CN115010911A - Polymeric steric hindrance amine and preparation method and application thereof - Google Patents
Polymeric steric hindrance amine and preparation method and application thereof Download PDFInfo
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- CN115010911A CN115010911A CN202210630614.2A CN202210630614A CN115010911A CN 115010911 A CN115010911 A CN 115010911A CN 202210630614 A CN202210630614 A CN 202210630614A CN 115010911 A CN115010911 A CN 115010911A
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- Prior art keywords
- alkyl
- groups
- alkyl interrupted
- interrupted
- hindered amine
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- 150000001412 amines Chemical class 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000001424 substituent group Chemical group 0.000 claims abstract description 28
- 239000004611 light stabiliser Substances 0.000 claims abstract description 25
- 239000002861 polymer material Substances 0.000 claims abstract description 15
- 239000003607 modifier Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- -1 -OH Chemical group 0.000 claims description 189
- 125000000217 alkyl group Chemical group 0.000 claims description 165
- 125000003118 aryl group Chemical group 0.000 claims description 45
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 36
- 125000000732 arylene group Chemical group 0.000 claims description 35
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 28
- 125000001072 heteroaryl group Chemical group 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 19
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 125000006850 spacer group Chemical group 0.000 claims description 12
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 10
- 239000003063 flame retardant Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 8
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 8
- 125000005549 heteroarylene group Chemical group 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- 125000004685 alkoxythiocarbonyl group Chemical group 0.000 claims description 6
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920006324 polyoxymethylene Polymers 0.000 claims description 6
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 6
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 5
- 125000004406 C3-C8 cycloalkylene group Chemical group 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 4
- 125000000266 alpha-aminoacyl group Chemical group 0.000 claims description 4
- 125000003435 aroyl group Chemical group 0.000 claims description 4
- 125000005333 aroyloxy group Chemical group 0.000 claims description 4
- 125000001589 carboacyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 4
- 125000005226 heteroaryloxycarbonyl group Chemical group 0.000 claims description 4
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 3
- 229930182556 Polyacetal Natural products 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920002396 Polyurea Polymers 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 2
- 125000002431 aminoalkoxy group Chemical group 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 125000005844 heterocyclyloxy group Chemical group 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- 239000012704 polymeric precursor Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000003712 anti-aging effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 57
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 22
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 10
- 150000005840 aryl radicals Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
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- 239000004698 Polyethylene Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002736 metal compounds Chemical group 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
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- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
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- 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 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
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- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 125000005561 phenanthryl group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- 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
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrogenated Pyridines (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a polymeric steric hindrance amine and a preparation method and application thereof. In the invention, the polymeric high molecular weight steric hindrance amine stabilizer is obtained by carrying out polymerization reaction on a high molecular matrix to be modified and a steric hindrance amine modifier. The novel steric hindrance amine light stabilizer has the advantages of high-efficiency anti-aging performance, high molecular weight, difficult emigration in a high polymer material product, good thermal stability and the like, and can also have good compatibility with different types of high polymer materials by changing substituent groups; the NOR amine ether type high molecular compound obtained by selecting the polymerization reaction of the steric hindrance amine modifier containing the NOR amine ether structure has the advantages of low alkalinity, flame retardance and the like. The preparation method provided by the invention is simpler, low-carbon and environment-friendly.
Description
Technical Field
The invention relates to the technical field of macromolecules, and particularly relates to a polymeric steric hindrance amine and a preparation method and application thereof.
Background
The polymer is used as a material with low cost and strong plasticity to play an increasingly important role in daily life, but the polymer material is subjected to yellowing, hardening and embrittlement phenomena in the using process due to invasion of factors such as oxygen, light, heat and the like. In order to alleviate this process, an antioxidant, thermal or optical additive is usually added during the processing of the polymer product to maintain the properties and ensure the service life of the polymer material.
Hindered Amine Light Stabilizers (HALS) are commonly used plastics additives, especially products of the piperidine series, e.g.
770、
938、UV-3838、
2020(EP782994)、
HS-950、
292、
379、UV-3929、
HS-625. However, the intrinsic basicity of piperidinyl groups itself significantly limits their range of use, for example, the mildly acidic environment of use can protonate piperidinyl groups to lose efficacy. Furthermore, this basic character also accelerates the hydrolysis process of parts of the polymeric material (e.g. PET). Therefore, the development of low-alkaline HALS products is also receiving increasing attention. Meanwhile, the multifunctionalization of the auxiliary agent is also a research hotspot in the field. For example, NOR type polymeric light stabilizers have not only the characteristics of low alkalinity, migration resistance, extraction resistance, etc., but also flame retardant properties. Polymeric NOR hindered amine stabilizers are therefore receiving increasing market and research and development attention.
Patent CN 100384826C describes a preparation method of NOR 371 by nucleophilic substitution reaction of Chimassorb 2020 with allyl bromide, oxidative rearrangement with peroxyacetic acid, and final hydrogenation reduction. However, in the production process, the synthesis step of NOR 371 is long, the process is complicated, and the cost of raw materials is high, so that the price of NOR 371 is high, and the application range of NOR is greatly limited.
Patent US 8765848B2 skillfully grafts small molecule HALS onto paraffin, which is a relatively convenient production route, but its effective piperidine ring content is greatly limited due to paraffin and modification of long chain structure on the graft.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polymeric sterically hindered amine light stabilizer, and a preparation method and application thereof.
In a first aspect of the present invention, there is provided a polymeric sterically hindered amine light stabilizer having the structure of formula (I):
A. b are the same or different sterically hindered amine structures.
n is the degree of polymerization of the polymeric sterically hindered amine and is an integer from 3 to 1000, preferably an integer from 3 to 200, more preferably an integer from 3 to 30, particularly preferably an integer from 3 to 25, and most preferably an integer from 3 to 20 (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20).
k and t each represent the average number of A, B grafted on each repeating unit, and k and t are independently selected from 0 to 10, preferably 0 to 5 (e.g., 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.5, 4.0, 4.5, 5.0), more preferably 0 to 3; particularly preferably 0 to 2, and (k + t). times.n.gtoreq.1; in another embodiment of the invention, k is selected from 0-2, t is selected from 0-1, and (k + t) × n ≧ 1; in one embodiment of the present invention, k is 0, t is 0.001 to 5 (preferably 0.7, 0.8); in another embodiment of the invention, t is 0, k is 0.001 to 5 (preferably 1.8);
R 1 selected from the group consisting of a single bond, C1-C22 alkylene, C3-C8 cycloalkylene, C4-C30 cycloalkylene alkyl, C6-C18 arylene; C7-C40 arylenealkyl; C1-C18 heterocyclylene; C2-C40 heterocyclylalkyl; wherein k hydrogen atoms in the above groups are substituted by A-O-; (R) 1 When the bond is a single bond, k is 0);
wherein said alkyl may be substituted by one or more of nitrogen, oxygen, sulfur, arylene, -C (═ O) -O-, -O-C (═ O) -O-, -C (═ O) -N (R) 3 )-、-N(R 3 )-C(＝O)-N(R 4 ) -a spacer alkyl group; or alkyl substituted by one or more of C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy, aryl;
said cycloalkaneA group may be substituted by one or more of nitrogen, oxygen, sulfur, arylene, -C (═ O) -O-, -O-C (═ O) -O-, -C (═ O) -N (R) — N 3 )-、-N(R 3 )-C(＝O)-N(R 4 ) Interrupted cycloalkyl, cycloalkyl which is also substituted by one or more C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy, aryl;
the aryl group comprises an all-carbon aryl group and a heteroaryl group, and the aryl group can be substituted by one or more C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy and aryl;
the heteroatom is selected from nitrogen, oxygen and sulfur.
Preferably, R 1 Selected from the group consisting of C1-C22 alkylene, C1-C18 heterocyclylene, C2-C40 heterocyclylene alkyl; more preferably, R 1 Selected from C1-C20 alkylene,
Wherein b is an integer from 1 to 20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20), e.g., R 1 Is selected from-CH 2 -CH 2 -、-(CH 2 ) 12 -、-(CH 2 ) 14 -、
-CH(CH 2 ) 14 -CH 2 -、
In one embodiment of the present invention, R is 1 Is C1-C22 alkylene; preferably, R is 1 Is C1-C20 alkylene; more preferably, R is 1 Selected from: c2 alkylene, C12 alkylene, C14 alkylene, C16 alkylene, e.g. -CH 2 -CH 2 -、-(CH 2 ) 12 -、-(CH 2 ) 14 -、-CH(CH 2 ) 14 -CH 2 -、
Most preferably, said R 1 Is C2 alkylene;
in another embodiment of the present invention, R is 1 Is C1-C18 heterocyclylene or C2-C40 heterocyclylalkyl, e.g.
(e.g. in
)。
R 2 Selected from the group consisting of C1-C22 alkylene, C3-C8 cycloalkylene, C4-C30 cycloalkylene alkyl, C6-C18 arylene, C7-C40 arylene alkyl, C1-C18 heterocyclylene, C2-C40 heterocyclylene alkyl; wherein t hydrogen atoms in the above groups are substituted by B-O-; when R is 2 When the aryl is C6-C18 arylene, t is 0;
wherein said alkyl may be substituted by one or more of nitrogen, oxygen, sulfur, arylene, -C (═ O) -O-, -O-C (═ O) -O-, -C (═ O) -N (R) 3 )-、-N(R 3 )-C(＝O)-N(R 4 ) -a spacer alkyl group; or alkyl substituted by one or more of C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy, aryl;
said cycloalkyl may be optionally substituted by one or more of nitrogen, oxygen, sulfur, arylene, -C (═ O) -O-, -O-C (═ O) -O-, -C (═ O) -N (R) 3 )-、-N(R 3 )-C(＝O)-N(R 4 ) Interrupted cycloalkyl, cycloalkyl which is also substituted by one or more C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy, aryl;
the aryl group comprises an all-carbon aryl group and a heteroaryl group, and the aryl group can be substituted by one or more C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy and aryl;
the heteroatom is selected from nitrogen, oxygen and sulfur.
Preferably, R is 2 Selected from: C1-C15 alkylene, C6-C10 arylene, e.g. - (CH) 2 ) 14 -, ethylene, methyleneRadicals, phenylene radicals (e.g. for
In particular
)、-(CH 2 ) 6 -, naphthylene (for example)
In particular to
) In particular, R 2 Is methylene;
X 1 、X 2 independently selected from: single bond, -O-, -S-, -N (R) 3 ) -, in which R 3 Selected from: H. C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, C6-C18 aryl, C4-C20 heteroaryl;
preferably, said X 1 、X 2 Independently selected from: a single bond, -O-, -NH-.
More preferably, X is 1 、X 2 Are all single bonds;
Y 1 and Y 2 Independently selected from: single bond, -O-, -S-, -N (R) 4 ) -, in which R 4 Selected from the group consisting of: C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, C6-C18 aryl, C4-C20 heteroaryl;
preferably, said Y is 1 And Y 2 Independently selected from: a single bond, -O-, -NH-.
More preferably, said Y is 1 And Y 2 Are all-O-.
R T1 、R T2 Are the same or different end capping groups.
Further, said R T1 Selected from:
-OH, C1-C12 alkyl (such as methyl, ethyl, propyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl), C1-C12 alkoxy, wherein X is selected from: phenyl, naphthyl, C1-C30 alkyl (such as methyl, ethyl, propyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, C25 alkyl, C26 alkyl, C27 alkyl, C28 alkyl, C29 alkyl, C30 alkyl), R A Selected from: C1-C12 alkyl (such as methyl, ethyl, propyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl);
further, R is T2 Selected from: -H, C1-C12 alkyl (e.g. methyl, ethyl, propyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl), -OH, C1-C12 alkoxy; further, the polymeric hindered amine described above may have the following structure:
h. o is an integer of 1 to 30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30), respectively, e.g., h is an integer of 2 to 22; o is an integer from 6 to 22, C is A linking site available for the structure-O-A,
preferably, the polymeric hindered amine may have the following structure:
more preferably, the polymeric hindered amine may have the following structure:
further, the hindered amine structure has a structure represented by general formula (II):
wherein G is 1 、G 2 Independently selected from: C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, or G 1 And G 2 Together with the carbon atoms to which they are commonly attached form a 3-8 membered cycloalkyl group and a 3-8 membered heterocycloalkyl group;
preferably, G 1 、G 2 Each independently selected from: C1-C6 alkyl;
more preferably still, the first and second liquid crystal compositions are,G 1 、G 2 each independently selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, most preferably, G 1 、G 2 Are both methyl;
E 1 、E 2 、E 3 independently selected from: -O-,
and E 1 And E 2 Cannot be simultaneously-O-or
And, E 2 And E 3 Cannot be simultaneously-O-or
a is 0, 1 or 2, preferably, a is 1; preferably, E 1 、E 2 、E 3 Independently selected from:
w is selected from: oxygen, N-R 7 、NOH、NOR 7 、CHR 7 (ii) a Wherein R is 7 Selected from: C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, C6-C18 aryl, C4-C20 heteroaryl, preferably, W is oxygen;
wherein R is 5 And R 6 Independently selected from: hydrogen, -OR 8 、-N(R 8 )C(＝O)R 9 、-O-C(＝O)-R 8 、-O-C(＝O)O-R 8 、-R 8 、-NR 8 R 9 Or R 8 And R 9 Together with the N atom to which they are both attached form a 5-7 membered heterocycloalkyl, -N (R) 8 )C(＝O)NR 9 、
Or R 5 And R 6 Together with the C atom to which they are both attached form a 3-8 membered carbocyclic ring or a 5-8 membered heterocycloalkyl or a 16-20 membered polyspirocyclic group, preferably, R 5 And R 6 Independently selected from: hydrogen, -O-C (═ O) -R 8 ；
Wherein R is 8 、R 9 Independently selected from: hydrogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, heteroalkyl, heterocyclyloxy, heterocyclyloxyamidoalkylamino, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (═ O) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (═ S) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by a combination of the above spacer groups, heteroaryl, and combinations thereof, Alkyl substituted with one or more substituents, aryl substituted with one or more substituents, heteroaryl substituted with one or more substituents, heteroalkyl substituted with one or more substituents, cycloalkyl substituted with one or more substituents; the substituents are selected from the group consisting of: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyloxy, heteroaryloxy, cycloalkyloxy, heteroalkylacyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, aminoalkylacyloxy, aminoalkylaminoacylamino, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more-OC (═ O) O-, alkyl interrupted by one or more-C (═ O) -O-, alkyl interrupted by one or more-C (═ S) O-, alkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heteroalkyloxy, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonylalkyl, alkoxythiocarbonyl, alkoxythioacyl, aminoalkyloxy, aminoalkylacyloxy, aminoalkylaminoacyloxy, aminoalkylaminoacylamino, alkylaminoalkylamino, alkyl interrupted by one or more-C (═ O-, (S) O-, alkyl, Alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groupsAlkyl interrupted by one or more amine groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by combinations of the above spacer groups.
Further, R 8 、R 9 May be independently selected from: hydrogen, alkyl (e.g. C1-C22 alkyl, C1-C18 alkyl, especially C1-C18 alkyl),
Wherein i is an integer from 0 to 22, j is an integer from 0 to 21, and wherein said C1-C18 alkyl group may be: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, -C 16 H 33 In particular, R 8 、R 9 May each be independently selected from: methyl, -C 16 H 33 (ii) a More particularly, R 8 Is methyl.
R 10 Selected from: hydrogen, C1-C22 alkyl (e.g. C1-C10 alkyl, C1-C8 alkyl, especially C1-C8 alkyl), 3-8 membered cycloalkyl, C6-C30 aryl, C4-C20 heteroarylene, where the C1-C8 alkyl can be methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, especially R 10 Is n-butyl.
Y 3 、Y 4 Each independently selected from: a single bond, N, O; y is 3 、Y 4 When it is a single bond or O, the corresponding R 12 、R 14 Is absent.
R 11 、R 12 、R 13 、R 14 Each independently selected from: hydrogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, heteroalkyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (═ O) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more alkynyl groupsS) O-interrupted alkyl, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more substituents, aryl substituted by one or more substituents, heteroaryl substituted by one or more substituents, heteroalkyl substituted by one or more substituents, cycloalkyl substituted by one or more substituents; the substituents are selected from the group consisting of: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyloxy, heteroaryloxy, cycloalkyloxy, heteroalkylacyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more-OC (═ O) O-, alkyl interrupted by one or more-C (═ O) -S, alkyl interrupted by one or more-C (═ S) O-, alkyl interrupted by one or more amide groups, Alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by combinations of the above spacer groups; or, R 11 And R 12 And Y in the middle thereof 4 Forming a heterocyclic group; or, R 13 And R 14 And Y in the middle thereof 3 Forming a heterocyclic group;
further, R 11 、R 12 、R 13 、R 14 May each be independently selected from: hydrogen, C1-C22 alkyl (e.g. C1-C10 alkyl, e.g. methyl, ethyl, n-propyl, isopropyl, n-butylN-pentyl, n-hexyl,
) 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl (e.g. phenyl, naphthyl, anthryl, phenanthryl, etc.)
) Aryl of C6-C30, heteroaryl of C4-C20; or, R 11 And R 12 And Y in the middle thereof 4 To form a 3-to 8-membered heterocycloalkyl group (e.g.
) (ii) a Or R 13 And R 14 And Y in the middle thereof 3 To form a 3-to 8-membered heterocycloalkyl group (e.g.
Further, the sterically hindered amine is selected from the following structures:
Preferably, the sterically hindered amine is selected from the following structures:
more preferably, the sterically hindered amine is selected from the following structures:
most preferably, the sterically hindered amine is selected from the following structures:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
wherein k is 0 to 10, in particular k is 0.6; in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
wherein k is 0 to 10, in particular k is 0.6;
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
in one embodiment of the present invention, the polymeric sterically hindered amine light stabilizer has the following structure:
In a second aspect of the present invention, there is provided a method for preparing the polymeric sterically hindered amine light stabilizer of the first aspect, which comprises the step of polymerizing the polymer matrix to be modified and the sterically hindered amine modifier under the action of a catalyst and a hydroperoxide.
Further, the polymerization reaction comprises the steps of dissolving the parent polymer (III) to be modified and the hindered amine modifier (II) in a solvent or heating to a molten state, sequentially adding a catalyst and hydroperoxide, and reacting to generate the polymeric polymer sterically hindered amine shown in the general formula I, wherein the general formula is as follows:
wherein, the reactant 1 and the reactant 2 are steric hindrance amine modifier, and the parameter values in the general formula are as described above.
Further, reactant 1 is A-H or A-O · (free radical)A base).
Further, reactant 2 is B-H or B-O · (free radical).
Further, the above polymerization reaction may be carried out in a solvent, which may be selected from: tetrahydrofuran, 2-methyltetrahydrofuran, halogenated hydrocarbons (such as dichloromethane, dichloroethane, carbon tetrachloride and the like), acetonitrile, propionitrile, butyronitrile, aromatic hydrocarbons (such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene and the like), aliphatic hydrocarbons (such as petroleum ether, N-hexane, N-heptane, cyclohexane, N-octane and the like), alcohols (such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether), dimethyl sulfoxide, N-dimethylformamide, diphenyl ether, preferably, the solvent is selected from one or more of: aromatic hydrocarbons (e.g., benzene, toluene, xylene, chlorobenzene, dichlorobenzene, etc.), aliphatic hydrocarbons (e.g., petroleum ether, n-hexane, n-heptane, cyclohexane, n-octane, etc.), more preferably, the solvent is selected from: one or more of benzene, dichlorobenzene, and chlorobenzene.
Further, the catalyst is a metal compound, wherein the metal in the metal compound is selected from the group consisting of the metal elements of groups IVb, vb, VIb, VIIb and VIII of the periodic Table of the elements.
Further, the metal compound is selected from one or more of vanadyl acetylacetonate, vanadium (trivalent) acetylacetonate, cobalt carbonyl, chromium oxide (hexavalent), n-butyl titanate, isopropyl titanate, molybdenum hexacarbonyl, molybdenum trioxide, vanadium pentoxide, chromium trioxide and tungsten trioxide; preferably, the metal compound is selected from one or more of molybdenum trioxide, vanadium pentoxide, chromium trioxide and tungsten trioxide.
Further, the molar ratio of the used amount of the catalyst to the used amount of the hindered amine modifier is 1: 10000 to 6: 10, preferably 1: 100 to 3: 10, more preferably 1: 100 to 15: 100.
further, the reaction temperature of the polymerization reaction is 0 to 300 ℃, preferably 0 to 250 ℃, more preferably 25 to 100 ℃, and particularly preferably 45 to 150 ℃.
Further, the molar ratio of the usage amount of the hindered amine modifier to the long chain link in the polymer matrix is 1: 10 to 3: 1, preferably 1: 5 to 1:1, more preferably 1: 3 to 1: 2.
further, the hydroperoxide is inorganic hydroperoxide or organic hydroperoxide.
Further, the inorganic hydroperoxide comprises H 2 O 2 (ii) a The organic hydroperoxide includes alkyl hydroperoxide and aryl hydroperoxide, preferably, the alkyl hydroperoxide includes tertiary alkyl hydroperoxide (such as tert-butyl hydroperoxide, tert-amyl hydroperoxide, tert-hexyl hydroperoxide, tert-octyl hydroperoxide), and the aryl hydroperoxide includes ethylbenzene hydroperoxide, tetrahydronaphthalene peroxide or cumene hydroperoxide.
In some embodiments of the invention, the hydroperoxide is selected from the group consisting of: h 2 O 2 Tert-butyl hydroperoxide or cumene hydroperoxide.
Further, the hydroperoxide is used in an amount of 1 to 20 molar equivalents, preferably 1 to 10 molar equivalents, and more preferably 1 to 5 molar equivalents.
Further, the polymerization reaction is carried out in a protective gas, which may be a chemically inert noble gas such as nitrogen, helium or argon.
Further, the pressure of the polymerization reaction is 0.5 to 30bar, preferably 0.5 to 20bar, more preferably 0.5 to 10bar (e.g., 0.5bar, 1.01bar, 1.5bar, 2.0bar, 2.5bar, 3.0bar, 3.5bar, 4.0bar, 4.5bar, 5.0bar, 5.5bar, 6.0bar, 7.0bar, 7.5bar, 8.0bar, 8.5bar, 9.0bar, 9.5bar, 10.0bar, etc.).
In a third aspect of the present invention, a polymer additive is provided, which includes the polymeric sterically hindered amine structure described in the first aspect, and the polymer additive can be used as a light stabilizer and/or a flame retardant in the production, processing, and use processes of a polymer material product, so as to delay or organize aging of the polymer material product, improve the service performance of the polymer material product, and prolong the service life of the polymer material product.
Further, the polymer auxiliary may further include one or more of an antioxidant, a UV absorber, a hindered amine light stabilizer, a reinforcing agent, a filler, a flame retardant, a plasticizer, a lubricant, an emulsifier, a pigment, a rheological additive, a catalyst, a flow control agent, an optical brightener, a fire retardant, an antistatic agent, a foaming agent, and the like.
In a fourth aspect of the invention, there is provided a composition comprising a polymeric sterically hindered amine structure according to the first aspect and one or more organic substances which are sensitive to light, heat or oxidation.
Further, the composition may further include one or more of an antioxidant, a UV absorber, a hindered amine light stabilizer, a reinforcing agent, a filler, a flame retardant, a plasticizer, a lubricant, an emulsifier, a pigment, a rheological additive, a catalyst, a flow control agent, an optical brightener, a fire retardant, an antistatic agent, a foaming agent, and the like.
Further, the amount of polymeric sterically hindered amine in the composition depends on the nature of the organic material, the end use application and the additives, and the polymeric sterically hindered amine may be used in various proportions.
Further, the amount of polymeric sterically hindered amine in the composition may be, for example, from 0.01 to 5 wt%, such as 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 1%, 2%, 3%, 4%, 5%, preferably from 0.05 to 2 wt%, more preferably from 0.05 to 1 wt% by weight of the organic material.
Further, the organic substance may be selected from: polyolefin, acrylonitrile/butadiene/styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyurethane, polyester, polysulfone, polyurea, polystyrene, thermoplastic elastomer, or a combination of two or more thereof.
Further, the polyolefin may be obtained by polymerizing or copolymerizing an α -olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like, and some cyclic olefins alone, for example, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyvinyl chloride, ethylene-vinyl acetate copolymer and the like, preferably polyethylene or polypropylene.
Further, the polyacetal may be selected from: polyoxymethylene, polyoxymethylene containing ethylene oxide as comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
Further, the polyamide may be selected from: polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 66, polyamide 610, polyamide 69, polyamide 612, polyamide 46, polyamide 1212, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylylenediamine and adipic acid; polyamides obtained from hexamethylene and isophthalic or/and terephthalic acid in the presence or absence of an elastomer as modifier.
Further, the polyester may be selected from: polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones thereof, for example polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, and also block copolyether esters of hydroxyl-terminated polyether derivatives, and polyesters modified with polycarbonates or MBS.
Further, the thermoplastic elastomer may be selected from: polyolefin thermoplastic elastomers and block copolymer type polystyrene thermoplastic elastomers. The polyolefin thermoplastic elastomer includes a polyolefin resin such as polyethylene and polypropylene serving as a hard segment and a rubber composition such as ethylene-propylene-diene Elastomer (EPDM) serving as a soft segment. The block copolymer type polystyrene thermoplastic elastomer comprises polystyrene serving as a hard segment and a polydiene (such as polybutadiene or polyisoprene) serving as a soft segment. Alternatively, blends of polyolefin elastomers and polystyrene elastomers may also be used as the thermoplastic elastomer of the present invention. The methods for combining the soft segment and the hard segment in the thermoplastic elastomer can be roughly classified into simple blending, implantation by copolymerization, and dynamic crosslinking. Combinations of polystyrene thermoplastic elastomer segments include SBS, SIS, SEBS, SEPS, hydrogenated polymers of any of these four copolymers, hydrogenated polymers of SBR (HSBR), and blends of polypropylene with one or more of any of these polymers.
Further, the antioxidant may be selected from: phenolic and/or aminic antioxidants, phosphites, thioesters, and the like, for example, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168, and the like.
Further, the UV absorber may be selected from: salicylic acid esters, benzoic acid esters, benzophenones, benzotriazole and triazine ultraviolet absorbers.
Further, the hindered amine light stabilizer is selected from: hindered amine light stabilizers having a structure different from that of the compound of the present invention or a mixture thereof, for example, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, a polymer of succinic acid with 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol, Chimassorb 944, Chimassorb 2020, UV-3346, UV-3529, Tinuvin 770, Tinuvin622LD, Tinuvin 292, HS-625, HS-950 and the like.
Further, the filler and reinforcing agent may be selected from: calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flour or other natural product fibers, synthetic fibers and the like.
In a fifth aspect of the invention there is provided the use of a polymeric sterically hindered amine structure according to the first aspect in the preparation of a light stabilizer and/or flame retardant.
Furthermore, the light stabilizer and the flame retardant are used in the production, processing and use processes of the high polymer material product to delay or organize the aging of the high polymer material product, improve the service performance and prolong the service life of the high polymer material product.
In a sixth aspect of the present invention, there is provided the polymeric sterically hindered amine structure of the first aspect, and the use of the polymeric additive of the third aspect in the preparation of polymeric material articles.
Further, the polymer material product may be, for example, plastic, rubber, fiber, paint, adhesive, composite material, etc., which may be used in the fields of automobile interior or exterior decoration materials, floating devices, road traffic devices, agricultural products, electric appliances, furniture, footwear, sanitary products, health products, etc.
Further, the plastic product may be manufactured by any method known to those skilled in the art, including, but not limited to, extrusion blow molding, film casting, calendering, injection molding, blow molding, compression molding, thermoforming, spin forming, blow extrusion, and rotational casting.
In the invention, the polymeric high molecular weight steric hindrance amine stabilizer is obtained by carrying out polymerization reaction on a high molecular matrix to be modified and a steric hindrance amine modifier. The novel steric hindrance amine light stabilizer has the advantages of high-efficiency anti-aging performance, high molecular weight, difficult emigration in a high polymer material product, good thermal stability and the like, and can also have good compatibility with different types of high polymer materials by changing substituent groups; the NOR amine ether type high molecular compound obtained by selecting the polymerization reaction of the steric hindrance amine modifier containing the NOR amine ether structure has the advantages of low alkalinity, flame retardance and the like. The preparation method provided by the invention is simpler, low-carbon and environment-friendly.
The term C1-C22 alkylene as used herein includes C 1 Alkylene radical, C 2 Alkylene radical, C 3 Alkylene radical, C 4 Alkylene radical, C 5 Alkylene radical, C 6 Alkylene radical, C 7 Alkylene radical, C 8 Alkylene radical, C 9 Alkylene radical, C 10 Alkylene radical, C 11 Alkylene radical, C 12 Alkylene radical, C 13 Alkylene radical, C 14 Alkylene radical, C 15 Alkylene radical, C 16 Alkylene radical, C 17 Alkylene radical, C 18 Alkylene radical, C 19 Alkylene radical, C 20 Alkylene radical, C 21 Alkylene radical, C 22 An alkylene group.
The term C1-C20 alkylene as used herein includes C 1 Alkylene radical, C 2 Alkylene radical, C 3 Alkylene radical, C 4 Alkylene radical, C 5 Alkylene radical, C 6 Alkylene radical, C 7 Alkylene radical, C 8 Alkylene radical, C 9 Alkylene radical, C 10 Alkylene radical, C 11 Alkylene radical, C 12 Alkylene radical, C 13 Alkylene radical, C 14 Alkylene radical, C 15 Alkylene radical, C 16 Alkylene radical, C 17 Alkylene radical, C 18 Alkylene radical, C 19 Alkylene radical, C 20 An alkylene group.
The term C3-C8 cycloalkylene as used herein includes C 3 Cycloalkylene radical, C 4 Cycloalkylene radical, C 5 Cycloalkylene radical, C 6 Cycloalkylene radical, C 7 Cycloalkylene radical, C 8 Cycloalkylene radicals.
If an alkylene group is substituted with a cycloalkyl group, it is correspondingly "cycloalkylenealkyl".
If an alkylene group is substituted with an aryl group, it is correspondingly "arylenealkyl".
If an alkylene group is substituted by a heterocyclyl group, it is correspondingly "heterocyclylalkyl".
The term C6-C18 arylene as used herein includes C6 arylene, C7 arylene, C8 arylene, C9 arylene, C10 arylene, C11 arylene, C12 arylene, C13 arylene, C14 arylene, C15 arylene, C16 arylene, C17 arylene, C18 arylene.
The term C5-C18 heterocyclylene as used herein includes C5 heterocyclylene, C6 heterocyclylene, C7 heterocyclylene, C8 heterocyclylene, C9 heterocyclylene, C10 heterocyclylene, C11 heterocyclylene, C12 heterocyclylene, C13 heterocyclylene, C14 heterocyclylene, C15 heterocyclylene, C16 heterocyclylene, C17 heterocyclylene, C18 heterocyclylene.
The term C1-C12 alkyl as used herein includes C 1 Alkyl radical, C 2 Alkyl radical, C 3 Alkyl radical, C 4 Alkyl radical, C 5 Alkyl radical, C 6 Alkyl radical, C 7 Alkyl radical, C 8 Alkyl radical, C 9 Alkyl radical, C 10 Alkyl radical, C 11 Alkyl radical, C 12 An alkyl group.
The term C1-C18 alkyl as used herein includes C 1 Alkyl radical, C 2 Alkyl radical, C 3 Alkyl radical, C 4 Alkyl radical, C 5 Alkyl radical, C 6 Alkyl radical, C 7 Alkyl radical, C 8 Alkyl radical, C 9 Alkyl radical, C 10 Alkyl radical, C 11 Alkyl radical, C 12 Alkyl radical, C 13 Alkyl radical, C 14 Alkyl radical, C 15 Alkyl radical, C 16 Alkyl radical, C 17 Alkyl radical, C 18 An alkyl group.
The term C1-C30 alkyl as used herein includes C 1 Alkyl radical, C 2 Alkyl radical, C 3 Alkyl radical, C 4 Alkyl radical, C 5 Alkyl radical, C 6 Alkyl radical, C 7 Alkyl radical, C 8 Alkyl radical, C 9 Alkyl radical, C 10 Alkyl radical, C 11 Alkyl radical, C 12 Alkyl radical, C 13 Alkyl radical, C 14 Alkyl radical, C 15 Alkyl radical, C 16 Alkyl radical, C 17 Alkyl radical, C 18 Alkyl radical, C 19 Alkyl radical, C 20 Alkyl radical, C 21 Alkyl radical, C 22 Alkyl radical, C 23 Alkyl radical, C 24 Alkyl radical, C 25 Alkyl radical, C 26 Alkyl radical, C 27 Alkyl radical, C 28 Alkyl radical, C 29 Alkyl radical, C 30 An alkyl group.
The term C1-C12 alkoxy as used herein includes C 1 Alkoxy radical, C 2 Alkoxy radical, C 3 Alkoxy radical, C 4 Alkoxy radical, C 5 Alkoxy radical, C 6 Alkoxy radical, C 7 Alkoxy radical, C 8 Alkoxy radical, C 9 Alkoxy radical, C 10 Alkoxy radical, C 11 Alkoxy radical, C 12 An alkoxy group.
The term C3-C8 cycloalkyl as used herein includes C 3 Cycloalkyl radical, C 4 Cycloalkyl radical, C 5 Cycloalkyl radical, C 6 Cycloalkyl, C 7 Cycloalkyl radical, C 8 A cycloalkyl group.
The term C3-C8 cycloalkoxy as used in the present invention includes C 3 Cycloalkoxy, C 4 Cycloalkoxy, C 5 Cycloalkoxy, C 6 Cycloalkoxy, C 7 Cycloalkoxy, C 8 A cycloalkoxy group.
The term C1-C18 alkoxy as used herein includes C 1 Alkoxy radical, C 2 Alkoxy radical, C 3 Alkoxy radical, C 4 Alkoxy radical, C 5 Alkoxy radical, C 6 Alkoxy radical, C 7 Alkoxy radical, C 8 Alkoxy radical, C 9 Alkoxy radical, C 10 Alkoxy radical, C 11 Alkoxy radical, C 12 Alkoxy radical, C 13 Alkoxy radical, C 14 Alkoxy radical, C 15 Alkoxy radical, C 16 Alkoxy radical, C 17 Alkoxy radical, C 18 An alkoxy group.
The term C5-C18 aryl as used in the present invention includes C 5 Aryl radical, C 6 Aryl radical, C 7 Aryl radical, C 8 Aryl radical, C 9 Aryl radical, C 10 Aryl radical, C 11 Aryl radical, C 12 Aryl radical, C 13 Aryl radical, C 14 Aryl radical, C 15 Aryl radical, C 16 Aryl radical, C 17 Aryl radical, C 18 And (4) an aryl group.
The term aryl as used in this invention includes all-carbon aryl and heteroaryl, said aryl being optionally substituted with one or more C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy, aryl; by heteroaryl is meant an aromatic monocyclic or polycyclic ring system containing 5 to 14 ring atoms, preferably 5 to 10 ring atoms, wherein one or more of the ring atoms is not a carbon atom but for example a nitrogen, oxygen or sulfur atom.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given in detail for the purpose of better understanding the contents of the present invention and are not intended to limit the scope of the present invention. The reagents used in the examples of the present invention were all commercially available.
Example 1
330g of III-EX1(Mn 3301), 149gIV-EX1 and 1.5g of molybdenum trioxide are dissolved in 400mL of chlorobenzene, heated to 120 ℃ and then 202g of tert-butyl hydroperoxide (70% in water) are slowly added dropwise with stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to give 510g of the target product I-EX 1.
Molecular weight: 4850(Mn)
Dynamic viscosity (140 ℃): 120mPas
Example 2
350g of III-EX2 (Mn. RTM.4005), 230g of 230gIV-EX2 and 2.0g of molybdenum trioxide are dissolved in 400mL of chlorobenzene, heated to 120 ℃ and then 856g of tert-butyl hydroperoxide (70% strength in water) are slowly added dropwise with constant stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to yield 591g of the desired product I-EX 2.
Molecular weight: 6705(Mn)
Dynamic viscosity (140 ℃): 147mPas
Example 3
350g of III-EX3 (Mn. multidot.5001), 662gIV-EX3 and 2.1g of molybdenum trioxide are dissolved in 400mL of chlorobenzene, heated to 120 ℃ and 1125g of tert-butyl hydroperoxide (70% in water) are slowly added dropwise with stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to obtain 1042g of the target product I-EX 3.
Molecular weight: 14850(Mn)
Dynamic viscosity (140 ℃): 147mPas
Example 4
350g of III-EX4 (Mn. about.2051), 425gIV-EX3 and 3g of molybdenum trioxide are dissolved in 400mL of chlorobenzene, heated to 120 ℃ and 660g of tert-butyl hydroperoxide (70% strength aqueous solution) are slowly added dropwise with stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to give 810g of the desired product I-EX 4.
Molecular weight: 4730(Mn)
Dynamic viscosity (140 ℃): 147mPas
Example 5
384g of III-EX5(Mn 3850), 93gIV-EX2 and 1.5g of molybdenum trioxide are dissolved in 400mL of chlorobenzene, heated to 120 ℃ and 202g of tert-butyl hydroperoxide (70% strength in water) are slowly added dropwise with stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to give 503g of the desired product I-EX 5.
Molecular weight: 4830(Mn)
Dynamic viscosity (140 ℃): 143mPas
Example 6
384g of III-EX6(Mn 3850), 93gIV-EX2 and 1.5g of molybdenum trioxide are dissolved in 400mL of chlorobenzene, heated to 120 ℃ and 202g of tert-butyl hydroperoxide (70% strength in water) are slowly added dropwise with stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to give 510g of the target product I-EX 6.
Molecular weight: 4865(Mn)
Dynamic viscosity (140 ℃): 2453mPas
Example 7
384g of III-EX7(Mn 3843), 300gIV-EX7 and 1.5g of molybdenum trioxide are dissolved in 600mL of chlorobenzene, heated to 120 ℃ and 202g of tert-butyl hydroperoxide (70% strength in water) are slowly added dropwise with stirring for 12 h. After complete reaction, an excess of saturated sodium sulfite solution was added, stirred, phase-separated, filtered and the organic phase concentrated to give 687g of the desired product I-EX 7.
Molecular weight: 6830(Mn)
Dynamic viscosity (140 ℃): 4452mPas
Example 8
401 g of iii-EX8(Mn 4005), 126gIV-EX2 and 2.0g of molybdenum trioxide were dissolved in 400mL of chlorobenzene, heated to 120 ℃ and then 856g of tert-butyl hydroperoxide (70% in water) were slowly added dropwise with constant stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to obtain 528g of the target product I-EX 8.
Molecular weight: 5232(Mn)
Dynamic viscosity (140 ℃): 246mPas
Example 9
610g of III-EX9(Mn 4207), 232-232 gIV-EX2 and 2.0g of molybdenum trioxide are dissolved in 400mL of chlorobenzene, heated to 120 ℃ and then 856g of tert-butyl hydroperoxide (70% strength in water) are slowly added dropwise with constant stirring for 12 h. After complete reaction, excess saturated sodium sulfite solution was added, stirred, phase separated, filtered and the organic phase concentrated to yield 845g of the desired product I-EX 9.
Molecular weight: 5902(Mn)
Dynamic viscosity (140 ℃): 197mPas
Example 10 experiment for stabilizing Polypropylene Material
The basic formula comprises:
standard polymer: 79.8 wt% of thermoplastic polypropylene; 20 wt% hydrotalcite; 0.20 wt% of an antioxidant (AO-1010);
1# is 100 wt% standard polymer;
# 2 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 1);
# 3 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 2);
# 4 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 3);
# 5 is 99.2 wt% of standard polymer, 0.8 wt% of sterically hindered amine (example 4);
# 6 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 5);
7# 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 6);
# 8 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 7);
# 9 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 8);
# 10 is 99.2 wt% of standard polymer, 0.8 wt% of sterically hindered amine (example 9);
preparation of test samples:
the components are mixed in advance in a mixer, and then extruded and granulated on a double-screw extruder at 220 ℃. Dried at 80 ℃ for 8h and then injection molded using an injection molding machine at 240 ℃. Finally, xenon lamp aging test is carried out on the sample according to SAE J2527 standard, and the test result is shown in Table 1:
TABLE 1 Delta E of the xenon aged samples (low value is desired)
Example 9 stabilized thermoplastic polyethylene test
The basic formula is as follows:
standard polymer: 79.8 wt% of a thermoplastic polyethylene; 20 wt% calcium carbonate; 0.20 wt% of an antioxidant (AO-1010);
1# is 100 wt% standard polymer;
# 2 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 1);
# 3 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 2);
# 4 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 3);
# 5 is 99.2 wt% of standard polymer, 0.8 wt% of sterically hindered amine (example 4);
# 6 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 5);
7# 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 6);
# 8 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 7);
# 9 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 8);
# 10 is 99.2 wt% of standard polymer, 0.8 wt% of sterically hindered amine (example 9);
preparation of test samples:
the components are mixed in advance in a mixer, and then extruded and granulated on a double-screw extruder at 190 ℃. Drying at 80 deg.C for 8 hr, and blow molding at 200 deg.C with a film blowing machine. And finally, carrying out artificial xenon lamp accelerated aging test on the sample according to the GB/T16422.2-2014 standard, wherein the test result is shown in the table 2:
TABLE 2 tensile Strength Retention%
Example 10 test for stabilization of thermoplastic polyvinyl chloride
The basic formula is as follows:
standard polymer:
65.5 wt% thermoplastic polyvinyl chloride; 31.5 wt% plasticizer; 1.6 wt% epoxidized soybean oil; 1.4 wt% calcium zinc stabilizer;
# 1 is 100 wt% standard polymer;
no. 2 is 99.25 wt% standard polymer, 0.25 wt% UV-531; 0.50 wt% sterically hindered amine (example 1);
no. 3 is 99.25 wt% of standard polymer, 0.25 wt% of UV-531; 0.50 wt% sterically hindered amine (example 2);
no. 4 is 99.25 wt% standard polymer, 0.25 wt% UV-531; 0.50 wt% sterically hindered amine (example 3);
no. 5 is 99.25 wt% standard polymer, 0.25 wt% UV-531; 0.50 wt% sterically hindered amine (example 4);
no. 6 is 99.25 wt% of standard polymer, 0.25 wt% of UV-531; 0.50 wt% sterically hindered amine (example 5);
no. 7 is 99.25 wt% standard polymer, 0.25 wt% UV-531; 0.50 wt% sterically hindered amine (example 6);
no. 8 is 99.25 wt% standard polymer, 0.25 wt% UV-531; 0.50 wt% sterically hindered amine (example 7);
no. 9 is 99.25 wt% standard polymer, 0.25 wt% UV-531; 0.50 wt% sterically hindered amine (example 8);
no. 10 is 99.25 wt% of standard polymer, 0.25 wt% of UV-531; 0.50 wt% sterically hindered amine (example 9);
preparation of test samples:
the components were premixed in a mixer and then kneaded on a two-roll mill at 165 ℃ for 7 minutes to obtain the desired sample. Finally, the sample is subjected to xenon lamp aging test according to the GB/T16422.2-2014 standard, and the test result is shown in Table 3:
TABLE 3 retention of elongation at break%
Example 11 Performance testing as flame retardant in PP film
The basic formula is as follows:
standard polymer: 99.65 wt% thermoplastic polypropylene; 0.05 wt% calcium stearate; 0.30 wt% antioxidant (AO-1010: AO-168 ═ 1: 1);
1# is 100 wt% standard polymer;
# 2 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 1);
# 3 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 2);
# 4 is 99.2 wt% of standard polymer, 0.8 wt% of sterically hindered amine (example 3);
# 5 is 99.2 wt% of standard polymer, 0.8 wt% of sterically hindered amine (example 4);
# 6 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 5);
7# 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 6);
# 8 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 7);
# 9 is 99.2 wt% standard polymer, 0.8 wt% sterically hindered amine (example 8);
# 10 is 99.2 wt% of standard polymer, 0.8 wt% of sterically hindered amine (example 9);
preparation of test samples:
the components are mixed in advance in a mixer, and then extruded and granulated on a double-screw extruder at 220 ℃. Drying at 80 deg.C for 8 hr, and compression molding in hot press. Finally, the samples were subjected to flame retardancy tests in accordance with DIN 4102-B2, the test results being shown in Table 4:
TABLE 4 flame retardance of the samples
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents and the like included within the spirit and scope of the present invention.
The foregoing embodiments and methods described in this disclosure may vary based on the abilities, experience, and preferences of those skilled in the art.
The mere order in which the steps of a method are listed in the present invention does not constitute any limitation on the order of the steps of the method.
Claims (15)
1. A polymeric sterically hindered amine having the structure shown in formula (i):
A. b are the same or different sterically hindered amine structures;
n is the polymerization degree of the polymeric sterically hindered amine, and is an integer of 3-1000, preferably an integer of 3-20;
k and t represent the average number of A, B grafts per repeat unit, respectively, k and t are independently selected from 0-10, and (k + t) n.gtoreq.1;
R 1 selected from the group consisting of a single bond, C1-C22 alkylene, C3-C8 cycloalkylene, C4-C30 cycloalkylene alkyl, C6-C18 arylene; C7-C40 arylenealkyl; C1-C18 heterocyclylene; C2-C40 heterocyclylalkyl; wherein k hydrogen atoms in the above groups are substituted by A-O-;
R 2 selected from the group consisting of C1-C22 alkylene, C3-C8 cycloalkylene, C4-C30 cycloalkylene alkyl, C6-C18 arylene, C7-C40 arylene alkyl, C1-C18 heterocyclylene, C2-C40 heterocyclylene alkyl; wherein t hydrogen atoms in the above groups are substituted by B-O-; when R is 2 When the aryl is C6-C18 arylene, t is 0;
wherein said alkyl may be substituted by one or more of nitrogen, oxygen, sulfur, arylene, -C (═ O) -O-, -O-C (═ O) -O-, -C (═ O) -N (R) 3 )-、-N(R 3 )-C(＝O)-N(R 4 ) -a spacer alkyl group; or alkyl substituted by one or more of C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy, aryl;
said cycloalkyl may be substituted by one or more of nitrogen, oxygen, sulfur, arylene, -C (═ O) -O-, -O-C (═ O) -O-, -C (═ O) -N (R) (═ O) -O-, -C (═ O) - 3 )-、-N(R 3 )-C(＝O)-N(R 4 ) Interrupted cycloalkyl, cycloalkyl which is also substituted by one or more C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy, aryl;
the aryl group comprises an all-carbon aryl group and a heteroaryl group, and the aryl group can be substituted by one or more C1-C18 alkyl, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C1-C18 alkoxy and aryl;
the heteroatom is selected from nitrogen, oxygen and sulfur;
X 1 、X 2 independently selected from: single bond, -O-, -S-, -N (R) 3 ) -, in which R 3 Selected from: H. C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, C6-C18 aryl, C4-C20 heteroaryl;
Y 1 and Y 2 Independently selected from: single bond, -O-, -S-, -N (R) 4 ) -, in which R 4 Selected from: C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, C6-C18 aryl, C4-C20 heteroaryl;
R T1 、R T2 are the same or different end capping groups;
said R T1 Selected from:
-OH, C1-C12 alkyl, C1-C12 alkoxy, wherein X is selected from: phenyl, naphthyl, C1-C30 alkyl, R A Selected from: C1-C12 alkyl;
said R T2 Selected from: -H, C1-C12 alkyl, -OH, C1-C12 alkoxy;
the structure of the sterically hindered amine has a structure shown in a general formula (II):
wherein G is 1 、G 2 Independently selected from: C1-C22Alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, or G 1 And G 2 Together with the carbon atoms to which they are commonly attached form a 3-8 membered cycloalkyl group and a 3-8 membered heterocycloalkyl group;
E 1 、E 2 、E 3 independently selected from: -O-,
a is 0, 1 or 2, and E 1 And E 2 Cannot be simultaneously-O-or
And, E 2 And E 3 Cannot be simultaneously-O-or
W is selected from: oxygen, N-R 7 、NOH、NOR 7 、CHR 7 (ii) a Wherein R is 7 Selected from: C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, C6-C18 aryl, C4-C20 heteroaryl;
wherein R is 5 And R 6 Independently selected from: hydrogen, -OR 8 、-N(R 8 )C(＝O)R 9 、-O-C(＝O)-R 8 、-O-C(＝O)O-R 8 、-R 8 、-NR 8 R 9 Or R 8 And R 9 Together with the N atom to which they are both attached form a 5-7 membered heterocycloalkyl, -N (R) 8 )C(＝O)NR 9 、
Or R 5 And R 6 Together with the C atom to which they are both attached form a 3-8 membered carbocyclic ring or a 5-8 membered heterocycloalkyl or a 16-20 membered polyspirocyclic group; wherein R is 8 、R 9 Independently selected from: hydrogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, heteroalkyl, heterocyclyloxy, heterocyclyloxyamidoalkylamino, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (═ O) O-) O-interrupted alkyl, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (═ S) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more substituents, aryl substituted by one or more substituents, heteroaryl substituted by one or more substituents, heteroalkyl substituted by one or more substituents, cycloalkyl substituted by one or more substituents; the substituents are selected from the group consisting of: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyloxy, heteroaryloxy, cycloalkyloxy, heteroalkylacyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, aminoalkylacyloxy, aminoalkylaminoacylamino, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more-OC (═ O) O-, alkyl interrupted by one or more-C (═ O) -O-, alkyl interrupted by one or more-C (═ S) O-, alkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heteroalkyloxy, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonylalkyl, alkoxythiocarbonyl, alkoxythioacyl, aminoalkyloxy, aminoalkylacyloxy, aminoalkylaminoacyloxy, aminoalkylaminoacylamino, alkylaminoalkylamino, alkyl interrupted by one or more-C (═ O-, (S) O-, alkyl, Alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by a combination of the above spacer groups;
R 10 selected from: hydrogen, C1-C22 alkyl, 3-8 membered cycloalkyl, C6-C30 aryl, C4-C20 heteroarylene;
Y 3 、Y 4 each independently selected from:a single bond, N, O; y is 3 、Y 4 When it is a single bond or O, the corresponding R 12 、R 14 Is absent;
R 11 、R 12 、R 13 、R 14 each independently selected from: hydrogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, heteroalkyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (═ O) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (═ S) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more substituents, alkyl interrupted by one or more heteroaryl groups, alkyl interrupted by a combination of the above spacer groups, alkyl interrupted by one or more substituents, alkyl substituted by one or more substituents, and the like, Aryl substituted with one or more substituents, heteroaryl substituted with one or more substituents, heteroalkyl substituted with one or more substituents, cycloalkyl substituted with one or more substituents; the substituents are selected from the group consisting of: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aroyloxy, heteroaryloxy, cycloalkyloxy, heteroalkylacyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (═ O) O-, alkyl interrupted by one or more-OC (═ O) O-, alkyl interrupted by one or more-C (═ O) -S, alkyl interrupted by one or more-C (═ S) O-, alkyl interrupted by one or more amide groups, Alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkyne groupsAlkyl interrupted by one or more amine groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by combinations of the above spacer groups; or, R 11 And R 12 And Y in the middle thereof 4 Forming a heterocyclic group; or, R 13 And R 14 And Y in the middle thereof 3 To form a heterocyclic group.
2. A polymeric sterically hindered amine according to claim 1, wherein k and t are independently selected from the group consisting of 0-5; preferably 0 to 3; more preferably 0-2, and (k + t). times.n.gtoreq.1.
3. A polymeric sterically hindered amine according to claim 1, characterized in that it has the following structure:
4. A polymeric sterically hindered amine according to claim 1, wherein k is selected from the group consisting of 0 to 2, t is selected from the group consisting of 0 to 1, and (k + t) n.gtoreq.1;
said R 1 Selected from C1-C22 alkylene, C1-C18 heterocyclylene, C2-C40 heterocyclylene alkyl(ii) a Preferably, R 1 Selected from C1-C20 alkylene,
Wherein b is an integer of 1 to 20.
5. Polymeric sterically hindered amine according to claim 1, wherein R is 2 Selected from: C1-C15 alkylene, C6-C10 arylene;
preferably, R is 2 Selected from: - (CH) 2 ) 14 -, ethylene, methylene, phenylene, naphthylene, - (CH) 2 ) 6 -, more preferably, R 2 Is a methylene group;
wherein said phenylene is
Preferably, it is
Said naphthylene group is
Preferably a
6. A polymeric sterically hindered amine according to claim 1, wherein X is 1 、X 2 Independently selected from: a single bond, -O-, -NH-;
said Y 1 And Y 2 Independently selected from: a single bond, -O-, -NH-.
7. Polymeric sterically hindered amine according to claim 1, wherein G is 1 、G 2 Each independently selected from: C1-C6 alkyl, preferably, G 1 、G 2 Each independently selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, more preferably, G 1 、G 2 Are all methyl.
8. A polymeric sterically hindered amine according to claim 1 wherein a is 1;
said E 1 、E 2 、E 3 Independently selected from:
w is oxygen;
said R 5 And R 6 Independently selected from: hydrogen, -O-C (═ O) -R 8 ；
Said R 8 、R 9 Independently selected from: hydrogen, alkyl,
Wherein i is selected from an integer of 0 to 22, and j is selected from an integer of 0 to 21;
said R 10 Is n-butyl;
said R 11 、R 12 、R 13 、R 14 Each independently selected from: hydrogen, C1-C22 alkyl, 3-8 membered cycloalkyl, 3-8 membered heterocycloalkyl, C6-C30 aryl, C4-C20 heteroaryl; or, R 11 And R 12 And Y in the middle thereof 4 Form a 3-8 membered heterocycloalkyl, or R 13 And R 14 And Y in the middle thereof 3 Forming a 3-8 membered heterocycloalkyl group.
9. Polymeric sterically hindered amine according to claim 1, wherein R is 8 、R 9 Each independently selected from: c 1-18 An alkyl group; preferably, R 8 、R 9 Each independently selected from: methyl, -C 16 H 33 (ii) a More preferably, R 8 Is methyl.
10. A polymeric sterically hindered amine according to claim 1, wherein the sterically hindered amine structure is selected from the group consisting of:
preferably, the sterically hindered amine is selected from the following structures:
more preferably, the sterically hindered amine is selected from the following structures:
most preferably, the sterically hindered amine is selected from the following structures:
11. a polymeric sterically hindered amine according to claim 1, characterized in that it has the following structure:
12. a process for the preparation of a polymeric sterically hindered amine according to any of claims 1 to 11, which comprises the step of polymerizing a polymeric precursor to be modified and a hindered amine modifier in the presence of a catalyst and a hydroperoxide; the reaction formula is shown as follows:
wherein, the reactant 1 and the reactant 2 are steric hindrance amine modifier;
the reactant 1 is A-H or A-O,
the reactant 2 is B-H or B-O.
13. A composition comprising a polymeric sterically hindered amine according to any of claims 1 to 11 and one or more light, heat or oxidation sensitive organic substances selected from the group consisting of: polyolefin, acrylonitrile/butadiene/styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyurethane, polyester, polysulfone, polyurea, polystyrene, thermoplastic elastomer or a combination of two or more thereof.
14. Use of a polymeric sterically hindered amine according to any of claims 1 to 11 in the preparation of light stabilizers and/or flame retardants.
15. Use of a polymeric sterically hindered amine according to any of claims 1 to 11 in the preparation of an article of polymeric material;
preferably, the polymer material product is plastic, rubber, fiber, paint, adhesive or composite material.
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| US20030207967A1 (en) * | 2000-10-16 | 2003-11-06 | Laver Hugh Stephen | Stabilizers for power coatings |
| CN112126060A (en) * | 2019-06-25 | 2020-12-25 | 北京天罡助剂有限责任公司 | Polymeric high-molecular steric hindrance amine and preparation method thereof |
| CN114195921A (en) * | 2021-12-13 | 2022-03-18 | 天集化工助剂（沧州）有限公司 | Polymeric steric hindrance amine and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030207967A1 (en) * | 2000-10-16 | 2003-11-06 | Laver Hugh Stephen | Stabilizers for power coatings |
| CN112126060A (en) * | 2019-06-25 | 2020-12-25 | 北京天罡助剂有限责任公司 | Polymeric high-molecular steric hindrance amine and preparation method thereof |
| CN114195921A (en) * | 2021-12-13 | 2022-03-18 | 天集化工助剂（沧州）有限公司 | Polymeric steric hindrance amine and preparation method and application thereof |
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|---|---|---|---|---|
| CN115819759A (en) * | 2022-12-23 | 2023-03-21 | 天集化工助剂（沧州）有限公司 | Polymeric hindered amine and preparation method and application thereof |
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