CN110114311A - 反式甲硅烷基化催化 - Google Patents
反式甲硅烷基化催化 Download PDFInfo
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- 238000006555 catalytic reaction Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
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- 125000000217 alkyl group Chemical group 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005052 trichlorosilane Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- HICCMIMHFYBSJX-UHFFFAOYSA-N [SiH4].[Cl] Chemical compound [SiH4].[Cl] HICCMIMHFYBSJX-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
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- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
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- RGIKPRJGZCEBJO-UHFFFAOYSA-N [(chlorosilylamino)-dimethylsilyl]methane Chemical compound C[Si](C)(C)N[SiH2]Cl RGIKPRJGZCEBJO-UHFFFAOYSA-N 0.000 description 2
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 2
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001928 direct liquid injection chemical vapour deposition Methods 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001289 rapid thermal chemical vapour deposition Methods 0.000 description 2
- 238000000663 remote plasma-enhanced chemical vapour deposition Methods 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 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
- 238000007740 vapor deposition Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000062 azane Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 238000002365 hybrid physical--chemical vapour deposition Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000000869 ion-assisted deposition Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 230000035935 pregnancy Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- -1 sulfonic acid acyl Imines Chemical class 0.000 description 1
- RJFSDTDWWBECIL-UHFFFAOYSA-N trifluoro(methyl)-$l^{4}-sulfane Chemical compound CS(F)(F)F RJFSDTDWWBECIL-UHFFFAOYSA-N 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10773—Halogenated silanes obtained by disproportionation and molecular rearrangement of halogenated silanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10778—Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- Engineering & Computer Science (AREA)
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Abstract
一种用于制造氯化硅氮烷的方法。所述方法包括使以下项接触：(a)二硅氮烷；(b)氯硅烷；以及(c)催化剂，所述催化剂为以下项的锌盐：(i)磺酸或(ii)磺酸酰亚胺。
Description
本发明涉及一种用于催化反式甲硅烷基化反应的方法。
已知通过氯化锌来催化反式甲硅烷基化反应，如在D.E.Spielvogel和C.L.Frye,J.Organometallic Chem.[有机金属化学期刊],1978(161)165-169中所报道的。然而，本文报道的催化剂是更有效的。
由本发明解决的问题是对附加的用于反式甲硅烷基化反应的催化剂的需求。
发明内容
本发明提供了一种用于制造氯化硅氮烷的方法。所述方法包括使以下项接触：(a)二硅氮烷；(b)氯硅烷；以及(c)催化剂，所述催化剂为以下项的锌盐：(i)磺酸或(ii)磺酸酰亚胺。
具体实施方式
百分比是重量百分比(wt％)并且温度以℃计，除非另有说明。在室温(20℃-25℃)下进行操作，除非另有说明。烃基是通过除去氢原子而衍生自C1-C20烃的取代基。优选地，烃基是直链的或支链的。烯基是具有至少一个碳-碳双键的烃基。优选地，烯基具有一个碳-碳双键。烷基是可以是直链的或支链的饱和C1-C20烃基。
优选地，二硅氮烷仅被烃基、氯基团或其组合取代。在优选的实施例中，二硅氮烷是全烃基二硅氮烷。优选地，烃基是C1-C10烃基，优选C1-C6、优选C1-C4、优选甲基或乙基、优选甲基。优选地，烃基是烷基或具有一个双键的烯基。特别优选的全烃基二硅氮烷包括六甲基二硅氮烷、1,1,1-三氯-3,3,3-三甲基二硅氮烷以及1,1,3,3-四甲基-1,3-二乙烯基硅氮烷。
优选地，氯硅烷是氯取代的甲硅烷或二硅烷。优选地，氯硅烷具有至少两个氯基团，优选至少三个。特别优选的氯硅烷包括二氯硅烷、三氯硅烷和四氯硅烷。
优选地，氯化硅氮烷产物具有4至6个氯基团。优选地，氯化硅氮烷产物是六氯二硅氮烷或1,1,3,3-四氯二硅氮烷。
优选地，催化剂是具有至少一个三氟甲基的磺酸或酰亚胺的锌盐。优选地，磺酸是芳香族磺酸、甲磺酸、三氟甲磺酸或HO3S(CF2)xCF3，其中x是1至10的整数。优选地，芳香族磺酸是对-甲苯磺酸。优选地，x是至少2、优选至少3；优选不超过9、优选不超过8、优选不超过7、优选不超过6、优选不超过5。
优选地，将反应物(a)、(b)以及(c)在20℃至150℃；优选至少40℃、优选至少50℃；优选不大于100℃、优选不大于80℃的温度下加热。优选地，加热时间是0.5至8小时、优选0.5至2小时。合适的加热时间可以基于装置、其他参数等容易地确定。优选地，氯化硅氮烷通过蒸馏纯化。优选地，使反应物在75至150kPa的压力下接触。蒸馏典型地是在低于大气压下进行。
优选地，反应物(a)、(b)以及(c)在基本上不存在除了反应物之外的溶剂的情况下组合，即(a)、(b)以及(c)的反应混合物包含不超过5wt％、优选不超过1wt％、优选不超过0.5wt％、优选不超过0.2wt％的溶剂。优选地，反应物(a)或者(b)与反应物(c)组合并且然后与反应物(a)和(b)的另一种组合。优选地，包含(a)、(b)以及(c)的反应混合物基本上不含有腈类溶剂，例如乙腈；即，它包含不超过3wt％、优选不超过0.5wt％、优选不超过0.2wt％、优选不超过0.1wt％的腈类溶剂。
可以使用氯化硅氮烷产物，通过已知技术，包括例如物理气相沉积、原子层沉积(ALD)、或化学气相沉积(CVD)来形成硅-杂原子膜。物理气相沉积方法可以包括溅射。合适的溅射方法包括直流(DC)磁控溅射、离子束溅射、反应溅射、以及离子辅助溅射。典型地，沉积方法包括ALD或CVD。优选地，杂原子选自碳、氧和氮。
合适的ALD方法包括等离子体增强原子层沉积方法(PEALD)、空间原子层沉积(SALD)以及热原子层沉积(TALD)方法。当采用PEALD方法时，等离子体可以是上述等离子体中的任一种。等离子体可以任选地进一步含有载气如分子氮或氩气。等离子体是从等离子体形成气体形成的，所述等离子体形成气体可以包含分子氮和分子氢的混合物。
合适的CVD方法包括简单热气相沉积、等离子体增强化学气相沉积(PECVD)、电子回旋共振(ECRCVD)、大气压化学气相沉积(APCVD)、低压化学气相沉积(LPCVD)、超高真空化学气相沉积(UHVCVD)、气溶胶辅助化学气相沉积(AACVD)、直接液体注入化学气相沉积(DLICVD)、微波等离子体辅助化学气相沉积(MPCVD)、远程等离子体增强化学气相沉积(RPECVD)、原子层化学气相沉积(ALCVD)、热丝化学气相沉积(HWCVD)、混合物理-化学气相沉积(HPCVD)、快速热化学气相沉积(RTCVD)、以及气相外延化学气相沉积(VPECVD)、光辅助化学气相沉积(PACVD)、以及火焰辅助化学气相沉积(FACVD)。
实例
实例1：1,1,3,3-四氯二硅氮烷的合成。
将5.00g三氯硅烷与0.17g三氟甲磺酸锌和10.75g乙腈混合，使大部分的三氟甲磺酸锌溶解。在2分钟内添加1.49g六甲基二硅氮烷。然后将溶液加热至回流(38.5℃)，当三氯硅烷被消耗时其温度缓慢增加。继续加热52分钟，其中其达到51.3℃。温度保持2分钟并且然后允许缓慢冷却6分钟。去除热源。粗材料的GC示出70％产率的TCDZ。
实例2：1,1,3,3-四氯二硅氮烷的纯化。
将粗1,1,3,3-四氯二硅氮烷通过15cm Vigreux柱蒸馏以得到96％的1,1,3,3-四氯二硅氮烷。
实例3：1,1,1,3,3,3-六氯二硅氮烷的合成。
将0.25g三氟甲磺酸锌溶解在5.00g乙腈中，这可能需要一段时间来完全溶解。然后将混合物添加至11.75g四氯化硅中并加热至回流溶液。为了回流溶液，在5分钟内添加5.00g的1,1,1-三氯-3,3,3-三甲基二硅氮烷(制品1)。使反应回流约5小时。粗物质的GC-TCD示出了得到47.5％产率的混合物。
实例4：1,1,1,3,3,3-六氯二硅氮烷的纯化
将来自实例3的混合物通过15cm Vigreux柱蒸馏以收集1.24g的95％六氯二硅氮烷(19.4％的分离产率)。
实例5：1,1,1,3,3,3-六氯二硅氮烷的合成。
将负载的3％三氟甲磺酸锌溶解在乙腈中以将反应混合物的总质量的3％给予到具有四氯化硅的压力反应器中。将反应器加热至140℃并且在5小时内进料六甲基二硅氮烷并且冷却至室温以在粗混合物中得到2.8％产率的1,1,1,3,3,3-六氯二硅氮烷。
Claims (9)
1.一种用于制造氯化硅氮烷的方法；所述方法包括使以下项接触：(a)二硅氮烷；(b)氯硅烷；以及(c)催化剂，所述催化剂为以下项的锌盐：(i)磺酸或(ii)磺酸酰亚胺。
2.如权利要求1所述的方法，其中，所述二硅氮烷仅被烃基、氯基团或其组合取代。
3.如权利要求2所述的方法，其中，所述烃基是C1-C10烃基。
4.如权利要求3所述的方法，其中，所述氯硅烷是氯取代的甲硅烷。
5.如权利要求4所述的方法，其中，所述氯硅烷是四氯硅烷、三氯硅烷或二氯硅烷。
6.如权利要求5所述的方法，其中，所述催化剂是具有至少一个三氟甲基的磺酸或酰亚胺的锌盐。
7.如权利要求6所述的方法，其中，使(a)、(b)以及(c)在20℃至150℃的温度下接触。
8.如权利要求7所述的方法，其中，所述烃基是C1-C4烃基。
9.如权利要求8所述的方法，其中，所述磺酸是芳香族磺酸、甲磺酸、三氟甲磺酸或HO3S(CF2)xCF3，其中x是1至10的整数。
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| EP3562781A1 (en) | 2019-11-06 |
| US11345604B2 (en) | 2022-05-31 |
| KR102359491B1 (ko) | 2022-02-07 |
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| TWI752130B (zh) | 2022-01-11 |
| WO2018125476A1 (en) | 2018-07-05 |
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