JPH04308595A - Production of mono-exchanger compound in organosilicone compound - Google Patents
Production of mono-exchanger compound in organosilicone compoundInfo
- Publication number
- JPH04308595A JPH04308595A JP10196291A JP10196291A JPH04308595A JP H04308595 A JPH04308595 A JP H04308595A JP 10196291 A JP10196291 A JP 10196291A JP 10196291 A JP10196291 A JP 10196291A JP H04308595 A JPH04308595 A JP H04308595A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- exchanger
- formula
- mono
- expressed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000006227 byproduct Substances 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002252 acyl group Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 abstract description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 5
- CMDYPQVFOYDRTH-UHFFFAOYSA-N 2-trimethoxysilyloxyethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)OCCOC(=O)C(C)=C CMDYPQVFOYDRTH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 150000002440 hydroxy compounds Chemical class 0.000 abstract 1
- -1 1-methylvinyl Chemical group 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 125000005336 allyloxy group Chemical group 0.000 description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910008649 Tl2O3 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- QTQRFJQXXUPYDI-UHFFFAOYSA-N oxo(oxothallanyloxy)thallane Chemical compound O=[Tl]O[Tl]=O QTQRFJQXXUPYDI-UHFFFAOYSA-N 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Chemical group 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ACAPOTPSGQLCTL-UHFFFAOYSA-N 2-[dimethoxy-[2-(2-methylprop-2-enoyloxy)ethoxy]silyl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCO[Si](OC)(OC)OCCOC(=O)C(C)=C ACAPOTPSGQLCTL-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- VLFKGWCMFMCFRM-UHFFFAOYSA-N [diacetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 VLFKGWCMFMCFRM-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([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
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は有機珪素化合物における
交換反応を制御して、目的とするモノ交換体化合物を高
収率に製造することのできる方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a desired monoexchanger compound in high yield by controlling the exchange reaction in an organosilicon compound.
【０００２】0002
【従来の技術】有機珪素化合物、特にアルコキシ基やア
シルオキシ基を有する有機珪素化合物を、ヒドロキシル
基含有化合物やカルボキシル基含有化合物との交換反応
に付すにあたっては、次式に示す様な多段階の逐次平衡
反応を起こすことが知られており、目的とするモノ交換
体化合物を高収率に得ることは困難である。[Prior Art] When subjecting an organosilicon compound, especially an organosilicon compound having an alkoxy group or an acyloxy group, to an exchange reaction with a hydroxyl group-containing compound or a carboxyl group-containing compound, a multi-step sequential reaction is carried out as shown in the following formula. It is known that an equilibrium reaction occurs, making it difficult to obtain the desired monoexchanger compound in high yield.
【０００３】0003
【化５】[C5]
【０００４】（式中Ｒ１は炭素数１０以下の炭化水素残
基、Ｒ２は水素原子、または炭素数５以下のアルキル基
または炭素数５以下のアシル基、Ｒ３は炭素数２０以下
の有機残基、ｎは０，１または２を夫々意味する）(In the formula, R1 is a hydrocarbon residue having 10 or less carbon atoms, R2 is a hydrogen atom, an alkyl group having 5 or less carbon atoms, or an acyl group having 5 or less carbon atoms, and R3 is an organic residue having 20 or less carbon atoms. , n means 0, 1 or 2 respectively)
【０
００５】即ち上記平衡式で示す様に、反応生成物中には
モノ交換体化合物（Ａ） の他に、ジ交換体化合物（Ｂ
） やトリ交換体化合物（Ｃ） などの多交換体化合物
が混在しており、従ってモノ交換体化合物（Ａ） の収
率は低くならざるを得ない。0
That is, as shown in the above equilibrium equation, the reaction product contains not only the monoexchanger compound (A) but also the diexchanger compound (B).
) and tri-exchanger compound (C), and therefore the yield of mono-exchanger compound (A) must be low.
【０００６】この様な反応の典型例としては、例えばＪ
．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９４６ （６８） ７
３ に記載されているテトラエトキシシランとアリルア
ルコールの反応が公知であり、これによれば４つのエト
キシ基のうち１つがアリルオキシ基に交換されたモノ交
換体の他、エトキシ基のうち２つがアリルオキシ基に交
換されたジ交換体、エトキシ基のうち３つがアリルオキ
シ基に交換されたトリ交換体、並びに全てのエトキシ基
がアリルオキシ基に交換されたテトラ交換体が全て生成
して反応系中に混在し、従ってモノ交換体の収率が非常
に低くなる旨報告されている。A typical example of such a reaction is, for example, J
．． Am. Chem. Soc. , 1946 (68) 7
The reaction between tetraethoxysilane and allyl alcohol described in 3 is known, and according to this, in addition to a monoexchanged product in which one of the four ethoxy groups is replaced with an allyloxy group, two of the ethoxy groups are replaced with an allyloxy group. A di-exchanger in which three ethoxy groups are exchanged with allyloxy groups, a tri-exchanger in which three of the ethoxy groups are exchanged with allyloxy groups, and a tetra-exchanger in which all ethoxy groups are exchanged with allyloxy groups are all produced and mixed in the reaction system. However, it has been reported that the yield of the monoexchanger is therefore very low.
【０００７】しかるにこれらのモノ交換体は例えばゾル
ーゲル反応等によって各種機能性材料を製造するときの
原料として有用である他、反応性基を有することにより
各種機能性高分子製造用モノマーとしても有用であり、
モノ交換体を高収率で製造することのできる手段を確立
することが望まれている。However, these monoexchangers are not only useful as raw materials for producing various functional materials through sol-gel reactions, but also as monomers for producing various functional polymers because of their reactive groups. can be,
It is desired to establish a means by which monoexchangers can be produced in high yields.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記の様な事
情に注目してなされたものであって、モノ交換体化合物
を高収率で製造することのできる方法を提供しようとす
るものである。[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a method that can produce a monoexchanger compound in high yield. be.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成すること
のできた本発明の製造方法とは、一般式[Means for Solving the Problems] The manufacturing method of the present invention that can achieve the above object is based on the general formula
【００１０】0010
【化６】[C6]
【００１１】（式中Ｒ１，Ｒ２，ｎは夫々前と同じ意味
）で示される化合物（Ａ）に、一般式
Ｒ３−ＯＨ
（Ｂ）（式中Ｒ３は前と同じ
意味）で示される化合物（Ｂ）を反応させることによっ
て生成する生成物のうち、一般式(wherein R1, R2, n each have the same meanings as before), a compound (A) of the general formula R3-OH
(B) Among the products produced by reacting the compound (B) (in which R3 has the same meaning as before), the general formula
【００１２】0012
【化７】[C7]
【００１３】で示されるモノ交換体化合物（Ｃ）を、一
般式The monoexchanger compound (C) represented by the general formula
【００１４】[0014]
【化８】[Chemical formula 8]
【００１５】で示されるジ交換体化合物（Ｄ）や、一般
式The di-exchanger compound (D) represented by
【００１６】[0016]
【化９】[Chemical formula 9]
【００１７】で示されるトリ交換体化合物（Ｅ）等の多
交換体副生物から分離採取すると共に、分離除去された
前記多交換体副生物を前記化合物（Ａ）と化合物（Ｂ）
の反応系に添加することを要旨とするものである。従っ
て多交換体副生物は反応生成物から分離して循環的に反
応原料として再使用されることになり、モノ交換体化合
物（Ｃ）から多交換体副生物への平衡移動を抑制し、そ
の結果としてモノ交換体化合物（Ｃ）の収率向上が達成
されたのである。The multi-exchanger by-products such as the tri-exchanger compound (E) shown below are separated and collected, and the separated and removed multi-exchanger by-products are combined with the compound (A) and compound (B).
The gist of this is that it is added to the reaction system. Therefore, the multi-exchanger by-product is separated from the reaction product and cyclically reused as a reaction raw material, suppressing the equilibrium shift from the mono-exchanger compound (C) to the multi-exchanger by-product, and As a result, an improvement in the yield of the monoexchanger compound (C) was achieved.
【００１８】[0018]
【発明の構成の説明】以下本発明を更に詳述するが、説
明の便宜から、
第１工程
化合物（Ａ）、化合物（Ｂ）および第２工程からリサイ
クルされる多交換体副生物を反応させてモノ交換体化合
物（Ｃ）、並びに多交換体副生物からなる混合物を製造
するステップ、DESCRIPTION OF THE STRUCTURE OF THE INVENTION The present invention will be described in more detail below, but for convenience of explanation, the first step compound (A), the compound (B), and the multi-exchanger by-product recycled from the second step will be reacted. producing a mixture consisting of a mono-exchanger compound (C) and a multi-exchanger by-product;
【００１９】第２工程
第１工程で得られた混合物からモノ交換体化合物（Ｃ）
を分離採取するとともに、残りの多交換体副生物を第１
工程にリサイクルするステップ、の２工程に分けて述べ
ることとする。Second step Mono exchanger compound (C) is extracted from the mixture obtained in the first step.
At the same time, the remaining multi-exchanger by-products are collected in the first
This will be explained in two steps: the recycling step.
【００２０】第１工程で生成するのはモノ交換体化合物
（Ｃ） と多交換体副生物（Ｄ），（Ｅ），…の混合物
であり、これらの中からモノ交換体化合物（Ｃ） を目
的物質として分離する。分離手段は一切制限されず、化
合物（Ｃ） におけるＲ１，Ｒ２，Ｒ３，ｎの種類に応
じて最適の手段を採用すれば良い。代表的な手段として
は、蒸留、クロマトグラフィー、再結晶、抽出等の方法
が例示される。モノ交換体化合物（Ｃ） が分離された
後の多交換体副生物（Ｄ），（Ｅ），…を含む混合物、
或は、必要により個別に分離されたジ交換体化合物（Ｄ
） やトリ交換体化合物（Ｅ） 等はこれらを精製する
ことなくそのままリサイクルし、化合物（Ａ） と化合
物（Ｂ） の反応系に添加して交換反応を行なわせる。
多交換体副生物は化合物（Ａ） ，化合物（Ｂ） と混
合して反応系に添加しても、化合物（Ａ） ，化合物（
Ｂ） と別々に添加してもよい。第１工程と第２工程は
バッチ的に分離して行うこともできるが、回分操作的に
連続して行なうことも可能である。What is produced in the first step is a mixture of the mono-exchanger compound (C) and the multi-exchanger by-products (D), (E), etc., from which the mono-exchanger compound (C) is extracted. Separate as target substance. The separation means is not limited at all, and an optimal means may be adopted depending on the types of R1, R2, R3, and n in compound (C). Typical methods include methods such as distillation, chromatography, recrystallization, and extraction. A mixture containing polyexchanger by-products (D), (E), ... after the monoexchanger compound (C) is separated,
Alternatively, di-exchanger compounds (D
), the tri-exchanger compound (E), etc. are recycled as they are without purification, and added to the reaction system of compound (A) and compound (B) to carry out the exchange reaction. Even if the multi-exchanger by-product is mixed with compound (A) and compound (B) and added to the reaction system, compound (A) and compound (
B) may be added separately. The first step and the second step can be carried out separately in a batchwise manner, but they can also be carried out continuously in a batchwise manner.
【００２１】上記第１工程においては、上記反応が既述
の如く逐次的且つ可逆的であることにより、反応系内に
おいて不均化反応を起こす。従って原料化合物（Ａ）
および（Ｂ） 、並びにリサイクルされる多交換体副生
物（Ｄ），（Ｅ），…等のモル比に応じた反応制御が行
なわれることとなり、特に化合物（Ａ），（Ｂ） の量
を適当に選べば、第１工程における反応生成物中の各交
換体化合物（Ｃ），（Ｄ），（Ｅ），…の組成比を任意
の値に、且つ再現性良く制御することが可能となる。こ
こで原料化合物（Ａ），（Ｂ） の量は第２工程からリ
サイクルされる多交換体副生物混合体における各交換体
化合物（Ｄ），（Ｅ），…の組成を考慮して定めること
が推奨される。尚第１工程における反応原料中の総Ｓｉ
モル数と総ＯＲ３基モル数の比は、（０．１：１） 〜
（２０：１）、好ましくは（１：１） 〜（１０：１）
の範囲から選定すれば良い。In the first step, since the reaction is sequential and reversible as described above, a disproportionation reaction occurs within the reaction system. Therefore, the raw material compound (A)
and (B), and the recycled multi-exchanger by-products (D), (E), etc. The reaction will be controlled according to the molar ratio of the compounds (A), (B), etc. If selected appropriately, it is possible to control the composition ratio of each exchanger compound (C), (D), (E), ... in the reaction product in the first step to any value and with good reproducibility. Become. Here, the amounts of the raw material compounds (A) and (B) should be determined by considering the composition of each exchanger compound (D), (E), ... in the multi-exchanger byproduct mixture recycled from the second step. is recommended. In addition, the total Si in the reaction raw materials in the first step
The ratio of the number of moles to the total number of moles of OR3 groups is (0.1:1) ~
(20:1), preferably (1:1) to (10:1)
You can choose from the range.
【００２２】次に本発明で用いられるＲ１、Ｒ２および
Ｒ３の定義について説明する。Ｒ１で示される炭素数１
０以下の炭化水素残基としては、直鎖状または分岐状の
飽和もしくは不飽和アルキル基（例えばメチル，エチル
，プロピル，イソプロピル，ブチル，第２級ブチル，第
３級ブチル，ペンチル，イソペンチル，ヘキシル，ヘプ
チル，２−メチルヘキシル，３−メチルヘキシル，オク
チル，ノニル，デシル，ビニル，１−メチルビニル，ア
リール等）、芳香族残基（例えばフェニル，トリル，キ
シリル，ナフチル等），脂環式アルキル基（例えばシク
ロプロピル，シクロペンチル，シクロヘキシル，４−メ
チルシクロヘキシル等）が示される。Next, the definitions of R1, R2 and R3 used in the present invention will be explained. Carbon number 1 represented by R1
Zero or less hydrocarbon residues include linear or branched saturated or unsaturated alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, pentyl, isopentyl, hexyl). , heptyl, 2-methylhexyl, 3-methylhexyl, octyl, nonyl, decyl, vinyl, 1-methylvinyl, aryl, etc.), aromatic residues (e.g. phenyl, tolyl, xylyl, naphthyl, etc.), alicyclic alkyl Groups such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc. are indicated.
【００２３】Ｒ２で示される炭素数５以下のアルキル基
としては、メチル，エチル，プロピル，イソプロピル，
ブチル，第２級ブチル，第３級ブチル，ペンチル等の直
鎖状または分岐状アルキル基が例示される。また炭素数
５以下のアシル基としてはアセチル，プロピオニル，ブ
チリル，エトキシカルボニル，プロポキシカルボニル等
が例示される。従ってＯＲ２基としては、メトキシ，エ
トキシ，プロポキシ，ブトキシ等のアルコキシ基、或は
アセチルオキシ，プロピオニルオキシ，エトキシカルボ
ニルオキシ等のアシルオキシ基が得られる。The alkyl group having 5 or less carbon atoms represented by R2 includes methyl, ethyl, propyl, isopropyl,
Straight chain or branched alkyl groups such as butyl, secondary butyl, tertiary butyl, pentyl and the like are exemplified. Examples of the acyl group having 5 or less carbon atoms include acetyl, propionyl, butyryl, ethoxycarbonyl, propoxycarbonyl, and the like. Therefore, as the OR2 group, an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, or an acyloxy group such as acetyloxy, propionyloxy, ethoxycarbonyloxy, etc. can be obtained.
【００２４】Ｒ３で示される炭素数２０以下の有機残基
とは、反応性２重結合（例えばビニル，アクリロイル，
メタクリロイル等），エポキシ基，カルボニル基，カル
バモイル基，オキサゾリン骨格，直鎖状または分岐状ア
ルキル基，脂環式炭化水素基，芳香族炭化水素基等を有
する有機残基を意味し、Ｒ３−ＯＨとして示される化合
物はアルコール類，フェノール類またはカルボン酸類で
ある。The organic residue having 20 or less carbon atoms represented by R3 is a reactive double bond (such as vinyl, acryloyl,
R3-OH Compounds shown as are alcohols, phenols, or carboxylic acids.
【００２５】上記各種定義で例示された様な基を有する
化合物を例示すると、まず化合物（Ａ） としては、テ
トラメトキシシラン，テトラエトキシシラン，テトライ
ソプロポキシシラン，テトラブトキシシラン，メチルト
リメトキシシラン，メチルトリエトキシシラン，フェニ
ルトリメトキシシラン，フェニルトリエトキシシラン，
ジメチルジメトキシシラン，ジメチルジエトキシシラン
，ジフェニルジメトキシシラン，ジフェニルジエトキシ
シラン等のアルコキシシラン化合物；テトラアセトキシ
シラン，メチルトリアセトキシシラン，ジメチルジアセ
トキシシラン，フェニルトリアセトキシシラン等のアシ
ロキシシラン化合物；ジフェニルシランジオール等のシ
ラノール化合物等を挙げることができる。[0025] Examples of compounds having groups as exemplified in the various definitions above include compound (A) such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, Methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Alkoxysilane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane; acyloxysilane compounds such as tetraacetoxysilane, methyltriacetoxysilane, dimethyldiacetoxysilane, phenyltriacetoxysilane; diphenylsilane Examples include silanol compounds such as diols.
【００２６】次に化合物（Ｂ） としては、例えばNext, as the compound (B), for example,
【０
０２７】0
027]
【化１０】[Chemical formula 10]
【００２８】（式中Ｒ４は炭素数１〜１０のアルキレン
基またはオキシアルキレン基，Ｒ５は水素原子またはメ
チル基を示す）等が例示される。ここでアルキレン基と
してはエチレン，トリメチレン，テトラメチレン，ペン
タメチレン，ヘキサメチレン，ヘプタメチレン，オクタ
メチレン，ノナメチレン，デカメチレン，プロピレン，
エチルエチレン，２−メチルテトラメチレン，３−メチ
ルテトラメチレン等の直鎖状または分岐状アルキレン基
が例示され、またオキシアルキレン基としては、上記の
様に例示されたアルキレン基における炭素鎖が任意の位
置で酸素原子で中断された基が例示される。Examples include (in the formula, R4 represents an alkylene group or oxyalkylene group having 1 to 10 carbon atoms, and R5 represents a hydrogen atom or a methyl group). Here, the alkylene groups include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, propylene,
Examples include linear or branched alkylene groups such as ethylethylene, 2-methyltetramethylene, and 3-methyltetramethylene, and examples of oxyalkylene groups include those in which the carbon chain in the alkylene group exemplified above is arbitrary. An example is a group interrupted by an oxygen atom at a position.
【００２９】上記の様な化合物（Ｆ） 〜（Ｍ） につ
いてこれを更に具体例をもって説明すれば下記の通りで
ある。
ＣＨ３＝Ｃ（ＣＨ３）−ＣＯＯＣＨ２ＣＨ２ＯＨＣＨ２
＝Ｃ（ＣＨ３）−ＣＯＯＣＨ２ＣＨ２ＣＨ２ＯＨＣＨ２
＝Ｃ（ＣＨ３）−ＣＯＯＣＨ２ＣＨ（ＣＨ３）ＯＨＣＨ
２＝Ｃ（ＣＨ３）−ＣＯＯＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ
ＨＣＨ２＝Ｃ（ＣＨ３）−ＣＯＯＣＨ２ＣＨ２ＯＣＨ２
ＣＨ２ＯＨ
ＣＨ２＝ＣＨ−ＣＯＯＣＨ２ＣＨ（ＣＨ３）ＯＨＣＨ２
＝ＣＨ−ＣＯＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨＣＨ２＝
ＣＨ−ＣＨ２ＯＨ
ＣＨ２＝ＣＨ−ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＯＨＣＨ２
＝Ｃ（ＣＨ３）−ＣＯＮＨＣＨ２ＣＨ２ＯＨＣＨ２＝Ｃ
Ｈ−ＣＯＮＨＣＨ２ＣＨ２ＯＨＣＨ２＝Ｃ（ＣＨ３）−
ＣＯＯＨ
ＣＨ２＝ＣＨ−ＣＯＯＨ
ＣＨ２＝Ｃ（ＣＨ３）−ＣＯＮＨＣＨ２ＣＯＯＨＣＨ２
＝ＣＨ−ＣＨ２−ＣＯＯＨThe above compounds (F) to (M) will be further explained with specific examples as follows. CH3=C(CH3)-COOCH2CH2OHCH2
=C(CH3)-COOCH2CH2CH2OHCH2
=C(CH3)-COOCH2CH(CH3)OHCH
2=C(CH3)-COOCH2CH2CH2CH2O
HCH2=C(CH3)-COOCH2CH2OCH2
CH2OH CH2=CH-COOCH2CH(CH3)OHCH2
=CH-COOCH2CH2CH2CH2OHCH2=
CH-CH2OH CH2=CH-CH2CH2OCH2CH2OHCH2
=C(CH3)-CONHCH2CH2OHCH2=C
H-CONHCH2CH2OHCH2=C(CH3)-
COOH CH2=CH-COOH CH2=C(CH3)-CONHCH2COOHCH2
=CH-CH2-COOH
【００３０】[0030]
【化１１】[Chemical formula 11]
【００３１】第１工程および第２工程に示した交換反応
は触媒の存在下または非存在下に行なわれる。触媒とし
ては無機酸（塩酸，硝酸，硫酸，燐酸等），有機酸（蟻
酸，酢酸，プロピオン酸，しゅう酸，ｐ−トルエンスル
ホン酸等），有機アミン化合物（トリエチルアミン，ト
リプロピルアミン等），有機アルカリ金属化合物（ナト
リウムメトキシド，ナトリウムエトキシド，カリウムメ
トキシド，カリウムエトキシド，カリウム−ｔ−ブトキ
シド等），ゼオライト類，酸性もしくは塩基性イオン交
換樹脂，金属酸化物（Ｇａ２Ｏ３ ，Ｔｌ２Ｏ３ ，Ｓ
ｂ２Ｏ３，Ａｌ２Ｏ３等）等の液体状あるいは固体状の
酸または塩基を挙げることができる。中でも特に好まし
いのは、反応後の除去が容易という点で固体状触媒を用
いることが推奨される。The exchange reactions shown in the first and second steps are carried out in the presence or absence of a catalyst. Catalysts include inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc.), organic acids (formic acid, acetic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, etc.), organic amine compounds (triethylamine, tripropylamine, etc.), and organic acids. Alkali metal compounds (sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, etc.), zeolites, acidic or basic ion exchange resins, metal oxides (Ga2O3, Tl2O3, S
Examples include liquid or solid acids or bases such as b2O3, Al2O3, etc.). Among these, it is particularly preferred to use a solid catalyst because it can be easily removed after the reaction.
【００３２】また上記交換反応は、溶媒中または無溶媒
下に０〜２００ ℃、好ましくは４０〜１３０ ℃に加
温され、また反応系は加圧下、常圧下、減圧下の如何を
問わず、また更に（化９）に示した反応式に従って副生
するアルコール類またはカルボン酸類を除去しつつ反応
を行うことも可能である。反応系に用いる溶媒としては
、反応の進行に悪影響を与えない限り全て使用でき、代
表的なものとしては、トルエン，キシレン等の芳香族炭
化水素系溶媒；ヘキサン，ヘプタン，オクタン等の脂肪
族炭化水素系溶媒；クロロホルム，塩化メチレン，ジク
ロロエタン等のハロゲン化炭化水素系溶媒；テトラヒド
ロフラン，ジオキサン，ｎ−ブチルエーテル等のエーテ
ル系溶媒；メチルエチルケトン，メチルイソブチルケト
ン等のケトン系溶媒が使用される。[0032] The above exchange reaction is carried out in a solvent or in the absence of a solvent at a temperature of 0 to 200°C, preferably 40 to 130°C, and the reaction system may be under pressure, normal pressure, or reduced pressure. Furthermore, it is also possible to carry out the reaction while removing by-product alcohols or carboxylic acids according to the reaction formula shown in (Chemical Formula 9). Any solvent can be used in the reaction system as long as it does not adversely affect the progress of the reaction. Typical examples include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic carbonized solvents such as hexane, heptane, and octane. Hydrogen solvents; halogenated hydrocarbon solvents such as chloroform, methylene chloride and dichloroethane; ether solvents such as tetrahydrofuran, dioxane and n-butyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are used.
【００３３】[0033]
【発明の効果】本発明は上記の様に構成されているので
、アルコキシ基またはアシルオキシ基を有する有機珪素
化合物を、アルコール類またはカルボン酸類と交換反応
を行うに際して、モノ交換体化合物を高収率に製造する
ことが可能となった。Effects of the Invention Since the present invention is constructed as described above, when an organosilicon compound having an alkoxy group or an acyloxy group is exchanged with an alcohol or a carboxylic acid, a monoexchanger compound can be produced in high yield. It became possible to manufacture
【００３４】[0034]
【実施例】次に本発明を実施例により更に具体的に説明
するが、本発明はこれら実施例に限定されるものではな
い。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００３５】実施例１
（１） 多交換体副生物の調製
テトラメトキシシラン４００ｇと２−ヒドロキシエチル
メタクリレート１７１ｇと、アンバーリスト１５（酸性
イオン交換樹脂，ローム・アンド・ハース・ジャパン製
）３ｇ を２００ｍｍＨｇ 下に８０℃まで２時間かけ
て昇温し、留出する液（メタノール）がなくなるまで同
温度で保持した。室温まで冷却し、アンバーリスト１５
を濾別し、その濾液から１０ｍｍＨｇの減圧下に過剰の
テトラメトキシシランを留去し第１工程を終了した。残
渣にフェノチアジン（重合禁止剤）６０ｍｇを添加し、
０．２ｍｍＨｇ の減圧下に蒸留底部液の温度が１３０
℃になるまでまで蒸留を行い、メタクリロキシエトキ
シトリメトキシシラン（モノ交換体）１９２ｇを得た。
このときの蒸留残渣すなわち多交換体副生物１００ｇの
組成をＨＰＬＣにより分析すると、メタクリロキシエト
キシトリメトキシシラン１３．５ｇ（０．０５３９モル
），ジ（メタクリロキシエトキシ）ジメトキシシラン６
８．５ｇ（０．１９７ モル），トリ（メタクリロキシ
エトキシ）メトキシシラン１３．５ｇ（０．０３０２モ
ル））を含んでいた。Example 1 (1) Preparation of multi-exchanger by-product 400 g of tetramethoxysilane, 171 g of 2-hydroxyethyl methacrylate, and 3 g of Amberlyst 15 (acidic ion exchange resin, manufactured by Rohm & Haas Japan) were heated to 200 mmHg. The temperature was raised to 80° C. over 2 hours, and maintained at the same temperature until no liquid (methanol) was distilled out. Cool to room temperature and add Amberlyst 15
was separated by filtration, and excess tetramethoxysilane was distilled off from the filtrate under reduced pressure of 10 mmHg to complete the first step. Add 60 mg of phenothiazine (polymerization inhibitor) to the residue,
The temperature of the distillation bottom liquid was 130°C under a reduced pressure of 0.2mmHg.
Distillation was carried out until the temperature reached ℃, and 192 g of methacryloxyethoxytrimethoxysilane (monoexchanger) was obtained. HPLC analysis of the composition of the distillation residue, 100 g of the multi-exchanger by-product, revealed that 13.5 g (0.0539 mol) of methacryloxyethoxytrimethoxysilane, 6 g of di(methacryloxyethoxy)dimethoxysilane,
8.5 g (0.197 mol), tri(methacryloxyethoxy)methoxysilane 13.5 g (0.0302 mol)).
【００３６】（２） 第１工程
上で得た多交換体副生物１００ｇ，テトラメトキシシラ
ン３５７．６ｇ（２．３５ モル）および２−ヒドロキ
シエチルメタクリレート１００．５ｇ（０．７７２モル
）にアンバーリスト１５を３ｇ 加え２００ｍｍＨｇ
の下で８０℃まで２時間かけて昇温し、留出する液（メ
タノール）がなくなるまで同温度で保持した。室温まで
冷却し、アンバーリスト１５を濾別し、その濾液を１０
ｍｍＨｇの減圧下に加熱して過剰のテトラメトキシシラ
ンを留去し、残渣３０１ｇを得た。(2) Amberlyst was added to 100 g of the polyexchanger by-product obtained in the first step, 357.6 g (2.35 mol) of tetramethoxysilane, and 100.5 g (0.772 mol) of 2-hydroxyethyl methacrylate. Add 3g of 15 and make 200mmHg
The temperature was raised to 80° C. over 2 hours under the following conditions, and the temperature was maintained until no liquid (methanol) was distilled out. Cool to room temperature, filter off Amberlyst 15, and remove the filtrate from 10
Excess tetramethoxysilane was distilled off by heating under reduced pressure of mmHg to obtain 301 g of a residue.
【００３７】（３） 第２工程
上で得た残渣にフェノチアジン６０ｍｇを加え、０．２
ｍｍＨｇ の減圧下に蒸留低部液温度が１３０ ℃にな
るまで蒸留を行い、メタクリロキシエトキシトリメトキ
シシラン１９１ｇ（０．７６３モル）を得た。これは、
（２） において使用した２−ヒドロキシエチルメタク
リレートに対して９８％の収率であることを示している
。(3) Add 60 mg of phenothiazine to the residue obtained in the second step, and add 0.2
Distillation was carried out under a reduced pressure of mmHg until the temperature of the lower part of the distillation reached 130° C. to obtain 191 g (0.763 mol) of methacryloxyethoxytrimethoxysilane. this is,
This shows a yield of 98% based on the 2-hydroxyethyl methacrylate used in (2).
【００３８】実施例２〜７
実施例１のテトラメトキシシランのかわりに表１のＸを
用い、２−ヒドロキシエチルメタクリレートのかわりに
表１のＹを用いて、実施例１と同様に反応を行なった。
尚実施例５においては、触媒をＴｌ２Ｏ３に替えて行な
った。また実施例３，７においては交換反応実施時の圧
力を２００ｍｍＨｇ から１３０ｍｍＨｇ に変更した
。結果を表１に示す。Examples 2 to 7 Reactions were carried out in the same manner as in Example 1, using X in Table 1 instead of tetramethoxysilane in Example 1, and Y in Table 1 in place of 2-hydroxyethyl methacrylate. Ta. In Example 5, the catalyst was changed to Tl2O3. In Examples 3 and 7, the pressure during exchange reaction was changed from 200 mmHg to 130 mmHg. The results are shown in Table 1.
【００３９】[0039]
【表１】[Table 1]
Claims (1)
素原子または炭素数５以下のアルキル基または炭素数５
以下のアシル基、ｎは０，１または２をそれぞれ意味す
る）で示される化合物（Ａ）、および一般式：Ｒ３−Ｏ
Ｈ
（Ｂ）（式中Ｒ３は炭素数２０以下の
有機残基を意味する）で示される化合物（Ｂ）から、一
般式 【化２】 （式中Ｒ１，Ｒ２，Ｒ３およびｎはそれぞれ前と同じ意
味）で示されるモノ交換体化合物（Ｃ）を製造する方法
において、前記化合物（Ａ）と前記化合物（Ｂ）との反
応によって生成する生成物のうち、前記モノ交換体化合
物（Ｃ）を、一般式 【化３】 で示されるジ交換体化合物（Ｄ）や、一般式【化４】 で示されるトリ交換体化合物（Ｅ）等の多交換体副生物
から分離採取すると共に、分離除去された前記多交換体
副生物を化合物（Ａ）と化合物（Ｂ）との反応系に混合
して交換反応を行なわせることを特徴とするモノ交換体
化合物の製造方法。Claim 1: General formula [Formula 1] (wherein R1 is a hydrocarbon residue having 10 or less carbon atoms, R2 is a hydrogen atom, an alkyl group having 5 or less carbon atoms, or a carbon number 5 or less)
Compound (A) represented by the following acyl group, n means 0, 1 or 2, respectively), and the general formula: R3-O
H
(B) (In the formula, R3 means an organic residue having 20 or less carbon atoms) From the compound (B) represented by the general formula [Chemical formula 2] (wherein R1, R2, R3 and n are the same as before, In the method for producing a monoexchanger compound (C) represented by (meaning), among the products produced by the reaction of the compound (A) and the compound (B), the monoexchanger compound (C) is The di-exchanger compound (D) represented by the general formula [Chemical formula 3] and the tri-exchanger compound (E) represented by the general formula [Chemical formula 4] are separated and collected from the multi-exchanger by-products, and are also separated and removed. A method for producing a mono-exchanger compound, characterized in that the multi-exchanger by-product is mixed into a reaction system of compound (A) and compound (B) to carry out an exchange reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10196291A JPH04308595A (en) | 1991-04-05 | 1991-04-05 | Production of mono-exchanger compound in organosilicone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10196291A JPH04308595A (en) | 1991-04-05 | 1991-04-05 | Production of mono-exchanger compound in organosilicone compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04308595A true JPH04308595A (en) | 1992-10-30 |
Family
ID=14314495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10196291A Withdrawn JPH04308595A (en) | 1991-04-05 | 1991-04-05 | Production of mono-exchanger compound in organosilicone compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04308595A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06228165A (en) * | 1993-01-29 | 1994-08-16 | Shin Etsu Chem Co Ltd | Organosilicon compound and its production |
-
1991
- 1991-04-05 JP JP10196291A patent/JPH04308595A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06228165A (en) * | 1993-01-29 | 1994-08-16 | Shin Etsu Chem Co Ltd | Organosilicon compound and its production |
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