CN1063872A - 合成1-三甲硅基丙炔的新方法 - Google Patents
合成1-三甲硅基丙炔的新方法 Download PDFInfo
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- propine
- trimethylsilyl
- acetylene
- tmsp
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 15
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000007069 methylation reaction Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 11
- 239000013067 intermediate product Substances 0.000 claims description 3
- 238000002444 silanisation Methods 0.000 claims description 2
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000005649 metathesis reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- DCGLONGLPGISNX-UHFFFAOYSA-N trimethyl(prop-1-ynyl)silane Chemical compound CC#C[Si](C)(C)C DCGLONGLPGISNX-UHFFFAOYSA-N 0.000 abstract description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 238000006884 silylation reaction Methods 0.000 abstract 1
- NONFLFDSOSZQHR-UHFFFAOYSA-N 3-(trimethylsilyl)propionic acid Chemical compound C[Si](C)(C)CCC(O)=O NONFLFDSOSZQHR-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- 101000738322 Homo sapiens Prothymosin alpha Proteins 0.000 description 10
- 102100033632 Tropomyosin alpha-1 chain Human genes 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
合成1-三甲硅基丙炔的新方法,本发明属取代
的不饱和烃合成的新工艺,以乙炔为原料,有选择的
使其一活泼氢原子发生格氏反应,再经硅烷化反应得
到1-三甲硅基乙炔,进而从后者出发再经过格氏反
应和甲基化反应得到1-三甲硅基丙炔。产品含六甲
基硅氧烷低于350ppm,纯度高于99.5%,满足了由
阳离子复分解催化聚合反应制高分子量聚1-三甲硅
基丙炔的纯度要求。
Description
合成1-三甲硅基丙炔的新方法,本发明属于取代的不饱和烃的合成工艺。
1-三甲硅基丙炔(Trimethylsilylpropyne,TMSP)沸点99-100℃/760毫米汞柱,是新一代富氧膜材料聚1-三甲硅基丙炔(Polytrimethylsilylpropyne,PTMSP)的单体,迄今,合成TMSP的方法基本有两种:一是炔锂烃化法,采用丙炔为原料,在己烷中与四丁基锂反应得到Li取代的丙炔,然后与(CH3)3SiCl反应得到1-三甲硅基丙炔(K.Takada等,J.Appl.Polym.Sci.,30,1605(1985);T.Kinoshita等,Polym.Preprints.JPn.,35,2170(1985));二是传统的格氏法,即丙炔与格氏试剂反应生成CH3C≡CMgBr,然后再与(CH3)3SiCl(Me3SiCl)反应生成1-三甲硅基丙炔。炔锂烃化法反应使用高浓度烷基锂,条件非常苛刻,操作困难,产品价格昂贵且纯属实验室法,不宜规模生产;而传统格氏法尽管可规模制备,但合成过程中由Me3SiCl水解付反应产生的六甲基硅氧烷(M2,沸点101℃/760毫米汞柱)的存在使产物TMSP无法用来进行阳离子复分解聚合反应而生成PTMSP气体膜材料,M2的沸点与TMSP的很接近,普通的精馏柱难以分离付产物M2,用化学法分离常常引入新的杂质。
本发明的目的是采用合适的工艺路线,廉价而便利地生产出含M2低且适合进行阳离子复分解催化聚合反应的TMSP。
本发明设计的工艺路线的巧妙之处就在于从廉价的乙炔出发,经格氏反应和硅烷化反应先制取中间产物三甲硅基乙炔(Trime-thylsilylacetylene,TMSA),它的沸点是52℃/760毫米汞柱,因此在这段反应里,即便生成M2,也容易由普通的柱分馏将其分离,所得较纯的TMSA既可直接用作单体供催化聚合或共聚合制备功能高分子,在本发明中,又可以以它为原料再经格氏反应和甲基化反应制备TMSP,最终产物的分离纯化已简化为TMSP与TMSA分离,由于两者之间沸点相差48℃,可由普通的分馏柱进行分离,从而保证了产品TMSP中很低的M2含量,同时未反应的TMSA可循环使用。
本发明由于设计了先合成中间产物TMSA,再合成TMSP的工艺路线因而它既适用于实验室合成高纯TMSP,又可满足规模生产高纯TMSP的工艺要求。
本发明较详细的描述是:以乙炔为原料,有选择地使其中一个活泼氢原子反应,合成出三甲硅基乙炔,然后再通过格氏反应和甲基化反应两步得到经普通柱分馏可除去付产物M2(含量低于350ppm),纯度高于99.5wt%的TMSP。
本发明由乙炔制取TMSP反应的示意式如下述:
反应(1)是在乙炔饱和的四氢呋喃(THF)中进行的,反应温度10-30℃,反应过程中一边滴加稍过量的C2H5MgBr(EtMgBr)的THF溶液,一边通入气体乙炔,滴完后,再滴加适量的Me3SiCl溶液进行反应(2),反应物室温放置过夜,然后以电解质溶液分开有机层,干燥后的有机层进行柱分离收集52℃/760毫米汞柱的馏分即得中间产物TMSA;在含有EtMgBr的无水THF溶液里,通过滴加等当量的TSMA进行反应(3),回流后,再滴加稍过量的(CH3O)2SO2,长时间回流,进行反应(4),然后加电解质水溶液分出有机层,干燥后分馏取99-100℃馏份即为高纯TMSP,产率60%。
按本发明工艺所得TMSP产品,经1H-NMR,13C-NMR和质谱分析证明,其结构组成与标准的TMSP一致。
由本发明方法制备的TMSP的纯度与聚合性能与文献比较见表1
表1 TMSP纯度与性能比较
项目 | 文献方法 | 本发明方法 |
TMSP含量(wt%) | 95.922 | 99.780 |
M2含量(wt%) | 3.840 | 0.032 |
其它杂质含量 | 0.239 | 0.187 |
聚合反应性能 | 不能进行 | 反应性能好可制得Mwt≥5×105的PTMSP |
本发明的实施例如下:
实施例1(1)1-三甲硅基乙炔(TMSA)的制备:
20℃下在300毫升无水THF溶液中通入乙炔至饱和,滴加0.63摩尔的EtMgBr的THF溶液,滴完后继续通乙炔半小时,然后滴加75毫升Me3SiCl(0.59摩尔),20℃下反应10小时,放置过夜,然后加电解质水溶液分出有机层,用无水Na2SO4干燥,分馏得TMSA,沸点52℃,产率50%;
(2)TMSP的制备:
20℃下在含有0.41摩尔EtMgBr的无水THF溶液里滴加等当量的TMSA,加完后回流1小时,滴加稍过量的(CH3O)2SO2,再回流10小时,回收未反应的TMSA重复使用,加电解质水溶液分出有机层,用无水Na2SO4干燥后分馏取99-100℃馏份为TMSP,产率60%。
实施例2,反应均在15℃下进行,其它操作同实施例1。
实施例3,反应均在30℃下进行,其他操作同实施例1。
实施例4,反应均在10℃下进行,其他操作同实施例1。
Claims (1)
1、合成1-三甲硅基丙炔的方法,本发明的特征在于以乙炔为原料,先经格氏反应和硅烷化反应制取中间产物1-三甲硅基乙炔,再由1-三甲硅基乙炔经格氏反应和甲基化反应制得1-三甲硅基丙炔,反应按下列步骤进行:
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CN 91100585 CN1031711C (zh) | 1991-01-28 | 1991-01-28 | 合成1-三甲硅基丙炔的新方法 |
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CN 91100585 CN1031711C (zh) | 1991-01-28 | 1991-01-28 | 合成1-三甲硅基丙炔的新方法 |
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CN1063872A true CN1063872A (zh) | 1992-08-26 |
CN1031711C CN1031711C (zh) | 1996-05-01 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101921286A (zh) * | 2009-06-15 | 2010-12-22 | 上海瑞一医药科技有限公司 | 一种三甲基硅乙炔的合成工艺 |
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1991
- 1991-01-28 CN CN 91100585 patent/CN1031711C/zh not_active Expired - Fee Related
Cited By (2)
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CN101921286A (zh) * | 2009-06-15 | 2010-12-22 | 上海瑞一医药科技有限公司 | 一种三甲基硅乙炔的合成工艺 |
CN101921286B (zh) * | 2009-06-15 | 2013-06-05 | 海门瑞一医药科技有限公司 | 一种三甲基硅乙炔的合成工艺 |
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CN1031711C (zh) | 1996-05-01 |
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