JP4368243B2 - Method for producing branched pentasiloxane - Google Patents
Method for producing branched pentasiloxane Download PDFInfo
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- JP4368243B2 JP4368243B2 JP2004144420A JP2004144420A JP4368243B2 JP 4368243 B2 JP4368243 B2 JP 4368243B2 JP 2004144420 A JP2004144420 A JP 2004144420A JP 2004144420 A JP2004144420 A JP 2004144420A JP 4368243 B2 JP4368243 B2 JP 4368243B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 27
- FYBYQXQHBHTWLP-UHFFFAOYSA-N bis(silyloxysilyloxy)silane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH2]O[SiH3] FYBYQXQHBHTWLP-UHFFFAOYSA-N 0.000 title claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 239000003377 acid catalyst Substances 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 9
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 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 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007806 chemical reaction intermediate Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- -1 trimethylsiloxy group Chemical group 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000543 intermediate Substances 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
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RGMZNZABJYWAEC-UHFFFAOYSA-N Methyltris(trimethylsiloxy)silane Chemical compound C[Si](C)(C)O[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C RGMZNZABJYWAEC-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 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
- 239000002274 desiccant Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- RWRZXVJBHRYPJM-UHFFFAOYSA-N ethoxy-methyl-bis(trimethylsilyloxy)silane Chemical compound CCO[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C RWRZXVJBHRYPJM-UHFFFAOYSA-N 0.000 description 1
- RXDPPOMCFULIIG-UHFFFAOYSA-N ethyl tris(trimethylsilyl) silicate Chemical compound CCO[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C RXDPPOMCFULIIG-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ULFYRAYSKDXNLU-UHFFFAOYSA-N hydroxy-tris(trimethylsilyloxy)silane Chemical compound C[Si](C)(C)O[Si](O)(O[Si](C)(C)C)O[Si](C)(C)C ULFYRAYSKDXNLU-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ACXIAEKDVUJRSK-UHFFFAOYSA-N methyl(silyloxy)silane Chemical compound C[SiH2]O[SiH3] ACXIAEKDVUJRSK-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen 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
- 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
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-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
- 239000013638 trimer Substances 0.000 description 1
- HFMRLLVZHLGNAO-UHFFFAOYSA-N trimethylsilyloxysilicon Chemical compound C[Si](C)(C)O[Si] HFMRLLVZHLGNAO-UHFFFAOYSA-N 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、分岐状ペンタシロキサンの製造方法に関し、特に工業用油剤、衣類、装置の洗浄剤として有用なテトラキストリメチルシロキシシランの製造方法に関する。 The present invention relates to a method for producing branched pentasiloxane, and more particularly to a method for producing tetrakistrimethylsiloxysilane useful as a cleaning agent for industrial oils, clothing and equipment.
本発明は、分岐状ペンタシロキサンの製造方法に関する。分岐状ペンタシロキサン、特にテトラキストリメチルシロキシシラン（｛（ＣＨ３）３ＳｉＯ｝４Ｓｉ、以下Ｍ４Ｑと略す）は、工業用油剤、衣類や装置の洗浄剤として用いられる。珪素原子１個からなる原料テトラアルコキシシランや、珪素原子数が２、３、４の反応中間体成分（トリメチルシロキシトリアルコキシシラン、ビストリメチルシロキシジアルコキシシラン、トリストリメチルシロキシアルコキシシラン、トリストリメチルシロキシヒドロキシシラン等）は、ガラス等、表面に活性点を持つ基材の洗浄剤として使用した場合、基材と反応して表面処理される可能性が考えられるため、混入してくる量は最小限にとどめる事が望まれている。また、これらの原料シラン、及び反応中間体成分を衣料の洗浄剤として使用し、衣料に残存したまま着用した時には皮膚への刺激性を及ぼすことも考えられ、同様に混入量を最小限にとどめることが望まれる。 The present invention relates to a method for producing a branched pentasiloxane. Branched pentasiloxanes, particularly tetrakistrimethylsiloxysilane ({(CH 3 ) 3 SiO} 4 Si, hereinafter abbreviated as M4Q) are used as industrial oils, washing agents for clothes and devices. Raw material tetraalkoxysilane composed of one silicon atom, reaction intermediate components having 2, 3, and 4 silicon atoms (trimethylsiloxytrialkoxysilane, bistrimethylsiloxydialkoxysilane, tristrimethylsiloxyalkoxysilane, tristrimethylsiloxyhydroxy Silane, etc.), when used as a cleaning agent for substrates such as glass that have active sites on the surface, may be surface treated by reacting with the substrate, so the amount of contamination is minimized. It is hoped to stay. In addition, these raw material silanes and reaction intermediate components may be used as a cleaning agent for clothing, which may cause irritation to the skin when worn while remaining in clothing. It is desirable.
以上のことから、油剤として使用されるＭ４Ｑは、低沸点の珪素含有成分が少なく、９９．０％以上の高純度、特に９９．５％以上である事が望まれている。 From the above, it is desired that M4Q used as an oil agent has a low boiling point silicon-containing component and has a high purity of 99.0% or more, particularly 99.5% or more.
Ｍ４Ｑを得るための合成方法は、メチルトリストリメチルシロキシシラン（｛（ＣＨ３）３ＳｉＯ｝３ＳｉＣＨ３、以下Ｍ３Ｔと略す）の合成方法が参考となる。従来Ｍ３Ｔを製造する方法としては、下記の方法が知られている。 As a synthesis method for obtaining M4Q, a synthesis method of methyltristrimethylsiloxysilane ({(CH 3 ) 3 SiO} 3 SiCH 3 , hereinafter abbreviated as M3T) is referred. The following methods are known as conventional methods for producing M3T.
１．メチルトリクロロシランとトリメチルクロロシランを、メタノールの存在下に共加水分解する方法（国際公開ＷＯ２００１−１５６５８号、特開２００２−６８９３０号公報）。
２．メチルトリクロロシランとヘキサメチルジシロキサンを、過塩素酸触媒の存在下に反応させる方法（Ｄｏｋｌ． Ａｋａｄ． Ｎａｕｋ ＳＳＳＲ、 ２２７、 ６０７〜６１０（１９７６））。
３．メチルトリエトキシシランとヘキサメチルジシロキサンを、酸性のイオン交換樹脂の存在下に反応させる方法（Ｊ． Ｏｒｇａｎｏｍｅｔ． Ｃｈｅｍ．， ３４０， ３１−３６（１９８８））。
４．メチルトリアルコキシシランとヘキサメチルジシロキサンを、カルボン酸と酸触媒の存在下反応させる方法（特開平１１−２１７３８９号公報）。
５．メチルトリメトキシシラン、ヘキサメチルジシロキサン及びメタノール中に濃硫酸を添加した後、水とメタノールの混合物を滴下して反応させる方法（国際公開ＷＯ２００１−１５６５８号公報、特開２００２−６８９３０号公報）。
1. A method of cohydrolyzing methyltrichlorosilane and trimethylchlorosilane in the presence of methanol (International Publication Nos. WO2001-15658 and JP-A-2002-68930).
2. A method in which methyltrichlorosilane and hexamethyldisiloxane are reacted in the presence of a perchloric acid catalyst (Dokl. Akad. Nauk SSSR, 227, 607-610 (1976)).
3. A method in which methyltriethoxysilane and hexamethyldisiloxane are reacted in the presence of an acidic ion exchange resin (J. Organomet. Chem., 340, 31-36 (1988)).
4). A method of reacting methyltrialkoxysilane and hexamethyldisiloxane in the presence of a carboxylic acid and an acid catalyst (JP-A-11-217389).
5. A method in which concentrated sulfuric acid is added to methyltrimethoxysilane, hexamethyldisiloxane, and methanol, and then a mixture of water and methanol is dropped to cause a reaction (International Publication WO2001-15658, JP2002-68930A).
１．の方法でテトラキストリメチルシロキシシランを合成するには、テトラクロロシランとトリメチルクロロシランをメタノールの存在下に共加水分解すればよい。しかし、大量の水が必要であり、且つ反応の選択性が低いため収率が非常に低いという問題がある。 1. In order to synthesize tetrakistrimethylsiloxysilane by this method, tetrachlorosilane and trimethylchlorosilane may be cohydrolyzed in the presence of methanol. However, there is a problem that a large amount of water is required and the yield is very low because the selectivity of the reaction is low.
２．の方法でテトラキストリメチルシロキシシランを合成するには、テトラクロロシランとヘキサメチルジシロキサンを、過塩素酸触媒の存在下に反応すればよい。しかし、取り扱いの困難な過塩素酸を触媒として用いる必要があり、工業的な製造方法として適していない。 2. In order to synthesize tetrakistrimethylsiloxysilane by this method, tetrachlorosilane and hexamethyldisiloxane may be reacted in the presence of a perchloric acid catalyst. However, perchloric acid, which is difficult to handle, must be used as a catalyst, and is not suitable as an industrial production method.
３．の方法でテトラキストリメチルシロキシシランを合成するには、テトラエトキシシランとヘキサメチルジシロキサンを、酸性のイオン交換樹脂の存在下に反応すればよい。しかし、反応率を上げるためには大過剰のヘキサメチルジシロキサンを用いる必要がある。また、Ｍ３Ｔの合成においても反応中間体の１，１，１，３，５，５，５−ヘプタメチル−３−エトキシトリシロキサン（｛（ＣＨ３）３ＳｉＯ｝２Ｓｉ（ＯＣＨ２ＣＨ３）ＣＨ３、以下Ｍ２Ｔ（ＯＥｔ）と略す）が大量に残るという欠点がある。 3. In order to synthesize tetrakistrimethylsiloxysilane by this method, tetraethoxysilane and hexamethyldisiloxane may be reacted in the presence of an acidic ion exchange resin. However, in order to increase the reaction rate, it is necessary to use a large excess of hexamethyldisiloxane. Also in the synthesis of M3T, 1,1,1,3,5,5,5-heptamethyl-3-ethoxytrisiloxane ({(CH 3 ) 3 SiO} 2 Si (OCH 2 CH 3 ) CH, which is a reaction intermediate, is used. 3 , hereinafter abbreviated as M2T (OEt)).
さらに、ケイ素上にトリメチルシロキシ基を導入する場合、Ｍ３Ｔの時にはトリメチルシロキシ基を３個導入することになるが、２個目よりも３個目の反応性が低くなる。Ｍ４Ｑを合成する場合にはトリメチルシロキシ基を４個導入することになるため、４個目のトリメチルシロキシ基の反応性が、Ｍ３Ｔ合成における３個目のトリメチルシロキシ基の反応性よりもさらに低くなると考えられる。従って、Ｍ４Ｑを同様に合成した場合、反応中間体の１，１，１，５，５，５−ヘキサメチル−３−トリメチルシロキシ−３−エトキシトリシロキサン（｛（ＣＨ３）３ＳｉＯ｝３ＳｉＯＣＨ２ＣＨ３、以下Ｍ３Ｑ（ＯＥｔ）と略す）の残留量がより多くなると考えられ、高純度なテトラキストリメチルシロキシシランを得る方法としては適していない。 Further, when a trimethylsiloxy group is introduced onto silicon, three trimethylsiloxy groups are introduced at the time of M3T, but the reactivity of the third is lower than that of the second. When synthesizing M4Q, four trimethylsiloxy groups are introduced, so that the reactivity of the fourth trimethylsiloxy group is lower than the reactivity of the third trimethylsiloxy group in the M3T synthesis. Conceivable. Therefore, when M4Q is synthesized in the same manner, the reaction intermediate 1,1,1,5,5,5-hexamethyl-3-trimethylsiloxy-3-ethoxytrisiloxane ({(CH 3 ) 3 SiO} 3 SiOCH 2 The residual amount of CH 3 (hereinafter abbreviated as M3Q (OEt)) is considered to be larger, and is not suitable as a method for obtaining highly pure tetrakistrimethylsiloxysilane.
４．の方法でテトラキストリメチルシロキシシランを合成するには、テトラアルコキシシランとヘキサメチルジシロキサンを、カルボン酸と酸触媒の存在下に反応すればよい。しかし、Ｍ３Ｔの合成において反応中間体のＭ２Ｔ（ＯＥｔ）が残ってしまうことから、Ｍ４Ｑを同様に合成した場合、反応中間体のＭ３Ｑ（ＯＥｔ）残留量がより多くなると考えられ、高純度なＭ４Ｑを効率良く得る方法として満足すべきものではない。 4). In order to synthesize tetrakistrimethylsiloxysilane by this method, tetraalkoxysilane and hexamethyldisiloxane may be reacted in the presence of a carboxylic acid and an acid catalyst. However, since the reaction intermediate M2T (OEt) remains in the synthesis of M3T, it is considered that when M4Q is synthesized in the same manner, the residual amount of M3Q (OEt) in the reaction intermediate is increased. It is not satisfactory as a method for obtaining the above efficiently.
５．の方法でテトラキストリメチルシロキシシランを合成するには、テトラメトキシシラン、ヘキサメチルジシロキサン及びメタノール中に濃硫酸を添加した後、水とメタノールの混合物を滴下して反応すればよい。しかし、上記と同様にＭ３Ｔの合成において反応中間体の｛（ＣＨ３）３ＳｉＯ｝２Ｓｉ（ＣＨ３）ＯＣＨ３（以下Ｍ２Ｔ（ＯＭｅ）と略す）が残ってしまうことから、Ｍ４Ｑを同様に合成した場合、反応中間体の｛（ＣＨ３）３ＳｉＯ｝３ＳｉＯＣＨ３（以下Ｍ３Ｑ（ＯＭｅ）と略す）残留量がより多くなると考えられ、高純度なＭ４Ｑを効率良く得る方法として満足すべきものではない。 5. In order to synthesize tetrakistrimethylsiloxysilane by this method, after adding concentrated sulfuric acid to tetramethoxysilane, hexamethyldisiloxane and methanol, a mixture of water and methanol may be dropped and reacted. However, the reaction intermediate {(CH 3 ) 3 SiO} 2 Si (CH 3 ) OCH 3 (hereinafter abbreviated as M2T (OMe)) remains in the synthesis of M3T as described above. When synthesized, the residual amount of {(CH 3 ) 3 SiO} 3 SiOCH 3 (hereinafter abbreviated as M3Q (OMe)) of the reaction intermediate is considered to be larger, which is satisfactory as a method for efficiently obtaining high-purity M4Q. is not.
また、何れの方法においても、反応中間体である１，１，１，５，５，５−ヘキサメチル−３−トリメチルシロキシ−３−メトキシ（またはエトキシ）トリシロキサンのメトキシ基（またはエトキシ基）が加水分解された不純物、すなわち、１，１，１，５，５，５−ヘキサメチル−３−トリメチルシロキシ−３−ヒドロキシトリシロキサン（｛（ＣＨ３）３ＳｉＯ｝３ＳｉＯＨ、以下Ｍ３Ｑ（ＯＨ）と略す）の副生量を制御することについては何ら示唆されていない。 In either method, the methoxy group (or ethoxy group) of 1,1,1,5,5,5-hexamethyl-3-trimethylsiloxy-3-methoxy (or ethoxy) trisiloxane, which is a reaction intermediate, is added. Hydrolyzed impurities, namely 1,1,1,5,5,5-hexamethyl-3-trimethylsiloxy-3-hydroxytrisiloxane ({(CH 3 ) 3 SiO} 3 SiOH, hereinafter referred to as M3Q (OH) There is no suggestion of controlling the amount of by-products.
目的物であるＭ４Ｑを効率良く得るためには、反応中間体であるＭ３Ｑ（ＯＭｅ）やＭ３Ｑ（ＯＥｔ）の残留量を少なくすることによって反応収率を向上すること、Ｑ単位の縮合物、すなわち反応中間体や出発原料であるテトラアルコキシシランの縮合物である高沸点物（｛（ＣＨ３）３ＳｉＯ｝３ＳｉＯＳｉ｛ＯＳｉ（ＣＨ３）３｝３等）の副生を少なくすることによって反応収率を向上させることが必要である。さらに、目的物に対してより沸点の近い副生物であるＭ３Ｑ（ＯＨ）の残留量を少なくすることにより、蒸留精製工程の効率を向上させることが高純度品の収量を増加させるために重要である。 In order to efficiently obtain the target product M4Q, the reaction yield is improved by reducing the residual amount of M3Q (OMe) and M3Q (OEt), which are reaction intermediates, the condensate of Q units, Reaction is achieved by reducing the by-product of the reaction product and high-boiling products ({(CH 3 ) 3 SiO} 3 SiOSi {OSi (CH 3 ) 3 } 3 etc.), which are condensates of tetraalkoxysilane as a starting material. It is necessary to improve the yield. Furthermore, improving the efficiency of the distillation purification process by reducing the residual amount of M3Q (OH), which is a by-product with a boiling point closer to the target product, is important for increasing the yield of high-purity products. is there.
この不純物のリテンションタイムは、島津製ガスクロマトグラフィー装置ＧＣ１４Ｂを用い、カラム充填剤として商品名ＳＥ３０、液相３％品、カラム内径５ｍｍ、長さ３ｍ、検出器ＴＣＤ、インジェクション温度８０℃、８０℃での保持時間１分、昇温速度１５℃／分、最終温度３００℃で分析したとき、Ｍ３Ｑ（ＯＭｅ）が６．２分、Ｍ３Ｑ（ＯＥｔ）が６．３分、Ｍ３Ｑ（ＯＨ）が６．６分、Ｍ４Ｑが７．５分、高沸点成分は１０．５分〜１３．０分の間に数本検出される。これらの反応中間体、及びＭ３Ｑ（ＯＨ）と目的物であるＭ４Ｑのリテンションタイムがこのように非常に近いことから、これら成分の生成量が蒸留精製工程の効率を左右することになる。 The retention time of this impurity is a Shimadzu gas chromatography device GC14B, with a column name of SE30, a 3% liquid phase product, a column inner diameter of 5 mm, a length of 3 m, a detector TCD, an injection temperature of 80 ° C., 80 ° C. Analysis at a retention time of 1 minute, a heating rate of 15 ° C./minute, and a final temperature of 300 ° C., M3Q (OMe) is 6.2 minutes, M3Q (OEt) is 6.3 minutes, and M3Q (OH) is 6 .6 minutes, M4Q is 7.5 minutes, and several high-boiling components are detected between 10.5 minutes and 13.0 minutes. Since the retention times of these reaction intermediates and M3Q (OH) and the target product M4Q are very close in this way, the amount of these components produced determines the efficiency of the distillation purification process.
以上の様に、分岐状テトラシロキサンを収率良く製造する方法、特に高純度なＭ４Ｑを効率良く製造する方法は知られていなかった。本発明は、上記事情に鑑みなされたもので、分岐状ペンタシロキサン、特にテトラキストリメチルシロキシシランを効率的かつ高収率で得ることのできる製造方法を提供することを目的とする。 As described above, a method for producing branched tetrasiloxane with good yield, particularly a method for producing high-purity M4Q efficiently has not been known. This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method which can obtain branched pentasiloxane, especially tetrakis trimethylsiloxysilane in an efficient and high yield.
本発明者は、上記目的を達成するために鋭意検討を行った結果、ヘキサメチルジシロキサン、及び必要に応じて低級アルコールとの混合液中に強酸触媒を添加し、次いでテトラアルコキシシランを加え、冷却しながら水を加えて共加水分解を行ない、さらに加熱し、得られた反応物を蒸留精製することによって高純度のＭ４Ｑが高収率で得られる事を見出し、本発明に至ったものである。 As a result of intensive studies to achieve the above object, the present inventor added a strong acid catalyst in a mixed solution with hexamethyldisiloxane and, if necessary, a lower alcohol, and then added tetraalkoxysilane, It was found that high purity M4Q can be obtained in high yield by adding water while cooling, co-hydrolyzing, further heating, and purifying the resulting reaction product by distillation. is there.
本発明のＭ４Ｑ製造方法は、反応中間体であるアルコキシ体（Ｍ３Ｑ（ＯＭｅ）、Ｍ３Ｑ（ＯＥｔ）等）、及びＱ単位の２量体、３量体である高沸点物の生成量が少なくＭ４Ｑの生成収率が高いだけではなく、Ｍ３Ｑ（ＯＨ）生成量も少ないことから蒸留精製によるＭ４Ｑの高純度化が容易であり、効率よくＭ４Ｑを製造することが可能である。 The M4Q production method of the present invention has a low production amount of a high-boiling product that is an alkoxy compound (M3Q (OMe), M3Q (OEt), etc.) that is a reaction intermediate and a Q-unit dimer or trimer. In addition to the high production yield of M3Q, the amount of M3Q (OH) produced is small, so that M4Q can be easily purified by distillation purification, and M4Q can be produced efficiently.
以下、本発明について詳細に説明する。
本発明の分岐状テトラシロキサン類の製造方法は、下記一般式（１）で示されるテトラアルコキシシラン（Ｒは炭素数２〜１０の１価炭化水素基）と下記式（２）で示されるヘキサメチルジシロキサンを加水分解縮合反応させることを特徴とする下記式（３）で示される分岐状ペンタシロキサンの製造方法において、下記一般式（１）で示されるテトラアルコキシシラン１モルに対して、式（２）で示されるヘキサメチルジシロキサン２．０〜１０．０モル、酸触媒０．０１〜０．５モル、水２．５〜１０．０モルを用い、上記水を、テトラアルコキシシラン、ヘキサメチルジシロキサンおよび酸触媒から成る混合物に、混合物の温度（内温と言う場合がある）を０〜３０℃未満に維持しながら３０分間〜５時間にわたって添加し、水の添加終了後に混合物の温度を３０〜１００℃で３０分間〜５時間維持することを特徴とする分岐状ペンタシロキサンの製造方法である。
Ｓｉ（ＯＲ）４ （１）
（ＣＨ３）３ＳｉＯＳｉ（ＣＨ３）３ （２）
Ｓｉ｛ＯＳｉ（ＣＨ３）３｝４ （３）
Hereinafter, the present invention will be described in detail.
The branched tetrasiloxanes according to the present invention are produced by a tetraalkoxysilane (R is a monovalent hydrocarbon group having 2 to 10 carbon atoms) represented by the following general formula (1) and a hexagonal compound represented by the following formula (2). In the method for producing a branched pentasiloxane represented by the following formula (3), wherein methyldisiloxane is subjected to a hydrolytic condensation reaction, with respect to 1 mol of tetraalkoxysilane represented by the following general formula (1), the formula hexamethyldisiloxane 2.0-10.0 mole of the formula (2), the acid catalyst 0.01-0.5 mol, with water 2.5 to 10.0 moles, the water, tetraalkoxysilane, a mixture consisting of hexamethyldisiloxane and an acid catalyst, the temperature of the mixture (sometimes referred to as internal temperature) was added over 30 minutes between 5 hours while maintained below 0 to 30 ° C., the addition of water A method for producing branched pentasiloxane, characterized by maintaining the temperature of the mixture After the completion at 30 to 100 ° C. 30 minutes between 5 hours.
Si (OR) 4 (1)
(CH 3 ) 3 SiOSi (CH 3 ) 3 (2)
Si {OSi (CH 3 ) 3 } 4 (3)
ここで、Ｒは炭素数２〜１０の１価炭化水素基であり、Ｒの具体例はエチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ヘキシル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基を挙げることができるが、Ｒは互いに同一であっても異なっていてもよい。これらの中でも、特にエチル基ないしイソプロピル基が好ましい。 Here, R is a monovalent hydrocarbon group having 2 to 10 carbon atoms, and specific examples of R are ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- Examples thereof include a butyl group, an n-hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group, and R may be the same as or different from each other. Among these, an ethyl group or an isopropyl group is particularly preferable.
さらには、製造工程が、下記（Ａ）〜（Ｄ）からなることを特徴とする。
（Ａ）ヘキサメチルジシロキサン２．０〜１０．０モルと、必要に応じて炭素数１〜６の１価低級アルコール０．５〜１０．０モルと、酸触媒０．０１〜０．５モルを混合し、０〜３０℃未満に冷却する工程。
（Ｂ）上記の系に一般式（１）のテトラアルコキシシラン１．０モルを加える工程。
（Ｃ）内温を０〜３０℃未満に維持しながら、水２．５〜１０．０モルを加える工程。
（Ｄ）内温が３０〜１００℃となるように加熱する工程。
Furthermore, the manufacturing process is characterized by comprising the following (A) to (D).
(A) Hexamethyldisiloxane 2.0-10.0 mol, and optionally C1-C6 monovalent lower alcohol 0.5-10.0 mol, acid catalyst 0.01-0.5 The process of mixing moles and cooling to 0-30 degrees C or less.
(B) A step of adding 1.0 mol of tetraalkoxysilane of the general formula (1) to the above system.
(C) A step of adding 2.5 to 10.0 moles of water while maintaining the internal temperature below 0 to 30 ° C.
(D) The process of heating so that internal temperature may be 30-100 degreeC.
または、化学式Ｓｉ（ＯＣＨ３）４で示されるテトラメトキシシランと上記式（２）で示されるヘキサメチルジシロキサンを加水分解縮合反応させることを特徴とする上記式（３）で示される分岐状ペンタシロキサンの製造方法において、テトラメトキシシラン１モルに対して、式（２）で示されるヘキサメチルジシロキサン２．０〜１０．０モル、メタノール、エタノール、イソプロパノールから選択されるアルコール１．０〜５．０モル、酸触媒０．０１〜０．５モル、水２．５〜１０．０モルを用い、上記水を、テトラメトキシシラン、ヘキサメチルジシロキサンおよび酸触媒から成る混合物に、混合物の温度を０〜３０℃未満に維持しながら３０分間〜５時間にわたって添加し、上記アルコールは上記混合物中に存在しまたは上記水と共に添加され、水の添加終了後に混合物の温度を３０〜１００℃で３０分間〜５時間維持することを特徴とする分岐状ペンタシロキサンの製造方法を提供するものである。 Alternatively, a branched pentamer represented by the above formula (3), wherein a tetramethoxysilane represented by the chemical formula Si (OCH 3 ) 4 and a hexamethyldisiloxane represented by the above formula (2) are subjected to a hydrolytic condensation reaction. In the method for producing siloxane, 1.0 to 5 alcohol selected from 2.0 to 10.0 mol of hexamethyldisiloxane represented by the formula (2), methanol, ethanol and isopropanol with respect to 1 mol of tetramethoxysilane. 2.0 mole, the acid catalyst 0.01-0.5 mol, with water 2.5 to 10.0 moles, the water, tetramethoxysilane, a mixture consisting of hexamethyldisiloxane and an acid catalyst, the temperature of the mixture was added over 30 minutes between 5 hours while maintained below 0 to 30 ° C., the alcohol is present in said mixture or said Added with, there is provided a method for producing branched pentasiloxane, it characterized in that the temperature of the mixture after completion of the addition of water to maintain at 30 to 100 ° C. 30 minutes between 5 hours.
かかる製造工程が、下記（Ａ′）〜（Ｄ′）からなることを特徴とする。
（Ａ′）ヘキサメチルジシロキサン２．０〜１０．０モルと、メタノール、エタノール、イソプロパノールから選択されるアルコール１．０〜５．０モルと、酸触媒０．０１〜０．５モルを混合し、０〜３０℃未満に冷却する工程。
（Ｂ′）上記の系にテトラメトキシシラン１．０モルを加える工程。
（Ｃ′）内温を０〜３０℃未満に維持しながら、水２．５〜１０．０モルを加える工程。
（Ｄ′）内温が３０〜１００℃となるように加熱する工程。
This manufacturing process is characterized by comprising the following (A ′) to (D ′).
(A ') Mixing 2.0 to 10.0 mol of hexamethyldisiloxane, 1.0 to 5.0 mol of alcohol selected from methanol, ethanol and isopropanol, and 0.01 to 0.5 mol of acid catalyst And cooling to 0 to less than 30 ° C.
(B ') A step of adding 1.0 mol of tetramethoxysilane to the above system.
(C ′) A step of adding 2.5 to 10.0 moles of water while maintaining the internal temperature below 0 to 30 ° C.
(D ') The process of heating so that internal temperature may be 30-100 degreeC.
これらのテトラアルコキシシランは、常法により合成したものを精製して用いる事ができるが、テトラクロロシランとアルコールとから脱塩酸反応により合成した反応液を精製することなく用いることができる。 These tetraalkoxysilanes can be used by purifying those synthesized by a conventional method, but can be used without purifying a reaction solution synthesized by dehydrochlorination from tetrachlorosilane and alcohol.
テトラクロロシランとアルコールから脱塩酸反応により得られる未精製のテトラアルコキシシランは、一般に高純度であり、不純物としてアルコールと少量にジシロキサンを含有する。本反応に用いる未精製のテトラアルコキシシランの純度が５０％以上であれば問題ないが、８０％以上の純度である事が好ましく、特に好ましくは９０％以上の純度であることが望ましい。 Unpurified tetraalkoxysilane obtained by dehydrochlorination from tetrachlorosilane and alcohol is generally of high purity and contains alcohol and a small amount of disiloxane as impurities. There is no problem if the purity of the unpurified tetraalkoxysilane used in this reaction is 50% or more, but it is preferably 80% or more, and particularly preferably 90% or more.
（１）のテトラアルコキシシラン１．０モルに対してヘキサメチルジシロキサン２．０〜１０．０モルを用いることが好ましい。２．０モル未満だと反応中間体であるアルコキシ体（Ｍ３Ｑ（ＯＭｅ）、Ｍ３Ｑ（ＯＥｔ）等）の残存量が増加するため反応収率が低下し、１０．０モルを越えても収率の向上は期待できず、ポットイールドが低下してしまう。好ましくは２．５〜５．０モルである。 It is preferable to use 2.0 to 10.0 moles of hexamethyldisiloxane with respect to 1.0 mole of tetraalkoxysilane of (1). If the amount is less than 2.0 mol, the residual amount of the alkoxy intermediate (M3Q (OMe), M3Q (OEt), etc.), which is a reaction intermediate, increases, so that the reaction yield decreases. The improvement of this cannot be expected, and the pot yield will decrease. Preferably it is 2.5-5.0 mol.
本発明で反応溶媒として用いられるアルコールは炭素数１〜６の１価低級アルコールであり、具体例としてメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ペンタノール、ヘキサノールが挙げられるが、好ましくはメタノール、エタノール、イソプロパノールである。 The alcohol used as a reaction solvent in the present invention is a monovalent lower alcohol having 1 to 6 carbon atoms, and specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, and hexanol. Is preferably methanol, ethanol or isopropanol.
本発明で用いるアルコールの使用量は、（１）のテトラアルコキシシラン１．０モルに対して０．５〜１０．０モルである。０．５モル未満であると加水分解反応に必要な水の分散性が不足し、反応中間体の残存量増加や高沸点物の生成量が増加するため、収率が低下する。１０．０モルを越えるとポットイールドが低下してしまう。特に好ましくは１．０〜５．０モルである。 The usage-amount of the alcohol used by this invention is 0.5-10.0 mol with respect to 1.0 mol of tetraalkoxysilane of (1). If the amount is less than 0.5 mol, the dispersibility of water required for the hydrolysis reaction is insufficient, and the yield of the reaction intermediate is increased and the amount of high-boiling products generated is increased. If it exceeds 10.0 moles, the pot yield will decrease. Most preferably, it is 1.0-5.0 mol.
（１）のテトラアルコキシシランにおけるＲがメチル基を除くシラン、特にテトラエトキシシラン、テトライソプロポキシシランである場合、加水分解反応の進行と共にエタノール、あるいはプロパノールが副生し、水とアルコキシシランとの分散性が良くなるため、溶剤としてのアルコールを使用しなくても良い。ポット収率の点から、アルコールを必要としない合成方法が特に好ましい。 When R in the tetraalkoxysilane of (1) is a silane excluding a methyl group, particularly tetraethoxysilane or tetraisopropoxysilane, ethanol or propanol is by-produced as the hydrolysis reaction proceeds, and water and alkoxysilane Since dispersibility is improved, it is not necessary to use alcohol as a solvent. From the viewpoint of pot yield, a synthesis method that does not require alcohol is particularly preferred.
本発明で用いられる酸触媒としては、硫酸、塩酸、メタンスルホン酸、トリフルオロメタンスルホン酸などが挙げられる。特に、硫酸、トリフルオロメタンスルホン酸を用いることが好ましい。 Examples of the acid catalyst used in the present invention include sulfuric acid, hydrochloric acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like. In particular, it is preferable to use sulfuric acid or trifluoromethanesulfonic acid.
本発明で用いる酸触媒の使用量は、テトラアルコキシシラン１モルに対して０．０１〜０．５モル用いることが好ましく、更に好ましくは０．０２〜０．４モル用いることが望ましい。０．０１モル未満であると反応速度が遅くなるため反応時間が長くなり、０．５モルを越えると高沸点物の生成量が増加するため、収率が低下する。 The amount of the acid catalyst used in the present invention is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.4 mol, relative to 1 mol of tetraalkoxysilane. If the amount is less than 0.01 mol, the reaction rate becomes slow and the reaction time becomes longer. If the amount exceeds 0.5 mol, the yield of high-boiling substances increases and the yield decreases.
本反応で用いる水は、水単独で用いる事ができるが、アルコールを添加した水を用いることもできる。水にアルコールを添加する場合のアルコールとしては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノールなどが挙げられる。また、アルコールの合計使用量は先に述べたモル比の範囲内である。 The water used in this reaction can be used alone, but water to which an alcohol is added can also be used. Examples of alcohol when adding alcohol to water include methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol. The total amount of alcohol used is within the range of the molar ratio described above.
水の使用量は、テトラアルコキシシラン１モルに対して２．５〜１０．０モルを用いることが好ましい。２．５モル未満であると反応中間体であるＭ３Ｑ（ＯＲ）の残留量が増加するため収率が低下し、１０．０モルを越えても収率の向上は期待できず、ポットイールドが低下してしまう。好ましくは３．０〜８．０モルである。 As for the usage-amount of water, it is preferable to use 2.5-10.0 mol with respect to 1 mol of tetraalkoxysilane. If the amount is less than 2.5 mol, the residual amount of the reaction intermediate M3Q (OR) increases, so the yield decreases. Even if the amount exceeds 10.0 mol, no improvement in yield can be expected. It will decline. Preferably it is 3.0-8.0 mol.
本反応は、先ずヘキサメチルジシロキサンと必要に応じてアルコールを混合し、さらに酸触媒とテトラアルコキシシラン類を混合する。ヘキサメチルジシロキサン、アルコール、酸触媒、テトラアルコキシシランは同時に混合しても良いが、水を加える前に内温を０〜３０℃未満、好ましくは０〜２５℃、特に好ましくは０〜１５℃に冷却することが好ましい。内温が０℃未満で水を添加すると反応速度が遅くなるため反応時間が長くなりすぎ、３０℃を越えた状態で水を添加すると目的物の収率が低下してしまうため好ましくない。 In this reaction, first, hexamethyldisiloxane and an alcohol as necessary are mixed, and then an acid catalyst and tetraalkoxysilanes are mixed. Hexamethyldisiloxane, alcohol, acid catalyst, and tetraalkoxysilane may be mixed at the same time, but before adding water, the internal temperature is 0 to less than 30 ° C, preferably 0 to 25 ° C, particularly preferably 0 to 15 ° C. It is preferable to cool it. If water is added at an internal temperature of less than 0 ° C., the reaction rate is slowed down, so that the reaction time becomes too long. If water is added at a temperature exceeding 30 ° C., the yield of the target product is lowered, which is not preferable.
目的物の生成収率をより向上させるためにはヘキサメチルジシロキサンと必要に応じてアルコールを混合し、０〜３０℃未満とする。好ましくは０〜２５℃、特に好ましくは０〜１５℃とする。これに内温が３０℃を越えないように、好ましくは２５℃を越えないように、特に好ましくは１５℃を越えないように酸触媒を添加し、その温度で１０分〜１時間撹拌する。次いでテトラアルコキシシランを内温が０〜３０℃未満を保つ速度で、好ましくは０〜２５℃を保つ速度で、特に好ましくは０〜１５℃を保つ速度で添加し、その温度で１０分〜１時間撹拌してから水を添加することが好ましい。 In order to further improve the yield of the target product, hexamethyldisiloxane is mixed with alcohol as necessary to make the temperature 0 to less than 30 ° C. Preferably it is 0-25 degreeC, Most preferably, you may be 0-15 degreeC. An acid catalyst is added thereto so that the internal temperature does not exceed 30 ° C, preferably does not exceed 25 ° C, and particularly preferably does not exceed 15 ° C, and the mixture is stirred at that temperature for 10 minutes to 1 hour. Then, tetraalkoxysilane is added at a rate that keeps the internal temperature below 0 to 30 ° C, preferably at a rate that keeps 0 to 25 ° C, and particularly preferably at a rate that keeps 0 to 15 ° C. It is preferred to add water after stirring for a period of time.
本反応は更に水を加えて加水分解を行うが、水を加えると発熱するため、内温が０〜３０℃未満を維持するように冷却しながら加えることが良い。水を添加する際に内温が０℃未満となると反応速度が遅くなるために反応時間が長くなりすぎ、３０℃を越えると目的物の収率が低下してしまう。好ましくは０〜２５℃を維持するように添加することであり、特に好ましくは０〜１５℃を維持するように添加する。水の添加が終了してからは、さらに０〜３０℃で１０分〜５時間撹拌を続けることが好ましい。 This reaction is further hydrolyzed by adding water, but when water is added, heat is generated. Therefore, it is preferable to add while cooling so that the internal temperature is maintained at 0 to less than 30 ° C. When water is added, if the internal temperature is less than 0 ° C., the reaction rate becomes slow, so that the reaction time becomes too long, and if it exceeds 30 ° C., the yield of the target product is lowered. Preferably it is adding so that 0-25 degreeC may be maintained, Especially preferably, it adding so that 0-15 degreeC may be maintained. It is preferable to continue stirring at 0 to 30 ° C. for 10 minutes to 5 hours after the addition of water is completed.
本反応は更に内温を３０〜１００℃、好ましくは４０〜８０℃となるよう加熱し、３０分〜５時間、好ましくは１時間〜３時間撹拌を続けることが好ましい。こうすることによって反応中間体であるアルコキシ体（Ｍ３Ｑ（ＯＭｅ）、Ｍ３Ｑ（ＯＥｔ）等）とＭ３Ｑ（ＯＨ）の残留量が低下し、目的物であるＭ４Ｑの収率が向上する。 In this reaction, the internal temperature is further heated to 30 to 100 ° C., preferably 40 to 80 ° C., and stirring is preferably continued for 30 minutes to 5 hours, preferably 1 hour to 3 hours. By doing so, the residual amounts of the alkoxy intermediates (M3Q (OMe), M3Q (OEt), etc.) and M3Q (OH) which are reaction intermediates are reduced, and the yield of M4Q which is the target product is improved.
本発明の方法では、反応後に分液により水層を分離、有機層を重曹水などの塩基水溶液で中和を行う事が好ましい。更に洗液が中性となるまで有機層を水洗し、蒸留精製を行う。また、水洗後の反応液を無水硫酸ナトリウムや塩化カルシウムなどの乾燥剤を加えて脱水した後に、蒸留精製しても良い。 In the method of the present invention, the aqueous layer is preferably separated by liquid separation after the reaction, and the organic layer is preferably neutralized with a basic aqueous solution such as sodium bicarbonate water. Further, the organic layer is washed with water until the washing solution becomes neutral and purified by distillation. Alternatively, the reaction solution after washing with water may be dehydrated by adding a desiccant such as anhydrous sodium sulfate or calcium chloride, and then purified by distillation.
以下、本発明を実施例、比較例によって具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to a following example.
［実施例１〜６及び比較例１〜２］
表−１の仕込み物に示される仕込み量（上段はｇ数、下段のかっこ内はモル数を示す）にて、下記工程１〜６に従って加水分解反応を行いＭ４Ｑを得た。
[Examples 1-6 and Comparative Examples 1-2]
Hydrolysis reaction was carried out according to the following steps 1 to 6 to obtain M4Q with the amount of charge shown in the charge of Table-1 (the upper part indicates the number of g, and the lower part of the parenthesis indicates the number of moles).
（工程１）１０００ｍｌの４つ口ガラスフラスコに還流冷却器、温度計、及び攪拌機を取り付け、内部を窒素置換した。このフラスコに、ヘキサメチルジシロキサンとアルコールを仕込み、氷水浴で冷却し内温を１０℃とした。
（工程２）ここに、酸触媒を内温１０℃に保って３０分で滴下し、そのまま１０℃の温度で３０分間撹拌した。
（工程３）続いて、アルコキシシランを内温１０℃に保って４５分で滴下し、そのままの温度で１時間撹拌した。
（工程４）水を内温１０℃に保って１時間かけて滴下した。滴下終了後、更に５〜２５℃で１時間撹拌した。
（工程５）内温が５０℃になるよう加熱し、２時間撹拌した。
（工程６）得られた反応液を分液して水層を分離した後、有機層を重曹水、ついで水により洗浄した。
(Step 1) A 1000 ml four-necked glass flask was equipped with a reflux condenser, a thermometer, and a stirrer, and the interior was purged with nitrogen. The flask was charged with hexamethyldisiloxane and alcohol and cooled in an ice-water bath to adjust the internal temperature to 10 ° C.
(Step 2) The acid catalyst was added dropwise in 30 minutes while maintaining the internal temperature at 10 ° C., and the mixture was stirred as it was at 10 ° C. for 30 minutes.
(Step 3) Subsequently, the alkoxysilane was added dropwise in 45 minutes while maintaining the internal temperature at 10 ° C., and the mixture was stirred at that temperature for 1 hour.
(Step 4) Water was added dropwise over 1 hour while maintaining the internal temperature at 10 ° C. After completion of dropping, the mixture was further stirred at 5 to 25 ° C. for 1 hour.
(Step 5) The inner temperature was heated to 50 ° C. and stirred for 2 hours.
(Step 6) After separating the obtained reaction liquid and separating the aqueous layer, the organic layer was washed with an aqueous sodium bicarbonate solution and then with water.
上記した実施例１〜６，比較例１〜２により得られた有機層をガスクロマトグラフィー分析し、その結果を表１のＧＣ分析結果１に示す。 The organic layers obtained in Examples 1 to 6 and Comparative Examples 1 and 2 described above were subjected to gas chromatography analysis, and the results are shown in GC analysis result 1 in Table 1.
得られた有機層を蒸留して沸点８９．５〜９０．０℃／１．３ｋＰａの留分を取り出した。留分の収量及び収率とポットイールドは表１に示す。収率は目的物であるＭ４Ｑと、反応に使用したテトラアルコキシシランのモル比率から求めた。得られた留分をガスクロマトグラフィー分析し、その結果を表−１のＧＣ分析結果２に示す。純度９９．５％以上のテトラキストリメチルシロキシシラン（Ｍ４Ｑ）を得た。実施例に比べて比較例では収率もポットイールドも悪いことがわかる。 The obtained organic layer was distilled and a fraction having a boiling point of 89.5 to 90.0 ° C./1.3 kPa was taken out. The yield, yield and pot yield of the fraction are shown in Table 1. The yield was determined from the molar ratio of the target product, M4Q, and the tetraalkoxysilane used in the reaction. The obtained fraction was subjected to gas chromatography analysis, and the result is shown in GC analysis result 2 of Table-1. Tetrakistrimethylsiloxysilane (M4Q) having a purity of 99.5% or more was obtained. It can be seen that the yield and pot yield of the comparative example are worse than those of the example.
ガスクロマトグラフィー分析条件は、使用装置が島津製ＧＣ１４Ｂ、カラム充填剤は商品名ＳＥ３０、液相３％品、カラム内径５ｍｍ、長さ３ｍ、検出器はＴＣＤ、カラムインジェクション温度８０℃、８０℃での保持時間１分、昇温速度１５℃／分、最終温度３００℃で行った。また、蒸留装置は充填剤マクマホンを用い、内径２．５ｃｍ、長さ７０ｃｍの蒸留塔を使用した。不純物、及び目的物の同定は、マススペクトルとＮＭＲ分析で行った。 Gas chromatographic analysis conditions are as follows: GC14B manufactured by Shimadzu, column name: SE30, 3% liquid phase, column inner diameter 5 mm, length 3 m, detector TCD, column injection temperature 80 ° C., 80 ° C. The holding time was 1 minute, the heating rate was 15 ° C./minute, and the final temperature was 300 ° C. The distillation apparatus used was a McMahon filler, and a distillation tower having an inner diameter of 2.5 cm and a length of 70 cm was used. The impurities and the target product were identified by mass spectrum and NMR analysis.
［比較例３］
反応溶媒としてメタノールを使用せず、工程５の加熱撹拌工程を省き、工程４の水添加終了後に１０℃で３時間撹拌した以外は実施例１と同様に実施した。
[Comparative Example 3]
Methanol was not used as the reaction solvent, the heating and stirring step in Step 5 was omitted, and the same procedure was performed as in Example 1 except that the stirring was performed at 10 ° C. for 3 hours after the addition of water in Step 4.
［比較例４］
工程５の加熱撹拌工程を除き、工程４の水添加終了後に１０℃で３時間撹拌した以外は実施例１と同様に実施した。
[Comparative Example 4]
Except for the heating and stirring step in Step 5, the procedure was the same as that in Example 1 except that stirring was performed at 10 ° C. for 3 hours after the completion of water addition in Step 4.
［比較例５］
ヘキサメチルジシロキサン１９４４ｇ（１２．０モル）を用いた以外は実施例１と同様に実施した。
[Comparative Example 5]
The same procedure as in Example 1 was carried out except that 1944 g (12.0 mol) of hexamethyldisiloxane was used.
［比較例６］
水３６０ｇ（２０．０モル）を用いた以外は実施例１と同様に実施した。
[Comparative Example 6]
The same procedure as in Example 1 was performed except that 360 g (20.0 mol) of water was used.
［比較例７］
メタノール２５６ｇ（８．０モル）を用いた以外は実施例１と同様に実施した。
[Comparative Example 7]
The same operation as in Example 1 was carried out except that 256 g (8.0 mol) of methanol was used.
上記した比較例３〜７により得られた有機層をガスクロマトグラフィー分析し、その結果を表−２のＧＣ分析結果１に示す。 The organic layers obtained in Comparative Examples 3 to 7 described above were subjected to gas chromatography analysis, and the results are shown in GC analysis result 1 of Table-2.
得られた有機層を蒸留して沸点８９．５〜９０．０℃／１．３ｋＰａの留分を取り出した。留分の収量及び収率とポットイールドは表１に示す。さらに、得られた留分をガスクロマトグラフィー分析し、その結果を表１のＧＣ分析結果２に示す。いずれも収率またはポットイールドが良くないことがわかる。 The obtained organic layer was distilled and a fraction having a boiling point of 89.5 to 90.0 ° C./1.3 kPa was taken out. The yield, yield and pot yield of the fraction are shown in Table 1. Furthermore, the obtained fraction was subjected to gas chromatography analysis, and the results are shown in GC analysis result 2 in Table 1. It turns out that neither yield nor pot yield is good.
ここで、略号は下記の構造を示す。
Ｍ３Ｑ（ＯＭｅ）＝｛（ＣＨ３）３ＳｉＯ｝３ＳｉＯＣＨ３
Ｍ３Ｑ（ＯＥｔ）＝｛（ＣＨ３）３ＳｉＯ｝３ＳｉＯＣＨ２ＣＨ３
Ｍ３Ｑ（ＯＨ）＝｛（ＣＨ３）３ＳｉＯ｝３ＳｉＯＨ
Ｍ４Ｑ＝｛（ＣＨ３）３ＳｉＯ｝４Ｓｉ
Here, the abbreviations indicate the following structures.
M3Q (OMe) = {(CH 3 ) 3 SiO} 3 SiOCH 3
M3Q (OEt) = {(CH 3 ) 3 SiO} 3 SiOCH 2 CH 3
M3Q (OH) = {(CH 3 ) 3 SiO} 3 SiOH
M4Q = {(CH 3 ) 3 SiO} 4 Si
Claims (7)
Ｓｉ（ＯＲ）４ （１）
（ＣＨ３）３ＳｉＯＳｉ（ＣＨ３）３ （２）
Ｓｉ｛ＯＳｉ（ＣＨ３）３｝４ （３） A tetraalkoxysilane (R is a monovalent hydrocarbon group having 2 to 10 carbon atoms) represented by the following general formula (1) and a hexamethyldisiloxane represented by the following formula (2) are subjected to a hydrolytic condensation reaction. In the method for producing a branched pentasiloxane represented by the following formula (3), hexamethyldisiloxane 2.0 represented by the formula (2) is added to 1 mol of tetraalkoxysilane represented by the following general formula (1). 10.0 mol, acid catalyst 0.01-0.5 mol, with water 2.5 to 10.0 moles, the water, tetraalkoxysilane, a mixture consisting of hexamethyldisiloxane and an acid catalyst, a mixture JP that of was added over 30 minutes between 5 hours while maintained below 0 to 30 ° C. the temperature, the temperature of the mixture after completion of the addition of water to maintain at 30 to 100 ° C. for 30 minutes between 5 hours Method for producing a branched pentasiloxane to.
Si (OR) 4 (1)
(CH 3 ) 3 SiOSi (CH 3 ) 3 (2)
Si {OSi (CH 3 ) 3 } 4 (3)
（ＣＨ ３ ） ３ ＳｉＯＳｉ（ＣＨ ３ ） ３ （２）
Ｓｉ｛ＯＳｉ（ＣＨ ３ ） ３ ｝ ４ （３） Branched penta represented by the following following formula (3) for causing the formula Si (OCH 3) tetramethoxysilane and lower following formula represented by 4 hexamethyldisiloxane represented by (2) hydrolysis condensation reaction In the method for producing siloxane, 1.0 to 5 alcohol selected from 2.0 to 10.0 mol of hexamethyldisiloxane represented by the formula (2), methanol, ethanol and isopropanol with respect to 1 mol of tetramethoxysilane. 2.0 mole, the acid catalyst 0.01-0.5 mol, with water 2.5 to 10.0 moles, the water, tetramethoxysilane, a mixture consisting of hexamethyldisiloxane and an acid catalyst, the temperature of the mixture was added over 30 minutes between 5 hours while maintained below 0 to 30 ° C., the alcohol is present in said mixture or with the water Is pressurized, the manufacturing method of the branched pentasiloxane, characterized by maintaining the temperature of the mixture after completion of the addition of water at 30 to 100 ° C. 30 minutes between 5 hours.
(CH 3 ) 3 SiOSi (CH 3 ) 3 (2)
Si {OSi (CH 3 ) 3 } 4 (3)
（Ａ）ヘキサメチルジシロキサン２．０〜１０．０モルと、必要に応じて炭素数１〜６の１価低級アルコール０．５〜１０．０モルと、酸触媒０．０１〜０．５モルを混合し、０〜３０℃未満に冷却する工程。
（Ｂ）上記の系に一般式（１）のテトラアルコキシシラン１．０モルを加える工程。
（Ｃ）混合物の温度を０〜３０℃未満に維持しながら、水２．５〜１０．０モルを加える工程。
（Ｄ）混合物の温度が３０〜１００℃となるように加熱する工程。 The manufacturing method according to claim 1, wherein the manufacturing process includes the following (A) to (D).
(A) Hexamethyldisiloxane 2.0-10.0 mol, and optionally C1-C6 monovalent lower alcohol 0.5-10.0 mol, acid catalyst 0.01-0.5 The process of mixing moles and cooling to 0-30 degrees C or less.
(B) A step of adding 1.0 mol of tetraalkoxysilane of the general formula (1) to the above system.
(C) A step of adding 2.5 to 10.0 moles of water while maintaining the temperature of the mixture below 0 to 30 ° C.
(D) The process of heating so that the temperature of a mixture may be 30-100 degreeC.
（Ａ′）ヘキサメチルジシロキサン２．０〜１０．０モルと、メタノール、エタノール、イソプロパノールから選択されるアルコール１．０〜５．０モルと、酸触媒０．０１〜０．５モルを混合し、０〜３０℃未満に冷却する工程。
（Ｂ′）上記の系にテトラメトキシシラン１．０モルを加える工程。
（Ｃ′）混合物の温度を０〜３０℃未満に維持しながら、水２．５〜１０．０モルを加える工程。
（Ｄ′）混合物の温度が３０〜１００℃となるように加熱する工程。 The manufacturing method according to claim 2, wherein the manufacturing process comprises the following (A ') to (D').
(A ') Mixing 2.0 to 10.0 mol of hexamethyldisiloxane, 1.0 to 5.0 mol of alcohol selected from methanol, ethanol and isopropanol, and 0.01 to 0.5 mol of acid catalyst And cooling to 0 to less than 30 ° C.
(B ') A step of adding 1.0 mol of tetramethoxysilane to the above system.
(C ′) adding 2.5 to 10.0 moles of water while maintaining the temperature of the mixture below 0 to 30 ° C.
(D ') The process of heating so that the temperature of a mixture may be 30-100 degreeC.
The production method according to claim 1 or 3, wherein the tetraalkoxysilane of the general formula (1) is tetraethoxysilane and / or tetraisopropoxysilane.
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