WO2011070182A1 - Polymères ramifiés fonctionnalisés comprenant des polymères fonctionnalisés synthétisés par polymérisation anionique et applications correspondantes - Google Patents
Polymères ramifiés fonctionnalisés comprenant des polymères fonctionnalisés synthétisés par polymérisation anionique et applications correspondantes Download PDFInfo
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- WO2011070182A1 WO2011070182A1 PCT/ES2009/070572 ES2009070572W WO2011070182A1 WO 2011070182 A1 WO2011070182 A1 WO 2011070182A1 ES 2009070572 W ES2009070572 W ES 2009070572W WO 2011070182 A1 WO2011070182 A1 WO 2011070182A1
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- WIPO (PCT)
- Prior art keywords
- polymer
- functionalized multi
- arm
- anionic polymerization
- synthesized
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- 229920000642 polymer Polymers 0.000 title claims abstract description 261
- 125000000129 anionic group Chemical group 0.000 title abstract description 3
- 239000007822 coupling agent Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- -1 tere-butyl Chemical group 0.000 claims description 158
- 239000000178 monomer Substances 0.000 claims description 73
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 59
- 230000001070 adhesive effect Effects 0.000 claims description 56
- 239000000853 adhesive Substances 0.000 claims description 55
- 229920003023 plastic Polymers 0.000 claims description 37
- 239000004033 plastic Substances 0.000 claims description 37
- 229920001577 copolymer Polymers 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- 238000005859 coupling reaction Methods 0.000 claims description 20
- 125000006239 protecting group Chemical group 0.000 claims description 20
- 150000001993 dienes Chemical class 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000004793 Polystyrene Substances 0.000 claims description 16
- 239000010426 asphalt Substances 0.000 claims description 16
- 229920002223 polystyrene Polymers 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 238000010511 deprotection reaction Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 6
- 229920001195 polyisoprene Polymers 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004001 thioalkyl group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 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 claims description 5
- 125000003438 dodecyl 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 claims description 5
- 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 claims description 5
- 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 claims description 5
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 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 claims description 5
- 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 claims description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
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- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
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- 229920000728 polyester Polymers 0.000 claims description 4
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- 229910052710 silicon Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
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- 125000005647 linker group Chemical group 0.000 claims description 3
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- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 44
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
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- 150000001875 compounds Chemical class 0.000 description 4
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- 125000004719 1,1-dimethylpropylthio group Chemical group CC(CC)(S*)C 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
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- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
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- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
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- UTANVCZNJLPXGK-UHFFFAOYSA-N 1-nitrobut-1-ene Chemical class CCC=C[N+]([O-])=O UTANVCZNJLPXGK-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- OESGXAZAPLHJHR-UHFFFAOYSA-N 2,4-bis(ethenyl)-1-methylbenzene Chemical compound CC1=CC=C(C=C)C=C1C=C OESGXAZAPLHJHR-UHFFFAOYSA-N 0.000 description 1
- HMWCQCYUKQZPRA-UHFFFAOYSA-N 2,4-dimethyl-3-methylidenepent-1-ene Chemical compound CC(C)C(=C)C(C)=C HMWCQCYUKQZPRA-UHFFFAOYSA-N 0.000 description 1
- PJXJBPMWCKMWLS-UHFFFAOYSA-N 2-methyl-3-methylidenepent-1-ene Chemical compound CCC(=C)C(C)=C PJXJBPMWCKMWLS-UHFFFAOYSA-N 0.000 description 1
- KUFLEYZWYCAZCC-UHFFFAOYSA-N 2-methylhexa-1,3-diene Chemical compound CCC=CC(C)=C KUFLEYZWYCAZCC-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UTDCGTAAWGJIOW-UHFFFAOYSA-N 2h-indeno[1,2-g][1]benzofuran Chemical compound C1=C2C=CC=CC2=C2C1=C1OCC=C1C=C2 UTDCGTAAWGJIOW-UHFFFAOYSA-N 0.000 description 1
- QTTAWIGVQMSWMV-UHFFFAOYSA-N 3,4-dimethylhexa-1,3-diene Chemical compound CCC(C)=C(C)C=C QTTAWIGVQMSWMV-UHFFFAOYSA-N 0.000 description 1
- QXNYNMNRJMHGHH-UHFFFAOYSA-N 3-ethyl-2-methylpenta-1,3-diene Chemical compound CCC(=CC)C(C)=C QXNYNMNRJMHGHH-UHFFFAOYSA-N 0.000 description 1
- CTNXNQQXFSVMIY-UHFFFAOYSA-N 3-ethylidenehex-1-ene Chemical compound CCCC(=CC)C=C CTNXNQQXFSVMIY-UHFFFAOYSA-N 0.000 description 1
- GITIYCQMJWQMKC-UHFFFAOYSA-N 3-methylhepta-1,3-diene Chemical compound CCCC=C(C)C=C GITIYCQMJWQMKC-UHFFFAOYSA-N 0.000 description 1
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- SALPZWUZFRNPQX-UHFFFAOYSA-N 4,5-dimethylideneoctane Chemical compound CCCC(=C)C(=C)CCC SALPZWUZFRNPQX-UHFFFAOYSA-N 0.000 description 1
- DXFURPHVJQITAC-UHFFFAOYSA-N 4-benzyl-1-ethenyl-2-ethylbenzene Chemical compound C1=C(C=C)C(CC)=CC(CC=2C=CC=CC=2)=C1 DXFURPHVJQITAC-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- SUJWMMYTMBMNMU-UHFFFAOYSA-N 5-methylidenehept-3-ene Chemical compound CCC=CC(=C)CC SUJWMMYTMBMNMU-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- UTWQPORNJDITNO-UHFFFAOYSA-N [Li]CC(C)(C)COC(C)(C)C Chemical compound [Li]CC(C)(C)COC(C)(C)C UTWQPORNJDITNO-UHFFFAOYSA-N 0.000 description 1
- NOYJNZYBGPNSBH-UHFFFAOYSA-N [Li]CC(C)(C)COC(C)(C)CC Chemical compound [Li]CC(C)(C)COC(C)(C)CC NOYJNZYBGPNSBH-UHFFFAOYSA-N 0.000 description 1
- ANVNRAHPEDTMFH-UHFFFAOYSA-N [Li]CC(C)(C)CO[Si](C)(C)C Chemical compound [Li]CC(C)(C)CO[Si](C)(C)C ANVNRAHPEDTMFH-UHFFFAOYSA-N 0.000 description 1
- GMWUHMAPLSDANH-UHFFFAOYSA-N [Li]CC(C)(C)CO[Si](C)(C)C(C)(C)C Chemical compound [Li]CC(C)(C)CO[Si](C)(C)C(C)(C)C GMWUHMAPLSDANH-UHFFFAOYSA-N 0.000 description 1
- USSFRLVJYCNWHC-UHFFFAOYSA-N [Li]CC(C)(C)CSC(C)(C)C Chemical compound [Li]CC(C)(C)CSC(C)(C)C USSFRLVJYCNWHC-UHFFFAOYSA-N 0.000 description 1
- RSVYWYWBVXHSDW-UHFFFAOYSA-N [Li]CC(C)(C)CS[Si](C)(C)C(C)(C)C Chemical compound [Li]CC(C)(C)CS[Si](C)(C)C(C)(C)C RSVYWYWBVXHSDW-UHFFFAOYSA-N 0.000 description 1
- LFTMWNRSBLAIJA-UHFFFAOYSA-N [Li]CC(C)COC(C)(C)C Chemical compound [Li]CC(C)COC(C)(C)C LFTMWNRSBLAIJA-UHFFFAOYSA-N 0.000 description 1
- UJWYFUWYBLWJMJ-UHFFFAOYSA-N [Li]CC(C)COC(C)(C)CC Chemical compound [Li]CC(C)COC(C)(C)CC UJWYFUWYBLWJMJ-UHFFFAOYSA-N 0.000 description 1
- LDYXUKQWUIUHII-UHFFFAOYSA-N [Li]CC(C)CO[Si](C)(C)C(C)(C)C Chemical compound [Li]CC(C)CO[Si](C)(C)C(C)(C)C LDYXUKQWUIUHII-UHFFFAOYSA-N 0.000 description 1
- SBZGAMCIGCLBPI-UHFFFAOYSA-N [Li]CC(C)CSC(C)(C)C Chemical compound [Li]CC(C)CSC(C)(C)C SBZGAMCIGCLBPI-UHFFFAOYSA-N 0.000 description 1
- NYUKFJKJNQFHEF-UHFFFAOYSA-N [Li]CC(C)CS[Si](C)(C)C(C)(C)C Chemical compound [Li]CC(C)CS[Si](C)(C)C(C)(C)C NYUKFJKJNQFHEF-UHFFFAOYSA-N 0.000 description 1
- AAFLOLBQZLJHNV-UHFFFAOYSA-N [Li]CCCCCCN1CCCCCC1 Chemical compound [Li]CCCCCCN1CCCCCC1 AAFLOLBQZLJHNV-UHFFFAOYSA-N 0.000 description 1
- WMZZFCMPSRCNOL-UHFFFAOYSA-N [Li]CCCCCCOC(C)(C)CC Chemical compound [Li]CCCCCCOC(C)(C)CC WMZZFCMPSRCNOL-UHFFFAOYSA-N 0.000 description 1
- RECRMBNCQWURPI-UHFFFAOYSA-N [Li]CCCCCCO[Si](C)(C)C(C)(C)C Chemical compound [Li]CCCCCCO[Si](C)(C)C(C)(C)C RECRMBNCQWURPI-UHFFFAOYSA-N 0.000 description 1
- YPXSCJUWAUGUNO-UHFFFAOYSA-N [Li]CCCN(C)C Chemical compound [Li]CCCN(C)C YPXSCJUWAUGUNO-UHFFFAOYSA-N 0.000 description 1
- SDBDDKNUWKJCIF-UHFFFAOYSA-N [Li]CCCN([Si](C)(C)C(C)(C)C)[Si](C)(C)C(C)(C)C Chemical compound [Li]CCCN([Si](C)(C)C(C)(C)C)[Si](C)(C)C(C)(C)C SDBDDKNUWKJCIF-UHFFFAOYSA-N 0.000 description 1
- WHCOMNUPCDVDIB-UHFFFAOYSA-N [Li]CCCOC(C)(C)CC Chemical compound [Li]CCCOC(C)(C)CC WHCOMNUPCDVDIB-UHFFFAOYSA-N 0.000 description 1
- JAEXBTGIFJPRBR-UHFFFAOYSA-N [Li]CCCSC(C)(C)C Chemical compound [Li]CCCSC(C)(C)C JAEXBTGIFJPRBR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 229920005605 branched copolymer Polymers 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical class C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Definitions
- the present invention relates to functionalized multi-arm polymers comprising the reaction product of a coupling agent and a polymer synthesized by anionic polymerization, its synthesis processes and its different uses, especially as hot melt adhesives . Therefore the present invention belongs to the field of polymers.
- Oligomers formed by acrylic monomers (functionalized with at least one ester, carboxylic acid, anhydride or epoxy functional group) copolymerized with styrene have also been used successfully as coupling agents of anionically obtained polymers to obtain multi-arm polymers (US 7,517,934).
- poly (styrene-butadienyl) lithium copolymers were prepared in a first stage.
- a certain amount of the acrylic oligomer was added to the poly (styrene-butadiene) lithium copolymers in a ratio of less than 1, such that chain coupling was favored.
- the present invention is related to functionalized multi-arm polymers that come from the reaction between a polymer synthesized by anionic polymerization, from functionalized and protected initiators, of general formula Li-Q n -ZT- (AR 1 R 2 R 3 ) m , and a coupling agent having 1 to 30 functional groups.
- the present invention also deals with polymers obtained by deprotection of the protective group (AR 1 R 2 R 3 ) m , and hydrogenated functionalized multi-arm polymers. Also described are the processes for obtaining said polymers as well as their uses, especially in hot melt adhesive compositions, in plastics modification and in asphalt modification.
- the polymers of the invention have advantages in comparison with those of the state of the art, with respect to their mechanical, rheological properties in mixtures, and of interacting physically or chemically with different substrates. This allows them to be used advantageously in applications such as hot melt adhesives, in the modification of asphalts and in the modification of the impact of engineering plastics, among others.
- the first aspect to consider is a functionalized multi-arm polymer comprising the reaction product of:
- a coupling agent with a number of functional groups from 1 to 30, preferably from 5 to 20 is known in the art, which can be for example an oligomer formed by acrylic monomers (functionalized with at least one ester, carboxylic acid, anhydride or epoxy functional group) copolymerized with styrene (for example those described in US 7,517,934), or alternatively divinylbenzene (described in US 3,280,084 and US 3,949,020), or alternatively multifunctional chlorosilanes (Roovers, Hadjichristidis and Fetters (Macromolecules, volume 16, 214 (1983)), and Toporowski and Roovers (J.
- the preferred coupling agent is an oligomer obtained by polymerizing via free radicals at least one monomer selected from the group consisting of vinyl aromatic monomers and at least one monomer selected from the group consisting of epoxy-functional acrylic monomers, anhydride-functional acrylic monomers, ester-functional acrylic monomers, carboxy-functional acid acrylic monomers and any of their mixtures, where the coupling agent has a number average molecular weight from about 1,000 to about 10,000 g / mol, and a weight average molecular weight from about 1,500 to approximately 20,000 g / mol, where the functional groups present in the acrylic monomers are responsible of the coupling reactions;
- C1-C5 alkyl is understood as an alkyl chain of 1 to 5 carbon atoms, this being linear or branched, preferably linear, examples of such C1-C5 alkyl groups are methyl, ethyl, propyl, butyl and pentyl.
- the second in order for the coupling reaction to take place between the coupling agent and the polymer synthesized by anionic polymerization, the second must be active, or "live", totally or partially. These materials process more easily than linear ones, also exhibiting lower viscosity than a linear one of similar molecular weight.
- multi-arm polymers can also be advantageously used to alter the surface properties of unfunctionalized polymers.
- the functional groups of different nature than the non-functionalized polymers, separate and migrate to the surface of the mixture, thereby modifying their surface properties.
- the second aspect is the functionalized multi-arm polymers derived from those of the first aspect, such as the polymer obtainable by the deprotection of the protective group (AR 1 R 2 R 3 ) m present in the multi-arm functionalized polymers, as well as the multi-arm polymers Functionalized hydrogenates characterized in that they are obtainable by hydrogenation of any of the polymers defined in the first aspect or those obtainable by deprotection of these, defined in this second aspect.
- the third aspect to consider is a method for the preparation of any of the polymers as defined in the first and second aspects, which comprises reacting the polymer synthesized by anionic polymerization with the coupling agent, in addition to a method for obtaining a hydrogenated multi-arm polymer of the first aspect, characterized in that it comprises hydrogenating the functionalized multi-arm polymers at a temperature between 25 and 150 ° C before removing the protecting groups.
- the fourth aspect is a method for obtaining the hydrogenated multi-arm polymer of the second aspect, characterized in that it comprises hydrogenating the functionalized multi-arm polymers at a temperature between 25 and 150 ° C after eliminating the protective groups.
- the hydrogenated multi-arm polymers of the third and fourth aspects in addition to presenting the advantages described in the first and second aspects provide the materials with thermal, hydrolytic and ultraviolet radiation, essential for applications that require high thermal stability or where the materials in humid environments or the atmosphere.
- the fifth aspect is a method for obtaining unprotected multi-arm polymers as defined in the second aspect, characterized in that the protecting groups are removed by an acid, such as hydrochloric acid, acetic acid, p-toluenesulfonic acid, ion exchange resin.
- an acid such as hydrochloric acid, acetic acid, p-toluenesulfonic acid, ion exchange resin.
- Amberlyst ® 15 usually at the temperature solvent reflux of the multi-link polymers, or by other methods described in TW Greene and PGM Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, New York, 1991.
- the sixth aspect is an adhesive composition containing the functionalized multi-arm polymer according to the first and second aspects, characterized in that the reaction product contains approximately from 0.001 to 5% by weight of coupling agent based on the total amount of coupling agent and synthesized polymer by anionic polymerization, which were reacted according to the first aspect.
- the seventh aspect is a reinforced material or a composite material comprising the functionalized multi-arm polymer according to any of the first or second aspects, mixed with a reinforcing material or with a material to be reinforced.
- This reinforced material comprises, but is not limited to, asphalts, adhesives, mixtures with other plastics and nanomaterials.
- the eighth aspect is a modified asphalt comprising asphalt mixed with the functionalized multi-arm polymer according to any of the first or second aspects. Asphalts comprising polymers show good compatibility in the medium and good physical properties.
- the ninth aspect is a modified plastic comprising a plastic mixed with the functionalized multi-arm polymer as defined in any of the first and second aspects, the mixture contains approximately from 1 to 40 percent by weight of functionalized multi-arm polymer, based on the weight Totalized functionalized multi-arm polymer and plastic.
- the polymer improves physical properties, and especially the impact resistance with respect to virgin plastic.
- the amount of reactive chains of polymer synthesized by anionic polymerization is much greater in moles than those of the coupling agent, so it may not be that all are covalently bound to the coupling agent, although preferably between 1 and 30 chains of the polymer synthesized by polymerization anionic are covalently bound to the coupling agent.
- the functionalized multi-arm polymer of the formula Li-Q n -ZT- (AR 1 R 2 R 3 ) m described in the first aspect is characterized in that T is oxygen.
- the functionalized multi-arm polymer of the formula Li-Q n -ZT- (AR 1 R 2 R 3 ) m described in the first aspect is characterized in that T is nitrogen.
- the functionalized multi-arm polymer of the formula Li-Q n -ZT- (AR 1 R 2 R 3 ) m described in the first aspect is characterized in that T is sulfur.
- m is preferably 1 and when T is nitrogen, m is preferably 2.
- Z is a branched or unbranched hydrocarbyl linking group of 3 to 25 atoms of carbon.
- Z is propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
- R 1 , R 2 and R 3 groups together with A form the protective groups.
- O, N or S protecting groups are well known and used in the art.
- R 1 , R 2 and R 3 can be independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. tert-butyl. pentil, isopentil, neopentil and tert-pentile.
- Carbon-based protective groups are usually preferred, that is when A is carbon (C), because they are usually more readily available and economical, but when Z is oxygen (O) good results are obtained with silicon-based protective groups (Si).
- Polymers synthesized by anionic polymerization useful for the present invention are known in the state of the art. These polymers synthesized by anionic polymerization are likely to undergo termination reactions or coupling reactions with the coupling agents.
- Anionic polymerization is a well known technique that uses initiators, such as organic alkali metal initiators, to polymerize conjugated diolefins or other anionically polymerizable monomers. Anionic polymerization can be carried out in a continuous, batch or semi-continuous process.
- the polymers produced by anionic polymerization are commonly referred to as "living polymers," because each monomer reaction step creates a new carbanion, allowing the polymer to continue growing until the monomers have been fully consumed.
- the polymers remain active even after the monomers have been depleted, and will continue to react and grow if supplied. Additional monomer
- Anionic polymerization methodology can be found in "Anionic Polymerization: Principies and Practical Applications", Hsieh, HL, Quirk, Roderic P., Marcel Dekker Inc, New York, 1996, which is incorporated into the present application by reference.
- Anionic polymerization is a particularly attractive methodology for the production of block copolymers with well defined structures.
- the polymers obtained by this route can be radial, linear or branched polymers, depending on the functionalities of the initiators or coupling agents used to make them.
- Anionic polymerization is typically carried out in non-polar hydrocarbon solvents, at moderate temperatures, under vacuum or in an inert atmosphere, using highly purified reagents in order to avoid premature termination of the initiator or polymerized chains.
- the polymers can be homopolymers or copolymers, including both random and block copolymers.
- Commercial polymers synthesized by anionic polymerization, or anionically polymerized include thermoplastic, elastomeric, and thermoplastic-elastomeric polymers.
- Polymers synthesized by anionic polymerization for use in the present invention, have an average molecular weight at the peak of the distribution from about 3,000 g / mol to about 400,000 g / mol. This includes polymers synthesized by anionic polymerization having a molecular weight, from about 20,000 g / mol to 200,000 g / mol, although the invention is not limited to polymers that fall within these molecular weight ranges. In the present invention both the molecular weights of the polymers synthesized by anionic polymerization and the molecular weights of functionalized multi-arm polymers refer to the molecular weight at the peak of the distribution, M p .
- Conjugated diolefins (or dienes) suitable for use in obtaining these polymers synthesized by anionic polymerization are known in the art and include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene, 1,3-pentadiene, 2-methyl-3-ethyl-1, 3- butadiene, 2-methyl-3-ethyl-1, 3-pentadiene, 1,3-hexadiene, 2-methyl-1, 3- hexadiene, 1,3-heptadiene, 3-methyl-1, 3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1, 3-hexadiene, 3- n-propyl-1, 3-pentadiene, 4,5-diethyl-1, 3-octadiene, 2,4-diethyl-1, 3-butadiene, 2,3-di-n-
- anionically polymerizable alkenyl aromatic monomers include, but are not limited to: styrene, alpha-methylstyrene, vinyl toluene, 2- vinyl pyridine, 4-vinyl pyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha-alpha-methane, 2-alpha , 2-diphenyl-4-methylhexene and mixtures thereof, as well as their alkyl, cycloalkyl, aryl, and alkylaryl derivatives in which the total number of carbon atoms in the combined constituents is generally not more than 18.
- Examples of the latter compounds include: 3-methylstyrene, 3,5-diethylstyrene, 2- ethyl-4-benzylstyrene, 4-phenylstyrene, 4-p_-tolylstyrene, 4- (tert-butyl) -styrene, 2,4-divinyl toluene and 4,5-dimethyl-1-vinylnaphthalene.
- Other anionically polymerizable monomers include acrylamides, acrylonitriles, nitrobutenes, vinyl isocyanates, anhydrides, methacrylates, acrylates, carbodiimides, lactones, lactams, cyclic siloxanes, and ethylene.
- polystyrene polystyrene
- polybutadiene polyisoprene
- polyethers polyethers
- polyacetals polyphenylene oxides
- polyphenylene oxides polystyrene, polybutadiene, polyisoprene, polyethers, polyacetals, and polyphenylene oxides.
- These polymers can also be elastomers and thermoplastic elastomers made of block, gradual (tapered) or random copolymers of styrene (S), butadiene (B) and isoprene (I) of varying block sizes and quantity.
- thermoplastic elastomers examples include block copolymers SB, SI, SBR, (SB) m , S (where m is an integer), SBS, SIS, BSB, ISI, as well as their hydrogenated and partially hydrogenated counterparts , including SEBS, SEB, SEP and others.
- examples of polymers synthesized by anionic polymerization examples include linear elastomers produced by the copolymerization of at least one alkenyl aromatic monomer, and at least one conjugated diene monomer.
- the functionalized multi-arm polymer is characterized in that the polymer synthesized by anionic polymerization is synthesized from conjugated diene monomers and alkenyl aromatic monomers, and wherein the dienic part has an approximate content from 8 to 80 mol% of structures 1 ,2.
- the molar ratio of the alkenyl aromatic monomer with respect to the conjugated diene monomer preferably ranges from about 0.1 to about 1.0, preferably, about 0.2 to about 0.5 and more preferably, about from 0.3 to 0.4.
- the functionalized multi-arm polymer described in the first aspect is characterized in that the polymer synthesized by anionic polymerization is obtained from alkenyl aromatic monomers, conjugated diene monomers or mixtures from them.
- the present inventors have surprisingly detected that good results are obtained when they comprise polystyrene.
- the polymer synthesized by anionic polymerization is obtained from alkenyl aromatic monomers and conjugated diene monomers in a molar ratio of vinyl aromatic monomer with respect to conjugated diene monomer from about 0.05 to 1, 0.
- the functionalized multi-arm polymer comprises at least one polymer selected from the group consisting of polystyrene, polybutadiene, polyisoprene and random, block or progressive copolymers made from monomers selected from the group consisting of styrene, butadiene and isoprene.
- the molecular weights of the polymer arms of the invention can be adjusted according to need and varying the amount of polymerized monomers (n) but usually have a molecular weight at the peak of the distribution, M p , approximately from 3,000 to 300,000 g / mol
- M p molecular weight at the peak of the distribution
- the M p of the arms ranges from 20,000 g / mol to 200,000 g / mol.
- the molecular weight of the polymers synthesized by anionic polymerization in the present invention is conveniently measured by a Gel Permeation Chromatography (GPC) equipment, which has been calibrated using the universal calibration curve method. Calibration is carried out with polymers of known molecular weight and these must have the same molecular structure and the same composition as the polymers to be characterized. Polymers synthesized by anionic polymerization are essentially monodispersed (the ratio average molecular weight to weight / average molecular weight in number is close to one), it being appropriate to report the molecular weight at the peak of the distribution, M p , as the molecular weight of the polymer.
- GPC Gel Permeation Chromatography
- the molecular weight of the multi-arm polymers reported corresponds to the molecular weight at the peak of the distribution of the coupled chains.
- the determination of the degree of coupling of the branched polymers, that is the determination of the number of arms covalently bound to the multi-arm polymer, is determined by relating the molecular weight of the multi-arm polymer at the peak of the distribution with that of the molecular weight of the arm in the peak of distribution.
- the polymer synthesized by anionic polymerization may contain alkenyl aromatic, conjugated diene monomers or mixtures thereof which are anionically polymerized.
- the amount of monomers of conjugated dienes ranges from 8 to 80 mol%.
- Li-ZT- (AR 1 R 2 R 3 ) m examples include but are not limited to:
- omega (tert-alkoxy) -l-alkylthio such as 3- (1, 1-dimethylethoxy) -1-propylthio and 3- (tert-butyldimethylsilyloxy) -1-propylthio,
- omega- (tert-alkylthio) -1-alkylthio such as 3- (1,1-dimethylethylthio) -1-propyl lithium
- omega- (dialkylamino) -1-alkyl-lithiums such as 3- (dimethylamino) -1-propyllithium
- Li-ZT- (AR 1 R 2 R 3 ) m can be prepared when said formula represents compounds of formula Li-ZOC- R 1 R 2 R 3 , Li-Z-0-Si-R 1 R 2 R 3 , Li-ZN- (CR 1 R 2 R 3 ) 2 , Li-ZN- (CR 1 R 2 R 3 ) 2 , Li-ZS- CR 1 R 2 R 3 and Li-ZS-Si-R 1 R 2 R 3 by the reaction of their respective haloalkenes, eg CI-ZT- (AR 1 R 2 R 3 ) m and Br-ZT- (AR 1 R 2 R 3 ) m , with lithium metal using as an solvent an inert hydrocarbon at a temperature up to the reflux temperature.
- Tertiary amines 1-haloalkenes useful for the preparation of for example the Li-ZN- compounds (AR 1 R 2 R 3 ) 2 of the present invention are compounds with the following structure:
- Z being an integer from 1 to 7
- X a halogen, preferably Cl or Br.
- tertiary amines 1 -haloalkenes examples include but are not limited to:
- halo- or halide group being selected from chlorine and bromine.
- halo- or halide group being selected from chlorine and bromine.
- omega-hydroxy haloalkanes can be prepared by processes described in A. Alexaquis, M. Gardette, and S. Col ⁇ n, Tetrahedron Letters, 29,1988, 2951.
- T. Ferrari and P. Vogel SYNLETT, 1991, 233.
- halo- or halide group being selected from chlorine and bromine.
- protected omega-thio haloalkanes can be prepared by processes described in Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5893, J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51, 1995, 1 1883, DF Taber and Y. Wang, J. Org, Chem., 58,1993, 6470, FD Tosté and IWJ Still, Synlett, 1995, 159 and US Patent No. 5,493,044.
- the percentage of coupled chains may vary from about 2 to 98% by weight, with 1 to 30 chains of the polymer synthesized by anionic polymerization being preferably covalently bound to the coupling agent.
- the amount of coupling agent added is such that the molar ratio of polymer synthesized by anionic polymerization to coupling agent is 1: 1 to 30: 1.
- the polymer synthesized by anionic polymerization can have a molecular weight at the peak of the distribution from about 20,000 to 500,000 g / mol.
- the functionalized multi-arm polymer is characterized in that it has a molecular weight at the peak of the distribution from 5,000 to 2,000,000 g / mol.
- the coupling agent is in a smaller proportion, so in a preferred embodiment it ranges from 0.001 to 5% by weight of coupling agent based on the total amount of coupling agent and polymer synthesized by anionic polymerization of the reaction.
- the preferred coupling agent of the present invention is the oligomer obtained by free radical polymerization from: at least one monomer selected from the group consisting of alkenyl aromatic monomers, functional epoxy acrylic monomers and mixtures thereof; and at least one monomer selected from the group consisting of alkenyl aromatic monomers, epoxy-functional acrylic monomers, anhydride-functional acrylic monomers, ester-functional acrylic monomers, carboxylic acid acid acrylic monomers and any of their mixtures, where the coupling agent has a number average molecular weight from about 500 to about 10,000 g / mol, and a weight average molecular weight from about 1,000 to about 20,000 g / mol.
- the molecular weights average in weight or average in number are calculated by GPC, as described above, but in this case referred to polystyrene standards.
- This coupling agent is marketed for example as ADR-4318 ®, marketed by BASF.
- Preferred oligomers as coupling agents are those containing approximately 1 to 60 mol% of epoxy-functional acrylic monomers or carboxy-functional acid monomers.
- preferred coupling agents include divinylbenzene or alternatively multifunctional chlorosilanes. In another embodiment, mixtures of the preferred coupling agents can also be used. All preferred embodiments of the first aspect of the invention are valid for the second aspect.
- a preferred embodiment comprises reacting the polymer synthesized by anionic polymerization with the coupling agent.
- the coupling reaction is preferably carried out in the same reaction zone where the synthesis of the polymer synthesized by anionic polymerization is carried out.
- the polymer synthesized by anionic polymerization is synthesized in a first reaction stage and reacted with the coupling agent in a second reaction stage.
- the polymerization method comprises polymerizing the monomers of the polymer synthesized by anionic polymerization, adding a sufficient amount of terminating agent to deactivate a portion of the living chains in the polymer synthesized by anionic polymerization and reacting at least some of the chains living with the coupling agent.
- the proportion of coupling agent with respect to the polymer synthesized by anionic polymerization could be from 0.001 to 5% by weight.
- the average number of polymer chains synthesized by anionic polymerization that is reacted with the coupling agent is approximately from 2 to 30.
- the polymerization method cited according to the above aspects is preferably characterized in that from 2 to 90 mol% of the polymer synthesized by anionic polymerization undergoes coupling reactions, preferably between 20 and 60 mol%.
- Examples of hydrogenation methods useful for the present invention are described in US Patents 4,970,254, US 5,166,277, US 5,393,843, US 5,496,898 and US 5,583,185.
- the hydrogenation of the functionalized multi-arm polymer can be carried out in situ in the reaction medium, such as hexane, cyclohexane or heptane.
- the solution is contacted with hydrogen gas in the presence of a catalyst, such as a nickel, titanium, etc. catalyst.
- Hydrogenation is typically carried out at temperatures of 25 ° C to 150 ° C, with a typical hydrogen pressure of 0.5 atm to 20 atm.
- the progress of hydrogenation can be controlled by Infrared Spectroscopy (IR) or Nuclear Magnetic Resonance (NMR).
- IR Infrared Spectroscopy
- NMR Nuclear Magnetic Resonance
- the hydrogenation reaction is carried out until at least 85% of the unsaturations of the arms synthesized by anionic polymerization have been saturated, preferably until at least 90% of the unsaturation has been hydrogenated, and even more preferably it is continued until At least 99% of the installation has been hydrogenated.
- the deprotection step can be carried out before or after the optional hydrogenation of the unsaturated multi-arms.
- the protected polymer is mixed with an ion exchange resin such as Amberlysts ® 15 and heated to an elevated temperature, for example 150 ° C, or to the reflux temperature of the solvent (cyclohexane) to that the check out process is completed.
- tere-alkyl protecting groups can also be removed by the reaction of the polymer with trifluoro acetic acid or with p-toluenesulfonic acid.
- tere-alkyl deprotection can be found in TW Greene and PGM Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, New York, 1991, page 41.
- the tert-butyldimethylsilyl can be removed by treating the multi-arm polymer functionalized with acids, such as hydrochloric acid, acetic acid, D_-toluenesulfonic acid, Dowes 50W-X8, or, a source of fluoride ions, for example tetra-n-butylammonium fluoride, potassium fluoride and 18-crown-6, or a pyridine-hydrofluoric acid complex.
- acids such as hydrochloric acid, acetic acid, D_-toluenesulfonic acid, Dowes 50W-X8, or, a source of fluoride ions, for example tetra-n-butylammonium fluoride, potassium fluoride and 18-crown-6
- the present invention is not only limited to new polymers and their synthesis processes, but also encompasses compositions thereof.
- functionalized multi-arm polymers of the first and second aspects can be included in adhesive compositions.
- the polymer containing said adhesive compositions is characterized in that the reaction contains approximately from 0.001 to 5% by weight of coupling agent based on the total amount of coupling agent and polymer synthesized by anionic polymerization, which were reacted.
- Adhesives, especially hot melt adhesives, prepared with the polymers of the present invention exhibit better Peel, Tack and Shear properties than prior art hot melt adhesives.
- the adhesive composition may contain at least one additive selected from the group consisting of tactile resins, stabilizers, plasticizers and antioxidants.
- at least one additive selected from the group consisting of tactile resins, stabilizers, plasticizers and antioxidants.
- from about 15 to 30, and more preferably from 18 to 25, parts by weight of the multi-arm polymer object of this invention is mixed with other conventional adhesive formulation components, such as tactifiers, stabilizers, plasticizers and antioxidants, to confer to these adhesive compositions improved properties compared to adhesives made with the same composition, using the same type of polymer without the introduction of functional groups, protected or not, at the terminal positions and / or unsaturated chain hydrogenation.
- suitable tactifiers include resins with high and low softening points, which are compatible with the polymer.
- the amount of fixing resins in the composition ranges from about 45 to 65% by weight.
- Plasticizers generally known as extender oils, include mineral oils, paraffinic oils, and naphthenic oils. In some illustrative embodiments, the amount of plasticizer in the composition ranges from about 15 to 30% by weight.
- Antioxidants can be used to inhibit the processes of thermal oxidation and ultraviolet rays, and are commonly added to the adhesive composition in amounts of approximately 0.05 to 3% by weight. Examples of antioxidants include phenolic compounds, phosphites, amines and thio compounds.
- the composition comprises from 15 to 30% by weight of tactile resin, approximately from 15 to 30 percent by weight of plasticizer and approximately from 0.05 to 2 percent by weight of antioxidant.
- the adhesive compositions can be used in multiple applications, for example in packaging adhesives, labels and adhesive tapes, construction and as pressure sensitive adhesives for use in the manufacture of elastic disposable items.
- the polymers of the present invention are useful for reinforcing materials or for obtaining composite materials, whereby these polymers can be mixed with a reinforcing material or with the material to be reinforced.
- the materials to be reinforced can be selected from the group consisting of asphalt, plastics and tires. Good results are obtained when plastics selected from polyamides, polyurethanes, polyethers, polysulfones, polyether ketones, polyether ether ketones, polyimides, polyetherimides, polycarbonates, polyesters, polystyrene and copolymers thereof are reinforced.
- the reinforced or composite material is useful for the production of articles, which can be an extruded article, an injection molded article, a compression molded article or a tire.
- Asphalts may contain approximately 1 to 25% by weight of the functionalized multi-arm polymer based on the total weight of the asphalt and the functionalized multi-arm polymer.
- the modified asphalt contains about 5 to 20% by weight of the functionalized multi-arm polymer.
- These modified asphalt mixtures with the functionalized multi-arm polymers can be used in applications such as roads, asphalt membranes and the like.
- the polymers of the present invention are useful for modifying plastics, preferably using mixtures containing from about 1 to 40 percent by weight of functionalized multi-arm polymer, based on the total weight of the functionalized multi-arm polymer and the plastic.
- the plastic preferably contains at least one polymer that is selected from the group consisting of polystyrene, polybutadiene, polyisoprene and random, block or progressive copolymers made from monomers selected from the group consisting of styrene, butadiene and isoprene, and having a Average molecular weight at the peak of the distribution approximately from 3,000 to 300,000 g / mol.
- the functionalized multi-arm polymers mixed with plastic are preferably those characterized in that the reaction product contains about 0.1 to 8% by weight of coupling agent based on the total amount of functionalized multi-arm polymer.
- the polymer of the present invention preferably contains polystyrene for mixing in plastics.
- said plastic mixed with the polymer of the invention can be mixed with another plastic to be modified, the proportions of the plastic mixtures can vary from 1 to 40% by weight of modified plastic with the functionalized multi-arm polymer, based on the total weight of the Plastic and functionalized multi-arm polymer.
- the word "comprises” and its variants are not intended to exclude other technical characteristics, additives, components or steps.
- other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention.
- the following examples are provided by way of illustration, and are not intended to be limiting of the present invention.
- Multi-arm SB copolymers functionalized with protected or unprotected OH groups were synthesized in a 20 L Buchi reactor, using 3- (t-butyldimethylsilyloxy) -1-propyl lithium initiator, commercially known as PFI-103 and marketed by FMC.
- copolymers were characterized by GPC (THF as eluent, universal calibration curve) to obtain their molecular weight, their branching degree and their percentage of coupling, and by 1 H-NMR to determine their microstructure, composition and level of deprotection.
- ADR-4318 coupling agent (20% p cyclohexane solution, 0.79 g / mL density), 0.8 mL, 1.3 mL or 1.8 mL was added to give a molar ratio of coupling agent to initiator of 0.04, 0.07 and 0.1, respectively.
- the polymer solutions were deactivated with 4.7 mL of BHT solution (10% p in cyclohexane).
- the copolymers were characterized by GPC (THF as eluent, universal calibration curve) to obtain their molecular weight, their branching degree and their percentage of coupling, and by 1 H-NMR to determine their microstructure, composition and level of deprotection. In this way, multi-arm copolymers functionalized with tertiary amine were obtained at the ends of the chains and with the characteristics indicated in Table 2. Table 2. Characteristics of multi-arm copolymers functionalized with tertiary amine.
- ADR-4318 features.
- the pressure-sensitive hot-melt adhesives were formulated in a metal container equipped with a heating system and adjustable speed stirring system.
- the temperature was controlled in the range 177 ° C +/- 2 ° C.
- the preparation time was of the order of 2 hours for each adhesive sample.
- the adhesives were applied on a Mylar film (PET) 0.002 "thick at 165 ° C, and covered with silicone paper to prevent contamination.
- PET Mylar film
- the adhesives were stored in an area of controlled conditions at 50% humidity and 23 ° C. Before being characterized, specimens were obtained from the films impregnated with adhesives to determine 180 ° Peel, Loop Tack and Shear.
- the substrate used for the evaluations were stainless steel panels with a mirror finish All the evaluations were carried out in the area of controlled conditions (50% humidity and 23 ° C). The viscosity was measured on a Brookfield RVII viscometer. Adhesives were determined with the following equipment: Loop Tack Tether, AR-100 Relay Adhesion Tether, and Shear Bank.
- Table 4 shows the thermal, mechanical and viscosimetric characterization of adhesive formulations. Although there are differences in the viscosity of adhesives at 177 ° C, all were manageable and their values are typical for hot-melt adhesives. The softening temperature behavior has a tendency similar to that of viscosity, where the adhesive containing the RO-SEBS-r high vinyl sample has the highest value. The elongation values for the three adhesives are very high, so it is not possible to interpret their effect on the performance of the adhesives.
- Table 5 shows the results of the evaluation of the characteristics of the adhesives after being aged in an oven at 177 ° C. The results indicate that adhesives exceed the commercial stability specifications, since viscosities do not tend to increase before the required 72 hours. Normally, in SBS and SEBS products, the increase in viscosity is related to the gelation process of the polymers. Another demonstration of the thermal stability of adhesives is the absence of "skin" in samples subjected to thermal aging at 177 ° C in an oven for a period of 72 h.
- Table 6 shows the results of the evaluations related to the adhesiveness of the products.
- Shear it is clearly observed that both for the sample prepared with the protected functional group (RO-SEBS-r high vinyl), and for the sample made from the unprotected functional group (HO-SEBS-r high vinyl) , higher Shear values are obtained than for the sample prepared with the product without functionalization (SEBS-r high vinyl).
- the adhesive prepared with the protected functionalized hydrogenated polymer the improvement is greater than 100% with respect to the non-functionalized hydrogenated polymer, while for the adhesive prepared with the unprotected functionalized hydrogenated polymer the improvement is almost 200%.
- Loop Tack measurement represents the force of attraction between the surface of the adhesive on the substrate, so the impregnation density does not have much effect on this parameter. It is observed that for the sample prepared with the functionalized and protected hydrogenated polymer (RO-SEBS-r high vinyl) the adhesiveness decreases slightly, while for the adhesive prepared with the functionalized and unprotected hydrogenated polymer (HO-SEBS-r high vinyl) the adhesiveness is increased by approximately 50% with respect to the reference that is only hydrogenated (SEBS-r high vinyl). In the case of the 180 ° Peel measurement, the same trend as the one indicated for Loop Tack is observed, with the adhesive containing the HO-SEBS-r high vinyl rubber showing the maximum values.
- Adhesive formulations containing the Piccolyte HM-106 resin were prepared according to the recipe shown in Table 7.
- the adhesives were prepared in a 1 L glass reactor at 160 ° C, first adding the oil, followed by the antioxidant , of the resin, and of the polymer. The mixture was made in about 1 h, stirring continuously under a constant stream of nitrogen.
- the adhesives were applied on a Mylar film (PET) at 165 ° C, and covered with silicone paper to prevent contamination. From films impregnated with adhesives, specimens were obtained to determine Probé Tack and SAFT (shear adhesion failure time).
- the Probé Tack was determined on specimens of 2.5 cm on the side with a Digital Polyken Probé Tack Tester TMI 80-02-01 equipped with a 0.5 cm diameter stainless steel probe, according to ASTM D 2979
- the SAFT was carried out in a stove with forced air circulation (Cheminstruments) at 48 ° C and with weights of 0.25 kg.
- the substrate used for the evaluations were stainless steel panels with a mirror finish.
- the viscosity was measured on a Brookfield RVII viscometer model.
- the test tack of adhesives prepared with unhydrogenated polymers has a similar trend to those prepared with hydrogenated polymers.
- the adhesives containing the protected or unprotected functionalized polymers exhibit very similar tack values, being always higher than that of the adhesives prepared with the non-functionalized polymers, 1, 6 times higher in the case of non-hydrogenated polymers of medium vinyl, double in the case of those made with the hydrogenated rubbers of high vinyl, and 1, 5 times higher in the case of those made with the hydrogenated rubbers. It is also observed that an increase in the level of vinyl leads to a decrease in tack.
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Abstract
La présente invention concerne des polymères ramifiés fonctionnalisés qui comprennent le produit de la réaction d'un agent de couplage et d'un polymère synthétisé par polymérisation anionique. L'invention concerne également le procédé permettant d'obtenir lesdits polymères, ainsi que leurs différentes utilisations, notamment comme adhésifs thermofusibles.
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| RU2012128940/04A RU2528403C2 (ru) | 2009-12-10 | 2009-12-10 | Функционализированные мультиразветвленные полимеры, включающие функционализированные полимеры, синтезированные анионной полимеризацией, и их применение |
| ES09807445.3T ES2647920T3 (es) | 2009-12-10 | 2009-12-10 | Polímeros multibrazos funcionalizados que comprenden polímeros funcionalizados sintetizados por polimerización aniónica y sus aplicaciones |
| MX2012006690A MX352166B (es) | 2009-12-10 | 2009-12-10 | Polímeros multibrazos funcionalizados que comprenden polímeros funcionalizados sintetizados por polimerización aniónica y sus aplicaciones. |
| US12/996,060 US8987371B2 (en) | 2009-12-10 | 2009-12-10 | Functionalized multi-arm polymers which comprise functionalized polymers synthesized by anionic polymerization and their applications |
| CN200980163413.9A CN102781973B (zh) | 2009-12-10 | 2009-12-10 | 包含通过阴离子聚合而合成的官能化聚合物的官能化多臂聚合物以及它们的应用 |
| BR112012014030-2A BR112012014030B1 (pt) | 2009-12-10 | 2009-12-10 | polímero multibraços funcionalizado, polímero multibraços funcionalizado hidrogenado, método para a obtenção de um polímero multibraços hidrogenado, composição adesiva que contém o polímero multibraços funcionalizado, material reforçado ou composto que compreende o polímero multibraços funcionalizado, artigo, asfalto modificado, e, plástico modificado que compreende um plástico misturado com o polímero multibraços funcionalizado |
| JP2012542585A JP5744901B2 (ja) | 2009-12-10 | 2009-12-10 | アニオン重合によって合成された機能性ポリマーを含む機能性多分岐ポリマー、及びその使用 |
| CA2783871A CA2783871C (fr) | 2009-12-10 | 2009-12-10 | Polymeres a plusieurs ramifications fonctionnalises qui comprennent des polymeres fonctionnalises synthetises par polymerisation anionique et leurs applications |
| PCT/ES2009/070572 WO2011070182A1 (fr) | 2009-12-10 | 2009-12-10 | Polymères ramifiés fonctionnalisés comprenant des polymères fonctionnalisés synthétisés par polymérisation anionique et applications correspondantes |
| PL09807445T PL2511304T3 (pl) | 2009-12-10 | 2009-12-10 | Funkcjonalizowane polimery wieloramienne zawierające funkcjonalizowane polimery syntetyzowane przez anionową polimeryzację oraz ich zastosowania |
| EP09807445.3A EP2511304B1 (fr) | 2009-12-10 | 2009-12-10 | Polymères ramifiés fonctionnalisés comprenant des polymères fonctionnalisés synthétisés par polymérisation anionique et applications correspondantes |
| TW099142060A TW201129592A (en) | 2009-12-10 | 2010-12-03 | Functionalized multi-arm polymers which comprise functionalized polymers synthesized by anionic polymerization and their applications |
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| US9109073B1 (en) | 2014-08-19 | 2015-08-18 | The Goodyear Tire & Rubber Company | Bifunctionalized polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110770038A (zh) * | 2017-06-22 | 2020-02-07 | 米其林集团总公司 | 具有含热塑性聚合物和热塑性弹性体的组合物的非充气轮胎 |
| CN110770038B (zh) * | 2017-06-22 | 2021-12-21 | 米其林集团总公司 | 具有含热塑性聚合物和热塑性弹性体的组合物的非充气轮胎 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX352166B (es) | 2017-11-13 |
| EP2511304B1 (fr) | 2017-09-27 |
| CN102781973A (zh) | 2012-11-14 |
| MX2012006690A (es) | 2012-09-07 |
| BR112012014030B1 (pt) | 2021-02-17 |
| PL2511304T3 (pl) | 2018-05-30 |
| EP2511304A1 (fr) | 2012-10-17 |
| CA2783871A1 (fr) | 2011-06-16 |
| RU2012128940A (ru) | 2014-01-20 |
| JP5744901B2 (ja) | 2015-07-08 |
| TW201129592A (en) | 2011-09-01 |
| US20110251308A1 (en) | 2011-10-13 |
| CA2783871C (fr) | 2017-11-07 |
| US8987371B2 (en) | 2015-03-24 |
| RU2528403C2 (ru) | 2014-09-20 |
| BR112012014030A2 (pt) | 2020-08-25 |
| CN102781973B (zh) | 2016-10-19 |
| ES2647920T3 (es) | 2017-12-27 |
| JP2013513685A (ja) | 2013-04-22 |
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