TWI425040B - 聚合物用的穩定劑組成物 - Google Patents
聚合物用的穩定劑組成物 Download PDFInfo
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- TWI425040B TWI425040B TW096103272A TW96103272A TWI425040B TW I425040 B TWI425040 B TW I425040B TW 096103272 A TW096103272 A TW 096103272A TW 96103272 A TW96103272 A TW 96103272A TW I425040 B TWI425040 B TW I425040B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- carbon atoms
- alkyl
- phenyl
- substituted
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 79
- 229920000642 polymer Polymers 0.000 title claims description 33
- 239000003381 stabilizer Substances 0.000 title claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 198
- 125000004432 carbon atom Chemical group C* 0.000 claims description 191
- -1 aliphatic tertiary amine Chemical class 0.000 claims description 162
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 45
- 125000003342 alkenyl group Chemical group 0.000 claims description 43
- 239000006096 absorbing agent Substances 0.000 claims description 41
- 125000003545 alkoxy group Chemical group 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 33
- 229920001169 thermoplastic Polymers 0.000 claims description 33
- 150000001412 amines Chemical class 0.000 claims description 32
- 125000002947 alkylene group Chemical group 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 22
- 150000003512 tertiary amines Chemical class 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 19
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 19
- 229920001684 low density polyethylene Polymers 0.000 claims description 18
- 239000004702 low-density polyethylene Substances 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 11
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 claims description 8
- 241000208340 Araliaceae Species 0.000 claims description 8
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 8
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 8
- 235000008434 ginseng Nutrition 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical class CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 7
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 7
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical compound OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 claims description 6
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 5
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- BWJKLDGAAPQXGO-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-octadecoxypiperidine Chemical compound CCCCCCCCCCCCCCCCCCOC1CC(C)(C)NC(C)(C)C1 BWJKLDGAAPQXGO-UHFFFAOYSA-N 0.000 claims description 4
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- WTVNFKVGGUWHQC-UHFFFAOYSA-N decane-2,4-dione Chemical compound CCCCCCC(=O)CC(C)=O WTVNFKVGGUWHQC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 4
- 150000004060 quinone imines Chemical class 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- VQNRMLCRMNVBBP-UHFFFAOYSA-N aniline;oxalic acid Chemical class OC(=O)C(O)=O.NC1=CC=CC=C1 VQNRMLCRMNVBBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 claims description 2
- DVCRTABNYFFFFG-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-2-hydroxyphenyl)-(1,2,2,6,6-pentamethylpiperidin-3-yl)methyl]propanedioic acid Chemical compound CCCCC(C(C1CCC(N(C1(C)C)C)(C)C)C2=C(C(=CC(=C2)C(C)(C)C)C(C)(C)C)O)(C(=O)O)C(=O)O DVCRTABNYFFFFG-UHFFFAOYSA-N 0.000 claims description 2
- SAEZGDDJKSBNPT-UHFFFAOYSA-N 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione Chemical compound O=C1C(CCCCCCCCCCCC)CC(=O)N1C1CC(C)(C)N(C)C(C)(C)C1 SAEZGDDJKSBNPT-UHFFFAOYSA-N 0.000 claims description 2
- FBIXXCXCZOZFCO-UHFFFAOYSA-N 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione Chemical compound O=C1C(CCCCCCCCCCCC)CC(=O)N1C1CC(C)(C)NC(C)(C)C1 FBIXXCXCZOZFCO-UHFFFAOYSA-N 0.000 claims description 2
- IUDKJQVFFIJCQH-UHFFFAOYSA-N C(C(C(CC(=O)O)C(=O)O)C(=O)O)C(=O)OC1CC(NC(C1)(C)C)(C)C.NN Chemical compound C(C(C(CC(=O)O)C(=O)O)C(=O)O)C(=O)OC1CC(NC(C1)(C)C)(C)C.NN IUDKJQVFFIJCQH-UHFFFAOYSA-N 0.000 claims description 2
- LEGMPSODXUCYQS-UHFFFAOYSA-N C(C1=CC=CC=C1)=C1CC(NC(C1)(C)C)(C)C Chemical compound C(C1=CC=CC=C1)=C1CC(NC(C1)(C)C)(C)C LEGMPSODXUCYQS-UHFFFAOYSA-N 0.000 claims description 2
- LURRFVRIZCHPJD-UHFFFAOYSA-N CN(C(CCCCCN(C1CC(NC(C1)(C)C)(C)C)C)C1C=CC2=CC=CC=C12)C1CC(NC(C1)(C)C)(C)C Chemical compound CN(C(CCCCCN(C1CC(NC(C1)(C)C)(C)C)C)C1C=CC2=CC=CC=C12)C1CC(NC(C1)(C)C)(C)C LURRFVRIZCHPJD-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 claims description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 claims description 2
- VKVSLLBZHYUYHH-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-3-yl) butanedioate Chemical compound CC1(C)N(OCCCCCCCC)C(C)(C)CCC1OC(=O)CCC(=O)OC1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1 VKVSLLBZHYUYHH-UHFFFAOYSA-N 0.000 claims description 2
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 claims description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- 125000004970 halomethyl group Chemical group 0.000 claims description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 claims description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 125000002071 phenylalkoxy group Chemical group 0.000 claims description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 229940116351 sebacate Drugs 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- CGXOAAMIQPDTPE-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-amine Chemical compound CN1C(C)(C)CC(N)CC1(C)C CGXOAAMIQPDTPE-UHFFFAOYSA-N 0.000 claims 1
- YCOWPKCEXHRGBW-UHFFFAOYSA-N butyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 YCOWPKCEXHRGBW-UHFFFAOYSA-N 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 claims 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 49
- 229920001577 copolymer Polymers 0.000 description 39
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 239000012964 benzotriazole Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 229920002857 polybutadiene Polymers 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000005062 Polybutadiene Substances 0.000 description 8
- 229920002873 Polyethylenimine Polymers 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 229920001903 high density polyethylene Polymers 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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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
- C08K5/00—Use of organic ingredients
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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Description
本發明關於穩定型熱塑性聚合物,特別為聚烯烴膜。穩定組成物包括具有分子量大於400公克/莫耳之三級胺、UV-吸收劑及/或位阻胺光穩定劑(HALS)。本發明進一步的觀點為一種穩定熱塑性聚合物的方法及上述組成物用於穩定熱塑性聚合物的用途
與位阻胺結合的三級胺,特別為橋連型胺化合物,如二氮雜雙環辛烷(DABCO)及三氮雜金鋼烷衍生物被揭示在WO 00/09604及WO 98/36023中。本文所述之三級胺全部具有低分子量,在加工聚合物期間由於彼之揮發性及高遷移率而導致問題。
目前頃發現併入不必橋連化的脂肪族三級胺會導致與UV-吸收劑及/或位阻胺光穩定劑(HALS)強的協同效應。當聚合物暴露於常在溫室應用中實施的以硫為主之殺蟲劑處理時,則該協同效應被擴大。在該等條件下,含有三級胺及UV-吸收劑的聚合物之穩定性特別好。
UV-吸收劑、三級胺與HALS的組合在許多情況中提供最優的穩定化。
此外,UV-吸收劑的光穩定性增加。特別地,羥苯基三UV-吸收劑相對易感受與殺蟲劑的交互作用,尤其對於以硫為主之殺蟲劑。使用少量具有高分子量的脂肪族三級胺會增加彼之耐久性,即彼等在聚合物物件中的持久性。
對用作溫室罩的膜或護蓋物特別重要。這些結構通常係由低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)、乙烯基醋酸乙酯(EVA)或乙烯/丙烯酸丁酯(EBA)所製成,並包括許多具有功能性效應的添加劑:抗氧化劑,如酚、磷酸酯、內酯或羥胺;助滑劑與抗阻斷添加劑,如芥酸醯胺、油醯胺或二氧化矽;無機填充劑,如高嶺土、碳酸鈣、硫酸鋇、碳黑、菱水鎂鋁石;及顏料,如SmartlightRL 1000。彼等典型地以HALS、以或不以UV-吸收劑穩定化。
除了膜之外,例如由HDPE、PP、LDPE所製成的拉菲亞(raffia)常以相同的目的用於溫室或護蓋應用中。
膜及拉菲亞常暴露於作為用於保護農作物及花朵的殺蟲劑、除草劑及土壤消毒劑所使用的化學品。該等化合物最常以氯、硫及金屬(Cu、Fe)為主。所有這些物種能夠與穩定劑反應,導致膜比預期更早降解。已知硫最有效作為在溫室中昇華或噴霧的元素粉末及作為活性分子一部分(例如,威百(Vapam))二者。
除了與穩定劑的交互作用之外,硫被懷疑直接與聚烯烴基質交互作用,加速其降解。
最終,過去常用於改進農作物生產力的硫及以硫為主之化合物可與羥苯基-三交互作用,導致不僅比預期更早降解,並也喪失UV-過濾劑效果。
一些類型的農作物事實上受到太陽輻射的UV-組份而降級,該組份必須被濾掉以獲得高品質及產量。此外,一些微生物,例如,灰黴病菌(Botrytis Cinerea)可在特殊的UV-照射下增殖。這些害蟲有害於一些玫瑰花品種的培養〔R.Reuven等人之Development of photoselective PE films for control of foliar pathogens in greenhouse-grown crops,Plasticulture No.102,pg.7(1994);Y.Eheshel等人之”The use of UV absorbing plastic sheets to protect crops against insects and spread of virus diseases”,CIPA Congress 1997〕。
用作人工草坪的PP或PE膠帶為結合高的UV-光暴露(接著必須穩定化)與用作呈現人工草坪底部的橡膠之硫化劑的硫之污染的另一應用。該等系統的穩定性可進一步受到可充當降解助劑的顏料存在而影響。
本發明的一個觀點為一種穩定型聚合物組成物,其包含a)熱塑性聚合物;b)具有分子量大於400公克/莫耳之三級胺,其不是2,2,6,6-四甲基六氫吡啶衍生物;c1)UV-吸收劑,其係選自由羥苯基苯并三唑、羥苯基三、羥基二苯甲酮及草酸苯胺化物所組成的群組;或c2)來自位阻胺類別的光穩定劑;或c3)UV-吸收劑、組份c1)與組份c2)之位阻胺的混合物。特別地,本發明的一個觀點為一種穩定型聚合物組成物,其包含a)不含鹵素之熱塑性聚合物;b)具有分子量大於400公克/莫耳之脂肪族三級胺,其不是2,2,6,6-四甲基六氫吡啶衍生物;c1)UV-吸收劑,其係選自由羥苯基苯并三唑、羥苯基三、羥基二苯甲酮及草酸苯胺化物所組成的群組;或c2)來自位阻胺類別的光穩定劑;或c3)UV-吸收劑、組份c1)與組份c2)之位阻胺的混合物。
較佳地,三級胺具有大於500公克/莫耳之分子量,特別大於700公克/莫耳。
在一些情況中,可勝任的是組成物包含如上述定義之三級胺及UV-吸收劑。然而,當需要最大的穩定化時,則組成物包含三級胺、UV-吸收劑及位阻胺。
熱塑性聚合物的實例提供於下:1.單烯烴及二烯烴之聚合物類,例如,聚丙烯、聚異丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚乙烯基環己烷、聚異戊二烯或聚丁二烯,與環烯烴之聚合物類,例如,環戊烯或降莰烯、聚乙烯(其視需要可被交聯),例如,高密度聚乙烯(HDPE)、高密度與高分子量聚乙烯(HDPE-HMW)、高密度與超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)、(VLDPE)及(ULDPE)。
聚烯烴(即在先前段落中所舉例之單烯烴之聚合物類,以聚乙烯及聚丙烯較佳)可以不同且尤其以下列的方法製備:a)自由基聚合法(正常係在高壓及上升的溫度下)。
b)催化聚合法,其使用正常包括一或一種以上的週期表IVb、Vb、VIb或VIII族金屬之催化劑。這些金屬通常具有一或一種以上可經或π-或σ-配位之配位基,典型為氧化物、鹵化物、醇酸鹽、酯、醚、胺、烷基、烯基及/或芳基。這些金屬複合物可具有自由形式或被固定在基底上,典型為在活化之氯化鎂、氯化鈦(III)、氧化鋁或氧化矽上。這些催化劑可溶於或不溶於聚合介質中。催化劑可以其本身用在聚合法中或可使用另外的活化劑,典型為烷基金屬、氫化金屬、烷基鹵化金屬、烷基氧化金屬或烷基金屬,該金屬為週期表Ia、IIa及/或IIIa族元素。活化劑可方便地以另外的酯、醚、胺或矽烷醚基團改良。這些催化劑系統通常被稱為菲利浦(Phillips)、標準的印第安納油(Standard Oil Indiana)、齊格(Ziegler)(-納塔(Natta))、TNZ(DuPont)、茂金屬或單點催化劑(SSC)。
2.在1)之中所述之聚合物的混合物類,例如,聚丙烯與聚異丁烯之混合物、聚丙烯與聚乙烯之混合物(例如,PP/HDPE、PP/LDPE)及不同類型之聚乙烯的混合物(例如,LDPE/HDPE)。
3.單烯烴及二烯烴互相或與其它乙烯基單體之共聚物類,例如,乙烯/丙烯之共聚物、線性低密度聚乙烯(LLDPE)及其與低密度聚乙烯(LDPE)之混合物、丙烯/丁-1-烯之共聚物、丙烯/異丁烯之共聚物、乙烯/丁-1-烯之共聚物、乙烯/己烯之共聚物、乙基/甲基戊烯之共聚物、乙烯/庚烯之共聚物、乙烯/辛烯之共聚物、乙烯/乙烯基環己烷之共聚物、乙烯/環烯烴之共聚物(例如,乙烯/降莰烯,諸如COC)、乙烯/1-烯烴之共聚物,其中1-烯烴係當場產生、丙烯/丁二烯之共聚物、異丁烯/異戊二烯之共聚物、乙烯/乙烯基環己烯之共聚物、乙烯/丙烯酸烷基酯之共聚物、乙烯/甲基丙烯酸烷基酯之共聚物、乙烯/醋酸乙烯酯之共聚物或乙烯/丙烯酸之共聚物及彼之鹽類(離子聚合物)與乙烯與丙烯及二烯(如己二烯、二環戊二烯或亞乙基-降莰烯)之三聚物;及該等共聚物互相及與以上1)中所述之聚合物的混合物,例如,聚丙烯/乙烯-丙烯之共聚物、LDPE/乙烯-醋酸乙烯酯之共聚物(EVA)、LDPE/乙烯-丙烯酸之共聚物(EAA)、LLDPE/EVA、LLDPE/EAA及交替或無規則聚烯類/一氧化碳之共聚物,以及其與其它聚合物,例如,聚醯胺之混合物。
4.烴樹脂類(例如,C5
-C9
),包括其氫化修改物(例如,增黏劑)及聚烯類與澱粉之混合物。
來自1.)-4.)之均聚物及共聚物可具有任何包括對排、同排、半-同排或雜排之立體結構,其中以雜排聚合物較佳。也包括立體嵌段聚合物。
5.聚苯乙烯、聚(對-甲基苯乙烯)、聚(α-甲基苯乙烯)。
6.自乙烯基芳香族單體,包括苯乙烯、α-甲基苯乙烯、乙烯基甲苯的所有異構物,尤其為對-乙烯基甲苯,乙基苯乙烯、丙基苯乙烯、乙烯基聯苯、乙烯萘及乙烯蒽的所有異構物及其混合物所衍生之芳香族均聚物類及共聚物類。均聚物類及共聚物類可具有任何包括對排、同排、半-同排或雜排之立體結構,其中以雜排聚合物較佳。也包括立體嵌段聚合物。
6a.包括上述選自乙烯、丙烯、二烯、腈、酸、馬來酸酐、馬來醯亞胺、醋酸乙烯酯及氯乙烯或丙烯酸系衍生物及其混合物之乙烯基芳香族單體及共單體的共聚物類,例如,苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/乙烯(互聚物)、苯乙烯/甲基丙烯酸烷基酯、苯乙烯/丁二烯/丙烯酸烷基酯、苯乙烯/丁二烯/甲基丙烯酸烷基酯、苯乙烯/馬來酸酐、苯乙烯/丙烯腈/丙烯酸甲酯;高衝擊強度之苯乙烯共聚物與另一聚合物之混合物,例如,聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯之三聚物;及苯乙烯之嵌段共聚物,如苯乙烯/丁二烯/苯乙烯、苯乙烯/異戊二烯/苯乙烯、苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
6b.自6.)之中所述之聚合物的氫化法所衍生之氫化芳香族聚合物類,尤其包括藉由氫化雜排聚苯乙烯所製備之聚環己基乙烯(PCHE),常稱為聚乙烯基環己烷(PVCH)。
6c.自6a.)之中所述之聚合物的氫化法所衍生之氫化芳香族聚合物類
均聚物及共聚物可具有任何包括對排、同排、半-同排或雜排之立體結構,其中以雜排聚合物較佳。也包括立體嵌段聚合物。
7.乙烯基芳香族單體,如苯乙烯或α-甲基苯乙烯之接枝共聚物類,例如,在聚丁二烯上之苯乙烯、在聚丁二烯-苯乙烯或聚丁二烯-丙烯腈之共聚物上之苯乙烯、在聚丁二烯上之苯乙烯及丙烯腈(或甲基丙烯腈)、在聚丁二烯上之苯乙烯、丙烯腈及甲基丙烯甲酯、在聚丁二烯上之苯乙烯及馬來酸酐、在聚丁二烯上之苯乙烯、丙烯腈及馬來酸酐或馬來醯亞胺、在聚丁二烯上之苯乙烯及馬來醯亞胺、在聚丁二烯上之苯乙烯及丙烯酸或甲基丙烯酸烷基酯、在乙烯/丙烯/二烯之三聚物上之苯乙烯及丙烯腈、在聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上之苯乙烯及丙烯腈、在丙烯酸酯/丁二烯之共聚物上之苯乙烯及丙烯腈與彼等與在6)之中所列之共聚物的混合物,例如,已知為ABS、MBS、ASA或AES聚合物之共聚物混合物。
8.自α,β-不飽和酸及其衍生物所衍生之聚合物類,如聚丙烯酸酯及聚甲基丙烯酸酯;以丙烯酸丁酯修改衝擊性之聚(甲基丙烯酸甲酯)、聚丙烯醯胺及聚丙烯腈。
9.在8)之中所述之單體互相或與其它不飽和單體之共聚物類,例如,丙烯腈/丁二烯之共聚物、丙烯腈/丙烯酸烷基酯之共聚物、丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/鹵化乙烯之共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯之三聚物。
10.自不飽和醇及胺或其醯基衍生物或縮醛所衍生之聚合物類,例如,聚乙烯醇、聚醋酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚馬來酸乙烯酯、聚乙烯丁醛、聚苯二甲酸烯丙酯或聚烯丙基三聚氰胺;與彼等與以上1)中所述之烯烴的共聚物。
11.環族醚之均聚物類及共聚物類,如聚伸烷乙二醇、聚環氧乙烷、聚環氧丙烷或其與雙環氧丙基醚之共聚物。
12.聚縮醛類,如聚甲醛及那些包括環氧乙烷作為共單體之聚甲醛;以熱塑性聚胺基甲酸乙酯、丙烯酸酯或MBS改良之聚縮醛類。
13.聚氧化及硫化二甲苯類,及聚氧化二甲苯與苯乙烯聚合物或聚醯胺之混合物類。
14.一方面自羥基端聚醚、聚酯或聚丁二烯及另一方面自脂肪族或芳香族聚異氰酸酯所衍生之聚胺基甲酸乙酯類與其前驅體類。
15.自二胺及二羧酸及/或自胺基羧酸或對應之內醯胺所衍生之聚醯胺類及共聚醯胺類,例如聚醯胺4、聚醯胺6、聚醯胺6/6、6/10、6/9、6/12、4/6、12/12、聚醯胺11、聚醯胺12;自間-二甲苯二胺及己二酸開始的芳香族聚醯胺類;自六亞甲二胺及異苯二甲酸及/對苯二甲酸及以或不以彈性體作為改良劑所製備之聚醯胺類,例如,聚-2,4,4-三甲基六亞甲基對苯二甲醯胺或聚間苯二甲醯間苯二胺;及也為上述聚醯胺與聚烯烴、烯烴共聚物、離子共聚物或化學鍵結或接枝之彈性體之嵌段共聚物類;或與聚醚,例如與聚乙二醇、聚丙二醇或聚伸丁二醇之嵌段共聚物類;與以EPDM或ABS改良之聚醯胺類或共聚醯胺類;及在加工期間縮合之聚醯胺類(RIM聚醯胺系統)。
16.聚尿素類、聚醯亞胺類、聚醯胺-醯亞胺類、聚醚醯亞胺類、聚酯醯亞胺類、聚尿囊素類及聚苯并咪唑類。
17.自二羧酸及二元醇及/或羥基羧酸或對應之內酯所衍生之聚酯類,例如,聚對苯二甲酸乙烯酯、聚對苯二甲酸丁烯酯、聚對苯二甲酸-1,4-二羥甲基環己烷酯、聚萘酸伸烷基酯(PAN)及聚苯甲酸羥酯;與自羥基端聚醚所衍生之嵌段共聚醚酯類;也為以聚碳酸酯或MBS所改良之聚酯類。
18.聚碳酸酯類及聚酯碳酸酯類。
19.聚酮類。
20.聚碸類、聚醚碸類及聚醚酮類。
21.上述聚合物之摻合物類(聚摻合物類),例如,PP/EPDM、聚醯胺/EPDM或ABS、PVC/EVA、PVC/ABS、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/PBT、PVC/CPE、PVC/丙烯酸酯、POM/熱塑性PUR、PC/熱塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA6.6及共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
較佳地,熱塑性聚合物為低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)、聚丙烯(PP)或乙烯基醋酸乙酯(EVA)。
在特殊的具體實例中,組成物具有膜或膠帶型式。
例如,羥基二苯甲酮具有式I
2-羥苯基苯并三唑具有式IIa、IIb或IIc
2-羥苯基三具有式III
及草醯苯胺具有式(IV)
其中在式(I)化合物中,v為從1至3之整數及w為1或2之整數,以及取代基Z彼此獨立為氫;鹵素;羥基或具有1至12個碳原子之烷氧基;在式(IIa)化合物中,R1
為氫;具有1至24個碳原子之烷基;在烷基部分中具有1至4個碳原子之苯烷基;具有5至8個碳原子之環烷基;或下式之基
其中R4
及R5
彼此獨立為在每一情況中具有1至5個碳原子之烷基,或R4
與基Cn
H2n+1-m
一起形成具有5至12個碳原子之環烷基,m為1或2,n為從2至20之整數,及M為式-COOR6
之基,其中R6
為氫;具有1至12個碳原子之烷基;在烷基部分及烷氧基部分中於每一情況中具有1至20個碳原子之烷氧基烷基;或在烷基部分具有1至4個碳原子之苯烷基,R2
為氫;鹵素;具有1至18個碳原子之烷基;及在烷基部分中具有1至4個碳原子之苯烷基,及R3
為氫;氯;在每一情況中具有1至4個碳原子之烷基或烷氧基;或-COOR6
,其中R6
如上述所定義,基R1
及R2
中至少一者不為氫;在式(IIb)化合物中,T為氫;或具有1至6個碳原子之烷基,T1
為氫;氯;或在每一情況中具有1至4個碳原子之烷基或烷氧基,n為1或2,及如果n為1時,則T2
為氯;或式-OT3
或之基,及如果n為2時,則T2
為式或-O-T9
-O-之基;其中T3
為氫;具有1至18個碳原子且未被取代或被1至3個羥基或-OCOT6
取代之烷基;具有3至18個碳原子、被-O-或-NT6
-間斷一或多次且未被取代或被羥基或-OCOT6
取代之烷基;具有5至12個碳原子且未被取代或被羥基及/或具有1至4個碳原子之烷基取代之環烷基;具有2至18個碳原子且未被取代或被羥基取代之烯基;在烷基部分中具有1至4個碳原子之苯烷基;或式-CH2
CH(OH)-T7
或之基,T4
及T5
彼此獨立為氫;具有1至18個碳原子之烷基;具有3至18個碳原子且被-O-或-NT6
-間斷一或多次之烷基;具有5至12個碳原子之環烷基;苯基;被具有1至4個碳原子之烷基取代之苯基;具有3至8個碳原子之烯基;在烷基部分中具有1至4個碳原子之苯烷基;或具有2至4個碳原子之羥烷基,T6
為氫;具有1至18個碳原子之烷基;具有5至12個碳原子之環烷基;具有3至8個碳原子之烯基;苯基;被具有1至4個碳原子之烷基取代之苯基;在烷基部分中具有1至4個碳原子之苯烷基,T7
為氫;具有1至18個碳原子之烷基;未被取代或被羥基取代之苯基;在烷基部分中具有1至4個碳原子之苯烷基;或-CH2
OT8
,T8
為具有1至18個碳原子之烷基;具有3至8個碳原子之烯基;具有5至10個碳原子之環烷基;苯基;被具有1至4個碳原子之烷基取代之苯基;或在烷基部分中具有1至4個碳原子之苯烷基,T9
為具有2至8個碳原子之伸烷基;具有4至8個碳原子之伸烯基;具有4個碳原子之伸炔基;環伸己基;具有2至8個碳原子且被-O-間斷一或多次之伸烷基;或式-CH2
CH(OH)CH2
OT11
OCH2
CH(OH)CH2
-或-CH2
-C(CH2
OH)2
-CH2
-之基,T10
為具有2至20個碳原子且可被-O-間斷一或多次之伸烷基;或環伸己基,T11
為具有2至8個碳原子之伸烷基;具有2至18個碳原子且被-O-間斷一或多次之伸烷基;1,3-環伸己基;1,4-環伸己基;1,3-伸苯基;或1,4-伸苯基,或T10
及T6
與兩個氮原子一起為六氫吡環;在式(IIc)化合物中,R’2
為C1
-C12
烷基及k為從1至4之數字;在式(III)化合物中,u為1或2及r為從1至3之整數,取代基Y1
彼此獨立為氫;羥基;苯基或鹵素;鹵甲基;具有1至12個碳原子之烷基;具有1至18個碳原子之烷氧基;具有1至18個被基團-COO(C1
-C18
烷基)取代之碳原子的烷氧基,假使u是1,Y2
為具有1至18個碳原子之烷基;未被取代或被羥基、鹵素、具有1至18個碳原子之烷基或烷氧基取代之苯基;具有1至12個碳原子且被-COOH、-COOY8
、-CONH2
、-CONHY9
、-CONY9
Y10
、-NH2
、-NHY9
、-NY9
Y10
、-NHCOY11
、-CN及/或-OCOY11
取代之烷基;具有4至20個碳原子、被一或多個氧原子間斷且未被取代或被羥基或具有1至12個碳原子之烷氧基取代之烷基;具有3至6個碳原子之烯基;環氧丙基;未被取代或被羥基、具有1至4個碳原子之烷基及/或-OCOY11
取代之環己基;在烷基部分中具有1至5個碳原子且未被取代或被羥基、氯及/或甲基取代之苯烷基;-COY12
;或-SO2
Y13
,或如果u為2時,則Y2
為具有2至16個碳原子之伸烷基;具有4至12個碳原子之伸烯基;苯二甲基;具有3至20個碳原子、被一或多個-O-原子間斷及/或被羥基取代之伸烷基;-CH2
CH(OH)CH2
-O-Y15
-OCH2
CH(OH)CH2
;-CO-Y16
-CO-;-CO-NH-Y17
-NH-CO;或-(CH2
)m
-CO2
-Y18
-OCO-(CH2
)m
,其中m為1、2或3,Y8
為具有1至18個碳原子之烷基;具有3至18個碳原子之烯基;具有3至20個碳原子、被一或多個氧或硫原子或-NT6
-間斷及/或被羥基取代之烷基;具有1至4個碳原子且被-P(O)(OY14
)2
、-NY9
Y10
或-OCOY11
及/或羥基取代之烷基;具有3至18個碳原子之烯基;環氧丙基;或在烷基部分具有1至5個碳原子之苯烷基,Y9
及Y10
彼此獨立為具有1至12個碳原子之烷基;具有3至12個碳原子之烷氧基烷基;具有4至16個碳原子之二烷胺基烷基;或具有5至12個碳原子之環己基,或Y9
與Y10
一起為在每一情況中具有3至9個碳原子之伸烷基、氧雜伸烷基或氮雜伸烷基,Y11
為具有1至18個碳原子之烷基;具有2至18個碳原子之烯基;或苯基,Y12
為具有1至18個碳原子之烷基;具有2至18個碳原子之烯基;苯基;具有1至12個碳原子之烷氧基;苯氧基;具有1至12個碳原子之烷胺基;或苯胺基,Y13
為具有1至18個碳原子之烷基;苯基;或在烷基部分具有1至8個碳原子之烷苯基,Y14
為具有1至12個碳原子之烷基;或苯基,Y15
為具有2至10個碳原子之伸烷基;伸苯基;或-伸苯基-M-伸苯基-,其中M為-O-、-S-、-SO2
-、-CH2
-或-C(CH3
)2
-,Y16
為在每一情況中具有2至10個碳原子之伸烷基、氧雜伸烷基或硫雜伸烷基;伸苯基;或具有2至6個碳原子之伸烯基,Y17
為具有2至10個碳原子之伸烷基;伸苯基;或在烷基部分中具有1至11個碳原子之烷基伸苯基,及Y18
為具有2至10個碳原子之伸烷基;或具有4至20個碳原子且被氧間斷一或多次之伸烷基;在式(IV)化合物中,x為從1至3之整數,以及取代基L彼此獨立為氫;在每一情況中具有1至22個碳原子之烷基、烷氧基或烷硫基;苯氧基;或苯硫基。
C1
-C18
烷基可為直鏈或支鏈。具有至多18個碳原子之烷基的實例為甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、2-乙基丁基、正戊基、異戊基、1-甲基戊基、1,3-二甲基丁基、正己基、1-甲基己基、正庚基、異庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、壬基、癸基、十一烷基、1-甲基十一烷基、十二烷基、1,1,3,3,5,5-六甲基己基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基及十八烷基。
在式(IIa)化合物中,R1
可為氫或具有1至24個碳原子之烷基,如甲基、乙基、丙基、丁基、己基、辛基、壬基、十二烷基、十四烷基、十六烷基、十八烷基、十九烷基及二十烷基,並也為對應之支鏈異構物。而且,除了在烷基部分中具有1至4個碳原子之苯烷基,例如,苯甲基之外,R1
也可為具有5至8個碳原子之環烷基,例如,環戊基、環己基及環辛基,或為式之基,其中R4
及R5
彼此獨立為在每一情況中具有1至5個碳原子之烷基,特別為甲基,或R4
與Cn
H2n+1-m
基一起形成具有5至12個碳原子之環烷基,例如,環己基、環辛基及環癸基。M為式-COOR6
之基,其中R6
不僅為氫,並也為具有1至12個碳原子之烷基或在每一烷基部分及烷氧基部分中具有1至20個碳原子之烷氧基烷基。適合的烷基R6
為那些以R1
舉例者。適合的烷氧基烷基的實例為-C2
H4
OC2
H5
、-C2
H4
OC8
H17
及-C4
H8
OC4
H9
。作為具有1至4個碳原子之苯烷基的R6
為例如苯甲基、異丙苯基、α-甲基苯甲基或苯丁基。
除了氫及鹵素,例如,氯和溴之外,R2
也可為具有1至18個碳原子之烷基。該等烷基的實例指示在R1
的定義中。R2
也可為在烷基部分中具有1至4個碳原子之苯烷基,例如,苯甲基、α-甲基苯甲基及異丙苯基。
作為取代基之鹵素在所有情況中意味氟、氯、溴或碘,以氯或溴較佳,而以氯更佳。
R1
及R2
中至少一者必須不是氫。
除了氫及氯之外,R3
也可為在每一情況中具有1至4個碳原子之烷基或烷氧基,例如,甲基、丁基、甲氧基及乙氧基,並也為-COOR6
。
在式(IIb)化合物中,T為氫或具有1至6個碳原子之烷基,如甲基及丁基,T1
不僅為氫或氯,並也為在每一情況中具有1至4個碳原子之烷基或烷氧基,例如甲基、甲氧基及丁氧基,以及如果n為1時,則T2
為氯或式-OT3
或-NT4
T5
之基。T3
在此為氫或具有1至18個碳原子之烷基(參見R1
之定義)。這些烷基可被1至3個羥基或基-OCOT6
取代。而且,T3
可為具有3至18個碳原子之烷基(參見R1
之定義),其被-O-或-NT6
-間斷一或多次且未被取代或被羥基或-OCOT6
取代。作為環烷基之T3
的實例為環戊基、環己基或環辛基。T3
也可為具有2至18個碳原子之烯基。適合的烯基係衍生自在R1
之定義中所列舉之烷基。這些烯基可被羥基取代。作為苯烷基之T3
的實例為苯甲基、苯乙基、異丙苯基、α-甲基苯甲基或苯甲基。T3
也可為式-CH2
CH(OH)-T7
或之基。
和T3
一樣,T4
及T5
可彼此獨立不僅為氫,並也為具有1至18個碳原子之烷基或具有3至18個碳原子且被-O-或-NT6
-間斷一或多次之烷基。T4
及T5
也可為具有5至12個碳原子之環烷基,例如,環戊基、環己基及環辛基。作為烯基之T4
及T5
的實例可在T3
的說明中發現。作為在烷基部分中具有1至4個碳原子之苯烷基之T4
及T5
的實例為苯甲基或苯丁基。最終,這些取代基也可為具有1至3個碳原子之羥烷基。
如果n為2,則T2
為式或-O-T9
-O-之二價基。
除了氫之外,T6
(也參見於上)為烷基、環烷基、烯基、芳基或苯烷基;該等基的實例已提出於上。
除了氫及上述之苯烷基和長鏈烷基之外,T7
可為苯基或羥苯基,並也為-CH2
OT8
,其中T8
可為列舉的烷基、烯基、環烷基、芳基或苯烷基中之一。
二價基T9
可為具有2至8個碳原子之伸烷基,而該等基也可為支鏈。這也適用於伸烯基及伸炔基T9
。T9
也可為式-CH2
CH(OH)CH2
OT11
OCH2
CH(OH)CH2
-或-CH2
-C(CH2
OH)2
-CH2
-之基與環伸己基。
T10
為二價基,而且除了環伸己基之外,也為具有2至20個碳原子且可被-O-間斷一或多次之伸烷基。適合的伸烷基係衍生自在R1
之定義中所列舉之烷基。
T11
也為伸烷基。其包括2至8個碳原子,或如果其被-O-間斷一或多次,則其包括4至10個碳原子。T11
也為1,3-環伸己基、1,4-環伸己基、1,3-伸苯基或1,4-伸苯基。
T6
及T10
與兩個氮原子一起也可為六氫吡環。
在式(I)、(IIa)、(IIb)、(IIc)、(III)及(IV)化合物中的烷基、烷氧基、苯烷基、伸烷基、伸烯基、烷氧基烷基及環烷基以及還有烷硫基、氧雜伸烷基或氮雜伸烷基的實例可從以上敘述推論。
根據式IIa的那些化合物,通常以苯并三唑UV-吸收劑較佳。
式(I)、(IIa)、(IIb)、(IIc)、(III)及(IV)之UV吸收劑本身為已知的,並與彼之製備一起敘述在例如WO 96/28431、EP-A-323 408、EP-A-57 160、US 5 736 597(EP-A-436 608)、US 4 619 956、DE-A 31 35 810及GB-A 1 336 391中。取代基及各個化合物的較佳意義可從所述文件推論。
在另一具體實例中,羥苯基三類別的UV-吸收劑具有式(IV)
其中n為1或2;R1
、R’1
、R2
及R’2
彼此獨立為H;OH;C1
-C12
烷基;C2
-C6
烯基;C1
-C12
烷氧基;C2
-C18
烯氧基;鹵素;三氟甲基;C7
-C11
苯烷基;苯基;被C1
-C18
烷基、C1
-C18
烷氧基或鹵素取代之苯基;苯氧基;或被C1
-C18
烷基、C1
-C18
烷氧基或鹵素取代之苯氧基;R3
及R4
彼此獨立為H;C1
-C12
烷基;OR’7
;C2
-C6
烯基;C2
-C18
烯氧基;鹵素;三氟甲基;C7
-C11
苯烷基;苯基、被C1
-C18
烷基、C1
-C18
烷氧基或鹵素取代之苯基;苯氧基;或被C1
-C18
烷基、C1
-C18
烷氧基或鹵素取代之苯氧基;R6
為氫;C1
-C24
烷基;C5
-C12
環烷基;或C7
-C15
苯烷基;R7
(在其中n=1的情況中)及R’7
彼此獨立為氫或C1
-C18
烷基;或為C1
-C12
烷基,其被OH、C1
-C18
烷氧基、烯丙氧基、鹵素、-COOH、-COOR8
、-CONH2
、-CONHR9
、-CON(R9
)(R10
)、-NH2
、-NHR9
、-N(R9
)(R10
)、-NHCOR11
、-CN、-OCOR11
、苯氧基及/或被C1
-C18
烷基、C1
-C18
烷氧基或鹵素取代之苯氧基取代;或R7
為被-O-間斷且可被OH取代之C3
-C50
烷基;或R7
為C3
-C6
烯基;環氧丙基;C5
-C12
環烷基;被OH、C1
-C4
烷基或-OCOR11
取代之環己基;未被取代或被OH、Cl或CH3
取代之C7
-C11
苯烷基;-CO-R12
;或-SO2
-R13
;在其中n=2之情況中的R7
為C2
-C16
伸烷基;C4
-C12
伸烯基;苯二甲基;被O間斷及/或被OH取代C3
-C20
伸烷基,或為式-CH2
CH(OH)CH2
O-R20
-OCH2
CH(OH)CH2
-、-CO-R21
-CO-、-CO-NH-R22
-NH-CO或-(CH2
)m
-COO-R23
-OOC-(CH2
)m
-之基團,其中m為在從1至3之範圍內的數字,或為
R8
為C1
-C18
烷基;C2
-C18
烯基;羥乙基;被O、NH、NR9
或S間斷及/或被OH取代之C3
-C50
烷基;被-P(O)(OR14
)2
、-N(R9
)(R10
)或-OCOR11
及/或OH取代之C1
-C4
烷基;環氧丙基;C5
-C12
環烷基;苯基;C7
-C14
烷苯基;或C7
-C11
苯烷基;R9
及R10
彼此獨立為C1
-C12
烷基;C3
-C12
烷氧基烷基;C4
-C16
二烷胺基烷基;或C5
-C12
環烷基,或R9
與R10
一起為C3
-C9
伸烷基或-氧雜伸烷基或-氮雜伸烷基;R11
為C1
-C18
烷基;C2
-C18
烯基或苯基;C2
-C12
羥烷基;環己基;或為被-O-間斷且可被OH取代之C3
-C50
烷基;R12
為C1
-C18
烷基;C2
-C18
烯基;苯基;C1
-C18
烷氧基;C3
-C18
烯氧基;被O、NH、NR9
或S間斷及/或OH取代之C3
-C50
烷基;環己氧基;C7
-C14
烷基苯氧基;C7
-C11
苯烷氧基;苯氧基;C1
-C12
烷胺基;苯胺基;甲苯胺基;或萘胺基;R13
為C1
-C12
烷基;苯基;萘基;或C7
-C14
烷苯基;R14
為C1
-C12
烷基;甲苯基;或苯基;R20
為C2
-C10
伸烷基;被O、伸苯基或-伸苯基-X-伸苯基(其中X為-O-、-S-、-SO2
-、-CH2
-或-C(CH3
)2
-)間斷之C4
-C50
伸烷基;R21
為C2
-C10
伸烷基;C2
-C10
氧雜伸烷基;C2
-C10
硫雜伸烷基;C6
-C12
伸芳基;或C2
-C6
伸烯基;R22
為C2
-C10
伸烷基;伸苯基;伸甲苯基;二伸苯基甲烷;或基團;及R23
為C2
-C10
伸烷基;或被O間斷之C4
-C20
伸烷基。
鹵素在所有情況中為氟、氯、溴或碘。
烷基的實例為甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、2-乙基丁基、正戊基、異戊基、1-甲基戊基、1,3-二甲基丁基、正己基、1-甲基己基、正庚基、異庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、壬基、癸基、十一烷基、1-甲基十一烷基、十二烷基。
具有至多12個碳原子之烷氧基的實例為甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、戊氧基、異戊氧基、己氧基、庚氧基、辛氧基、癸氧基、十二烷氧基。
烯氧基的實例為丙烯氧基、丁烯氧基、戊烯氧基及己烯氧基。
C5
-C12
環烷基的實例為環戊基、環己基、環庚基、環辛基及環十二烷基。以C5
-C8
環烷基較佳,尤其為環己基。
經C1
-C4
烷基取代之C5
-C12
環烷基為例如甲基環己基或二甲基環己基。
經OH-及/或C1
-C10
烷基取代之苯基為例如甲苯基、二甲苯基、三甲苯基、第三丁苯基或3,5-二-第三丁基-4-羥苯基。
經烷氧基取代之苯基為例如甲氧基苯基、二甲氧基苯基或三甲氧基苯基。
C7
-C9
苯烷基的實例為苯甲基及苯乙基。
在苯基上被-OH及/或具有至多10個碳原子之烷基取代之C7
-C9
苯烷基為例如甲基苯甲基、二甲基苯甲基、三甲基苯甲基、第三丁基苯甲基或3,5-二-第三丁基-4-羥基苯甲基。
烯基的實例為烯丙基、2-甲基烯丙基、丁烯基、戊烯基及己烯基。以烯丙基較佳。在位置1中的碳原子較佳地為飽和狀態。
伸烷基的實例為亞甲基、伸乙基、伸丙基、三亞甲基、四亞甲基、五亞甲基、2,2-二甲基三亞甲基、五亞甲基、三甲基六亞甲基、八亞甲基及十亞甲基。
伸烯基的實例為伸丁烯基、伸戊烯基及伸己烯基。
C6
-C12
伸芳基係以伸苯基較佳。
被O間斷之烷基為例如-CH2
-CH2
-O-CH2
-CH3
、-CH2
-CH2
-O-CH3
-或-CH2
-CH2
-O-CH2
-CH2
-CH2
-O-CH2
-CH3
-。較佳為衍生自聚乙二醇者。通用敘述為-((CH2
)a
-O)b
-H/CH3
,其中a為從1至6之數字及b為從2至10之數字。
C2
-C10
氧雜伸烷基及C2
-C10
硫雜伸烷基可藉由一或多個碳原子被氧原子或硫原子取代而自上述伸烷基推論。
例如,羥苯基三UV-吸收劑為2-(2-羥苯基)-1,3,5-三,其為例如2,4,6-參(2-羥基-4-辛氧基苯基)-1,3,5-三、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲苯基)-1,3,5-三、2-(2,4-二羥苯基)-4,6-雙(2,4-二甲苯基)-1,3,5-三、2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲苯基)-1,3,5-三、2-(2-羥基-4-辛氧基苯基)-4,6-雙(4-甲苯基)-1,3,5-三、2-(2-羥基-4-十二烷氧基苯基)-4,6-雙(2,4-二甲苯基)-1,3,5-三、2-(2-羥基-4-十三烷氧基苯基)-4,6-雙(2,4-二甲苯基)-1,3,5-三、2-[2-羥基-4-(2-羥基-3-丁氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三、2-[2-羥基-4-(2-羥基-3-辛氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三、2-[4-(十二烷氧基/十三烷氧基-2-羥基丙氧基)-2-羥苯基]-4,6-雙(2,4-二甲苯基)-1,3,5-三、2-[2-羥基-4-(2-羥基-3-十二烷氧基丙氧基)苯基]-4,6-雙(2,4-二甲苯基)-1,3,5-三、2-(2-羥基-4-己氧基)苯基-4,6-二苯基-1,3,5-三、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三、2,4,6-參[2-羥基-4-(3-丁氧基-2-羥基丙氧基)苯基]-1,3,5-三、2-(2-羥苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三、2-{2-羥基-4-[3-(2-乙基己基-1-氧基)-2-羥基丙氧基]苯基}-4,6-雙(2,4-二甲苯基)-1,3,5-三及2-(2-羥基-4-(2-乙基己基)氧基)苯基-4,6-二(4-苯基)苯基-1,3,5-三。
特殊的羥苯基三UV-吸收劑為例如那些根據下式者:
a)R1=R2=CH(CH3
)-COO-C8
H17
,R3=R4=H;b)R1=R2=R3=CH(CH3
)-COO-C8
H17
,R4=H與c)R1=R2=R3=R4=CH(CH3
)-COO-C8
H17
之混合物,
羥苯基三UV-吸收劑為已知且部分為市售項目。彼等例如揭示在WO 96-28431中。
2-羥基二苯甲酮類的特殊實例為例如4-羥基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苯甲氧基及2’-羥基-4,4’-二甲氧基衍生物。
2-(2’-羥苯基)苯并三唑類的特殊實例為例如2-(2’-羥基-5’-甲苯基)-苯并三唑、2-(3’,5’-二-第三丁基-2’-羥苯基)苯并三唑、2-(5’-第三丁基-2’-羥苯基)苯并三唑、2-(2’-羥基-5’-(1,1,3,3-四甲基丁基)苯基)苯并三唑、2-(3’,5’-二-第三丁基-2’-羥苯基)-5-氯基苯并三唑、2-(3’-第三丁基-2’-羥基-5’-甲苯基)-5-氯基苯并三唑、2-(3’-第二丁基-5’-第三丁基-2’-羥苯基)苯并三唑、2-(2’-羥基-4’-辛氧基苯基)苯并三唑、2-(3’,5’-二-第三戊基-2’-羥苯基)苯并三唑、2-(3’,5’-雙(α,α-二甲基苯甲基)-2’-羥苯基)苯并三唑、2-(3’-第三丁基-2’-羥基-5’-(2-辛氧基羰乙基)苯基)-5-氯基苯并三唑、2-(3’-第三丁基-5’-[2-(2-乙基己氧基)-羰乙基]-2’-羥苯基)-5-氯基苯并三唑、2-(3’-第三丁基-2’-羥基-5’-(2-甲氧基羰乙基)苯基)-5-氯基苯并三唑、2-(3’-第三丁基-2’-羥基-5’-(2-甲氧基羰乙基)苯基)苯并三唑、2-(3’-第三丁基-2’-羥基-5’-(2-辛氧基羰乙基)苯基)苯并三唑、2-(3’-第三丁基-5’-[2-(2-乙基己氧基)羰乙基]-2’-羥苯基)苯并三唑、2-(3’-十二烷基-2’-羥基-5’-甲苯基)苯并三唑、2-(3’-第三丁基-2’-羥基-5’-(2-異辛氧基羰乙基)苯基)苯并三唑、2,2’-亞甲基-雙[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-酚]、2-[3’-第三丁基-5’-(2-甲氧基羰乙基)-2’-羥苯基]-2H-苯并三唑與聚乙二醇300之轉酯化產物、[R-CH2
CH2
-COO-CH2
CH2
-]2
,其中R=3’-第三丁基-4’-羥基-5’-2H-苯并三唑-2-苯基、2-[2’-羥基-3’-(α,α-二甲基苯甲基)-5’-(1,1,3,3-四甲基丁基)苯基]-苯并三唑、2-[2’-羥基-3’-(1,1,3,3-四甲基丁基)-5’-(α,α-二甲基苯甲基)-苯基]苯并三唑。
草醯胺類的特殊實例為例如4,4’-二辛氧基草醯苯胺、2,2’-二乙氧基草醯苯胺、2,2’-二辛氧基-5,5’-二-第三丁醯苯胺、2,2’-二-十二烷氧基-5,5’-二-第三丁醯苯胺、2-乙氧基-2’-乙基草醯苯胺、N,N’-雙(3-二甲胺基丙基)草醯苯胺、2-乙氧基-5-第三丁基-2’-乙醯苯胺及其與2-乙氧基-2’-乙基-5,4’-二-第三丁醯苯胺之混合物、以鄰-與對-甲氧基-二取代之草醯苯胺之混合物及以鄰-與對-乙氧基-二取代之草醯苯胺之混合物。
上述UV-吸收劑大部分為市售項目,且例如已知為來自Ciba Specialty Chemicals之Tinuvin109、171、326、327、328、350、360、384、400、405、411或Chimassorb81或來自Cytech Inc.之Cyasorb1164。
在許多情況中,可能有利的是使用來自不同類別的UV-吸收劑之組合物,例如,二苯甲酮UV-吸收劑與苯并三唑UV-吸收劑或羥苯基三UV-吸收劑與苯并三唑UV-吸收劑。如果使用該等組合物,則兩種UV-吸收劑之間的重量比為例如從1:5至5:1,例如從1:3至3:1,特別為1:1.5至1.5:1。
例如,位阻胺係選自由雙(2,2,6,6-四甲基-4-六氫吡啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-六氫吡啶基)琥珀酸酯、雙(1,2,2,6,6-五甲基-4-六氫吡啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-六氫吡啶基)癸二酸酯、正丁基-3,5-二-第三丁基-4-羥基苯甲基丙二酸雙(1,2,2,6,6-四甲基-4-六氫吡啶基)酯、1-羥乙基-2,2,6,6-四甲基-4-羥基六氫吡啶與琥珀酸之縮合物、N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺與4-第三辛胺基-2,6-二氯基-1,3,5-三之直鏈或環族縮合物、參(2,2,6,6-四甲基-4-六氫吡啶基)氮基三醋酸酯、肆(2,2,6,6-四甲基-4-六氫吡啶基)-1,2,3,4-丁烷四羧酸酯、1,1’-(1,2-乙烷二基)-雙(3,3,5,5-四甲基-4-六氫吡酮)、4-苯甲醯基-2,2,6,6-四甲基六氫吡啶、4-硬脂氧基-2,2,6,6-四甲基六氫吡啶、雙(1,2,2,6,6-五甲基六氫吡啶基)-2-正丁基-2-(2-羥基-3,5-二-第三丁基苯甲基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮雜螺旋[4.5]癸烷-2,4-二酮、雙(1-辛氧基-2,2,6,6-四甲基六氫吡啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基六氫吡啶基)琥珀酸酯、N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺與4-嗎啉基-2,6-二氯基-1,3,5-三之直鏈或環族縮合物、2-氯基-4,6-雙(4-正丁胺基-2,2,6,6-四甲基六氫吡啶基)-1,3,5-三與1,2-雙(3-胺丙基胺基)乙烷之縮合物、2-氯基-4,6-二-(4-正丁胺基-1,2,2,6,6-五甲基六氫吡啶基)-1,3,5-三與1,2-雙(3-胺丙基胺基)乙烷之縮合物、8-乙醯基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮雜螺旋[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-六氫吡啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-六氫吡啶基)吡咯烷-2,5-二酮、4-十六烷氧基-與4-硬脂氧基-2,2,6,6-四甲基六氫吡啶之混合物、N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺與4-環己胺基-2,6-二氯基-1,3,5-三之縮合物、1,2-雙(3-胺丙基胺基)乙烷與2,4,6-三氯基-1,3,5-三及4-丁胺基-2,2,6,6-四甲基六氫吡啶之縮合物(CAS登錄第[136504-96-6]號)、1,6-己二胺與2,4,6-三氯基-1,3,5-三及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基六氫吡啶之縮合物(CAS登錄第[192268-64-7]號)、N-(2,2,6,6-四甲基-4-六氫吡啶基)-正十二烷基琥珀醯亞胺、N-(1,2,2,6,6-五甲基-4-六氫吡啶基)-正十二烷基琥珀醯亞胺、2-十一烷基-7,7,9,9-四甲基-1-氧雜-3,8-二氮雜-4-酮基螺旋[4,5]癸烷、7,7,9,9-四甲基-2-環十一烷基-1-氧雜-3,8-二氮雜-4-酮基螺旋[4,5]癸烷與環氧氯丙烷之反應產物、1,1-雙(1,2,2,6,6-五甲基-4-六氫吡啶氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N’-雙-甲醯基-N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺、具有1,2,2,6,6-五甲基-4-羥基六氫吡啶之4-甲氧基亞甲基丙二酸之二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-六氫吡啶基)]矽氧烷、馬來酸酐-α-烯烴共聚物與2,2,6,6-四甲基-4-胺基六氫吡啶或1,2,2,6,6-五甲基-4-胺基六氫吡啶之反應產物及US-6117995之實施例2的化合物所組成的群組。
位阻胺化合物較佳地選自由下列的市售產品所組成的群組:DASTIB 845(RTM)、TINUVIN 770(RTM)、TINUVIN 765(RTM)、TINUVIN 144(RTM)、TINUVIN 123(RTM)、TINUVIN 371(RTM)、TINUVIN 111(RTM)、TINUVIN 783(RTM)、TINUVIN 791(RTM)、MARK LA 52(RTM)、MARK LA 57(RTM)、MARK LA 62(RTM)、MARK LA 67(RTM)、HOSTAVIN N 20(RTM)、HOSTAVIN N 24(RTM)、SANDUVOR 3050(RTM)、DIACETAM 5(RTM)、SUMISORB TM 61(RTM)、UVINUL 4049(RTM)、SANDUVOR PR 31(RTM)、GOODRITE UV 3034(RTM)、GOODRITE UV 3150(RTM)、GOODRITE UV 3159(RTM)、GOODRITE 3110 x 128(RTM)、UVINUL 4050 H(RTM)、CHIMASSORB 944(RTM)、CHIMASSORB 2020(RTM)、CYASORB UV 3346(RTM)、CYASORB UV 3529(RTM)、DASTIB 1082(RTM)、CHIMASSORB 119(RTM)、UVASIL 299(RTM)、UVASIL 125(RTM)、UVASIL 2000(RTM)、UVINUL 5050 H(RTM)、LICHTSCHUTZSTOFF UV 31(RTM)、LUCHEM HA B 18(RTM)、MARK LA 63(RTM)、MARK LA 68(RTM)、UVASORB HA 88(RTM)、TINUVIN 622(RTM)、HOSTAVIN N 30(RTM)及FERRO AM 806(RTM)。
特別佳的是TINUVIN 770(RTM)、TINUVIN 371(RTM)、TINUVIN 791(RTM)、TINUVIN 622(RTM)、TINUVIN 783(RTM)、CHIMASSORB 944(RTM)、CHIMASSORB 2020(RTM)及CHIMASSORB 119(RTM)。
例如,三級胺為式(a)至(j)化合物
其中R301
、R302
及R303
獨立為C10
-C36
烷基;R304
、R305
及R306
獨立為C9
-C36
烷基;R310
及R311
獨立為氫或C1
-C18
烷基;R307
及R308
獨立為C1
-C8
伸烷基;k為從之數字;n為從2至20之數字;m為從4至20之數字;及x,y獨立為從3至20之數字。
較佳為式(a)之三級胺。
三級胺大部分為市售項目或可根據標準方法製備。
典型地,三級胺係以熱塑性聚合物重量為基準計0.1-2重量%之量存在,較佳為0.2-1重量%。
例如,UV-吸收劑係以熱塑性聚合物重量為基準計0.01-2重量%之量存在,較佳為0.2-2重量%。
例如,位阻胺係以熱塑性聚合物重量為基準計0.01-2重量%之量存在,較佳為0.1-1重量%。
較佳地,三級胺、UV-吸收劑及/或位阻胺的總量係以熱塑性聚合物重量為基準計0.2至4重量%。
穩定型物質也可另外包括各種慣用的添加劑,例如:1.抗氧化劑類1.1.烷基化單酚類,例如,2,6-二-第三丁基-4-甲酚、2-第三丁基-4,6-二甲酚、2,6-二-第三丁基-4-乙酚、2,6-二-第三丁基-4-正丁酚、2,6-二-第三丁基-4-異丁酚、2,6-二-環戊基-4-甲酚、2-(α-甲基環己基)-4,6-二甲酚、2,6-二-十八烷基-4-甲酚、2,4,6-三環己酚、2,6-二-第三丁基-4-甲氧基甲酚、在側鏈上的直鏈或支鏈壬酚、例如,2,6-二壬基-4-甲酚、2,4-二甲基-6-(1’-甲基十一烷-1’-基)酚、2,4-二甲基-6-(1’-甲基十七烷基-1’-基)酚、2,4-二甲基-6-(1’-甲基十三烷基-1’-基)酚及其混合物。
1.2.烷硫基甲酚類,例如,2,4-二辛硫基甲基-6-第三丁酚、2,4-二辛硫基甲基-6-甲酚、2,4-二辛硫基甲基-6-乙酚、2,6-二-十二烷硫基甲基-4-壬酚。
1.3.氫醌類及烷基化氫醌類,例如,2,6-二-第三丁基-4-甲氧酚、2,5-二-第三丁基氫醌、2,5-二-第三戊基氫醌、2,6-二苯基-4-十八烷氧酚、2,6-二-第三丁基氫醌、2,5-二-第三丁基-4-羥基苯基甲基醚、3,5-二-第三丁基-4-羥基苯基甲基醚、硬脂酸3,5-二-第三丁基-4-羥基苯酯、雙(3,5-二-第三丁基-4-羥苯基)己二酸酯。
1.4.生育酚類,例如,α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及其混合物(維它命E)。
1.5.羥基化硫代二苯醚類,例如,2,2’-硫代雙(6-第三丁基-4-甲酚)、2,2’-硫代雙(4-辛酚)、4,4’-硫代雙(6-第三丁基-3-甲酚)、4,4’-硫代雙(6-第三丁基-2-甲酚)、4,4’-硫代雙(3,6-二-第二戊酚)、4,4’-雙(2,6-二甲基-4-羥苯基)二硫化物。
1.6.亞烷基雙酚類,例如,2,2’-亞甲基雙(6-第三丁基-4-甲酚)、2,2’-亞甲基雙(6-第三丁基-4-乙酚)、2,2’-亞甲基雙[4-甲基-6-(α-甲基環己基)酚]、2,2’-亞甲基雙(4-甲基-6-環己酚)、2,2’-亞甲基雙(6-壬基-4-甲酚)、2,2’-亞甲基雙(4,6-二-第三丁酚)、2,2’-亞乙基雙(4,6-二-第三丁酚)、2,2’-亞乙基雙(6-第三丁基-4-異丁酚)、2,2’-亞甲基雙[6-(α-甲基苯甲基)-4-壬酚]、2,2’-亞甲基雙[6-(α,α-二甲基苯甲基)-4-壬酚]、4,4’-亞甲基雙(2,6-二-第三丁酚)、4,4’-亞甲基雙(6-第三丁基-2-甲酚)、1,1-雙(5-第三丁基-4-羥基-2-甲苯基)丁烷、2,6-雙(3-第三丁基-5-甲基-2-羥基苯甲基)-4-甲酚、1,1,3-參(5-第三丁基-4-羥基-2-甲苯基)丁烷、1,1-雙(5-第三丁基-4-羥基-2-甲苯基)-3-正-第十二烷基巰基丁烷、乙二醇雙[3,3-雙(3’-第三丁基-4’-羥苯基)丁酸酯]、雙(3-第三丁基-4-羥基-5-甲苯基)二環戊二烯、雙[2-(3’-第三丁基-2’-羥基-5’-甲基苯甲基)-6-第三丁基-4-甲苯基]對苯二甲酸酯、1,1-雙-(3,5-二甲基-2-羥苯基)丁烷、2,2-雙(3,5-二-第三丁基-4-羥苯基)丙烷、2,2-雙-(5-第三丁基-4-羥基-2-甲苯基)-4-正-第十二烷基巰基丁烷、1,1,5,5-四(5-第三丁基-4-羥基-2-甲苯基)戊烷。
1.7. O-、N-及S-苯甲基化合物類,例如,3,5,3’,5’-四-第三丁基-4,4’-二羥基二苯甲醚、4-羥基-3,5-二甲基苯甲基巰基醋酸十八烷基酯、4-羥基-3,5-二-第三丁基苯甲基巰基醋酸十三烷基酯、參(3,5-二-第三丁基-4-羥基苯甲基)胺、雙(4-第三丁基-3-羥基-2,6-二甲基苯甲基)二硫代對苯二甲酸酯、雙(3,5-二-第三丁基-4-羥基苯甲基)硫化物、3,5-二-第三丁基-4-羥基苯甲基巰基醋酸異辛酯。
1.8.羥基苯甲基化丙二酸酯類,例如,-2,2-雙(3,5-二-第三丁基-2-羥基苯甲基)丙二酸二-十八烷基酯、2-(3-第三丁基-4-羥基-5-甲基苯甲基)丙二酸二-十八烷基酯、2,2-雙(3,5-二-第三丁基-4-羥基苯甲基)丙二酸二-十二烷基巰基乙酯、雙[4-(1,1,3,3-四甲基丁基)苯基]-2,2-雙(3,5-二-第三丁基-4-羥基苯甲基)丙二酸酯。
1.9.芳香族羥基苯甲基化合物類,例如,1,3,5-參(3,5-二-第三丁基-4-羥基苯甲基)-2,4,6-三甲苯、1,4-雙(3,5-二-第三丁基-4-羥基苯甲基)-2,3,5,6-四甲苯、2,4,6-參(3,5-二-第三丁基-4-羥基苯甲基)酚。
1.10.三化合物類,例如,2,4-雙(辛巰基)-6-(3,5-二-第三丁基-4-羥基苯胺基)-1,3,5-三、2-辛巰基-4,6-雙(3,5-二-第三丁基-4-羥基苯胺基)-1,3,5-三、2-辛巰基-4,6-(3,5-二-第三丁基-4-羥基苯氧基)-1,3,5-三、2,4,6-參(3,5-二-第三丁基-4-羥基苯氧基)-1,2,3-三、1,3,5-參(3,5-二-第三丁基-4-羥基苯甲基)異氰尿酸酯、1,3,5-參(4-第三丁基-3-羥基-2,6-二甲基苯甲基)異氰尿酸酯、2,4,6-參(3,5-二-第三丁基-4-羥基苯乙基)-1,3,5-三、1,3,5-參(3,5-二-第三丁基-4-羥苯基丙醯基)-六氫-1,3,5-三、1,3,5-參(3,5-二環己基-4-羥基苯甲基)異氰尿酸酯。
1.11.膦酸苯甲酯類,例如,2,5-二-第三丁基-4-羥基苯甲基膦酸二甲酯、3,5-二-第三丁基-4-羥基苯甲基膦酸二乙酯、3,5-二-第三丁基-4-羥基苯甲基膦酸二-十八烷基酯、5-第三丁基-4-羥基-3-甲基苯甲基膦酸二-十八烷基酯、3,5-二-第三丁基-4-羥基苯甲基膦酸之單乙酯的鈣鹽。
1.12.醯胺酚類,例如,4-羥基月桂醯苯胺、4-羥基硬脂醯苯胺、N-(3,5-二-第三丁基-4-羥苯基)胺基甲酸辛酯。
1.13. β-(3,5-二-第三丁基-4-羥苯基)丙酸之酯類,其具有單-或多元醇,例如,具有甲醇、乙醇、正辛醇、異辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三乙二醇、異戊四醇、參(羥乙基)異氰尿酸酯、N,N’-雙(羥乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥甲基-1-磷酸-2,6,7-三氧雜雙環[2.2.2]辛烷。
1.14. β-(5-第三丁基-4-羥基-3-甲苯基)丙酸之酯類,其具有單-或多元醇,例如,具有甲醇、乙醇、正辛醇、異辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三乙二醇、異戊四醇、參(羥乙基)異氰尿酸酯、N,N’-雙(羥乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥甲基-1-磷酸-2,6,7-三氧雜雙環[2.2.2]辛烷;3,9-雙[2-{3-(3-第三丁基-4-羥基-5-甲苯基)丙醯氧基}-1,1-二甲基乙基]-2,4,8,10-四氧雜螺旋[5.5]-十一烷。
1.15. β-(3,5-二環己基-4-羥苯基)丙酸之酯類,其具有單-或多元醇,例如,具有甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三乙二醇、異戊四醇、參(羥乙基)異氰尿酸酯、N,N’-雙(羥乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥甲基-1-磷酸-2,6,7-三氧雜雙環[2.2.2]辛烷。
1.16. 3,5-二-第三丁基-4-羥苯基醋酸之酯類,其具有單-或多元醇,例如,具有甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三乙二醇、異戊四醇、參(羥乙基)異氰尿酸酯、N,N’-雙(羥乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥甲基-1-磷酸-2,6,7-三氧雜雙環[2.2.2]辛烷。
1.17. β-(3,5-二-第三丁基-4-羥苯基)丙酸之醯胺類,例如,N,N’-雙(3,5-二-第三丁基-4-羥苯基丙醯基)六亞甲基二醯胺、N,N’-雙(3,5-二-第三丁基-4-羥苯基丙醯基)三亞甲基二醯胺、N,N’-雙(3,5-二-第三丁基-4-羥苯基丙醯基)醯肼、N,N’-雙[2-(3-[3,5-二-第三丁基-4-羥苯基]丙醯氧基)乙基]草醯胺(自Uniroyal供應之NaugardXL-1)。
1.18.抗壞血酸(維它命C)
1.19.亞胺系抗氧化劑類,例如,N,N’-二-異丙基-對-伸苯基二胺、N,N’-二-第二丁基-對-伸苯基二胺、N,N’-雙(1,4-二甲苯基)-對-伸苯基二胺、N,N’-雙(1-乙基-3-甲基戊基)-對-伸苯基二胺、N,N’-雙(1-甲基戊基)-對-伸苯基二胺、N,N’-二環己基-對-伸苯基二胺、N,N’-二苯基-對-伸苯基二胺、N,N’-雙(2-萘基)-對-伸苯基二胺、N-異丙基-N’-苯基-對-伸苯基二胺、N-(1,3-二甲基丁基)-N’-苯基-對-伸苯基二胺、N-(1-甲基庚基)-N’-苯基-對-伸苯基二胺、N-環己基-N’-苯基-對-伸苯基二胺、4-(對-甲苯磺醯胺基)二苯胺、N,N’-二甲基-N,N’-二-第二丁基-對-伸苯基二胺、二苯胺、N-烯丙基二苯胺、4-異丙氧基二苯胺、N-苯基-1-萘胺、N-(4-第三辛苯基)-1-萘胺、N-苯基-2-萘胺、辛基化二苯胺,例如,p,p’-二-第三辛基二苯胺、4-正丁基胺酚、4-丁醯基胺酚、4-壬醯基胺酚、4-十二烷醯基胺酚、4-十八醯基胺酚、雙(4-甲氧基苯基)胺、2,6-二-第三丁基-4-二甲胺基甲酚、2,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、N,N,N’,N’-四甲基-4,4’-二胺基二苯基甲烷、1,2-雙[(2-甲苯基)胺基]乙烷、1,2-雙(苯胺基)丙烷、(鄰-甲苯基)雙胍、雙[4-(1’,3’-二甲基丁基)苯基]胺、第三辛基化N-苯基-1-萘胺、單-與二烷基化第三丁基/第三辛基二苯胺之混合物、單-與二烷基化壬基二苯胺之混合物、單-與二烷基化十二烷基二苯胺之混合物、單-與二烷基化異丙基/異己基二苯胺之混合物、單-與二-烷基化第三丁基二苯胺之混合物、2,3-二氫-3,3-二甲基-4H-1,4-苯并噻、吩噻、單-與二烷基化第三丁基/第三辛基吩噻之混合物、單-與二烷基化第三辛基吩噻之混合物、N-烯丙基吩噻、N,N,N’,N’-四苯基-1,4-二胺基丁-2-烯、N,N-雙(2,2,6,6-四甲基六氫吡啶-4-基六亞甲基二胺、雙(2,2,6,6-四甲基六氫吡啶-4-基)癸二酸酯、2,2,6,6-四甲基六氫吡啶-4-酮、2,2,6,6-四甲基六氫吡啶-4-醇。
2.金屬去活化劑類,例如,N,N’-二苯基草醯胺、N-水楊醛基-N’-水楊醯肼、N,N’-雙(水楊醯基)肼、N,N’-雙(3,5-二-第三丁基-4-羥苯基丙醯基)肼、3-水楊醯胺基-1,2,4-三唑、雙(亞苯甲基)草醯基二醯肼、草醯苯胺、異苯二甲醯基二醯肼、癸二醯基雙苯醯肼、N,N’-二乙醯基己二醯基二醯肼、N,N’-雙(水楊醯基)草醯基二醯肼、N,N’-雙(水楊醯基)硫代丙醯基二醯肼。
3.亞磷酸酯類及亞膦酸酯類,例如,亞磷酸三苯酯、亞磷酸二苯烷基酯、亞磷酸苯基二烷基酯、亞磷酸參(壬苯基)酯、亞磷酸三月桂酯、亞磷酸三-十八烷基酯、二亞磷酸二硬脂基異戊四醇酯、亞磷酸參(2,4-二-第三丁苯基)酯、二亞磷酸二異癸基異戊四醇酯、二亞磷酸雙(2,4-二-第三丁苯基)異戊四醇酯、二亞磷酸雙(2,4-二-異丙苯基苯基)異戊四醇酯、二亞磷酸雙(2,6-二-第三丁基-4-甲苯基)異戊四醇酯、二亞磷酸雙-異癸氧基異戊四醇酯、二亞磷酸雙(2,4-二-第三丁基-6-甲苯基)異戊四醇酯、二亞磷酸雙(2,4,6-參(第三丁基)苯基)異戊四醇酯、三亞磷酸三硬脂基山梨醇酯、4,4’-聯苯基二亞膦酸肆(2,4-二-第三丁苯基)酯、6-異辛氧基-2,4,8,10-四-第三丁基-12H-二苯并[d,g]-1,3,2-二氧磷雜八環、亞磷酸雙(2,4-二-第三丁基-6-甲苯基)甲酯、亞磷酸雙(2,4-二-第三丁基-6-甲苯基)乙酯、6-氟基-2,4,8,10-四-第三丁基-12-甲基-二苯并[d,g]-1,3,2-二氧磷雜八環、2,2’,2”-氮基[三乙基參(3,3’,5,5’-四-第三丁基-1,1’-聯苯-2,2’-二基)亞磷酸酯]、(3,3’,5,5’-四-第三丁基-1,1’-聯苯-2,2’-二基)亞磷酸2-乙基己酯、5-丁基-5-乙基-2-(2,4,6-三-第三丁基苯氧基)-1,3,2-二氧雜磷雜環丙烷。
下列的亞磷酸酯尤其較佳:亞磷酸參(2,4-二-第三丁苯基)酯(Irgafos168,Ciba-Geigy)、亞磷酸參(壬苯基)酯、
4.羥胺類,例如,N,N-二苯甲基羥胺、N,N-二乙基羥胺、N,N-二辛基羥胺、N,N-二月桂基羥胺、N,N-二-十四烷基羥胺、N,N-二-十六烷基羥胺、N,N-二-十八烷基羥胺、N-十六烷基-N-十八烷基羥胺、N-十七烷基-N-十八烷基羥胺、自氫化獸脂胺所衍生之N,N-二烷基羥胺。
5.硝酮類,例如,N-苯甲基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、自氫化獸脂胺所衍生之N,N-二烷基羥胺所衍生之硝酮。
6.硫代協同劑類,例如,硫代二丙酸二月桂酯或硫代二丙酸二硬脂酯。
7.過氧化物去除劑類,例如,β-硫代二丙酸之酯,例如,月桂酯、硬脂酯、肉豆蔻酯或十三烷基酯、巰基苯并咪唑、2-巰基苯并咪唑之鋅鹽、二丁基二硫代胺基甲酸鋅、二-十八烷基二硫化物、異戊四醇肆(β-十二烷巰基)丙酸酯。
8.鹼性共穩定劑類,例如三聚氰胺、聚乙烯基吡咯烷酮、二氰二醯胺、氰尿酸三烯丙酯、尿素衍生物、肼衍生物、胺、聚醯胺、聚胺基甲酸乙酯、高碳脂肪酸之鹼金屬鹽類及鹼土金屬鹽類,例如,硬脂酸鈣、硬脂酸鋅、山萮酸鎂、硬脂酸鎂、蓖麻醇酸鈉及棕櫚酸鉀、焦兒茶酸銻或焦兒茶酸鋅。
9.成核劑類,例如,無機物質,如滑石、金屬氧化物,如二氧化鈦或氧化鎂,較佳為鹼土金屬之磷酸鹽、碳酸鹽或硫酸鹽;有機化合物,如單-或多羧酸及其鹽類,例如4-第三丁基苯甲酸、己二酸、二苯基醋酸、琥珀酸鈉或苯甲酸鈉;聚合物化合物,例如離子共聚合物(〝離子聚合物〞)。尤其佳為1,3:2,4-雙(3’,4’-二甲基亞苯甲基)山梨醇、1,3:2,4-二(對甲基二亞苯甲基)山梨醇及1,3:2,4-二(亞苯甲基)山梨醇。
10.填充劑類及強化劑類,例如,碳酸鈣、矽酸鹽、玻璃纖維、玻璃珠、石綿、滑石粉、高嶺土、雲母、硫酸鋇、金屬氧化物與氫氧化物、碳黑、石墨、木粉及其它天然產品的粉末或纖維、合成纖維。
11.其它添加劑類,例如,增塑劑、潤滑劑、乳化劑、顏料、流變添加劑、催化劑、流動控制劑、光學增亮劑、防火劑、抗靜電劑及吹塑劑。
12.苯并呋喃酮類及吲哚酮類,例如,那些在U.S.4,325,863、U.S.4,338,244、U.S.5,175,312、U.S.5,216,052、U.S.5,252,643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839或EP-A-0591102中所述者或3-[4-(2-乙醯氧基乙氧基)苯基]-5,7-二-第三丁基苯并呋喃-2-酮、5,7-二-第三丁基-3-[4-(2-硬脂醯氧基乙氧基)苯基]苯并呋喃-2-酮、3,3’-雙[5,7-二-第三丁基-3-(4-[2-羥基乙氧基]苯基)苯并呋喃-2-酮]、5,7-二-第三丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮、3-(4-乙醯氧基-3,5-二甲苯基)-5,7-二-第三丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-第三戊醯氧基苯基)-5,7-二-第三丁基苯并呋喃-2-酮、3-(3,4-二甲苯基)-5,7-二-第三丁基苯并呋喃-2-酮、3-(2,3-二甲苯基)-5,7-二-第三丁基苯并呋喃-2-酮。
上述更多的穩定劑及添加劑通常以從0.01%至2%的量被使用。
本發明的主題也為如上述之組成物,其另外包括更多選自由酚系抗氧化劑、亞磷酸酯或亞膦酸酯及苯并呋喃酮或吲哚酮所組成的群組之穩定劑。
可將上述組份及更多添加劑藉由已知的方法併入欲穩定之熱塑性聚合物中,例如,在成形之前或期間或藉由溶解或分散之化合物加入熱塑性聚合物中,若適當時,接著蒸發溶劑。組份可加入具有粉末、顆粒或母液型式的熱塑性聚合物中,其包括例如從2.5至25重量%之濃度的這些組份。
若必要時,可將組份在併入熱塑性聚合物之前互相熔融摻合。彼等也可在聚合之前或期間加入熱塑性聚合物中。
根據本發明所穩定的物質可以各種廣泛的型式被使用,例如,膜、纖維、膠帶、模具組成物或型材。
根據本發明的熱塑性聚合物的加工或變形的實例為:射出吹塑、擠壓、吹塑、滾塑、模內裝飾(反向射出)、搪塑、注塑、共注塑、成形、壓塑、加壓、膜擠壓(鑄膜;吹模)、纖維紡絲(編織、未編織)、拉引(單軸、雙軸)、退火、深拉、壓延、機械變形、燒結、共擠壓、塗佈、壓疊、交聯(輻射、過氧化物、矽烷)、蒸氣沉積、焊接在一起、膠合、熱成形、管材擠壓、型材擠壓、薄片擠壓、擠壓塗佈、減黏裂煉(過氧化物、熱)、纖維熔融吹塑、紡粘、表面處理(電暈放電、火燄、電漿)、消毒(藉由γ射線電子束)、澆鑄聚合(R&M法,RAM擠壓)、凝膠塗佈及膠帶擠壓。
組成物較佳地具有可用於包裝、垃圾場、壓疊、農業與園藝、溫室、護蓋物、隧道、青貯飼料、大梱包裹、游泳池、廢物袋、壁紙、拉伸膜、拉菲亞、鹹水淡化用膜、電池及連接器的膜型式。
特別有利的是農業與園藝應用,如溫室、護蓋物、隧道、遮陽網、青貯飼料及拉菲亞。
本發明進一步的觀點為穩定不含鹵素之熱塑性聚合物的方法,其包含將具有分子量大於400公克/莫耳之不為2,2,6,6-四甲基六氫吡啶衍生物的脂肪族三級胺、選自由羥苯基苯并三唑、羥苯基三、羥基二苯甲酮及草酸苯胺化合物所組成的群組之UV-吸收劑、來自位阻胺類別之光穩定劑、或UV-吸收劑與位阻胺之混合物併入熱塑性聚合物中;以及具有分子量大於400公克/莫耳之不為2,2,6,6-四甲基六氫吡啶衍生物的脂肪族三級胺;及選自由羥苯基苯并三唑、羥苯基三、羥基二苯甲酮及草酸苯胺化合物所組成的群組之UV-吸收劑;或來自位阻胺類別之光穩定劑;或UV-吸收劑與位阻胺之混合物用於穩定不含鹵素之熱塑性聚合物的用途。
已提出定義及優先選擇;彼等也適用於本發明的其它觀點。
屬於二級及三級胺群組之聚乙烯亞胺也適合於本發明的想法。該等聚乙烯亞胺的實例提出於下。
以下的實施例說明本發明。
將15.1公克聚乙烯亞胺(分子量:800)(0.35莫耳單體)溶解在150毫升異丙醇中;將16.2公克(0.0878莫耳)十二醛溶解在50毫升相同的醇中及在惰性氣體下滴入先前的溶液中:反應為放熱。將混合物溫熱至沸騰及蒸餾出100毫升溶劑。在冷卻至周圍溫度之後,將混合物濃縮及回收29.7公克黃色油(產率=99%)。
1
H NMR δ ppm 0.78(t,3H);1-3.5(m,38.6H)。
將15.4公克聚乙烯亞胺(分子量:800)(0.36莫耳單體)溶解在200毫升正丁醇中;將在75毫升水中的29.7公克(0.22莫耳)碳酸鉀之溶液加入最初溶液中。將雙相系統在氮氣下放置在劇烈攪動下。在85℃之溫度下,將59.7公克(0.18莫耳)十八烷基溴緩慢滴入系統中。在這些條件下2小時之後,將混合物冷卻至周圍溫度及將水層分開。將有機相濃縮。在鹽沉澱之後,將其濾除。將溶液濃縮及獲得58.3公克黃色固體(產率=96%)。
1
H NMR δ ppm 0.84(t,3H);1.2(s,30.8H),2.0-3.0(m,6.9H)。
將40.0公克十八胺(0.15莫耳)溶解在250毫升乙醇及30毫升水中。將混合物放置在攪動下及加入5.3公克(0.18莫耳)對-甲醛,接著將系統溫熱至75℃經4小時。在冷卻至周圍溫度之後,獲得固體沉澱物,將其過濾及在90℃下乾燥。得到40.7公克濕固體(97%)。
1
H NMR δ ppm 0.86(t,3H);1.0-1.5(m,29.6H),2.37(t,1.8H),3.3(s,1.8H)。
將40.0公克十二胺(0.22莫耳)溶解在200毫升乙醇及50毫升水中。將混合物放置在攪動下及加入7.8公克(0.26莫耳)對-甲醛,接著將系統溫熱至75℃經4小時。將混合物濃縮及濾除150毫升溶劑,加入200毫升正己烷及將相分開。將氫化卡布酸(hydrocarburic)相濃縮及獲得42.5公克黃色油(99%)。
1
H NMR δ ppm 0.84(t,3H);1.0-1.5(m,20.8H),2.37(t,2.0H),3.3(s,1.8H)。
將10.0公克聚乙烯亞胺(分子量:800)(0.23莫耳單體)溶解在100毫升異丙醇中;將21.4公克(0.12莫耳)十二醛在惰性氣體下加入先前溶液中:反應為放熱。將混合物溫熱至沸騰及蒸餾出70毫升溶劑。在冷卻至周圍溫度之後,將混合物濃縮及回收29.1公克黃色油(99%)。
1
H NMR δ ppm 0.80(t,3H);1.2(s,19.5H),2.0-3.2(m,9.2H)。
將20.0公克N-乙基-二乙醇胺(0.15莫耳)懸浮在20毫升二甲苯中及加入21.9公克琥珀酸二甲酯。將混合物加熱至沸騰溫度及蒸餾出一些溶劑。在冷卻之後,加入作為催化劑的0.3公克第三丁酸鉀及將混合物在氮氣流下加熱至150℃經2.5小時,接著使溫度上升至180℃經4小時。在冷卻之後,將混合物以甲苯稀釋及以水清洗,將有機相分開,乾燥及濃縮。獲得26.1公克棕色油(81%)。
1
H NMR δ ppm 1.0(t,3H);2.6(s,6.0H),2.7(t,4.0H),4.1(t,4.0H)。
將20.0公克聚乙烯亞胺及10.1公克月桂酸甲酯放入50毫升單頸燒瓶中及在大氣壓力下加熱至185℃經1小時。將壓力在相同的溫度下減低至1毫米Hg。在冷卻至周圍溫度之後,回收28.4公克黃色油(99%)。
1
H NMR δ ppm 0.8(t,3H);1.1(s,16.0H),1.5(s,11.3H),2.0-3.6(m,40.9H)。
製備以LDPE(來自Polimeri Europa之Riblene FF29)吹塑擠壓之膜,並將其暴露於阿特拉斯(Atlas)耐氣候色牢度儀(WOM乾燥)及Q-UV耐氣候設計中。為了模擬暴露於硫的環境,故將每一膜事先暴露於元素硫蒸氣中。
在測量UVA降解之前,先將膜以水清洗,以便移除硫。UV吸收劑的降解以UV-可見光光譜法監控及在280-380奈米範圍內以透射率計算。聚合物基質降解係使用FT-IR光譜法的羰基增加量而追蹤。
將結果呈現在表1-4中。
表1顯示羰基增加量,且驚訝地調配物2及3好像非常相似,雖然2不包括HALS。
表2顯示在以硫處理及暴露於WOM之膜在280-380奈密範圍內的透射率。可看出含有三-十二胺之膜的透射率由於較低的UV吸收劑降解而維持較長時間的低值。
表3及4分別顯示在暴露於WOM中沒有硫污染之膜的羰基增加量及殘餘伸長率。
可清楚地看出三-十二胺(TDA)與UVA 1之組合能夠使也沒有硫存在的膜得到某些穩定性。
根據實施例1製備更多組成物,並在暴露於WOM之後測定羰基增加量。將結果提出於表1及2中。
根據實施例B1製備LDPE膜,所使用的胺為支鏈聚乙烯亞胺(PEI)(分子量:15000),一種攜帶二級及三級胺之聚合物結構。以下的表1顯示直到達成50%之餘留的拉伸長率為止的時間(T50)。將樣品以硫處理且暴露於WOM。
根據實施例B1製備一些LDPE膜,所使用的胺為Akzo Nobel的市售商品(表1)。以下的表2顯示直到達成50%之餘留的拉伸長率為止的時間(T50)。將樣品以硫處理且暴露於WOM。
所使用的穩定劑:TDA為三-十二胺UVA 1為
HALS 1為TinuvinNOR 371,其被敘述在US 6 117 995中。
Tinuvin327為來自Ciba Specialty Chemicals之市售UV吸收劑。
Claims (18)
- 一種穩定型聚合物組成物,其包含a)不含鹵素之熱塑性聚合物;b)具有分子量大於400公克/莫耳之脂肪族三級胺,其不是2,2,6,6-四甲基六氫吡啶衍生物;c1)UV-吸收劑,其係選自由羥苯基苯并三唑、羥苯基-三、羥基二苯甲酮及草酸苯胺化物所組成的群組;或c2)來自位阻胺類別的光穩定劑;或c3)UV-吸收劑、組份c1)與組份c2)之位阻胺的混合物。
- 根據申請專利範圍第1項之組成物,其中該熱塑性聚合物為低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)、聚丙烯(PP)或乙烯基醋酸乙酯(EVA)。
- 根據申請專利範圍第1項之組成物,其具有膜或膠帶型式。
- 根據申請專利範圍第1項之組成物,其中羥基二苯甲酮具有式I
羥苯基苯并三唑具有式IIa、IIb或IIc 羥苯基三具有式III 及草酸苯胺化物具有式(IV) 其中在式(I)化合物中,v為從1至3之整數及w為1 或2之整數,以及取代基Z彼此獨立為氫;鹵素;羥基;或具有1至12個碳原子之烷氧基;在式(IIa)化合物中,R1 為氫;具有1至24個碳原子之烷基;在烷基部分中具有1至4個碳原子之苯烷基;具有5至8個碳原子之環烷基;或下式之基 其中R4 及R5 彼此獨立為具有在每一情況中1至5個碳原子之烷基,或R4 與基Cn H2n+1-m 一起形成具有5至12個碳原子之環烷基,m為1或2,n為從2至20之整數,及M為式-COOR6 之基,其中R6 為氫;具有1至12個碳原子之烷基;在烷基部分及烷氧基部分中具有在每一情況中1至20個碳原子之烷氧基烷基;或在烷基部分具有1至4個碳原子之苯烷基,R2 為氫;鹵素;具有1至18個碳原子之烷基;及在烷基部分中具有1至4個碳原子之苯烷基,及R3 為氫;氯;具有在每一情況中1至4個碳原子之烷基或烷氧基;或-COOR6 ,其中R6 如上述所定義,基R1 及R2 中至少一者不為氫;在式(IIb)化合物中,T為氫;或具有1至6個碳原子之烷基, T1 為氫;氯;或在每一情況中具有1至4個碳原子之烷基或烷氧基,n為1或2,及如果n為1時, 則T2 為氯;或式-OT3 或之基,及 如果n為2時,則T2 為式或-O-T9 -O-之 基;其中T3 為氫;具有1至18個碳原子且未被取代或被1至3個羥基或-OCOT6 取代之烷基;具有3至18個碳原子、被-O-或-NT6 -間斷一或多次且未被取代或被羥基或-OCOT6 取代之烷基;具有5至12個碳原子且未被取代或被羥基及/或具有1至4個碳原子之烷基取代之環烷基;具有2至18個碳原子且未被取代或被羥基取代之烯基;在烷基部分中具有1至4個碳原子之苯烷基;或式-CH2 CH(OH)-T7 或之基, T4 及T5 彼此獨立為氫;具有1至18個碳原子之烷基;具有3至18個碳原子且被-O-或-NT6 -間斷一或多次之烷基;具有5至12個碳原子之環烷基;苯基;被具有1至4個碳原子之烷基取代之苯基;具有3至8個碳原子之烯基;在烷基部分中具有1至4個碳原子之苯烷基;或具有2至4 個碳原子之羥烷基,T6 為氫;具有1至18個碳原子之烷基;具有5至12個碳原子之環烷基;具有3至8個碳原子之烯基;苯基;被具有1至4個碳原子之烷基取代之苯基;在烷基部分中具有1至4個碳原子之苯烷基,T7 為氫;具有1至18個碳原子之烷基;未被取代或被羥基取代之苯基;在烷基部分中具有1至4個碳原子之苯烷基;或-CH2 OT8 ,T8 為具有1至18個碳原子之烷基;具有3至8個碳原子之烯基;具有5至10個碳原子之環烷基;苯基;被具有1至4個碳原子之烷基取代之苯基;或在烷基部分中具有1至4個碳原子之苯烷基,T9 為具有2至8個碳原子之伸烷基;具有4至8個碳原子之伸烯基;具有4個碳原子之伸炔基;環伸己基;具有2至8個碳原子且被-O-間斷一或多次之伸烷基;或式-CH2 CH(OH)CH2 OT11 OCH2 CH(OH)CH2 -或-CH2 -C(CH2 OH)2 -CH2 -之基,T10 為具有2至20個碳原子且可被-O-間斷一或多次之伸烷基;或環伸己基,T11 為具有2至8個碳原子之伸烷基;具有2至18個碳原子且被-O-間斷一或多次之伸烷基;1,3-環伸己基;1,4-環伸己基;1,3-伸苯基;或1,4-伸苯基,或T10 及T6 與兩個氮原子一起為六氫吡環;在式(IIc)化合物中, R’2 為C1 -C12 烷基及k為從1至4之數字;在式(III)化合物中,u為1或2及r為從1至3之整數,取代基Y1 彼此獨立為氫;羥基;苯基或鹵素;鹵甲基;具有1至12個碳原子之烷基;具有1至18個碳原子之烷氧基;具有1至18個被基團-COO(C1 -C18 烷基)取代之碳原子的烷氧基;如果u是1,Y2 為具有1至18個碳原子之烷基;未被取代或被羥基、鹵素、具有1至18個碳原子之烷基或烷氧基取代之苯基;具有1至12個碳原子且被-COOH、-COOY8 、-CONH2 、-CONHY9 、-CONY9 Y10 、-NH2 、-NHY9 、-NY9 Y10 、-NHCOY11 、-CN及/或-OCOY11 取代之烷基;具有4至20個碳原子、被一或多個氧原子間斷且未被取代或被羥基或具有1至12個碳原子之烷氧基取代之烷基;具有3至6個碳原子之烯基;環氧丙基;未被取代或被羥基、具有1至4個碳原子之烷基及/或-OCOY11 取代之環己基;在烷基部分中具有1至5個碳原子且未被取代或被羥基、氯及/或甲基取代之苯烷基;-COY12 ;或-SO2 Y13 ,或如果u為2時,則Y2 為具有2至16個碳原子之伸烷基;具有4至12個碳原子之伸烯基;苯二甲基;具有3至20個碳原子、被一 或多個-O-原子間斷及/或被羥基取代之伸烷基;-CH2 CH(OH)CH2 -O-Y15 -OCH2 CH(OH)CH2 ;-CO-Y16 -CO-;-CO-NH-Y17 -NH-CO;或-(CH2 )m -CO2 -Y18 -OCO-(CH2 )m ,其中m為1、2或3,Y8 為具有1至18個碳原子之烷基;具有3至18個碳原子之烯基;具有3至20個碳原子、被一或多個氧或硫原子或-NT6 -間斷及/或被羥基取代之烷基;具有1至4個碳原子且被-P(O)(OY14 )2 、-NY9 Y10 或-OCOY11 及/或羥基取代之烷基;具有3至18個碳原子之烯基;環氧丙基;或在烷基部分具有1至5個碳原子之苯烷基,Y9 及Y10 彼此獨立為具有1至12個碳原子之烷基;具有3至12個碳原子之烷氧基烷基;具有4至16個碳原子之二烷胺基烷基;或具有5至12個碳原子之環己基,或Y9 與Y10 一起為在每一情況中具有3至9個碳原子之伸烷基、氧雜伸烷基或氮雜伸烷基,Y11 為具有1至18個碳原子之烷基;具有2至18個碳原子之烯基;或苯基,Y12 為具有1至18個碳原子之烷基;具有2至18個碳原子之烯基;苯基;具有1至12個碳原子之烷氧基;苯氧基;具有1至12個碳原子之烷胺基;或苯胺基,Y13 為具有1至18個碳原子之烷基;苯基;或在烷基部分具有1至8個碳原子之烷苯基,Y14 為具有1至12個碳原子之烷基;或苯基,Y15 為具有2至10個碳原子之伸烷基;伸苯基;或-伸 苯基-M-伸苯基-,其中M為-O-、-S-、-SO2 -、-CH2 -或-C(CH3 )2 -,Y16 為在每一情況中具有2至10個碳原子之伸烷基、氧雜伸烷基或硫雜伸烷基;伸苯基;或具有2至6個碳原子之伸烯基,Y17 為具有2至10個碳原子之伸烷基;伸苯基;或在烷基部分中具有1至11個碳原子之烷基伸苯基,及Y18 為具有2至10個碳原子之伸烷基;或具有4至20個碳原子且被氧間斷一或多次之伸烷基;在式(IV)化合物中,x為從1至3之整數,以及取代基L彼此獨立為氫;在每一情況中具有1至22個碳原子之烷基、烷氧基或烷硫基;苯氧基;或苯硫基。 - 根據申請專利範圍第1項之組成物,其中該羥苯基三類別的UV-吸收劑具有式(IV)
其中n為1或2;R1 、R’1 、R2 及R’2 彼此獨立為H;OH;C1 -C12 烷基; C2 -C6 烯基;C1 -C12 烷氧基;C2 -C18 烯氧基;鹵素;三氟甲基;C7 -C11 苯烷基;苯基;被C1 -C18 烷基、C1 -C18 烷氧基或鹵素取代之苯基、苯氧基;或被C1 -C18 烷基、C1 -C18 烷氧基或鹵素取代之苯氧基;R3 及R4 彼此獨立為H、C1 -C12 烷基、OR’7 ;C2 -C6 烯基;C2 -C18 烯氧基;鹵素;三氟甲基;C7 -C11 苯烷基;苯基;被C1 -C18 烷基、C1 -C18 烷氧基或鹵素取代之苯基;苯氧基;或被C1 -C18 烷基、C1 -C18 烷氧基或鹵素取代之苯氧基;R6 為氫;C1 -C24 烷基;C5 -C12 環烷基;或C7 -C15 苯烷基;R7 (在其中n=1的情況中)及R’7 彼此獨立為氫;或C1 -C18 烷基;或為C1 -C12 烷基,其被OH、C1 -C18 烷氧基、烯丙氧基、鹵素、-COOH、-COOR8 、-CONH2 、-CONHR9 、-CON(R9 )(R10 )、-NH2 、-NHR9 、-N(R9 )(R10 )、-NHCOR11 、-CN、-OCOR11 、苯氧基及/或被C1 -C18 烷基、C1 -C18 烷氧基或鹵素取代之苯氧基取代;或R7 為被-O-間斷且可被OH取代之C3 -C50 烷基;或R7 為C3 -C6 烯基;環氧丙基;C5 -C12 環烷基;被OH、C1 -C4 烷基或-OCOR11 取代之環己基;未被取代或被OH、Cl或CH3 取代之C7 -C11 苯烷基;-CO-R12 ;或-SO2 -R13 ;在其中n=2的情況中,R7 為C2 -C16 伸烷基;C4 -C12 伸烯基;苯二甲基;被O間斷及/或被OH取代C3 -C20 伸烷基,或為式-CH2 CH(OH)CH2 O-R20 -OCH2 CH(OH)CH2 -、-CO-R21 -CO-、-CO-NH-R22 -NH-CO或 -(CH2 )m -COO-R23 -OOC-(CH2 )m -之基團,其中m為在從1至3之範圍內的數字,或為 R8 為C1 -C18 烷基、C2 -C18 烯基、羥乙基、被O、NH、NR9 或S間斷及/或被OH取代之C3 -C50 烷基;被-P(O)(OR14 )2 、-N(R9 )(R10 )或-OCOR11 及/或OH取代之C1 -C4 烷基;環氧丙基;C5 -C12 環烷基;苯基;C7 -C14 烷苯基;或C7 -C11 苯烷基;R9 及R10 彼此獨立為C1 -C12 烷基;C3 -C12 烷氧基烷基;C4 -C16 二烷胺基烷基;或C5 -C12 環烷基,或R9 與R10 一起為C3 -C9 伸烷基或-氧雜伸烷基或-氮雜伸烷基;R11 為C1 -C18 烷基;C2 -C18 烯基或苯基;C2 -C12 羥烷基;環己基;或為被-O-間斷且可被OH取代之C3 -C50 烷基;R12 為C1 -C18 烷基;C2 -C18 烯基;苯基;C1 -C18 烷氧基;C3 -C18 烯氧基;被O、NH、NR9 或S間斷及/或OH取代之C3 -C50 烷基;環己氧基;C7 -C14 烷基苯氧基;C7 -C11 苯烷氧基;苯氧基;C1 -C12 烷胺基;苯胺基;甲苯胺基;或萘胺基;R13 為C1 -C12 烷基;苯基;萘基;或C7 -C14 烷苯基;R14 為C1 -C12 烷基;甲苯基;或苯基;R20 為C2 -C10 伸烷基;被O、伸苯基或-伸苯基-X-伸苯基(其中X為-O-、-S-、-SO2 -、-CH2 -或-C(CH3 )2 -)間斷之C4 -C50 伸烷基; R21 為C2 -C10 伸烷基;C2 -C10 氧雜伸烷基;C2 -C10 硫雜伸烷基;C6 -C12 伸芳基;或C2 -C6 伸烯基;R22 為C2 -C10 伸烷基;伸苯基;伸甲苯基;二伸苯基甲烷或 基團;及R23 為C2 -C10 伸烷基;或被O間斷之C4 -C20 伸烷基。 - 根據申請專利範圍第1項之組成物,其中該UV-吸收劑為下式之化合物
;G1=CH(CH3 )-COO-C2 H5 , d)R1=R2=CH(CH3 )-COO-C8 H17 ,R3=R4=H;e)R1=R2=R3=CH(CH3 )-COO-C8 H17 ,R4=H與 f)R1=R2=R3=R4=CH(CH3 )-COO-C8 H17 之混合物, - 根據申請專利範圍第1項之組成物,其中該位阻胺係選自由雙(2,2,6,6-四甲基-4-六氫吡啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-六氫吡啶基)琥珀酸酯、雙(1,2,2,6,6-五甲基-4-六氫吡啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-六氫吡啶基)癸二酸酯、正丁基-3,5-二-第三丁基-4-羥基苯甲基丙二酸雙(1,2,2,6,6-四甲基-4-六氫吡啶基)酯、1-羥乙基-2,2,6,6-四甲基-4-羥基六氫吡啶與琥珀酸之縮合物、N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺與4-第三辛胺基-2,6-二氯基-1,3,5-三之直鏈或環族縮合物、參(2,2,6,6-四甲基-4-六氫吡啶基)氮基三醋酸酯、肆(2,2,6,6-四甲基-4-六氫吡啶基)-1,2,3,4-丁烷四羧酸酯、1,1’-(1,2-乙烷二基)-雙(3,3,5,5-四甲基-4-六氫吡酮)、4-苯甲醯基-2,2,6,6-四甲基六氫吡啶、4-硬脂氧基-2,2,6,6-四甲基六氫吡啶、雙(1,2,2,6,6-五甲基六氫吡啶基)-2-正丁基-2-(2-羥基-3,5-二-第三丁基苯甲基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮雜螺旋[4.5]癸烷-2,4-二酮、雙(1-辛氧基-2,2,6,6-四甲基六氫吡啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基六氫吡啶基)琥珀酸酯、N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺與4-嗎啉基-2,6-二氯基-1,3,5-三之直鏈或環族縮合物、2-氯基-4,6-雙(4-正丁胺基-2,2,6,6-四甲基六氫吡啶基)-1,3,5-三與1,2-雙(3-胺丙基胺基)乙烷之縮合物、2-氯基-4,6-二-(4-正丁胺基-1,2,2,6,6-五甲基六氫吡啶基)-1,3,5-三與1,2-雙(3-胺丙基胺基)乙烷之縮合物、8-乙醯基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮雜螺旋[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-六氫吡啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-六氫吡啶基)吡咯烷-2,5-二酮、4-十六烷氧基-與4-硬脂氧基-2,2,6,6-四甲基六氫吡啶之混合物、N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺與4-環己胺基-2,6-二氯基-1,3,5-三之縮合物、1,2-雙(3-胺丙基胺基)乙烷與2,4,6-三氯基-1,3,5-三及4-丁胺基-2,2,6,6-四甲基六氫吡啶之縮合物(CAS登錄第[136504-96-6]號)、1,6-己二胺與2,4,6-三氯基-1,3,5-三及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基六氫吡啶之縮合物(CAS登錄第[192268-64-7]號)、N-(2,2,6,6-四甲基-4-六氫吡啶基)-正十二烷基琥珀醯亞胺、N-(1,2,2,6,6-五甲基-4-六氫吡啶基)-正十二烷基琥珀醯亞胺、2-十一烷基-7,7,9,9-四甲基-1-氧雜-3,8-二氮雜-4-酮基螺旋[4,5]癸烷、7,7,9,9-四甲基-2-環十一烷基-1-氧雜-3,8-二氮雜-4-酮基螺旋[4,5]癸烷與環氧氯丙烷之反應產物、1,1-雙(1,2,2,6,6-五甲基-4-六氫吡啶氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N’-雙-甲醯基-N,N’-雙(2,2,6,6-四甲基-4-六氫吡啶基)六亞甲基二胺、具有1,2,2,6,6-五甲基-4-羥基六氫吡啶之4-甲氧基亞甲基丙二酸之二酯、聚[甲基丙基-3-氧基 -4-(2,2,6,6-四甲基-4-六氫吡啶基)]矽氧烷、馬來酸酐-α-烯烴共聚物與2,2,6,6-四甲基-4-胺基六氫吡啶或1,2,2,6,6-五甲基-4-胺基六氫吡啶之反應產物及US-6117995之實施例2的化合物所組成的群組。
- 根據申請專利範圍第1項之組成物,其中該三級胺為下式之化合物
其中R301 、R302 及R303 獨立為C10 -C36 烷基;R304 、R305 及R306 獨立為C9 -C36 烷基;R310 及R311 獨立為氫或C1 -C18 烷基;R307 及R308 獨立為C1 -C8 伸烷基;k為從之數字;n為從2至20之數字;m為從4至20之數字;及x,y獨立為從3至20之數字。 - 根據申請專利範圍第8項之組成物,其中該三級胺為式(a)化合物。
- 根據申請專利範圍第1項之組成物,其中該三級胺係以熱塑性聚合物重量為基準計0.1-2重量%之量存在。
- 根據申請專利範圍第1項之組成物,其中該UV-吸收劑係以熱塑性聚合物重量為基準計0.01-2重量%之量存在。
- 根據申請專利範圍第1項之組成物,其中該位阻胺係以熱塑性聚合物重量為基準計0.01-2重量%之量存在。
- 根據申請專利範圍第1項之組成物,其中三級胺、UV-吸收劑及/或位阻胺的總量係以熱塑性聚合物重量為基準計從0.2至4重量%。
- 根據申請專利範圍第1項之組成物,其另外包括更多選自由酚系抗氧化劑、亞磷酸酯或亞膦酸酯及苯并呋喃酮或吲哚酮所組成的群組之穩定劑。
- 一種穩定不含鹵素之熱塑性聚合物的方法,其包含 將具有分子量大於400公克/莫耳之不為2,2,6,6-四甲基六氫吡啶衍生物的脂肪族三級胺;選自由羥苯基苯并三唑、羥苯基三、羥基二苯甲酮及草酸苯胺化合物所組成的群組之UV-吸收劑;來自位阻胺類別之光穩定劑;或UV-吸收劑與位阻胺之混合物併入不含鹵素之熱塑性聚合物中。
- 一種具有分子量大於400公克/莫耳之不為2,2,6,6-四甲基六氫吡啶衍生物的脂肪族三級胺;及選自由羥苯基苯并三唑、羥苯基三、羥基二苯甲酮及草酸苯胺化合物所組成的群組之UV-吸收劑用於穩定不含鹵素之熱塑性聚合物的用途。
- 一種具有分子量大於400公克/莫耳之不為2,2,6,6-四甲基六氫吡啶衍生物的脂肪族三級胺;及來自位阻胺類別之光穩定劑用於穩定不含鹵素之熱塑性聚合物的用途。
- 一種具有分子量大於400公克/莫耳之不為2,2,6,6-四甲基六氫吡啶衍生物的脂肪族三級胺;及UV-吸收劑與位阻胺之混合物用於穩定不含鹵素之熱塑性聚合物的用途。
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| KR20080094670A (ko) | 2008-10-23 |
| ZA200805900B (en) | 2009-10-28 |
| IL192789A0 (en) | 2009-02-11 |
| US8173728B2 (en) | 2012-05-08 |
| ECSP088659A (es) | 2008-09-29 |
| BRPI0707359A2 (pt) | 2011-05-03 |
| US20100222471A1 (en) | 2010-09-02 |
| TW200740900A (en) | 2007-11-01 |
| EP1979406B1 (en) | 2012-10-24 |
| BRPI0707359B1 (pt) | 2018-10-09 |
| BRPI0707359A8 (pt) | 2018-04-03 |
| WO2007088114A1 (en) | 2007-08-09 |
| ES2398248T3 (es) | 2013-03-14 |
| CA2636831A1 (en) | 2007-08-09 |
| MX2008009972A (es) | 2008-08-14 |
| CN101379122A (zh) | 2009-03-04 |
| CA2636831C (en) | 2014-08-12 |
| MA30219B1 (fr) | 2009-02-02 |
| PT1979406E (pt) | 2013-01-28 |
| PL1979406T3 (pl) | 2013-03-29 |
| CN101379122B (zh) | 2012-09-26 |
| KR101368176B1 (ko) | 2014-03-14 |
| JP5308165B2 (ja) | 2013-10-09 |
| EP1979406A1 (en) | 2008-10-15 |
| MX304143B (es) | 2012-10-09 |
| JP2009525370A (ja) | 2009-07-09 |
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