-containing antioxidant may comprise one or more thioester groups. The sulphur-containing antioxidant may be a sulphur-containing phenolic antioxidant.
The sulphur-containing antioxidant may be a solid at ambient conditions (as previously defined). The sulphur-containing antioxidant may be a solid at a temperature of about °C and about 1 atmosphere pressure i.e. 101.325 kPa.
The sulphur-containing antioxidant may comprise, for example, 4,6-bis(octylthiomethyl)-o-cresol (LOWINOXT" 520 -CAS 110553-27-0); zo 2,2'thiodiethylene bis[3(3,5-di-t-butyl 4 hydroxyphenyl)propionate] (ANOXTm70 -CAS 41484-35-9); dilauryl thiodipropionate (NAUGARDThl DLTDP -CAS 123-28-4); distearyl thiodipropionate (NAUGARDThl DSTSP -CAS 693-36-7); ditridecylthiodipropionate (NAUGARDThl DTDTDP -CAS 10595-72-9); pentaerythritol tetrakis ((3-laurylthiopropionate) (NAIJGARDTM 412S -CAS 29598-76-3); 2,4-bis(dodecylthiomethyl)-6-methylphenol (IRGANOXT" 1726 -CAS 110675-26-8, available from BASF); and/or compatible mixtures of two or more thereof.
The sulphur-containing antioxidant may comprise pentaerythritol tetrakis 03-laurylthiopropionate) (NAUGARDT" 412S -CAS 29598-76-3).
The sulphur-containing antioxidant may be present in an amount of from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, from about 40% to about 60%, or from about 45% to about 55%, by weight of the antidegradant blend.
The antidegradant blend may comprise an anti-acid. The anti-acid may comprise stearates, for example of lithium, sodium, calcium, zinc, magnesium or aluminium; oxides, such as zinc oxide or magnesium oxide or titanium dioxide; artificial or natural carbonates, such as calcium carbonate or hydrotalcite. The anti-acid may comprise calcium stearate.
The anti-acid may be present in an amount of from about 1% to about 60%, from about 2% to about 50%, from about 3% to about 40%, from about 6% to about 30%, or from to about 8% to about 25%, by weight of the antidegradant blend.
The antidegradant blend may be a solid at ambient conditions (as previously defined). The antidegradant blend may be a solid at a temperature of about 25 °C and about 1 atmosphere pressure i.e. 101.325 kPa.
The antidegradant blend may be provided as a powder blend, in granular form, or in the form of non-dust blend granules, for example.
According to an aspect of the present invention, there is provided an antidegradant blend comprising: a. an aminic component; b. an inorganic phosphite antioxidant; c. a phenolic antioxidant; and d. an organic phosphite antioxidant.
According to an aspect of the present invention, there is provided an antidegradant blend comprising: a. an aminic component; b. an inorganic phosphite antioxidant; c. a phenolic antioxidant; d. a sulphur-containing antioxidant; and e. an anti-acid.
According to an aspect of the present invention, there is provided an antidegradant blend comprising: a. an aminic component; b. an inorganic phosphite antioxidant; and c. an anti-acid.
According to an aspect of the present invention, there is provided an antidegradant blend comprising: a. bis(octadecyl)hydroxylamine (CAS 143925-92-2) and/or amines, bis(hydrogenated rape-oil alkyl)methyl, N-oxides (CAS 204933-93-7), present in an amount of from about 0.1% to about 30% by weight of the antidegradant blend; b. sodium hypophosphite, present in an amount of from about 0.1% to about 40% by weight of the antidegradant blend; c. tetrakismethylene(3,5-di-t-butyl 4 hydroxyhydrocinnamate) methane (CAS 6683-19-8), present in an amount of from about 1% to about 60% by weight of the antidegradant blend; and d. tris(2,4-di-t-butylphenyl)phosphite (CAS 31570 04 4), present in an amount of from about 10% to about 90% by weight of the antidegradant blend.
According to an aspect of the present invention, there is provided an antidegradant blend comprising: a. 4,4'-bis(a,a-dimethylbenzyl) diphenylamine (CAS 10081-67-1), present in an amount of from about 0.1% to about 30% by weight of the antidegradant blend; b. sodium hypophosphite, present in an amount of from about 0.1% to about 40% by weight of the antidegradant blend; c. tetrakismethylene(3,5-di-t-butyl 4 hydroxyhydrocinnamate) methane (CAS 6683-19-8), present in an amount of from about 1% to about 60% by weight of the antidegradant blend; d. pentaerythritol tetrakis ((3-laurylthiopropionate) (CAS 29598-76-3), present in an amount of from about 10% to about 90% by weight of the antidegradant blend; and e. calcium stearate, present in an amount of from about 1% to about 60% by weight of the antidegradant blend.
The antidegradant blend may comprise one or more further additives, selected from lactone radical scavengers, acrylate radical scavengers, clarifiers, antiblocks, UV absorbers or stabilisers, processing aids and/or chelating agents. Other additives may include lactates and/or benzoates, for example of calcium or sodium.
According to an aspect of the present invention, there is provided a method of maintaining colour formation in a polymeric base material using an antidegradant blend of the present invention.
According to an aspect of the present invention, there is provided a method of reducing colour formation in a polymeric base material using an antidegradant blend of the present invention.
The aforementioned methods may be applicable over the course of article manufacture conditions, prior to article manufacture, during storage, and/or during containment in an extruder at elevated temperatures while awaiting formation into a material.
According to an aspect of the present invention, there is provided use of the antidegradant blend of the invention to stabilise a polymer. The polymer may be a polyolefin.
According to an aspect of the present invention, there is provided a polymeric composition, comprising a polymeric base material and the antidegradant blend of the invention.
The antidegradant blend may be present in the polymeric composition in an amount of from about 0.01% to about 5% by weight of the polymeric composition. For example, the antidegradant blend may be present in an amount of from about 0.01% to about 2%, from about 0.01% to about 1%, or from about 0.1% to about 0.5% by weight of the polymeric composition.
The polymeric base material in the polymeric composition may comprise a polyolefin, polystyrene, polyacrylonitrile, a polyacrylate, a polyurethane, a polyamide, a polyester, a polycarbonate, polyvinyl chloride, polyoxyarylenes, polyoxyalkylenes, an elastomer, a rubber and/or suitable mixtures, blends or copolymers thereof.
The polymeric base material may comprise a polyolefin.
The polyolefin may comprise a homopolymer or a copolymer.
The polyolefin may comprise polyethylene, polypropylene, polybutylene or a higher polyalkene.
The polyolefin may comprise polyethylene and/or polypropylene.
The polyethylene may comprise low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE) and/or high density polyethylene (HDPE).
The polyolefin may comprise a copolymer of ethylene, propylene and/or butylene. The copolymer may be a random copolymer or a block copolymer. For example, the polyolefin may comprise an ethylene/propylene block copolymer, an ethylene/propylene random copolymer, an ethylene/propylene/butylene random terpolymer or an ethylene/propylene/butylene block terpolymer.
The polyolefin may be produced using a catalyst selected from Ziegler-Natta, chromium or metallocene catalysts.
Additionally or alternatively, the polymeric base material may comprise a rubber. For example, the polymeric base material may comprise a styrenic block copolymer. The styrenic block copolymer may be selected from styrene-butadiene-styrene (SBS); styrene-isoprene-styrene (SIS); styrene-ethylene/butylene-styrene (SEBS); styreneethylene/propylene (SEP); styrene-butadiene rubber (SBR); or suitable mixtures or blends thereof.
Additionally or alternatively, the polymeric base material may comprise an ethylene vinyl acetate polymer, for example EVA.
According to an aspect of the present invention, there is provided a useful article manufactured from the polymeric composition of the invention. The article may comprise extruded nonwoven material (such as a meltspun spunbond or meltblown fabric), an extruded or blown film, or a moulded article of manufacture.
The antidegradant blend, which when added to a polymeric base material, may cause the yellowness index of the polymeric base material (measured by ASTM D1925) to rise less over five passes through an extruder at 260 °C in air, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
The antidegradant blend, which when added to a polymeric base material, may cause the yellowness index of the polymeric base material (measured by ASTM D1925) to rise by at least 20% less, by at least 30% less, by at least 50% less, by at least 60% less, by at least 70%, or by at least 80% less, over five passes through an extruder at 260 °C in air, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
The antidegradant blend, which when added to a polymeric base material, may cause 25 the yellowness index of the polymeric base material (measured by ASTM D1925) to rise by less than 2.3, less than 2, less than 1.8, less than 1.5, or less than 1, over five passes through an extruder at 260 °C in air.
The antidegradant blend, which when added to a polymeric base material, may result in the yellowness index of the polymeric base material (measured by ASTM D1925) being at least 20% less, at least 40% less, at least 50% less, at least 80% less, at least 90% less, at least 95% less or at least 100% less, after five passes through an extruder at 260 °C in air, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
The antidegradant blend, which when added to a polymeric base material, may result s in the yellowness index of the polymeric base material (measured by ASTM D1925) being less than 2.2, less than 1, less than 0.5, less than 0.3, less than 0.1 or less than 0.05, after five passes through an extruder at 260 °C in air.
The antidegradant blend, which when added to a polymeric base material, may cause the melt flow rate of the polymeric base material (measured by ASTM D1238L with a temperature of 230 °C, a 2.16 kg weight and a 2.095 mm die) to rise by less than 20 g/10 min, less than 12 g/10 min, less than 7 g/10 min, less than 6 g/10 min, or less than 2 g/10 min, over five passes through an extruder at 260 °C in air.
The antidegradant blend, which when added to a polymeric base material, may cause the melt flow rate of the polymeric base material (measured by ASTM D1238L with a temperature of 230 °C, a 2.16 kg weight and a 2.095 mm die) to rise by less than 250%, by less than 110%, by less than 90%, by less than 80%, by less than 70%, or by less than 60%, over five passes through an extruder at 260 °C in air.
The antidegradant blend, which when added to a polymeric base material, may cause the yellowness index of the polymeric base material (measured by ASTM D1925) to rise less over three weeks in an oven at 130 °C, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
The antidegradant blend, which when added to a polymeric base material, may cause the yellowness index of the polymeric base material (measured by ASTM D1925) to rise by at least 10% less, by at least 15% less, by at least 20% less, or by at least 25% less, over three weeks in an oven at 130 °C, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
The antidegradant blend, which when added to a polymeric base material, may cause the yellowness index of the polymeric base material (measured by ASTM D1925) to rise by less than 6, less than 5.5, less than 5, or less than 4.6, over three weeks in an oven at 130 °C.
The antidegradant blend, which when added to a polymeric base material, may result in the yellowness index of the polymeric base material (measured by ASTM D1925) being at least 10% less, at least 20% less, at least 30% less, or at least 35% less, after three weeks in an oven at 130 °C, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
The antidegradant blend, which when added to a polymeric base material, may result in the yellowness index of the polymeric base material (measured by ASTM D1925) being less than 5.4, less than 5, less than 4.5, less than 4, or less than 3.5 after three weeks in an oven at 130 °C.
For the avoidance of doubt, all features relating to the antidegradant blend may apply, where appropriate, to the use of the antidegradant blend, methods pertaining to colour 20 formation, and to the polymeric composition, and vice versa.
The invention will now be more particularly described with reference to the following examples.
EXAMPLES
PREPARATION OF THE POLYMERIC COMPOSITION
The polymeric base material was a commercially available polypropylene 30 homopolymer for Samples 1 to 4 and 8 to 30, and a polypropylene homopolymer with a lower MFR for Samples 5 to 7.
Numerous antidegradant blends were prepared.
Table 1 shows the different components that were used in the antidegradant blends.
TABLE 1
Component Shorthand Type Sodium hypophosphite Na Hyp Inorganic phosphite antioxidant Calcium stearate CaSt Acid scavenger ALKANOXTM 240 A240 Organic phosphite antioxidant ANOXTM 20 A20 Phenolic antioxidant NAUGARDTM 412S 412S Sulphur-containing antioxidant IRGASTABTm FS042 FS042 Bis(octadecyl)hydroxylamine 65% (CAS 143925-92-2) GENOXTM EP EP Antioxidant amine oxide (delivers a hydroxylamine on heating) (CAS 20493393-7) NAUGARDTM 445 445 Diphenyl aminic antioxidant AMINOXIm AMOX Diphenyl aminic antioxidant Tables 2 and 3 show the various antidegradant blends that were prepared. The % amounts shown in the table are % by weight of the overall polymeric composition.
TABLE 2
Na Hyp A240 FS042 Total Sample A20 (%) EP (%) (%) (%) (%) (%) 1 (Comp) 0.08 0.04 0.12 2 (Comp) 0.08 0.04 0.015 0.135 3 0.0075 0.08 0.04 0.0075 0.135 4 (Comp) 0.015 0.08 0.04 - - 0.135 (Comp) - 0.0925 0.0925 0.03 - 0.215 6 0.015 0.0925 0.0925 0.015 - 0.215 7 (Comp) 0.03 0.0925 0.0925 - - 0.215 8 (Comp) - 0.08 0.04 - - 0.12 9 0.015 0.08 0.04 0.015 - 0.15 (Comp) - 0.08 0.04 0.03 - 0.15 11 (Comp) 0.03 0.08 0.04 - - 0.15 12 0.01 0.08 0.04 0.02 - 0.15 13 0.02 0.08 0.04 0.01 - 0.15 14 0.025 0.08 0.04 0.005 0.15 0.015 0.08 0.04 0.005 0.14 16 0.0275 0.08 0.04 0.0025 0.15 17 0.02 0.08 0.04 0.0025 - 0.1425 18 0.01 0.08 0.04 0.0025 0.1325 19 0.025 0.08 0.04 0.005 0.15 0.015 0.08 0.04 - 0.015 0.15 21 (Comp) - 0.08 0.04 - 0.03 0.15 22 (Comp) - 0.08 0.04 - - 0.12 23 0.0275 0.08 0.04 0.0025 0.15 Samples 1, 2, 4, 5, 7, 8, 10, 11, 21 and 22 are comparative examples, in which Samples 1, 8 and 22 represent industry standard antidegradant blends. Each of the above-identified antidegradant blends was compounded with the polypropylene base material in an extruder at a temperature of 230 °C under nitrogen to form a polymeric composition.
TABLE 3
Sample Na CaSt A20 412S FS042 (Y0) 445 AMOX ( % ) Total Hyp ( % ) ( % ) ( % ) ( % ) ( % ) (%) 24 (Comp) - 0.03 0.03 0.15 - 0.09 - 0.30 0.02 0.03 0.03 0.15 0.09 0.32 26 0.0175 0.03 0.03 0.15 0.0025 0.09 - 0.32 27 (Comp) - 0.03 - - - 0.09 - 0.12 28 0.02 0.03 0.09 0.14 29 (Comp) 0.03 0.09 0.12 0.02 0.03 - - - - 0.09 0.14 Samples 24, 27 and 29 are comparative examples. Each of the above-identified antidegradant blends was compounded with the polypropylene base material in an extruder at a temperature of 230 °C under nitrogen to form a polymeric composition.
COLOUR STABILITY
Each of the polymeric compositions referenced in Tables 2 and 3 were multi-passed through an extruder at 260 °C under air. Extrusion experiments were performed on a 25 mm SS BrabenderTM Extruder. After each pass through the extruder the polymer sample is cooled in a water bath, dried and chipped to give pellets which were analysed and subjected to the same procedure again. The discolouration of the compositions was measured in terms of Yellowness Index using a colorimeter (XriteTM Color i7) according to YI ASTM D1925. Each YI measurement is the average of 4 measured values. YI values were taken following compounding (pass 0) and after passes 1, 3 and 5. The lower the YI value, the less discolouration of the composition. The results are shown in Table 4.
TABLE 4
Sample YI Value Pass 0 Pass 1 Pass 3 Pass 5 1 (Comp) -0.26 2.71 5.60 8.03 2 (Comp) -0.23 1.35 3.98 6.27 3 -0.59 -0.45 -0.02 0.90 4 (Comp) -1.10 0.23 1.49 2.28 (Comp) 0.01 1.49 4.67 8.44 6 -0.33 0.08 0.08 1.23 7 (Comp) -0.23 1.29 2.47 3.10 8 (Comp) -0.56 1.45 3.93 5.46 9 -0.48 0.45 0.83 1.72 (Comp) -0.35 1.01 2.77 4.34 11 (Comp) -1.02 0.09 0.83 1.10 12 -0.74 -0.35 0.19 0.66 13 -0.68 -0.21 0.37 1.08 14 -1.04 -0.31 -0.08 0.32 -0.84 -0.53 -0.05 0.56 16 -0.72 -0.64 -0.37 0.02 17 -1.06 -0.25 -0.06 0.80 18 -1.20 -0.48 0.01 0.50 19 -0.95 -0.64 -0.38 0.27 -0.71 -0.47 -0.04 0.23 21 (Comp) 0.29 1.84 4.18 5.13 22 (Comp) -0.44 1.72 5.08 6.91 23 -0.96 -0.99 -0.62 -0.14 24 (Comp) -0.41 0.4 2.54 4.45 -0.34 0.24 1.16 2.01 26 -0.51 -0.17 0.97 1.43 27 (Comp) -0.19 0.27 1.01 2.03 28 -0.37 0.12 1.12 1.57 29 (Comp) 6.16 17.19 29.55 35.35 6.31 17.39 28.95 31.76 From the results, it can be seen that the polymeric compositions stabilised with the antidegradant blends in accordance with the present invention (Samples 3, 6, 9, 12 to 20 and 23) show significantly less discolouration than the polymeric compositions stabilised with the industry standard antidegradant blends (Samples 1, 8 and 22). It has surprisingly been found that the best performance, when using a mixture of sodium hypophosphite and an aminic component along with phenolic and organic phosphite antioxidants, occurs when the blend consists of a smaller proportion of hydroxylamine (1-20%) and a larger proportion of sodium hypophosphite (80-99%).
This can most clearly be seen with Samples 16 and 23.
It can also be seen that the polymeric compositions stabilised with the antidegradant blends in accordance with the present invention (Samples 25, 26, 28 and 30) show significantly less discolouration than the polymeric compositions stabilised with the equivalent blends without sodium hypophosphite (Samples 24, 27 and 30).
MELT FLOW RATE
The melt flow rate of the polymeric composition of Samples 1 to 30 were determined following compounding (pass 0) and after pass 5, using a CEAST-rm 7026 Melt Flow Tester according to standard test method ASTM D1238L with a temperature of 230 °C, a 2.16 kg weight and a 2.095 mm die. An increase in the melt flow rate is indicative of unfavourable degradation of the sample, because it is desirable for the properties of the polymeric composition to be maintained, rather than changed, on processing.
The results are shown in Tables 5 and 6.
TABLE 5
Sample Melt Flow Rate (g/10 min) Pass 0 Pass 5 1 (Comp) 9.77 14.91 2 (Comp) 9.26 16.35 3 8.85 14.30 4 (Comp) 10.18 16.27 (Comp) 2.81 5.57 6 2.34 4.07 7 (Comp) 2.34 4.52 8 (Comp) 8.82 15.40 9 8.94 15.01 (Comp) 9.23 17.56 11 (Comp) 9.43 14.39 12 8.63 13.46 13 8.64 14.75 14 8.76 14.23 8.82 13.70 16 8.84 14.71 17 9.41 15.00 18 9.09 15.59 19 8.87 14.61 8.86 14.64 21 (Comp) 9.31 17.24 22 (Comp) 8.91 15.47 23 8.35 14.63 From the results it can be seen that the polymeric compositions stabilised using the antidegradant blends according to the present invention (Samples 3, 6, 9, 12 to 20 and 23) retained melt flow rate similarly to the polymeric compositions stabilised using industry standard antidegradant blends (Samples 1, 8, and 22).
TABLE 6
Sample Melt Flow Rate (g/10 min) Pass 0 Pass 3* / 5** 24 (Comp) 8.49 17.32** 9.17 18.96** 26 8.61 19.84** 27 (Comp) 10.39 25.59* 28 10.75 24.10* 29 (Comp) 8.91 28.92** 8.69 27.88** From the results it can be seen that the polymeric compositions stabilised using the antidegradant blends according to the present invention (Samples 25, 26, 28 and 30) retained melt flow rate similarly to the polymeric compositions stabilised using the 10 antidegradant blends (Samples 24, 27 and 30).
The melt flow for samples 27 and 28 were measured at pass 3 as the pass 5 results were off scale for the test. MFR values for samples 27 to 30 are higher than for 24 to 26 as much less antioxidant loading has been used.
COLOUR FASTNESS TO BURNT GAS FUMES
The fastness of a polymer and additives to burnt gas fumes is determined on a semi-quantitative basis by exposing the compounded polymer pellets to burnt gas fumes in 20 a chamber at a temperature of 60 °C for a period of 48hrs and monitoring the discolouration of the compositions in terms of Yellowness Index using a colorimeter at 24hrly intervals according to the procedure of AATCC 23. The lower the YI value, the less discolouration of the composition. The results are shown in Table 7.
TABLE 7
Sample YI Value 0 hrs 24hrs 48hrs 8 (Comp) -0.53 4.92 7.82 9 -0.45 3.56 5.92 (Comp) -0.38 1.05 2.87 11 (Comp) -1.08 3.10 5.44 12 -0.69 2.44 4.52 13 -0.51 3.92 6.81 14 -0.93 2.49 5.00 -0.99 4.20 7.44 16 -0.92 4.41 8.26 From the results, it can be seen that the polymeric compositions stabilised with the antidegradant blend in accordance with the present invention (Samples 9 and 12 to 16) show less or equal discolouration to the polymeric compositions stabilised with the comparative blends (Samples 8, 10, and 11).
COLOUR FASTNESS TO OVEN AGING
The fastness of a polymer and additives to oven aging is determined on a semi-quantitative basis by exposing the compounded polymer pellets in a glass petri dish 15 to oven aging at 130 °C for a period of 3 weeks and monitoring the discolouration of the compositions in terms of Yellowness Index using a colorimeter (XriteTM Color i7) according to YI ASTM D1925 at weekly intervals. The lower the YI value, the less discolouration of the composition. The results are shown in Table 8.
TABLE 8
Sample YI Value 0 wks 1 wk 2 wks 3 wks 8 (Comp) -0.77 2.08 4.12 5.41 16 -1.16 0.25 1.78 3.41 From the results, it can be seen that the polymeric composition stabilised with the antidegradant blend in accordance with the present invention (Sample 16) shows less discolouration than the polymeric composition stabilised with the industry standard blend (Sample 8).
Claims (45)
- CLAIMS1. An antidegradant blend, comprising: a. an aminic component; b. an inorganic antioxidant or reducing agent; and c. one or more of: i. a phenolic antioxidant; ii. an organic phosphite antioxidant; iii. a sulphur-containing antioxidant; and iv. an anti-acid.
- 2. The antidegradant blend according to Claim 1, wherein the blend is absent any buffering agent having the capacity to buffer in aqueous solution at a pH range from 4 to 8.
- 3. The antidegradant blend according to Claim 1 or Claim 2 which, when added to a polymeric base material, causes the yellowness index of the polymeric base material (measured by ASTM D1925) to rise less over five passes through an extruder at 260 °C in air, than that of the same polymeric base material to which an equivalent w/w amount of an equivalent antidegradant blend, absent one or both of component a. and component b., has been added.
- 4. The antidegradant blend according to any one of claims 1 to 3, wherein the inorganic antioxidant or reducing agent comprises one or more of a metal phosphite, a metal hypophosphite, a metal thiosulphate, a metal bisulphite, a metal metabisulphite, a metal hydrosulphite and/or mixtures of any two or more thereof.
- 5. The antidegradant blend according to Claim 4, wherein the inorganic antioxidant or reducing agent comprises metal hypophosphite, optionally sodium hypophosphite.
- 6. The antidegradant blend according to Claim 5, wherein the metal hypophosphite is anhydrous or hydrated.
- 7. The antidegradant blend according to Claim 6, wherein the metal hypophosphite is provided in mono-hydrated form.
- 8. The antidegradant blend according to any one of claims 1 to 7, wherein the inorganic antioxidant or reducing agent is present in an amount of from about 0.1% to about 40%, from about 1% to about 30%, from about 5% to about 25%, from about 10% to about 20%, or from about 14% to about 18%, by weight of the antidegradant blend.
- 9. The antidegradant blend according to any one of claims 1 to 8, wherein the inorganic antioxidant or reducing agent is a solid at a temperature of about 50°C or lower, a temperature of about 40 °C or lower, a temperature of about 30 °C or lower, or a temperature of about 25 °C or lower, and about 1 atmosphere pressure.
- 10. The antidegradant blend according to any one of claims 1 to 9, wherein the aminic component comprises a secondary amine, optionally a secondary arylam ine.
- 11. The antidegradant blend according to any one of claims 1 to 10, wherein the aminic component has the general formula R-NH-R wherein each R independently denotes a hydrogen, hydrocarbyl or aromatic group, the or each hydrocarbyl and/or aromatic group having at least 1 carbon atom and may or may not be substituted.
- 12. The antidegradant blend according to any one of claims 1 to 11, wherein the aminic component comprises 4,4'-bis(a,a-dimethylbenzyl) diphenylamine; mixed butylated, octylated diphenylamine; octylated diphenylamine; nonylated diphenylamine; styrenated diphenylamine; diphenylamine; polymerised 1,2- dihydro-2,2,4-trimethylquinoline; N,N-bis-(1,4-dimethylpenty1)-p- phenylenediam ine; acetone diphenylamine; reaction products of diphenylamine and acetone; 1,4-benzenediamine, N,N'-mixed phenyl and tolyl derivatives; N(1,3-dimethylbuty1)-N'-phenyl-p-phenylenediamine; 1,4-Benzenediamine N,N'-mixed phenyl and tolyl derivatives; N,N'-diphenyl-p-phenylendiamine; Nisopropyl-N'-phenyl-1,4-phenylenediamine; 2,4,6-tris-(N-1,4-dimethylpentyl-pphenylenediamino)-1,3,5-triazine. and/or compatible mixtures of two or more thereof
- 13. The antidegradant blend according to any one of claims 1 to 12 wherein the aminic component comprises a hydroxylamine, a hydroxylamine precursor and/or one or more hydroxylamine derivatives.
- 14. The antidegradant blend according to Claim 13, wherein the hydroxylamine has the general formula RxRyNOH wherein each R independently denotes an optionally branched hydrocarbyl group having from 1 to 25 carbon atoms.
- 15. The antidegradant blend according to Claim 13 or Claim 14, wherein the hydroxylamine com prises N, N-dibenzylhydroxylam ine; N, N- diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-ditetradecylhydroxylamine; N,N-dihexadecylhydroxylam ine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; bis(octadecyl)hydroxylamine; and/or compatible mixtures of two or more thereof.
- 16. The antidegradant blend according to any one of claims 13 to 15, wherein the hydroxylamine precursor comprises an amine oxide.
- 17. The antidegradant blend according to Claim 16, wherein the amine oxide has the general formula RxRyR,NO wherein each R independently denotes an optionally branched hydrocarbyl group having from 1 to 25 carbon atoms.
- 18. The antidegradant blend according to Claim 16 or Claim 17, wherein the amine oxide comprises bis(hydrogenated rape-oil alkyl)methyl, N-oxides.
- 19. The antidegradant blend according to any one of claims 1 to 18, wherein the aminic component is a solid at a temperature of about 50°C or lower, a temperature of about 40 °C or lower, a temperature of about 30 °C or lower, or a temperature of about 25 °C or lower, and about 1 atmosphere pressure.
- 20. The antidegradant blend according to any one of claims 1 to 19, wherein the aminic component is present in an amount of from about 0.1% to about 30%, from about 0.1% to about 20%, from about 0.5% to about 15%, from about 1% to about 10%, or from about 2% to about 4%, by weight of the antidegradant blend.
- 21. The antidegradant blend according to any one of claims 1 to 20 wherein the ratio of inorganic antioxidant or reducing agent to am inic component is from about 1:15 to about 15:1, from about 1:3 to about 14:1, from about 1:1 to about 13:1, from about 2:1 to about 12:1, or from about 5:1 to about 12:1.
- 22. The antidegradant blend according to any one of claims 1 to 21, wherein the antidegradant blend comprises a phenolic antioxidant.
- 23. The antidegradant blend according to Claim 22, wherein the phenolic antioxidant comprises a partially hindered phenolic antioxidant and/or a hindered phenolic antioxidant.
- 24. The antidegradant blend according to Claim 22 or Claim 23, wherein the phenolic antioxidant is present in an amount of from about 1% to about 60%, from about 5% to about 55%, from about 10% to about 50%, from about 20% to about 45%, or from about 25% to about 35%, by weight of the antidegradant blend.
- 25. The antidegradant blend according to any one of claims 1 to 24, wherein the antidegradant blend comprises an organic phosphite antioxidant.
- 26. The antidegradant blend according to Claim 25, wherein the organic phosphite antioxidant is present in an amount of from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, from about 40% to about 65%, or from about 50% to about 60%, by weight of the antidegradant blend.
- 27. The antidegradant blend according to any one of claims 1 to 26, wherein the antidegradant blend comprises a sulphur-containing antioxidant.
- 28. The antidegradant blend according to Claim 27, wherein the sulphur-containing antioxidant comprises one or more thioether groups and/or one or more thioester groups.
- 29. The antidegradant blend according to Claim 27 or Claim 28, wherein the sulphur-containing antioxidant is present in an amount of from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, from about 40% to about 60%, or from about 45% to about 55%, by weight of the antidegradant blend.
- 30. The antidegradant blend according to any one of claims 1 to 29, wherein the antidegradant blend comprises an anti-acid.
- 31. The antidegradant blend according to Claim 30, wherein the anti-acid comprises stearates, optionally of lithium, sodium, calcium, zinc, magnesium or aluminium; oxides, optionally zinc oxide, magnesium oxide or titanium dioxide; and/or artificial or natural carbonates, optionally calcium carbonate or hydrotalcite.
- 32. The antidegradant blend according to Claim 30 or Claim 31, wherein the anti-acid comprise calcium stearate.
- 33. The antidegradant blend according to any one of claims 30 to 32, wherein the anti-acid is present in an amount of from about 1% to about 60%, from about 2% to about 50%, from about 3% to about 40%, from about 6% to about 30%, or from about 8% to about 25%, by weight of the antidegradant blend.
- 34. The antidegradant blend according to Claim 1 comprising: a. an aminic component; b. an inorganic phosphite antioxidant; c. a phenolic antioxidant; and d. an organic phosphite antioxidant.
- 35. The antidegradant blend according to Claim 1 comprising: a. an aminic component; b. an inorganic phosphite antioxidant; c. a phenolic antioxidant; d. a sulphur-containing antioxidant; and e. an anti-acid.
- 36. The antidegradant blend according to Claim 1 comprising: a. an aminic component; b. an inorganic phosphite antioxidant; and c. an anti-acid.
- 37. The antidegradant blend according to Claim 1 comprising: a. bis(octadecyl)hydroxylamine and/or amines, bis(hydrogenated rape-oil alkyl)methyl, N-oxides, present in an amount of from about 0.1% to about 30% by weight of the antidegradant blend; b. sodium hypophosphite, present in an amount of from about 0.1% to about 40% by weight of the antidegradant blend; c. tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane, present in an amount of from about 1% to about 60% by weight of the antidegradant blend; and d. tris(2,4-di-t-butylphenyl)phosphite, present in an amount of from about 10% to about 90% by weight of the antidegradant blend.
- 38. The antidegradant blend according to Claim 1 comprising: a. 4,4'-bis(a,a-dimethylbenzyl) diphenylamine, present in an amount of from about 0.1% to about 30% by weight of the antidegradant blend; b. sodium hypophosphite, present in an amount of from about 0.1% to about 40% by weight of the antidegradant blend; c. tetrakismethylene(3,5-di-t-butyl 4 hydroxyhydrocinnamate) methane, present in an amount of from about 1% to about 60% by weight of the antidegradant blend; d. pentaerythritol tetrakis ((3-laurylthiopropionate), present in an amount of from about 10% to about 90% by weight of the antidegradant blend; and e. calcium stearate, present in an amount of from about 1% to about 60% by weight of the antidegradant blend.
- 39. Use of an antidegradant blend according to any one of claims 1 to 38 to stabilise a polymer.
- 40. The use according to Claim 39 where the polymer is a polyolefin.
- 41.A polymeric composition, comprising a polymeric base material and an antidegradant blend according to any one of claims 1 to 38.
- 42. The polymeric composition according to Claim 41, wherein the antidegradant blend is present in an amount of from about 0.01% to about 5%, from about 0.01% to about 2%, from about 0.01% to about 1%, or from about 0.1% to about 0.5% by weight of the polymeric composition.
- 43. The polymeric composition according to Claim 41 or Claim 42, wherein the aminic component is present in the polymeric composition in an amount less than about 45 ppm, less than about 35 ppm, or less than about 30 ppm.
- 44. The polymeric composition according to any one of claims 41 to 43 wherein the polymeric base material comprises a polyolefin, polystyrene, polyacrylonitrile, a polyacrylate, a polyurethane, a polyamide, a polyester, a polycarbonate, polyvinyl chloride, an elastomer, a rubber and/or suitable mixtures, blends or copolymers thereof
- 45.A useful article manufactured from a polymeric composition according to any one of claims 41 to 44.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1907631.4A GB2584307A (en) | 2019-05-30 | 2019-05-30 | Antidegradant blend |
| PCT/EP2020/064932 WO2020239963A1 (en) | 2019-05-30 | 2020-05-28 | Antidegradant blend |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1907631.4A GB2584307A (en) | 2019-05-30 | 2019-05-30 | Antidegradant blend |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB201907631D0 GB201907631D0 (en) | 2019-07-17 |
| GB2584307A true GB2584307A (en) | 2020-12-02 |
Family
ID=67385922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1907631.4A Withdrawn GB2584307A (en) | 2019-05-30 | 2019-05-30 | Antidegradant blend |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB2584307A (en) |
| WO (1) | WO2020239963A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4190851A1 (en) * | 2021-12-01 | 2023-06-07 | LANXESS Deutschland GmbH | Polyamide-based products |
| WO2023099128A1 (en) * | 2021-12-01 | 2023-06-08 | Lanxess Deutschland Gmbh | Polyamide-based products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0389640A1 (en) * | 1988-09-09 | 1990-10-03 | Sumitomo Chemical Company Limited | Resin composition having excellent heat stability and weatherability |
| EP0538509A1 (en) * | 1990-04-25 | 1993-04-28 | Sumitomo Chemical Company, Limited | Highly antioxidant resin composition |
| US5414030A (en) * | 1991-12-24 | 1995-05-09 | Sumitomo Chemical Company, Limited | Agricultural film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3691131A (en) | 1971-02-01 | 1972-09-12 | Ciba Geigy Corp | Stabilized polyamide compositions |
| CN102503821B (en) | 2011-11-22 | 2014-04-02 | 江苏利田科技股份有限公司 | Clean production method of alkoxylation glycerol triacrylate |
| GB2562466B (en) | 2017-05-04 | 2022-01-05 | Si Group Switzerland Chaa Gmbh | Composition |
| GB2567456B (en) | 2017-10-12 | 2021-08-11 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
| GB201807302D0 (en) | 2018-05-03 | 2018-06-20 | Addivant Switzerland Gmbh | Antidegradant blend |
-
2019
- 2019-05-30 GB GB1907631.4A patent/GB2584307A/en not_active Withdrawn
-
2020
- 2020-05-28 WO PCT/EP2020/064932 patent/WO2020239963A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0389640A1 (en) * | 1988-09-09 | 1990-10-03 | Sumitomo Chemical Company Limited | Resin composition having excellent heat stability and weatherability |
| EP0538509A1 (en) * | 1990-04-25 | 1993-04-28 | Sumitomo Chemical Company, Limited | Highly antioxidant resin composition |
| US5414030A (en) * | 1991-12-24 | 1995-05-09 | Sumitomo Chemical Company, Limited | Agricultural film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4190851A1 (en) * | 2021-12-01 | 2023-06-07 | LANXESS Deutschland GmbH | Polyamide-based products |
| WO2023099128A1 (en) * | 2021-12-01 | 2023-06-08 | Lanxess Deutschland Gmbh | Polyamide-based products |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201907631D0 (en) | 2019-07-17 |
| WO2020239963A1 (en) | 2020-12-03 |
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