MXPA97005334A - Hidrosilacion in esteres without hidrox portions - Google Patents
Hidrosilacion in esteres without hidrox portionsInfo
- Publication number
- MXPA97005334A MXPA97005334A MXPA/A/1997/005334A MX9705334A MXPA97005334A MX PA97005334 A MXPA97005334 A MX PA97005334A MX 9705334 A MX9705334 A MX 9705334A MX PA97005334 A MXPA97005334 A MX PA97005334A
- Authority
- MX
- Mexico
- Prior art keywords
- carbon atoms
- group
- further characterized
- monovalent hydrocarbon
- formula
- Prior art date
Links
- 125000004185 ester group Chemical group 0.000 title 1
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- -1 polysiloxane copolymer Polymers 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 150000002148 esters Chemical class 0.000 claims description 25
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 3
- 230000000996 additive Effects 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 59
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- 239000006260 foam Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 18
- 102100000129 CHURC1 Human genes 0.000 description 18
- 101710014631 CHURC1 Proteins 0.000 description 18
- 229910052697 platinum Inorganic materials 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012258 stirred mixture Substances 0.000 description 12
- AXISYYRBXTVTFY-UHFFFAOYSA-N Isopropyl myristate Chemical compound CCCCCCCCCCCCCC(=O)OC(C)C AXISYYRBXTVTFY-UHFFFAOYSA-N 0.000 description 10
- 229940074928 isopropyl myristate Drugs 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- XUGNVMKQXJXZCD-UHFFFAOYSA-N Isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229940075495 isopropyl palmitate Drugs 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- LPIIHZYLVPPMLX-UHFFFAOYSA-N molecular hydrogen;silicon Chemical compound [Si].[H][H] LPIIHZYLVPPMLX-UHFFFAOYSA-N 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 230000001809 detectable Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920005830 Polyurethane Foam Polymers 0.000 description 7
- 210000004027 cells Anatomy 0.000 description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 239000011496 polyurethane foam Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229920000582 Polyisocyanurate Polymers 0.000 description 3
- 229920001451 Polypropylene glycol Polymers 0.000 description 3
- IGWHDMPTQKSDTL-JXOAFFINSA-N [(2R,3S,4R,5R)-3,4-dihydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl dihydrogen phosphate Chemical compound O=C1NC(=O)C(C)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(O)=O)O1 IGWHDMPTQKSDTL-JXOAFFINSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011495 polyisocyanurate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XFDQLDNQZFOAFK-UHFFFAOYSA-N 2-benzoyloxyethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOC(=O)C1=CC=CC=C1 XFDQLDNQZFOAFK-UHFFFAOYSA-N 0.000 description 2
- 210000000497 Foam Cells Anatomy 0.000 description 2
- 229920001821 Foam rubber Polymers 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 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 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-Dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 1
- LXODQLXKQIJVNK-UHFFFAOYSA-N 2-(2-benzoyloxypropoxy)propyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)COC(C)COC(=O)C1=CC=CC=C1 LXODQLXKQIJVNK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-Butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 206010073316 Accidental exposures to product Diseases 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N Dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M Sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 229960003212 Sodium propionate Drugs 0.000 description 1
- WCLDITPGPXSPGV-UHFFFAOYSA-N Tricamba Chemical compound COC1=C(Cl)C=C(Cl)C(Cl)=C1C(O)=O WCLDITPGPXSPGV-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 231100000818 accidental exposure Toxicity 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DHAZIUXMHRHVMP-UHFFFAOYSA-N butyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCCCC DHAZIUXMHRHVMP-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002939 deleterious Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl 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])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 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 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- GBFHNZZOZWQQPA-UHFFFAOYSA-J platinum(4+);tetrachloride;dihydrochloride Chemical compound [H+].[H+].Cl[Pt-2](Cl)(Cl)(Cl)(Cl)Cl GBFHNZZOZWQQPA-UHFFFAOYSA-J 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004808 supercritical fluid chromatography Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Abstract
The present invention relates to a process for preparing a polyether polysiloxane copolymer characterized in that it comprises reacting: a) organohydrogensiloxane, b) unsaturated polyoxyalkylene polyesters, and c) a solvent without hydroxyl portions, in the presence of a noble metal hydrosilation catalyst. in an inert atmosphere and at a temperature not exceeding the temperature at which the organohydrogenosiloxane reacts with the solven
Description
HYDROSILATION IN STERES WITHOUT HYDROXILIUM PORTIONS
DESCRIPTION
Background and field of the invention.
The preparation of siloxane-oxyalkylene copolymers ("Copolymers") is well known by means of the hydrosilation reaction of an organohydrogensiloxane and an unsaturated polyoxyalkylene. Generally, the hydrosilation reaction is carried out in a hydrocarbon, highly volatile, low molecular weight, such as benzene, toluene or xylene to make the reactants compatible and to aid in the transfer and filtration of the copolymer, or to moderate the exothermicity of the hydrosilation . Less typically, the hydrosilation reaction can be carried out without a solvent or in an oxygen-containing solvent such as an ether, a polyether or a low or high molecular weight alcohol. In most of the aforementioned processes, the hydrocarbon solvent is removed after the hydrosilation reaction has been completed, since in most cases the solvent is very flammable, toxic, or in some way harmful to the final product or the later stages of the process in which the copolymer is used. For example, with mono-alcohols in polyurethane foam applications, the hydroxyl functionalities will enter the urethane reaction and act as chain terminators of reaction in a deleterious manner. The removal of such solvents increases the intermittent cycle times and requires the removal of the solvent in an environmentally safe manner such as incineration. Moreover, there are foaming problems when removing many of the solvents and one can rarely extract all the solvent from the solution. Few examples have been reported in the literature where for some reason or other it has not been necessary or desirable to separate the copolymer from the reaction solvent. For example, U.S. Patent No. 4,520,160 discloses the use of saturated higher alcohols, such as isostearyl alcohol, as a reaction solvent which does not intentionally require removal from the resulting copolymer when it is subsequently used in compositions of personal care as emulsifiers. US Patents Nos. 4,857,583 and 5,153,293 also disclose that high boiling point polyols or monocarboxylate esters of an alkanediol do not intentionally need to be removed from the resulting copolymer when it is subsequently used in polyurethane foam formulations. However, the hydroxyl functionality of the solvents can compete with the unsaturated polyoxyalkylene for the SiH sites in the main structure of the siloxane, as well as the above-mentioned reaction with the isocyanate in the polyurethane foam. It is therefore an object of the present invention to provide an improved process for the preparation of copolymers using superior solvents. The present invention focuses on an improved process for the preparation of copolymers and the copolymer compositions obtained therefrom. These copolymers are prepared by means of a hydrosilation reaction between an organohydrogenpolysiloxane and unsaturated polyoxyalkylene polyethers, in the presence of an ester containing no hydroxyl groups and, optionally, in the presence of specific additives. The esters not only help in the preparation of the copolymer, but if it is left in the copolymer, it also helps in its later handling and serves as a beneficial component of the composition that contains a copolymer. Benefits include reduction in viscosity and pour point for easy transfer of copolymer, improved polyol solubility and foam fluidity when the copolymer is used to stabilize polyurethane and polyisocyanurate foams, the production of clear compositions and the reduction of window fogging when the copolymer is used to make automotive interior foams.
The process for making a modified polyether polysiloxane polysiloxane of the present invention includes reacting (a) organohydrogensiloxanes; (b) unsaturated polyoxyalkylene polyethers; and (c) an ester solvent without hydroxyl portions, in the presence of a noble metal hydrosilation catalyst in an inert atmosphere and at a temperature which does not exceed the temperature at which the organohydrogenosiloxane reacts with the solvent. The present invention also includes the intermediate product of components (a) - (c) and the resulting copolymeric composition in the solvent.
Organohydrosiloxanes
The organohydrogensiloxanes used in the present invention are those represented by the general chemical formula R ^ SiO ^. ^ Wherein R denotes a free monovalent hydrocarbon radical of non-saturation aliphatic, a has a value of from 1 to 3.0, b has a value of from 0 to 1 and the sum of a + b has a value from 1.0 to 3.0. The organohydrogensiloxane can have any combination of siloxane units selected from the group consisting of R3Si01 / 2, RjHSiO ^, R2Si02 / 2, RHSiO2 / 2, RH2Si01 / 2, RSi03 / 2, HSi03 / 2 and Si04 / 2 guaranteeing, of course , that the organohydrogenpolysiloxane contain sufficient siloxane units containing R to ensure from about 1 to about 3 R radicals per silicon atom and sufficient siloxane units containing H to ensure from 0.01 to 1 hydrogen atoms bound by silicon, for each silicon and a total of R radicals and hydrogen atoms bonded by silicon from 1.5 to 3, for each silicon. The selection of the siloxane groups will determine, as is clear to those with average skill in the art, the structure of the resulting copolymer, so that one can have linear siloxane, Q (ie, crossed) and T structures. R represent substituted or unsubstituted monovalent hydrocarbon radicals of from 1 to 12 carbon atoms. Examples of suitable radicals R are alkyl radicals (such as methyl, ethyl, propyl, butyl, decyl), cycloaliphatic radicals (such as (cyclohexyl and cyclooctyl), aryl radicals (such as phenyl, tolyl and xylyl) and the groups substituted hydrocarbons (such as heptafluoropropyl) R is preferably methyl Siloxane fluids are commonly prepared as is well known in the field or can be obtained commercially.
Polyethers
The polyoxyalkylene polyethers are of the formula: Ri (OCH2CH2) z (OCH2CHR) w-OR2, or R2O (CH [R3] CH2O) w (CH2CH2O) z-CR42-C = C-CR42- (OCH2CH2) z (OCH2 [R3] CH) wR2
wherein R1 denotes an unsaturated organic group containing from 3 to 10 carbon atoms such as allyl, methallyl, propargyl or 3-pentynyl. When the unsaturation is olefinic, it is desirably terminal to facilitate the termination of hydrosilation. R2 is selected from the group consisting of hydrogen, alkyl groups containing from one to eight carbon atoms, alkylene groups containing from 3 to 10 carbon atoms, acyl groups containing from 2 to 8 carbon atoms or a trialkylsilyl group. Preferably R2 is hydrogen, methyl, n-butyl or the t-butyl, allyl, methallyl or acetyl group. R3 and R4 are monovalent hydrocarbon groups such as C, -C20 alkyl groups (e.g., methyl, ethyl, isopropyl, 2-ethylhexyl, cyclohexyl and stearyl), or aryl groups (e.g., phenyl and naphthyl), or alkaryl groups (for example, benzyl, phenethyl and nonylphenyl). R4 can also be hydrogen. Methyl is the most preferred group R3 and R4. Z has a value from 0 to 100 and w has a value from 0 to 120. Preferred values of z and w are 1 to 50 inclusive. The unsaturated polyether, whether comprising alkyne groups or olefinic end groups, can be a randomly distributed or clogged oxyalkylene copolymer.
The amount of polyether used in the hydrosilation depends on the amount of active hydrogen in the siloxane (i.e., SiH groups). The stoichiometric ratio of the unsaturated groups in the polyether to the SiH groups should be from 1: 1 to 1.5: 1. If a structure copolymer [AB] n (ie, alternating polyether, A, / siloxane, B, hindered) is desired, then the maximum ratio should be approximately 1.2: 1.
Sodium solvents
The present invention utilizes liquid carboxylate esters with high boiling point as the hydrosilation reaction solvents. The esters have no hydroxyl group that can interfere with the hydrosilation reaction. The esters of this invention have the general formula R5 (COOR6) n or R5COO (CH2CH20) a (CH [R3] CH20) bOCR5 in which R3 is as defined for the polyethers, and a and b are from 0 to 120, preferably 0 to 50. R5 is a linear or branched alkyl, aryl, alkaryl or cycloaliphatic group of valence equal to the number, n, of ester functional groups. R6 is a monovalent hydrocarbon radical derived from an alcohol. The total number of carbon atoms in R5 and R4 should be at least eight and preferably at least 10. R5 and R6 may also include ether bonds, sulfur bonds and amino groups, as long as these functionalities do not impede the hydrosilation reaction. R5 and R6 may also include internally or stearically hindered unsaturated hydrocarbon groups that do not interfere with the hydrosilation reaction. Examples of R5 include C8H17, CI4H29, C16H33, cyclohexanediyl, butoxyethyl, adipyl, azelayl, sebacyl, oleyl, phenyl, phthalyl, and cinnamyl. Examples of R6 are methyl, isopropyl, neopentyl, octyl, dodecyl, cyclohexyl, benzyl, and stearyl. The esters must have boiling points greater than 170 ° C at atmospheric pressure, and preferably higher than 200 ° C. The ester solvent (s) are inert under the conditions of the hydrosilation reaction and are essentially non-toxic (non-hazardous). Examples of the preferred esters are isopropyl palmitate (IPP), butyl myristate (BYM) or isopropyl myristate (IPM), diethylene glycol dibenzoate, dipropylene glycol dibenzoate, polypropylene glycol dibenzoate. Natural esters that do not contain hydroxyl groups are also preferred. Still further, esters derived from natural fatty acids or alcohols, or a mixture thereof, are also contemplated herein as useful. The ester must also be free of impurities which may poison the hydrosilation catalyst, or impair the performance of the copolymer in its applications. The ester not only aids in the preparation of the copolymer, but when it remains in the copolymer, it also aids in its subsequent handling and serves as a beneficial and necessary component of the compositions containing the copolymer. In general, it has been found that from 5 to about 60 weight percent, and more preferably from about 20 to about 50 weight percent, of the carboxylate ester gives good results.
Optional additives
The hydrosilation reaction may be carried out in the presence of optional additives such as the salts of carboxylic acids described in U.S. Patent No. 4,847,398, or the stearically hindered nitrogen compounds of the U.S. Patent No. No. 5,193,103 or the phosphate salts of U.S. Patent No. 5,159,096, such patents are incorporated herein by reference. Depending on the method of making the reagents and the solvents, one or more of these additives may be present when polar solvents are used for the hydrosilation of unsaturated polyethers with organohydrogensiloxanes. For example, a low, but sometimes adequate level of carboxylic acid salts or salts of phosphates may already be present in the olefinically substituted polyoxyalkylene due to accidental exposure to traces of oxygen during the subsequent protection of the hydroxyl groups with aliphatic groups, metal, methyls or acylos. In such an example, the intentional use of salt or other additives may not be necessary. Other common additives are well known and can also be used.
Hydrosilation catalysts
The hydrosilation reaction is facilitated using catalytic amounts of a catalyst containing noble metal. Such catalysts are well known and include rhodium-containing catalysts, palladium and platinum. They are reviewed in the compendium, "Comprehensive Handbook on Hydrosilation," edited by B. Marciniec, relevant parts of which are incorporated herein by reference. Chloroplatinic acid and the platinum complexes of 1,3-divinyltetramethyldisiloxane are particularly preferred. The catalyst is used in a sufficiently effective amount to initiate, maintain and complete the hydrosilation reaction. The amount of catalyst is generally in the range of from about 1 to about 100 parts per million (ppm) of noble metal, based on the total parts of the mixture of reactants and solvents. The catalyst concentrations of 5 to 50 ppm are preferred.
Copolymers
The resulting copolymers can be linear siloxanes with pendent structure of polyethers (ridge), structure T, structure Q or Copolymers [AB] n. The resulting structure depends on the selection of the starting siloxanes and polyethers and it is clear for that of average skill in the art how to choose the starting materials to achieve specific structures.
Hydrosilation reaction
Hydrosilation reactions are well known in the field, see for example Marciniec, loc.cit. The process of the present invention includes (1) forming a mixture of: (a) organohydrogensiloxanes; (b) unsaturated polyoxyalkylene polyethers; (c) an ester solvent and (d) optionally, an additive, (2) maintaining the mixture in an inert atmosphere at a temperature which does not exceed the temperature at which the organohydrogenosiloxane reacts with the solvent, (3) adding to the mixing, a catalytic amount of a noble metal hydrosilation catalyst, before or after heating; (4) maintain the temperature of the mixture below about 125 ° C, to control the isomerization of allyl to propenyl and allow the reaction to be conducted so that less than 0.1 ce of SiH free of H2 per gram of reaction mixture remain in the composition. Optionally, one can also recover the copolymer in the mixture with residual solvent of high boiling point. Recovery can be effected by a variety of methods, including distillation, solvent extraction, supercritical chromatography, column chromatography, although it is not necessary. The reaction temperatures vary from 70 to 120 ° C. The reaction pressure is usually atmospheric pressure, but can be varied as required.
Applications
The Copolymers and the Copolymer / solvent compositions prepared by the process of the present invention are particularly useful as, and have been found to be excellent and efficient surfactants for, the preparation of rigid closed and open cell foams, foam rubber, foam for automotive interiors and flexible polyurethane polyurethane foams. Copolymers can provide rigid polyurethane foams and automotive interiors with more than 90% open cells. It has been found that the copolymers of this invention provide superior performance levels to the polyurethane and polyisocyanurate foams with the solvent in situ and obviate the need to remove the solvent from the reaction mixture in which the copolymer was prepared. Copolymers prepared with 30 weight percent isopropyl myristate (IPM) have improved the fluidity in the polyurethane foam commonly used in electrical appliances by up to 20%. In addition, the surfactants prepared in IPM show a higher solubility in some polyols and impart an improvement in storage stability to the formulations containing these polyols and surfactants. Other surfactants prepared with IPM or IPP provide rigid open-cell hydrosholed foams, the desired energy absorption capacity and impact resistance. Furthermore, these surfactants do not contribute substantially or excessively to fogging windows when the foams are used in automotive interior frames. The polyurethanes produced in accordance with the present invention can be employed in the same areas as conventional flexible, rigid polyurethanes, foam rubber and automotive interior foams. For example, the foams of the present invention can be used with advantage in the manufacture of cushions, mattresses, cushions, under carpets, packaging material, thermal insulators, automotive interior foam and the like. Copolymers and Copolymer / solvent compositions can also be used in personal care applications, shampoo formulations, hand creams, body lotions and hair sprays. The compositions are especially advantageous because they are clear and odorless. Personal care formulations, such as those described in U.S. Patent No. 4,782,095, are advantageously prepared without further addition of emollients and emulsifiers. Copolymers can also be used in radiation-curable coatings applications such as overprint varnishes.
Examples
The following examples illustrate the embodiments of the present invention, but are not intended to limit the scope thereof. Examples 1-8 are comparative examples in which commonly known hydrosilation reaction solvents are employed. Examples 9-22 demonstrate the production of copolymers in high boiling ester solvents free of hydroxyl functionalities with improved hydrosilation reaction characteristics and reduced product volatility without removal of the reaction solvent of the resulting surfactant product. While examples 9-12 illustrate hydrosilations with ester solvent contents of 40-50% by weight, examples 13-22 employ minor amounts (approximately 20% by weight).
List of materials and abbreviations
M = (CH3) 3SiOH, D = (CH3) 2SiOH, D '= CH3SiHO, M' = (CH3) 2SiHOií 100HA550-OAc = allyl polyether protected with acetoxy with 100% by weight of ethylene oxide (EO) -608 molecular weight daltons (mp) 75HA750-OH = non-protected allyl polyether with 75 weight percent EO / 25 weight percent propylene oxide (PO) - molecular weight 750 daltons. 100HA750-OMe = methyl protected polyether with 100 percent by weight of EO - molecular weight of 780 daltons. 75HA750-OMe = methyl protected polyether with 75 weight percent EO / 25 weight percent PO - molecular weight 780 daltons.
75HA1500-OMe = methyl protected polyether with 75 weight percent EO / 25 weight percent PO - molecular weight 1530 daltons. UA-11 is the alkylated benzene UCANE Alkylate-11 from Union Carbide Corporation, SC-100 is the long-chain aliphatic solvent Exxon Solvent SC-11, LB-165 is polypropylene glycol monobutyl ether, DPG is dipropylene glycol, IPA is isopropyl alcohol, CPA it is a catalyst solution of hexachloroplatinic acid in ethanol and TMP is 2,2,6,6-tetramethyl-4-piperidinol. In addition to the SiH full-reaction tests, the Copolymer products of Examples 1-22 were evaluated for product clarity, viscosity at 25 ° C, volatility and performance as surfactants in polyurethane foam formulations.
Example 1 (comparative)
To a well-stirred mixture of 180 grams of
CH2 = CHCH (CH3) 0 (CH2CH20) 34 (CH2CHCH30) 26 (CH3) CHCH = CH2, 67.0 grams of HMe2SiO (Me2SiO) 24SiMe2H and 175 grams (50 weight percent) of solvent UA-11 the air was extracted by means of a nitrogen jet and heated to 85 ° C. HE
added a solution of H2PtCl6-6H20 in ethanol to the mixture in sufficient quantity to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 4 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous and clear solution of a copolymer was obtained which did not contain gel particles and detectable levels of residual silane hydrogen. Its viscosity at 25 ° C was 4292 cSt.
Example 2 (comparative example)
To a well stirred mixture of 155.7 grams of CH2 = CHCH (CH3) O (CH2CH2O) 41 (CH2CHCH3O) 20 (CH3) CHCH = CH2, 19.3 grams of HMe2SiO (Me2SiO) 3SiMe2H and 175 grams (50 weight percent) of solvent UA-11 the air was extracted by means of a stream of nitrogen and heated to 85 ° C. A solution of H2PtCl6-6H20 in ethanol was added to the mixture in sufficient quantity to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 3.5 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous, clear solution of a copolymer was obtained which did not contain gel particles and detectable levels of residual silane hydrogen. Its viscosity at 25 ° C was 1062 cSt.
Example 3 (comparative example)
To a well-stirred mixture of 116.2 grams of
CH2 = CHCH (CH3) O (CH2CH2O) 41 (CH2CHCH3O) 20 (CH3) CHCH = CH2, 58.8 grams of HMe2SiO (Me2SiO)? 9SiMe2H and 175 grams (50 weight percent) of Exxon solvent
SC-100 the air was extracted by means of a stream of nitrogen and heated to 85 ° C.
A solution of H2PtCl6-6H2O in ethanol was added to the mixture in sufficient amount to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 2.5 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A clear solution of a copolymer was obtained that did not contain gel particles and detectable levels of residual silane hydrogen. Its viscosity at 25 ° C was 512 cSt.
Example 4 (comparative example)
To a well stirred mixture of 123 grams of CH2 = CHCH (CH3) 0 (CH2CH20) 34 (CH2CHCH30) 26 (CH3) CHCH = CH2, 77.0 grams of HMe2SiO (Me2SiO) 24SiMe2H and 200 grams (50 weight percent) of CH3CH2CH2CH20 (CH2CHCH3) 13OH was extracted from the air by means of a jet of
nitrogen and heated to 85 ° C. A solution of H2PtCl6-6H20 in ethanol was added to the mixture in sufficient quantity to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 21 hours. The content of silane hydrogen was analyzed, being 2.0 g H2 / gram. The reaction mixture was rectalized with 20 ppm platinum to allow it to react for a further 9 hours at 85 ° C. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. An extremely hazy viscous solution of a copolymer with a residual silanic hydrogen content of 2.0 ce H2 / gram and a viscosity at 25 ° C of 1689 cSt was obtained.
Example 5 (comparative example)
To a well stirred mixture of 108 grams of CH2 = CHCH (CH3) O (CH2CH2O) 41 (CH2CHCH3O) 20 (CH3) CHCH = CH2, 67.0 grams of
HMe2SiO (Me2SiO) 24SiMe2H and 175 grams (50 weight percent) of DPG were extracted by means of a nitrogen jet and heated to 85 ° C. A solution of H2PtCl6-6H2O in ethanol was added to the mixture in sufficient amount to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 26 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. An extremely hazy viscous solution of a copolymer with a residual silanic hydrogen content of 2.0 ce H2 / gram and a viscosity at 25 ° C of 1741 cSt was obtained.
Example 6 (comparative example)
To a well-stirred mixture of 120 grams of
CH2-CHCH (CH3) 0 (CH2CH20) 34 (CH2CHCH30) 36 (CH3) CHCH = CH2, 54.8 grams of
HMe2SiO (Me2SiO) 17SiMe2H, 0.175 grams of sodium propionate and 175 grams (50 weight percent) of IPA were extracted from the air by means of a jet of nitrogen and
it was heated to 80 ° C. A solution of H2PtCl6-6H2O in ethanol was added to the mixture in sufficient amount to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 3 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous and clear solution of a copolymer without residual silane hydrogen and a viscosity at 25 ° C of 2051 cSt was obtained.
Example 7 (comparative example) To a well stirred mixture of 108 grams of CH2 = CHCH (CH3) O (CH2CH2O) 41 (CH2CHCH3O) 20 (CH3) CHCH = CH2, 67.0 grams of HMe2SiO (Me2SiO) 24SiMe2H, and 175 grams ( 50 percent by weight) of toluene, the air was extracted by means of a nitrogen stream and heated to 85 ° C. Added one
Solution of H2PtCl6-6H2O in ethanol to the mixture in sufficient quantity to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 6 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous and clear solution of a copolymer with a residual srnanic hydrogen content of less than 0.1 ce H2 / gram and a viscosity at 25 ° C of 2585 cSt was obtained.
Example 8 (comparative example)
To a well-stirred mixture of 155.8 grams of CH2 = CHCH20 (CH2CH20) 173 (CH2CHCH30) 197CH3, 54.1 grams of Me3SiO
(Me2SiO) 60 (MeHSiO) 7SiMe3, and 140 grams (50 weight percent) of toluene was extracted from the air by means of a stream of nitrogen and heated to 85 ° C. Added one
Solution of H2PtCl6-6H20 in ethanol to the mixture in sufficient quantity to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 1.5 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A clear solution of a copolymer was obtained which did not contain detectable levels of residual silane hydrogen and which showed a viscosity at 25 ° C of 97 cSt.
Example 9
To a well-stirred mixture of 108 grams of
CH2 = CHCH (CH3) 0 (CH2CH2O) 34 (CH2CHCH3O) 26 (CH3) CHCH = CH2, 67 grams of HMe2SiO (Me2SiO) 24SiMe2H, and 175 grams (50 weight percent) of IPP was extracted from the air by means of a stream of nitrogen and heated to 85 ° C. A solution of H2PtCl6-6H20 in ethanol was added to the mixture in sufficient quantity to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 1.5 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous and clear solution of a copolymer was obtained which did not contain detectable levels of residual silane hydrogen and which had a viscosity at 25 ° C of 6366 cSt.
Example 10
To a well-stirred mixture of 108 grams of
CH2 = CHCH (CH3) O (CH2CH2O) 41 (CH2CHCH3O) 20 (CH3) CHCH = CH2, 67.0 grams of HMe2SiO (Me2SiO) 19SiMe2H, and 175 grams (50 weight percent) of IPM was extracted by air from a nitrogen jet and heated to 85 ° C. A solution of H2PtCl6-6H2O in ethanol was added to the mixture in sufficient amount to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 1.25 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous and clear solution of a copolymer was obtained which did not contain detectable levels of residual silanic hydrogen and which had a viscosity at 25 ° C of 3943 cSt. Example 11
To a well-stirred mixture of 108 grams of
CH2-CHCH (CH3) O (CH2CH2O) 41 (CH2CHCH3O) 20 (CH3) CHCH = CH2, 67.0 grams of HMe2SiO (Me2SiO) 24SiMe2H, and 175 grams (50 weight percent) of BYM were air extracted through from a jet of nitrogen and heated to 85 ° C. A solution of H2PtCl6-6H2O in ethanol was added to the mixture in sufficient amount to provide 20 ppm of platinum. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 3 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous and clear solution of a copolymer was obtained which did not contain detectable levels of residual silane hydrogen and which had a viscosity at 25 ° C of 1646 cSt.
Example 12
To a well-stirred mixture of 103.9 grams of
CH2 = CHCH20 (CH2CH20) 173 (CH2CHCH30) 197 (CH3), 36.1 grams of
Me3SiO (Me2SiO) 60 (MeHSiO) 7SiMe3, and 93.3 grams (40 weight percent) of IPP were extracted from the air by means of a stream of nitrogen and heated to 85 ° C. A solution of H2PtCl6-6H2O in ethanol, in sufficient amount to provide 20 ppm of platinum, was added to the mixture. The source of heat was removed and the exothermic hydrosilation reaction was allowed to take place until no further increase in temperature was noted. The necessary heat was added to the mixture to maintain its temperature at 85 ° C for 2 hours. Care was taken not to allow the reaction vessel to exceed 100 ° C at any time. A viscous and clear solution of a copolymer was obtained which did not contain detectable levels of residual silane hydrogen and which had a viscosity at 25 ° C of 199 cSt.
Example 13-22
Examples 13-22 illustrate the synthesis of copolymers in about 20 weight percent of IPM, IPP or polypropylene glycol dibenzoate (BENZOFLEX® 400, sold commercially by Velsicol Chemical Corporation) in accordance with the hydrosilation procedures described above. The quantities of raw material used are indicated in the following tables. All hydrosilations were completed with a single catalyst addition.
RAW MATERIAL EJ. 13 EJ. 14 EJ. 15 EJ. 16 EJ. 17
MD32D'96M, gm 35.7 MD43 2D'6 gM, gm 51.1 32.2 MD4? D'9M, gm 50.0 M'D60D'10M \ gm 50.0
75HA750-OMe, gm 143.9 75HA750-OH, gm 110.9 121.2
75HA1500-OMe, gm 121.0 100HA550-OAc, gm 92.6 IPM, g 43.0 43.0 43.0 43.0 43.0
TMP, gm 0.11 0.11
CPA, ml 0.5 0.5 0.5 0.5 0.5
EXOTHERMICITY, ° C 23 21 5 6 13.5 min 2.7 1.5 2.0 1.5 2.0
VISCOSITY, cSt at 25 ° c 164 260 337 212.5 273.8 RAW MATERIAL EJ. 18 EJ. 19 EJ. 20 EJ. 21 EJ. 22
MD32D'96M, gm 35.8 MD43 2D'68M, gm 51.0 32.2 MD41D'9M, gm 50.0 M'D60D'10M \ gm 50.0
75HA750-OMe, gm 137.5 75HA750-OH, gm 114.8 111.2
75HA1500-OMe, gm 140.0 100HA550-OAc, gm 92.6 IPP, gm 43.0 43.0 43.0 BenzoflexR 400, gm 43.0 48.0
TMP, gm 0.11 0.12
CPA, ml 0.5 0.5 0.5 0.5 0.5
EXOTHERMICITY, ° C 22 10 6 4 12 min 2.7 2.0 1.6 2.5 1.5
VISCOSITY, cSt at 25 ° c 175.5 293 387.5 512.5 940
The data shows that all the hydrosilations proceed until they are completed with observable exothermicities. Copolymers have viscosities, pour points and surface activities which make them suitable as surfactants for rigid polyurethane and polyisocyanurate foams. In particular, the copolymer of example 14 showed 20% improved fuid on the product without solvent in a rigid, hydrosprayed foam formulation. The copolymer of example 15 was soluble in polyols used for electric appliance foams HCFC-141b, while the product without solvents was not. Thus, it provides premixes of storage stable polyols which produce foams with processing and acceptable properties.
Volatility tests
The volatility of the reaction product was determined by the following method (ASTM D 4559-92): (A) Pre-weigh a 2-inch alumina container up to 0.1 mg. (B) Add approximately 1 gram of heavy sample to 0.1 mg. (C) Repeat steps A and B for duplication of the determination. (D) Heat for 1 hour at 110 ° C at atmospheric pressure in a forced draft low temperature furnace at a temperature of 110 ° C. (E) Cool the sample in air for 10 minutes and weigh again. Volatility was calculated using the following equation: Solids weight percent = 100 - [(B-A) * 100 / B] where A = weight of the sample after heating and B = weight of the sample before heating. Volatility is reported as the average of the two results up to 0.1%.
The data indicate that ethers solvents with higher boiling points (examples 9-12) provide an easy hydrosilation reaction while providing homogeneous and clear copolymers with minimal volatility.
Foam test
The copolymer products of examples 1-12 were evaluated in the following open cell and hydrosop lated foam formulation. A mixture of 100 parts of a polyol base, 1.00 parts of the previous surfactant (not counting the solvent) and 0.2 parts of NIAX A-400 catalyst, 0.9 parts of NIAX A-305 catalyst, and 1 part of water, were shaken in a abundant. To the above mixture was added 264 parts of polymeric MDI (methylene diphenylene diisocyanate) and the resulting mixture was mixed in a high speed mixer for 5 seconds and emptied into a one gallon paper cup. The mixture was allowed to foam and rise to maximum height and was cured at room temperature for 3 minutes. The cured foam was evaluated by measuring the structure and uniformity of the foam cell.
Foam Quantity Type of Clarity Time Uniformed Weight Viscosity example of solvent reaction HACH grade of molecular2 cSt.3 solvent Hr. foam cell1 1 50% UA-11 3.5 1.28 2.8 39100 4292
2 50% UA-11 3.5 .56 2.2 22500 1062
3 50% SC-100 2.5 5.0 1.8 27200 512
4 50% LB-165 30.0 > 200 10 ND 1689
50% DPG 26.0 > 200 9.8 ND 1741
6 50% IPA 3.0 .43 1.7 36000 2051
7 50% Toluene 6.0 2.6 6.1 45000 2585
8 40% Toluene 1.5 3.6 2.0 21000 97 9 50% IPP 1.5 .38 1.3 37000 6366
50% IPM 1.25 1.17 1.2 36000 3943
11 50% BYM 3.0 4.9 4.3 29000 1646
12 40% IPP 2.0 4.0 2.0 20000 199
1. The uniformity of the foam cell is judged by the structure of the foam where a 1 has a small uniform cell structure and a 10 has a coarse, non-uniform and large cell structure. The foams were evaluated in triplicate and the values were averaged.
2. The peak average molecular weight as measured in a "Waters GPC", flow rate 1 mL / min, tetrahydrofuran solvent in Styragel columns. 3. Cannon-Fenske at 25 ° C. The data indicates that high-boiling ester solvents (examples 9-12) provide an easy hydrosilation reaction while providing clear homogeneous copolymers which impart excellent cell structure uniformity and high foam open cell content rigid.
Claims (15)
1. A process for making a polyether polysiloxane copolymer characterized in that it comprises reacting: (a) organohydrogensiloxane; (b) unsaturated polyoxyalkylene polyethers; and (c) an ester solvent without hydroxyl portions; in the presence of a noble metal hydrosilation catalyst in an inert atmosphere and at a temperature not exceeding the temperature at which the organohydrogenosiloxane reacts with the solvent.
2. A process according to claim 1, further characterized in that the esters have a boiling point greater than 170 ° C.
3. A process according to claim 1, further characterized in that the silane is of the formula R ^ SiO ^. ^.
4. A process according to claim 1, further characterized in that the polyethers are of the formula R1 (OCH2CH2) z (OCH2CHR3) w-OR2, or R0 (CH [R3] CH20) w (CH2CH20) 2-CR 2 -C = C-CR42- (OCH2CH2) z (OCH2 [R3] CH) wR2 wherein R1 denotes an unsaturated organic group containing from 3 to 10 carbon atoms, R2 is selected from the group consisting of hydrogen, alkyl groups which contain from one to eight carbon atoms, alkylene groups containing from 3 to 10 carbon atoms, acyl groups containing from 2 to 8 carbon atoms or a trialkylsilyl group, R3 and R4 are monovalent hydrocarbon groups, R4 can also be hydrogen , Z has a value of 0 to 100 and w has a value of 0 to 120.
5. A process according to claim 1, further characterized in that the esters are of the formula R * (COOR6) not R5COO (CH2CH20) a ( CH [R] CH20) bOCR5 in which R3 is a monovalent hydrocarbon group, a and b are 0 to 120, R5 is a straight or branched alkyl, aryl, a Laryl or cycloaliphatic of valence equal to the number, n, R6 is a monovalent hydrocarbon radical derived from an alcohol and the total number of carbon atoms in R5 and R6 must be at least eight.
6. A process according to claim 1, further characterized in that the reaction is carried out in the presence of an additive selected from the group consisting of carboxylic acid salts, stearically hindered nitrogen compounds or phosphate salts.
7. A composition for making a polyether polysiloxane copolymer characterized in that it comprises: (a) organohydrogensiloxane; (b) polyoxyalkylene polyethers; and (c) an ester solvent without hydroxyl portions.
8. The composition according to claim 7, further characterized in that the siloxane is of the formula R ^ SiO ^ ..,., ^.
9. The composition according to claim 7, further characterized in that the polyethers are of the formula Ri (OCH2CH2) z (OCH2CHR3) w-OR2, or R2O (CH [R] CH2O) w (CH2CH2O) z-CR 2- C = C-CR 2- (OCH 2 CH 2) 2 (OCH 2 [R] CH) wR 2 wherein R 1 denotes an unsaturated organic group containing from 3 to 10 carbon atoms, R 2 is selected from the group consisting of hydrogen, alkyl groups which contain from one to eight carbon atoms, alkylene groups containing from 3 to 10 carbon atoms, acyl groups containing from 2 to 8 carbon atoms or a trialkylsilyl group, R3 and R4 are monovalent hydrocarbon groups, R4 can also be hydrogen , Z has the value from 0 to 100 and w has a value from 0 to 120.
10. The composition according to claim 7, further characterized in that the esters are of the formula R5 (COOR < R5COO (CH2CH20) a ( CH [R3] CH20) bOCR5 in which R3 is a monovalent hydrocarbon group, a and b are 0 to 120, R5 is a straight or branched group alkyl, aryl, alkaryl or cycloaliphatic of valence equal to the number, n, R6 is a monovalent hydrocarbon radical derived from an alcohol and the total number of carbon atoms in R5 and R6 must be at least eight.
11. A polyether polysiloxane copolymer composition characterized in that it comprises (a) a polyoxyalkylene polysiloxane copolymer, and (b) an ester solvent without hydroxyl portions.
12. A composition according to claim 11, further characterized in that the polyether polysiloxane copolymer has a structure selected from the group consisting of: linear, T, Q and [AB] n.
13. A composition according to claim 11, further characterized in that the esters are of the formula R5 (COOR6) not R5COO (CH2CH20) a (CH [R3] CH20) bOCR5 in which R3 is a monovalent hydrocarbon group, a and b are 0 to 120, R5 is a linear or branched alkyl, aryl, alkaryl or cycloaliphatic group of valence equal to the number, n, R6 is a monovalent hydrocarbon radical derived from an alcohol and the total number of carbon atoms in R5 and R6 should be be at least eight
14. A composition according to claim 11, further characterized in that the ester is a natural ester without a hydroxyl group.
15. A composition according to claim 11. further characterized in that the ether is derived from a natural fatty acid or alcohol, or a mixture thereof.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/559,341 US5648444A (en) | 1995-11-15 | 1995-11-15 | Hydrosilation in esters without hydroxyl moieties |
US08559341 | 1995-11-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
MX9705334A MX9705334A (en) | 1998-07-31 |
MXPA97005334A true MXPA97005334A (en) | 1998-11-09 |
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