MXPA97008019A - Union of anionic polymers with tri alcoxisilanos that have silicon-hydrog links - Google Patents
Union of anionic polymers with tri alcoxisilanos that have silicon-hydrog linksInfo
- Publication number
- MXPA97008019A MXPA97008019A MXPA/A/1997/008019A MX9708019A MXPA97008019A MX PA97008019 A MXPA97008019 A MX PA97008019A MX 9708019 A MX9708019 A MX 9708019A MX PA97008019 A MXPA97008019 A MX PA97008019A
- Authority
- MX
- Mexico
- Prior art keywords
- radial
- polymer according
- initiator
- polymer
- polymers
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 88
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive Effects 0.000 claims abstract description 8
- 239000000565 sealant Substances 0.000 claims abstract description 8
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005304 joining Methods 0.000 claims abstract description 4
- 150000001993 dienes Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 230000000977 initiatory Effects 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000007792 addition Methods 0.000 description 10
- 238000009739 binding Methods 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 229940098779 methanesulfonic acid Drugs 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- -1 styrene Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000004072 triols Chemical class 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- JILPJDVXYVTZDQ-UHFFFAOYSA-N Lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 230000001681 protective Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HWBIQJOWCBKZJW-UHFFFAOYSA-N $l^{1}-silanyloxysilicon Chemical compound [Si]O[Si] HWBIQJOWCBKZJW-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N Chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N Hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N Neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M Tetra-n-butylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N Triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 125000004171 alkoxy aryl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000005418 aryl aryl group Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000000075 primary alcohol group Chemical group 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-M 2-ethylhexanoate Chemical compound CCCCC(CC)C([O-])=O OBETXYAYXDNJHR-UHFFFAOYSA-M 0.000 description 1
- XRBQEYWBWZFUIJ-UHFFFAOYSA-N 2-ethylhexanoic acid;nickel Chemical compound [Ni].CCCCC(CC)C(O)=O XRBQEYWBWZFUIJ-UHFFFAOYSA-N 0.000 description 1
- 229920000180 Alkyd Polymers 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N Barbituric acid Chemical group O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000004821 Contact adhesive Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N Disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UKOVZLWSUZKTRL-UHFFFAOYSA-N Naphthalid Chemical compound C1=CC(C(=O)OC2)=C3C2=CC=CC3=C1 UKOVZLWSUZKTRL-UHFFFAOYSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N Oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N Tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001567 Vinyl ester Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011141 high resolution liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002492 poly(sulfones) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing Effects 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000002633 protecting Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- ZHERPVLBGALJPP-UHFFFAOYSA-N trimethoxymethylsilicon Chemical compound COC([Si])(OC)OC ZHERPVLBGALJPP-UHFFFAOYSA-N 0.000 description 1
- 239000004591 urethane sealant Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
A high yield of the three-branched radial anionic polymers is produced by the process of joining the metal-terminated anionic polymers with a trialkoxylan having a silicon-hydrogen bond, preferably trimethoxysilane. The metal-terminated anionic polymer is preferably produced by initiating the polymerization with a protected functional initiator which is readily converted to the terminal hydroxyl groups or derivatives thereof, and finds use in adhesives, sealants, and coatings.
Description
UNION DS. ANIONIC POLYMERS WITH TRIALC0XI3ILAN03 THAT HAVE SILICON-HYDROGEN GLYCLES
Field of the Invention
This invention relates to the union of anionic polymers and functionalized radial polymers, used as components in adhesives, sealants, and coatings. 10 Field of the Invention
Anionic polymerization of conjugated dienes with lithium initiators, such as sec-butyllithium, and hydrogenation of residual unsaturation have been described in many references including U.S. Patent Specification. No. Re. 27,145 which teaches a relationship between the amount of the 1,2-addition of butadiene and the temperatures of
glass transition of the hydrogenated butadiene polymers. Any polymerization using protected functional primers having the structure:: > 5 Ref.25948
are described in US Patent Specification No. 5,331,058 wherein R1, R2, and R3 are preferably alkyl, alkoxy, aryl, or alkaryl groups having from 1 to 10 carbon atoms, and A 'is preferably a linking group by middle of a bridge, straight or branched chain, having at least 2 carbon atoms. The initiators of the general structure (1), in which R1 = t-butyl and R2 = R3 = methyl, ethyl, or n-propyl and A 'is a linking group by means of an unsubstituted or substituted propyl bridge with alkyl or a linking group via an unsubstituted or substituted alkyl octyl bridge, it was later shown that they will be preferred due to their higher activity in US Patent Specification No. 5,391,663. Polymerization with such a protected functional initiator, followed by coronation at the ends to produce a second terminal functional group, produces difunctional polymers which can sometimes be prepared by crowning the prepared polymers at the ends with difunctional initiators such as 1-4. dilithiobutane and lithium naphthalide. However, the use of a protected functional primer allows the formation of heterofunctional polymers having at least two different terminal functional groups on each difunctional molecule. A preferred way to prepare the difunctional polymers described in United States of America Patent Specification No. 5,416,168 is to use a protected functional initiator having the structure:
CH3 I
CH3-Si-0-CH2-A "-CH2-LÍ I (A) CH3
wherein A "is a cyclohexyl group or a group -CR'R", wherein R 'represents a linear alkyl group having from 1 to 10 carbon atoms and R "represents a hydrogen atom or a linear alkyl group having from 1 to 10 carbon atoms The compounds of the structure (A) initiate the polymerization of the conjugated monomers at moderate polymerization temperatures.The protected functional group survives the hydrogenation of the conjugated dienes polymers and is easily removed by the hydrolysis in the presence, for example, of the methanesulfonic acid The initiators of the structure (A) can be used to manufacture telechelic polymers by crowning the ends with ethylene oxide or oxetane.
The joining of anionic polymers to make radial polymers is described in many references, including U.S. Patent Specification No. 4,185,042 which teaches that the difficulty to obtain complete binding with tetramethoxysilane or trimethoxymethylsilane is overcome using an epoxide group with two or three alkoxy groups to make the radial anionic polymers. The epoxide group reacts readily with a lithium-terminated anionic polymer leaving a hydroxyl group at the binding site. A more efficient bonding can also be achieved using chlorosilanes, such as trichloromethylsilane. However, the by-product of the binding reaction, LiCl, can be a problem in subsequent process steps, particularly if the product is to be hydrogenated. It is an object of the present invention to join the anionic polymers in a high yield to form the radial polymer without introducing the hydroxyl functionality into the binding site. The achievement of the established object could be the most beneficial for the hydrogenated radial anionic polymers that have only terminal hydroxy groups.
Detailed description of the invention
The present invention provides a radial anionic polymer obtainable by a process comprising the process steps of preparing a linear anionic polymer terminated in a metal, containing protected functional groups, by the polymerization of a conjugated diene, such as butadiene or isoprene, or a monovinyl aromatic compound, such as styrene, or combinations thereof, using a metal-protected functional initiator, such as a protected, functional mono-lithium initiator, and joining a plurality of the linear anionic polymers using a trialkoxysilane having a silicon-hydrogen bond. The present invention further comprises the process for manufacturing a radial anionic polymer of the invention which comprises these process steps. The process of the lithium initiator is well known and is described in U.S. Patent Specifications. Nos. 4,039,593 and Re. 27,145. Typical, active polymeric structures that can be manufactured with lithium initiators include:
X-B-Li X-B / A-Li X-A-B-Li X-B-A-Li X-B-B / A-Li X-B / A-B-Li X-A-B-A-Li
wherein B represents polymerized units of one or more conjugated diene hydrocarbons, A represents polymerized units of one or more vinyl aromatic compounds, B / A represents randomly polymerized units of the conjugated diene hydrocarbons and vinyl aromatic monomers, and X is the residue of the lithium initiator. In the present invention, X is preferably a trimethylsilyl ether group as described below and the cleavage or cleavage of trimethylsilyl ether leaves a primary alcohol group similar to neopentyl in this position. These primary alcohols have a different reactivity than other primary alcohol groups which will lead to different reaction rates for the ends of the chain with the diisocyanates and the dicarboxylic acids. This difference in reactivity velocities could be very useful in the design of materials where gradual polymerization is desired. Anionic polymerization of the conjugated dienes and other unsaturated monomers using the protected functional initiators having the structure R1R2R3Si-0-A '-Li (Structure 1.) is described in US Patent Specification No. 5,331,058 wherein R1, R2 , and R3 are preferably alkyl, alkoxy, aryl, or alkaryl groups having from 1 to 10 carbon atoms, and A 'is preferably a linking group by means of a straight or branched chain bridge having at least 2 carbon atoms. A preferred protected functional initiator for making the homopolymers of the conjugated dienes and the block or random copolymers of the conjugated dienes and vinyl aromatics have a trimethyl silyl protecting group with the structure:
CH3 I
CH3-Si-0-CH2-A "-CH2-LÍ | (A) CH3
Where A "represents a cyclohexyl group or a group -CR 'R" -, where R' represents a linear alkyl having from 1 to 10 carbon atoms and R "represents a hydrogen atom or a linear alkyl group having from 1 to 10 carbon atoms The compounds of structure (A) initiate the polymerization of conjugated dienes monomers such as butadiene and isoprene at moderate polymerization temperatures.The protected functional group survives the hydrogenation of the diene polymers conjugates and is easily removed by hydrolysis in the presence of, for example, methanesulfonic acid The preferred initiators used in the present invention are similar to s-butyllithium with respect to the economical operating temperature and low amounts of the inactive initiator and a controlled, uniform level of 1,2-addition of the diene in the produced polymer, however, preferred initiators have the advantage of placing a group of silyl ether at the beginning of the polymer chain which serves as a "masked" or "protected" alcohol, capable of conversion to a group of alcohol of the neopentyl, primary type, after the polymerization is completed by reaction with acids or bases under low cost, mild conditions, or as described in the Patent specification International No. 91/12277. Although the initiators described in US Patent Specification No. 5,331,058 could generally produce, after polymerization and deprotection, a polymer having a primary alcohol functionality, a polymer having a primary alcohol functionality of the neopentyl type, obtained from the initiators of Structure (A), must have improved thermal stability and the condensation polymers derived therefrom must have improved hydrolytic stability. The condensation polymers derived from the products made with these initiators must also have an improved hydrolytic stability. The improved thermal stability of neopentyl alcohol and the hydrolytic characteristics of its derivatives are summarized in Advanced Organic Chemistry, Third Edition, by J. March, John Wiley & amp;; Sons, New York (1985) (see pages 285, 299, 390, 514, 944, 955, 959, and references therein). It is reasonable that polymers having this special structure could have similarly improved properties. The initiators used in the present invention are very active at room temperature and the polymerization is preferably initiated at a temperature in the range from 15 ° C to 60 ° C, more preferably from 30 ° C to 40 ° C. Generally, it can be contemplated to keep the polymerization temperature below 100 ° C; Above this temperature, lateral reactions that change the microstructure and limit the efficiency of the joint can become important. The polymerizations can be carried out over a range of solids levels, preferably in the range from 5% to 80% by weight of the polymer, more preferably from 10% to 40% by weight. For polymerizations with a high solids content, it is preferable to add the monomer in increments to avoid exceeding the desired polymerization temperature. If the initiator is to be added to the complete monomer charge, it is preferable to operate the polymerization at a level in the range of 10% to 20% solids. It is preferable to add the alkoxysilanes of the present invention to a ratio of an alkoxy group per active chain. That is, to produce a radial polymer with three branches, one mole of trialkoxysilane is added for every three moles of the polymeric lithium ion. It is preferable to carry out the binding reaction at a temperature in the range from 30 ° C to 80 ° C. It is also preferable to add the binding agent as soon as the polymerization is complete. If the polymeric lithium ion is aided or left at this temperature for prolonged periods of time, limiting reactions that limit bonding may occur. When the conjugated diene is 1,3-butadiene and when the conjugated diene polymer is hydrogenated, the anionic polymerization of the conjugated diene hydrocarbons is typically controlled with the structure modifiers such as diethyl ether or glyme (1, 2-diethoxyethane) to obtain the desired amount of 1,2 addition. As described in US Patent Specification No. Re 27,145, the level of 1,2 addition of a butadiene polymer or copolymer can greatly affect the rheology and elastomeric properties of the polymer after hydrogenation. The hydrogenated polymers exhibit thermal stability and resistance to improved environmental factors, in the adhesive, sealant or coating, finishes. The 1,2-addition of the 1,3-butadiene polymers having terminal functional groups influences the viscosity of the polymers as described in greater detail below. A 1.2 addition of about 40% is achieved during the polymerization at 50 ° C with at least 6% by volume of diethyl ether or 1000 ppm of glyme. In general, vinyl contents in this range are desirable if the product is to be hydrogenated, while low vinyl contents are preferred if the polymer is to be used in its unsaturated form. The protected functional primers are preferred as described below and are prepared as described in US Patent Specification No. 5,331,058. A variety of processes for the removal of protective groups are already known; for a review, see T. W. Greene, "Protective Groups in Organic Synthesis," J. Wiley and Sons, New York, 1981. A preferable process could involve easily handled, relatively low toxic, and economic reagents. In a preferred process, the preferred trimethyl silyl group is removed by the reaction of the polymer solution with from 1 to 10 equivalents (end silyl groups of the base) of the strong organic acid, preferably methanesulfonic acid (MSA), in the presence from 0.1% to 2% by weight of water and from 5% to 50% by volume of isopropanol (IPA) at 50 ° C. The process of the invention can lead to the release of fine particles of lithium bases which are preferably removed prior to hydrogenation, if any, as described in U.S. Patent Specification. No. 5,166,277. The lithium bases can interfere with the hydrogenation of the polymer, especially if the hydrogenation is to be carried out at a high solids content. However, as detailed in the Examples, an acceptable hydrogenation can be achieved without the removal of lithium when the binding agents of the present invention are employed. The hydrogenation of at least 90%, preferably at least 95%, of the unsaturation in the low molecular weight butadiene polymers is preferably achieved with the nickel catalysts as described in U.S. Patent Specifications. Nos. Re. 27,145 and 4,970,254 and U.S. Patent Specification. No. 5,166,277. The preferred nickel catalyst is a mixture of nickel 2-ethylhexanoate and triethylaluminum. It is preferable to extract the nickel catalyst after hydrogenation, by stirring the polymer solution with aqueous phosphoric acid (from 2 to 30 weight percent), at a volume ratio of 0.5 parts of aqueous acid with respect to 1 part of the solution polymer, at 50 ° C for 30 to 60 minutes while being sprayed with a mixture of oxygen in nitrogen. The presence of elevated levels of lithium chloride during acid extraction, which could occur if a chlorosilane binding agent is used, requires special engineering considerations. Due to the high corrosiveness of acidic aqueous solutions that have a high chloride content towards carbon steel and most stainless steel alloys, the use of relatively expensive special glass or alloys could be recommended for surface contact of the extraction vessel with the acid. Conjugated, radial, saturated or unsaturated dienes polymers having approximately three terminal functional groups, are selected from the hydroxyl, carboxyl, phenol, epoxy, and amine groups; these latter functional groups can be obtained from the additional derivation of the hydroxyl groups. These products can be used without solvents when the viscosity of the polymer is less than 500 poises at the mixing and application temperature. Radial, three-branched hydrogenated butadiene or isoprene polymers, having two terminal hydroxyl groups per molecule and a viscosity of less than 500 poises at the mixing and application temperatures, are produced by limiting the molecular weight of the maximum point to a range from 500 to 20,000 and limiting the 1,2-addition of the hydrogenated butadiene to an amount in the range from 30% to 70%, preferably from 40% to 60%. After polymerization and, optionally, hydrogenation and washing of the polymer, the trimethylsilyl group at the front of the preferred polymer chain is removed to generate the hydroxyl functional group of the neopentyl, primary, desired type. This step is often referred to as a checkout. A variety of the processes for the removal of the silyl protecting group are already known; for a review, see TW Greene, "Protective Groups in Organic Synthesis," J. Wiley and Sons, New York, 1981. Deprotection preferably involves easily manipulable reagents, relatively low toxicity, economics, and reduced cost process conditions, soft. The reaction with tetrabutylammonium fluoride in tetrahydrofuran (THF), as described in International Patent Specification No. WO 91 112277, is disadvantageous because of the high cost and toxicity of the reagents. In a preferred process, the trimethylsilyl group is removed after the hydrogenation and during the aqueous washing of the acid for the removal of the spent Ni / Al hydrogenation catalyst. This technique avoids the cost associated with a separate process step for check out. For the preparation of an unsaturated polymer wherein the extraction of the hydrogenation catalyst is not required, hydrolysis in the presence of methanesulfonic acid, as described above, is preferred. For some applications, such as coatings prepared by curing the polymer with amino resins in the presence of a strong organic acid catalyst, it may be preferable to use the polymer in its "protected" form. The viscosity of the protected polymer is lower and conditions such as those described above must effect deprotection (generate alcohol) during curing. The conjugated diene polymers produced as described above have the conventional utilities for terminal functionalized polymers, such as the formation of adhesives, coating and sealing agents. Additionally, polymers can be used to modify polyurethanes, polyesters, polyamides, polycarbonates, and epoxy resins. A preferred radial anionic polymer has terminal functional groups and is produced by the process comprising the steps of polymerizing linear lithium-terminated anionic polymers from conjugated dienes, such as isoprene or butadiene, or combinations of conjugated dienes and aromatics of monoalkenyl, such as styrene, using a protected functional initiator having the structure:
CH3 CK3-Si-0-CH2-A "-CH2-LI (A) CH3
wherein A "represents a cyclohexyl group or a group -CR'R" -, wherein R 'represents a linear alkyl having from 1 to 10 carbon atoms and R "represents a hydrogen atom or a linear alkyl group having from 1 to 10 carbon atoms, join the linear anionic polymers with a trialkoxysilane having a silicon-hydrogen bond, preferably trimethoxysilane, hydrogenate the polymerized conjugated diene, and react the hydrogenated radial polymer with a compound that replaces the trimethylsilyl groups of the initiator of lithium with hydrogen to give the terminal hydroxyl groups The most preferred process for manufacturing the terminally functionalized radial polymer uses the initiator having the following structure:
CH3 CH3 CH3-S IÍ-O-CH2-CI-CH2-LÍ (B) I I
CH3 CH3
(3-lithium-2,2-dimethyl-1-trimethylsilyloxypropane) to produce the linear conjugated diene polymers having a molecular weight of the maximum point in the range from 500 to 200,000, more preferably from 500 to 20,000. After binding with trimethoxysilane, the polymers can be unsaturated when the 1-2 addition is in the range of 5 to 95% or hydrogenated when the 1.2 addition is in the range of 30% to 70%. The radial polymers preferably have in the range from 2.75 to 3.0, more preferably from 2.95 to 3.0, terminal hydroxyl groups per molecule.
The polymers of the present invention, especially the above preferred forms, are useful in adhesives (including pressure sensitive adhesives, contact adhesives, laminating adhesives and assembly adhesives), sealants (such as architectural urethane sealants), coatings (such as automotive top coatings, epoxy metal primers, polyester coil coatings, and alkyd maintenance coatings), films (such as those that require heat and solvent resistance), and thermosetting and thermoplastic parts molded and extruded (for example injection molded polyurethane rolls or cylinders, thermoplastics, or automotive facies and dampers, thermosetting, injection molded, by reaction) and consequently the present invention also provides a composition suitable for such uses, which comprises a polymer d e the present invention. The additional components are usually incorporated in such compositions. A composition of the present invention may contain plasticizers, such as rubber or rubber extender plasticizers, or composition oil or organic or inorganic pigments and dyes. Oils of rubber or rubber composition are well known in the art and include both oils with a high content of saturated materials and oils with a high aromatic content. Preferred plasticizers are highly saturated oils, for example TUFFLO 6056 and 6204 oil made by Garco and process oils, for example SHELLFLEX 371 oil made by Shell (TUFFLO and SHELLFLEX are registered names). The amounts of the oil of rubber or rubber composition employed in such compositions can vary from 0 to 500 phr, preferably from 0 to 100 phr, and more preferably from 0 to 60 phr. The original components of the present invention are stabilizers which inhibit or retard degradation by heat, oxidation, film formation and color formation. The stabilizers are typically added to commercially available compounds to protect the polymers against degradation by heat and oxidation during preparation, use and storage at elevated temperature of the composition. Various types of fillers and pigments can be included in a coating or sealing formulation. This is especially true for exterior coatings or sealants in which the fillers are added not only to create the desired attraction but also to improve the performance of the coatings or sealants such as their resistance to environmental agents. A wide variety of fillers can be used. Suitable fillers include calcium carbonate, clays, talcs, silica, zinc oxide, and titanium dioxide. The amount of the filler is usually in the range of 0 to 65% by weight based on the solvent-free portion of the formulation, depending on the type of filler used and the application for which the coating or sealant is proposed. A particularly preferred filler is titanium dioxide. The conjugated, trihydroxylated diene polymers of the present invention may also be blended or combined with other polymers to improve their flexibility and / or impact resistance. Such polymers are generally condensation polymers including polyamides, polyurethanes, vinyl alcohol polymers, vinyl ester polymers, polysulfones, polycarbonates and polyesters, including those similar to polyacetones, which have a recurring ester bond in the molecule, and those similar to polyalkylene acrylates, including polyalkylene terephthalates, having a structure formed by the polycondensation of a dicarboxylic acid with a glycol. The mixtures or combinations can be made in the reactor or in a subsequent composition step. The present invention is further illustrated by the following examples. The molecular weights of the maximum point are measured using gel permeation chromatography
(CPG) calibrated with polybutadiene standards having known molecular weights of the maximum point. The solvent for the CPG analyzes was tetrahydrofuran. The percentage of the 1,2-additions of the polybutadiene, the molecular weight, and the extent of hydrolysis of the protected alcohol were measured by 13 C NMR or 1 H NMR in the chloroform solution. High Resolution Liquid Chromatography
(HPLC) can also be used to determine the relative amounts of the desired trihydroxy material (triol), and the mono-hydroxy or di-hydroxy material, which could have resulted from incomplete binding. Where used, the separation by CLgAR was carried out with a phase column of DIOL of 250 mm x 4.6 mm x 5 microns using gradient graduated heptane / tetrahydrofuran. An evaporative light scattering or scattering detector can be used to quantify the sample.
Examples
Example 1
The reaction of the preferred lithium initiator of US-A-5, 391, 663 with the polymerization effectively initiated by butadiene and the reaction of the active polymer product with trimethoxysilane produced, after isolation, a high yield of 1 , 4-polybutadienil triol superior, with three branches. A solution of 3- (t-butyldimethylsilyloxy) -1-propyllithium (RLi) (105.71 g of the solution, 12.8% by weight of RLi, 0.075 mole of RLi) in cyclohexane was added, under nitrogen, to a solution of butadiene monomer (100 g, 1.85 moles) of the degree of polymerization, in cyclohexane (856 g) with vigorous stirring in a glass autoclave at 30 ° C. The resulting exothermic reaction raised the temperature of the solution to 47 ° C in about 37 minutes. The temperature was then increased to 60 ° C. After a total reaction time of 137 minutes, a small sample was removed and then quenched with methanol, then 3.1 g (0.025 mol) of trimethoxysilane was added to the autoclave. The temperature of the reaction was increased to 70 ° C. After 1 hour, the temperature was lowered to 40 ° C and 3.3 ml of methanol was added. A large amount of the white precipitate (lithium methoxide) has formed in the course of the reaction. The solution is washed with 200 ml of 3 wt% aqueous phosphoric acid at about 57 ° C, and a sample is dried for analysis. The sample collected prior to the addition of the binding agent was found to have a numerical average molecular weight (Mn) of 1.470 when measured by a Nuclear Magnetic Resonance of 13C which compares the ratio of the carbon signal that is attributed to the segment of the initiator alkyl with the total carbon signal for the sample; this compares favorably with the expected value of 1,500. The analysis of this sample to verify the vinyl content, also using an NMR technique, found that 11% of the butadiene has been added by the 1,2-polymerization producing a pendant vinyl unsaturation with the remainder added by the polymerization 1, 4 that provides the chained unsaturation species. The numerical average molecular weight as measured by a gel permeation chromatography (CPG) technique was found to be 1,200. The true value is probably lower because this molecular weight is close to the linear operating limit of the column. After the binding reaction, a single peak was observed and the Mn was increased to 2,800, approximately three times the molecular weight of the branch. After decanting the aqueous layer, a solution containing 232 ml of isopropanol, 12.7 ml of methanesulfonic acid and 1.7 ml of water was added to the polymeric cement. The reaction was allowed to proceed at about 55 ° C for 2.5 hours. The cement was washed with dilute aqueous potassium carbonate and then with water, and dried on a rotary evaporator. The analysis of 13C Rg was consistent with the 97% hydrolysis of silyl ether. The HPLC chromatogram of this product consisted of two peaks or maximum values; 90% of the area was at a very high retention time, consistent with the expected triol product, the remaining 10% was at the retention time assigned to the diol. No mono-functional or non-functional material was detected.
Example 2
A radial butadiene polymer was prepared using the preferred initiator, 3-lithium-2,2-dimethyl-1-trimethyl-silyloxypropane and hydrogenated using a Ni / Al catalyst; the saturated polymer product was deprotected under the conditions used to extract the spent hydrogenation catalyst yielding the desired hydrogenated poly (ethylene / butylene) triol. A solution of 3-lithium-2,2-dimethyl-1-trimethylsilyloxypropane (RLi) (71.54 g of the solution, 11.6% by weight of RLi, 0.05 mole of RLi) in cyclohexane was added, under nitrogen, to a solution of the butadiene monomer of the polymerization degree (100 g, 1.85 mmol) in a mixed diethyl ether / cyclohexane solvent (712 g of cyclohexane / 100 g of diethyl ether) with vigorous stirring in a glass autoclave at 30 ° C. The resulting exothermic reaction raised the temperature of the solution to 62 ° C in about 15 minutes. 2.04 g (0.017 moles) of trimethoxysilane are added to the autoclave at this time. The temperature is maintained at about 40 ° C for 40 minutes and then 2.2 ml of methanol are added. A large amount of the white precipitate (lithium methoxide) has formed in the course of the reaction. The CPG analysis of the bound product indicated a single peak with an Mn of 5,000, which is in agreement with the expected triol molecular weight of 6,000. Although no sample was taken of the "branching" prior to binding, the ratio of the initiator residues ("X" in the previous structures) to the monomeric butadiene residues, determined by XH, NMR, may be used. to estimate the numerical average molecular weight of the branch.
The value of the measurement of 2,000 ± 100 is in accordance with the expected value of 2,000. The hydrogenation catalyst (Ni / Al) for this experiment was previously prepared by combining the 2-ethylhexanoate with triethylaluminum in cyclohexane in amounts sufficient to give a ratio of 2.5 moles of Al to 1 mole of Ni. The polymeric cement was transferred to a 500 cc steel autoclave and sprayed with hydrogen at 40 ° C. No filtration or centrifugation step was used to remove the precipitated lithium methoxide, but most of it has settled during rest and was not transferred. The reactor was then pressurized to 4,826 kPa (700 psig) with hydrogen and the Ni / Al catalyst was added in aliquots. The temperature of the reaction was maintained between 60 ° C and 80 ° C. A sufficient amount of the Ni / Al catalyst was eventually added to bring the concentration of the total Ni solution to 200 ppm. After 2 hours of hydrogenation, an aliquot was removed and analyzed later to verify the C = C portions that did not react, using an ozone titration technique; at this time the catalyst concentration was 200 ppm. This analysis found that up to 98% of the starting polybutadienyl unsaturation has been hydrogenated (0.14 meq / g). The hydrogenation continued after increasing the catalyst concentration to 290 ppm. The analysis of the final product indicated up to 99% of the hydrogenation of the unsaturation (0.03 meq / g). The majority of the hydrogenation catalyst settled during rest. 323 g of the essentially clear cement were transferred to a resin pan and the protecting groups were removed by hydrolysis with methanesulfonic acid and water in the presence of isopropanol (3.14 g, 1.5 g and 77 g, respectively) as described in Example 1. After washing this solution with water and removing the solvent, a colorless, clear, viscous liquid was obtained; the product became cloudy when cooled due to a light crystallinity imparted by the 1.4 hydrogenated repeat units. There is no evidence of residues of any of the lithium salts or the hydrogenation catalyst. 1 H RgMN indicated 97% hydrolysis of the silyl ether protecting groups with respect to the desired hydroxyl product.
It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following
Claims (9)
1. A radial anionic polymer, characterized in that it can be obtained by a process comprising the steps of: preparing a metal-terminated linear anionic polymer, containing protected functional groups, by the polymerization of a conjugated diene, a monovinyl aromatic compound, or a combination thereof, using a protected functional metal initiator; and joining a plurality of the linear anionic polymers using a trialkoxysilane having a silicon-hydrogen bond.
2. A radial polymer according to claim 1, characterized in that the trialkoxysilane is trimethoxysilane.
3. A radial polymer according to claim 1 or claim 2, characterized in that the metal initiator is a protected functional initiator of the general formula CH3 CH3-S Ii-0-CH2-A "-CH2- i I (A) CH3 wherein A" represents a cyclohexyl group or a group -CR'R ", wherein R 'represents a linear alkyl group having from 1 to 10 carbon atoms and R "represents a hydrogen atom or a linear alkyl group having from 1 to 10 carbon atoms.
4. A radial polymer according to claim 3, characterized in that A "in the initiator is -CR'R" - and R "is methyl.
5. A radial polymer according to claim 4, characterized in that R 'is methyl.
6. A radial polymer according to any of claims 1 to 5, characterized in that the radial polymer comprises or contains polymerized conjugated dienes, and, following bonding, the following additional steps are carried out: hydrogenating the polymerized conjugated diene; and reacting the hydrogenated radial polymer with a compound that replaces the trimethylsilyl groups of the lithium initiator with hydrogen, to give the terminal hydroxyl groups.
7. A radial polymer according to claim 6, characterized in that the linear anionic polymer comprises the homopolyisoprene or the homopolybutadiene having an average molecular weight in the range of 500 to 200,000, more preferably from 500 to 20,000, when measured with the chromatography of gel permeation calibrated with polybutadiene standards.
8. A process for the preparation of a radial anionic polymer according to claim 1, characterized in that it comprises the process steps that were described in any of claims 1 to 7.
9. A composition for use in adhesives, sealants and coatings, films and thermosetting and thermoplastic molded and extruded parts, characterized in that it comprises a polymer according to any of claims 1 to 7.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US42483695A | 1995-04-19 | 1995-04-19 | |
US424836 | 1995-04-19 | ||
PCT/EP1996/001637 WO1996033223A1 (en) | 1995-04-19 | 1996-04-17 | Coupling of anionic polymers with trialkoxysilanes having silicon-hydrogen bonds |
Publications (2)
Publication Number | Publication Date |
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MX9708019A MX9708019A (en) | 1997-11-29 |
MXPA97008019A true MXPA97008019A (en) | 1998-07-03 |
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