CN1317488A - Process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination - Google Patents
Process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination Download PDFInfo
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- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 26
- BWROMPNXPAWQEP-UHFFFAOYSA-N chloro(chloromethyl)silane Chemical compound ClC[SiH2]Cl BWROMPNXPAWQEP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 21
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 31
- 238000010992 reflux Methods 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 15
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- OOCUOKHIVGWCTJ-UHFFFAOYSA-N chloromethyl(trimethyl)silane Chemical group C[Si](C)(C)CCl OOCUOKHIVGWCTJ-UHFFFAOYSA-N 0.000 claims description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- JAYBZWYBCUJLNQ-UHFFFAOYSA-N dichloro-(chloromethyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCl JAYBZWYBCUJLNQ-UHFFFAOYSA-N 0.000 claims description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 210000003298 dental enamel Anatomy 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- PAJFATIYVLZNFC-UHFFFAOYSA-N chloromethyl(dimethyl)silicon Chemical compound C[Si](C)CCl PAJFATIYVLZNFC-UHFFFAOYSA-N 0.000 claims 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims 1
- 239000005052 trichlorosilane Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000012071 phase Substances 0.000 description 38
- 239000000047 product Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- -1 methyl bromide Grignard reagent Chemical class 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
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GGNALUCSASGNCK-UHFFFAOYSA-N carbon dioxide;propan-2-ol Chemical compound O=C=O.CC(C)O GGNALUCSASGNCK-UHFFFAOYSA-N 0.000 description 1
- ZCJSXNPBZLWTCC-UHFFFAOYSA-N chloro-(chloromethyl)-methylsilane Chemical compound C[SiH](Cl)CCl ZCJSXNPBZLWTCC-UHFFFAOYSA-N 0.000 description 1
- BHLKIZCNPYDMOY-UHFFFAOYSA-N chloromethyl(dimethyl)silane Chemical compound C[SiH](C)CCl BHLKIZCNPYDMOY-UHFFFAOYSA-N 0.000 description 1
- WIAGUYRDWNBPDR-UHFFFAOYSA-N chloromethyl(methyl)silane Chemical compound C[SiH2]CCl WIAGUYRDWNBPDR-UHFFFAOYSA-N 0.000 description 1
- AZFVLHQDIIJLJG-UHFFFAOYSA-N chloromethylsilane Chemical compound [SiH3]CCl AZFVLHQDIIJLJG-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N methyl bromide Substances BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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Abstract
Description
本发明涉及有机硅试剂的制备方法，具体地说，它是以分子式为CH3Si(CH3)mCl3-m,m=0-2的甲基氯硅烷为原料，在不需要任何特殊紫外光源条件下，仅依靠室内一般可见光照射进行的气相氯化反应，从而得到较高产率的分子式为ClCH2Si(CH3)mCl3-m,m=0-2的多氯甲基氯硅烷的方法和装置，属有机合成范畴。The present invention relates to a preparation method of organosilicon reagent, specifically, it uses methylchlorosilane with molecular formula CH 3 Si(CH 3 ) m Cl 3-m , m=0-2 as raw material, without any special Under the condition of ultraviolet light source, the gas-phase chlorination reaction carried out only by indoor general visible light irradiation can obtain polychloromethylchlorosilane with the molecular formula of ClCH 2 Si(CH 3 )mCl 3-m , m=0-2 in higher yield The method and device belong to the category of organic synthesis.
氯甲基硅烷(ClCH2Si(CH3)pCl3-p，P=0-3)是一系列非常重要的有机硅试剂，被广泛用在农药、医药以及有机合成等领域。Chloromethylsilane (ClCH 2 Si(CH 3 )pCl 3-p , P=0-3) is a series of very important organosilicon reagents, which are widely used in the fields of pesticide, medicine and organic synthesis.
有关氯甲基氯硅烷(ClCH2Si(CH3)mCl3-m,m=0-2)的制备最早是由Gilliam等人〖W.F.Gilliam,H.A.Liebhafsky and A.F.Winslow,J.A.C.S.,1941,63,801；W.F.Gilliam and R.O.Sauer,ibid.,1944,66,1793〗通过紫外光照射下甲基氯硅烷(Si(CH3)pCl4-p,P=1-3)的液相氯化反应制备的，但结果不太理想，而且多氯代产物较多；1946年，Whitmore等人〖参见：Whitmore,Sommer,Am.Soc.68 p481-4831946〗曾试图参照上述方法，首次以四氯化碳为溶剂、四甲基硅烷为原料，并在五氯化磷存在下通过光照反应制备了氯甲基三甲基硅烷，但同样得到了较多的多氯代产物。1947年，Whitmore等人〖参见：Whitmore,Sommer；Am.Soc.,69,1976,1947〗又利用二甲基氯甲基氯硅烷与溴甲烷镁格氏试剂在乙醚中反应制备了氯甲基三甲基硅烷。同样，Rodel〖参见：Vgl.Roedel；Am.Soc.,71,271,1949〗也与1949年利用上述格氏试剂法制备了氯甲基三甲基硅烷。1954-1989年期间，尽管也有文献报导〖参见：Ponomarenko,V.A.Et al.,Dokl.Akad.Nauk SSSR,Ser.Khim.,1954,94,485；Seyferth,D.Et al.,J.A.C.S.,1955,77,907；Inorg.Synth.,1960,6.,37；Pola,J.Et al.,Coll.Czech.Chem.Comm.,1973,38,1522；Wojnowski,W.Et al.,Przem.Chem.,1989,68,409〗利用气相光氯化反应制备了氯甲基甲基二氯硅烷与氯甲基三氯硅烷，但均指出反应必须在紫外光照射下进行，而且也有着火的危险，并且也得到了较多的多氯代副产物；1985年，M.Bordeau等人〖参见：M.Bordeau,S.M.Djamei,R.Calas,J.Dunogues；J.Organomet.Chem.,1985,288,N2,131-138〗利用二甲基氯甲基氯硅烷与四甲基硅烷在三氯化铝存在下制备了氯甲基三甲基硅烷。1988年，V.D.Sheludyakov等人〖参见：V.D.Sheludyakov,V.I.Zhun,M.I.Shumilim,V.N.Bochkarev,T.F.Slyusarenko；Zh.Obshch.Ximii,58,N7,1583-1588,1988〗又以氯甲基三氯硅烷为原料，通过碘甲烷镁格氏反应制备了氯甲基三甲基硅烷。1989年，Mottsarev G.V.等人〖参见：Mostarev G.V.,Inshakova V.T.,Raskina,A.D.；Zh.Obshch.Khim.,1989,59(11),2628(Russ)〗认为：无论是通过四甲基硅烷的热氯化还是通过四甲基硅烷的光氯化均得不到氯甲基三甲基硅烷，原因是由于四甲基硅烷的低沸点影响了热氯化时AIBN的引发，而光氯化初期会有着火的危险，因此使氯化反应无法进行；最近日本三共公司曾利用分批通氯的方式，在紫外光照射下制备氯甲基二甲基氯硅烷，但操作非常烦琐，而且结果也不理想；The preparation of chloromethylchlorosilane (ClCH 2 Si(CH 3 ) m Cl 3-m , m=0-2) was first prepared by Gilliam et al. , ibid., 1944,66,1793〗Prepared by the liquid-phase chlorination reaction of methylchlorosilane (Si(CH 3 ) p Cl 4-p , P=1-3) under ultraviolet light irradiation, but the result is not quite Ideal, and there are many polychlorinated products; in 1946, Whitmore et al [see: Whitmore, Sommer, Am. Silane was used as a raw material, and chloromethyltrimethylsilane was prepared by light reaction in the presence of phosphorus pentachloride, but more polychlorinated products were also obtained. In 1947, Whitmore et al [see: Whitmore, Sommer; Am.Soc., 69, 1976, 1947] used dimethyl chloromethyl silane and methyl bromide Grignard reagent to react in ether to prepare chloromethyl tris Methylsilane. Similarly, Rodel [see: Vgl.Roedel; Am.Soc., 71,271,1949] also prepared chloromethyltrimethylsilane by using the above-mentioned Grignard reagent method in 1949. During 1954-1989, although there are also literature reports [see: Ponomarenko, VAEt al., Dokl. Akad. Nauk SSSR, Ser. .Synth.,1960,6.,37; Pola,J.Et al.,Coll.Czech.Chem.Comm.,1973,38,1522;Wojnowski,W.Et al.,Przem.Chem.,1989,68,409 〗Chloromethylmethyldichlorosilane and chloromethyltrichlorosilane were prepared by gas-phase photochlorination reaction, but both pointed out that the reaction must be carried out under ultraviolet light irradiation, and there is also a danger of fire, and more Polychlorinated by-products; 1985, M.Bordeau et al. [See: M.Bordeau, SMDjamei, R.Calas, J.Dunogues; J.Organomet.Chem., 1985,288,N2,131-138〗 using two Chloromethyltrimethylsilane was prepared from methylchloromethylchlorosilane and tetramethylsilane in the presence of aluminum trichloride. In 1988, VD Sheludyakov et al [see: VD Sheludyakov, VI Zhun, MIShumilim, VNBochkarev, TFSlyusarenko; Zh.Obshch.Ximii, 58, N7, 1583-1588, 1988] took chloromethyl trichlorosilane as raw material, passed through magnesium iodide Grignard reaction prepared chloromethyltrimethylsilane. In 1989, Mottsarev GV et al [see: Mostarev GV, Inshakova VT, Raskina, AD; Zh.Obshch.Khim., 1989,59(11), 2628(Russ)] thought that: whether it is through the heat of tetramethylsilane Neither chlorination nor photochlorination of tetramethylsilane can obtain chloromethyltrimethylsilane, because the low boiling point of tetramethylsilane affects the initiation of AIBN during thermal chlorination, and the initial stage of photochlorination will There is a danger of fire, so the chlorination reaction cannot be carried out; recently, the Sankyo Company of Japan has used the method of batch chlorine to prepare chloromethyl dimethyl chlorosilane under ultraviolet light irradiation, but the operation is very cumbersome and the result is not good. ideal;
综上所述，溶液氯化法较难控制，而且多氯代副产物较多；格氏法条件苛刻，较难工业化，而且成本也较高。姜标等人报道了“一种通过气相光氯化反应制备氯甲基三甲基硅烷的方法和装置”(CN00119457.1)，得到较为满意的结果。To sum up, the solution chlorination method is more difficult to control, and there are more polychlorinated by-products; the Grignard method has harsh conditions, is difficult to industrialize, and the cost is also high. Jiang Biao et al reported "A method and device for preparing chloromethyltrimethylsilane by gas-phase photochlorination" (CN00119457.1), and obtained relatively satisfactory results.
本发明的目的就是提供一种简便易行、易工业化、成本较低、且副产物较少，转化率较高的制备一系列氯甲基氯硅烷的方法和装置。The object of the present invention is to provide a method and device for preparing a series of chloromethylchlorosilanes which are simple, easy to implement, easy to industrialize, low in cost, less by-products, and high in conversion rate.
本发明的方法中的反应是在可见光或日光灯的光照下进行，所用原料是分子式为CH3Si(CH3)mCl3-m,m=0-2的甲基氯硅烷，如四甲基硅烷、三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷等；The reaction in the method of the present invention is carried out under the illumination of visible light or fluorescent lamp, and the raw material used is methylchlorosilane with molecular formula CH 3 Si(CH 3 ) m Cl 3-m , m=0-2, such as tetramethyl Silane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, etc.;
本发明所用氯化气体可以是纯氯气也可以是一种氯气与惰性气体的混合气体，所述的惰性气体可以是氮气、氦气、氩气等，其中混合气体中惰性气体的含量为0-80％，最好为20-50％。The chlorinated gas used in the present invention can be pure chlorine or a mixed gas of chlorine and an inert gas, and the inert gas can be nitrogen, helium, argon, etc., wherein the content of the inert gas in the mixed gas is 0- 80%, preferably 20-50%.
本发明采用的气相氯化反应，原料气体与氯气的摩尔比为1∶0.1-0.75，最好为1∶0.15-0.43，通常原料气体的流量可以通过反应釜中原料的加热速度或输入原料的量来控制。The gas-phase chlorination reaction that the present invention adopts, the mol ratio of feed gas and chlorine is 1: 0.1-0.75, is preferably 1: 0.15-0.43, and the flow rate of feed gas can pass through the heating rate of raw material in the reactor or input raw material amount to control.
本发明中反应温度为50-80℃。反应时间与反应釜的大小及反应釜中的原料有关。通常反应时间为1-24h，但以3-10h为好。In the present invention, the reaction temperature is 50-80°C. The reaction time is related to the size of the reactor and the raw materials in the reactor. Usually the reaction time is 1-24h, but preferably 3-10h.
本发明所用的气相氯化反应装置是一种特制的反应器，由原料釜或反应釜、气相反应器、气相反应器、回流冷凝器、填料和加热装置组成。如附图1所示。图中1-原料釜或反应釜，2-气相反应器，3-回流冷凝器，4-填料柱，5-加热装置，T1-反应器液相温度计，T2-气相温度计。在反应时，反应釜1中原料的气化量可以通过加热装置5的加热温度控制；反应釜1与气相反应器2之间需配有填料柱4，以确保原料与产品的充分分离；气相反应器2的材质可以是一般的玻璃，也可以是石英玻璃、陶瓷或搪瓷。对于不同的原料，气相反应器需配有不同的散热介质，散热介质可以是水冷，也可以在反应器周围安装风扇；气相反应器不需要配备特殊的紫外光源，通常室内的可见光或日光灯即可保证氯化进行；另外还可以根据反应釜大小配备1-5个气相反应器，以增加反应速度。The gas-phase chlorination reaction device used in the present invention is a special reactor, which is composed of a raw material kettle or a reaction kettle, a gas-phase reactor, a gas-phase reactor, a reflux condenser, a filler and a heating device. As shown in Figure 1. In the figure 1-raw material tank or reaction tank, 2-gas phase reactor, 3-reflux condenser, 4-packed column, 5-heating device, T1-reactor liquid phase thermometer, T2-gas phase thermometer. During the reaction, the gasification amount of the raw material in the
通过本发明方法，可以分别得到氯甲基三甲基硅烷、氯甲基二甲基氯硅烷、甲基氯甲基二氯硅烷或氯甲基三氯硅烷等产品，其操作条件与物理参数如表1所示。By the method of the present invention, products such as chloromethyltrimethylsilane, chloromethyldimethylchlorosilane, methylchloromethyldichlorosilane or chloromethyltrichlorosilane can be obtained respectively, and its operating conditions and physical parameters are as follows: Table 1 shows.
表1．原料与产物结构、物理参数，以及气相氯化反应一览表 
本发明采用的气相氯化方法，不需要特殊的紫外光源，以一系列上述甲基氯硅烷为原料，通过加热形成气体，在气相反应器内与氯气汇合，在室内一般可见光下进行氯化反应，生成氯甲基氯硅烷。形成的产物氯甲基氯硅烷随即回流入原料釜或反应釜，如此循环，只要控制好加热速度与氯气流量，即可保证有90-95％以上的甲基氯硅烷完全被氯化为氯甲基氯硅烷，而只有极少的多氯代副产物产生。The gas-phase chlorination method adopted in the present invention does not require a special ultraviolet light source. A series of the above-mentioned methyl chlorosilanes are used as raw materials to form gas by heating, which is combined with chlorine gas in a gas-phase reactor, and the chlorination reaction is carried out under normal visible light indoors. , to generate chloromethylchlorosilane. The formed product, chloromethylchlorosilane, immediately flows back into the raw material tank or reactor, and so on, as long as the heating rate and the flow rate of chlorine gas are controlled, more than 90-95% of the methylchlorosilane can be completely chlorinated into chloroform chlorochlorosilanes with minimal production of polychlorinated by-products.
本发明的方法不仅是一种简便易行、成本较低、副产物较少、转化率较高的方法，而且是一种制备氯甲基氯硅烷的工业化方法The method of the present invention is not only a simple and easy method with low cost, less by-products and high conversion rate, but also an industrialized method for preparing chloromethylchlorosilane
通过以下的实施例将有助进一步理解本发明，但不能限制本发明的内容。The following examples will help to further understand the present invention, but cannot limit the content of the present invention.
实施例1以四甲基硅烷为原料通过气相氯化反应制备氯甲基三甲基硅烷的方法
准备气相氯化反应装置如图1所示，500毫升反应器用冰冻盐水冷却至0-5度，同时打开气相反应器与回流冷凝器的冷却系统，气相反应器冷却介质通常采用室温水，如5-30℃室温水均可，回流冷凝器通常可采用干冰-异丙醇丙酮或超强冰冻盐水介质。将400ml四甲基硅烷注入上述反应器，通高纯N2置换反应系统中的氧气，然后开启电磁搅拌，加热，待体系回流稳定时，此时反应瓶液相温度T1为27-28℃，气相温度T2为28℃，慢慢打开氯气阀，此时氯化反应即迅速进行，同时气相反应器的器壁上有油状物出现，并且尾气呈酸性。控制加热速度，使回流适中，同时应控制氯气流量，使反应速度不要过于剧烈。随着氯化反应的进行，反应瓶内温度T1会不断升高，待釜内温度升至80℃时停止反应。取样送GC分析，反应液中各组份含量如表1所示。Prepare gas-phase chlorination reaction device as shown in Figure 1, 500 milliliters of reactors are cooled to 0-5 degree with frozen brine, open the cooling system of gas-phase reactor and reflux condenser simultaneously, the cooling medium of gas-phase reactor adopts room temperature water usually, as 5 Water at room temperature of -30°C is acceptable, and dry ice-isopropanol acetone or super frozen saline medium can usually be used for the reflux condenser. Inject 400ml of tetramethylsilane into the above reactor, replace the oxygen in the reaction system with high-purity N2 , then turn on the electromagnetic stirring, and heat until the reflux of the system is stable. At this time, the liquid phase temperature T1 of the reaction bottle is 27-28°C. The gas phase temperature T2 is 28°C, slowly open the chlorine gas valve, and the chlorination reaction proceeds rapidly at this time, and at the same time, oily matter appears on the wall of the gas phase reactor, and the tail gas is acidic. Control the heating rate so that the reflux is moderate, and at the same time control the flow of chlorine gas so that the reaction rate is not too violent. As the chlorination reaction proceeds, the temperature T1 in the reaction flask will continue to rise, and the reaction will stop when the temperature in the kettle rises to 80°C. Sampling was sent to GC analysis, and the contents of each component in the reaction solution are shown in Table 1.
常压精馏，小于98度馏份回收套用；收集98-99℃馏份为产品氯甲基三甲基硅烷，GC分析纯度为98％；大于99度馏份为多氯代副产物。Atmospheric distillation, recovery of fractions less than 98°C; collection of 98-99°C fractions is the product chloromethyltrimethylsilane, GC analysis purity is 98%; fractions greater than 99°C are polychlorinated by-products.
实施例2以三甲基氯硅烷为原料通过气相氯化反应制备氯甲基二甲基氯硅烷的方法Example 2 The method for preparing chloromethyldimethylsilyl chloride by gas-phase chlorination reaction using trimethylchlorosilane as raw material
准备气相氯化反应装置如图1所示，预先将回流冷凝器的冷却系统打开，回流冷凝器采用冰冻盐水介质即可，气相反应器不需要冷却介质。将400ml三甲基氯硅烷注入上述反应器中，通高纯N2置换反应系统中的氧气，然后开启电磁搅拌，加热，待体系回流稳定时，此时反应器液相温度T1为57-58℃，气相温度T2为58℃，慢慢打开氯气阀，此时氯化反应即迅速进行，同时气相反应器的器壁上有油状物出现，并且尾气呈酸性。控制加热速度，使回流适中，同时应控制氯气流量，使反应速度不要过于剧烈。随着氯化反应的进行，反应瓶内温度T1会不断升高，待釜内温度升至100℃时停止反应。取样送GC分析，反应液中各组份含量如表1所示。Prepare the gas-phase chlorination reaction device as shown in Figure 1. The cooling system of the reflux condenser is opened in advance, and the reflux condenser can use frozen brine as a medium, and the gas-phase reactor does not need a cooling medium. Inject 400ml of trimethylchlorosilane into the above reactor, replace the oxygen in the reaction system with high-purity N2 , then turn on the electromagnetic stirring, and heat until the reflux of the system is stable. At this time, the liquid phase temperature T1 of the reactor is 57-58 °C, the gas phase temperature T2 is 58 °C, slowly open the chlorine valve, at this time the chlorination reaction proceeds rapidly, and at the same time, oily matter appears on the wall of the gas phase reactor, and the tail gas is acidic. Control the heating rate so that the reflux is moderate, and at the same time control the flow of chlorine gas so that the reaction rate is not too violent. As the chlorination reaction proceeds, the temperature T1 in the reaction bottle will continue to rise, and the reaction will stop when the temperature in the kettle rises to 100°C. Sampling was sent to GC analysis, and the contents of each component in the reaction solution are shown in Table 1.
常压精馏，小于113度馏份回收套用；收集113-115℃馏份为产品氯甲基二甲基氯硅烷，GC分析纯度为98％；大于115度馏份为多氯代副产物。Atmospheric distillation, recovery of fractions less than 113°C; collection of fractions at 113-115°C is the product chloromethyl dimethyl chlorosilane, GC analysis purity is 98%; fractions greater than 115°C are polychlorinated by-products.
实施例3以二甲基二氯硅烷为原料通过气相氯化反应制备甲基氯甲基二氯硅烷的方法Example 3 The method for preparing methylchloromethyldichlorosilane by gas-phase chlorination reaction using dimethyldichlorosilane as raw material
准备气相氯化反应装置如图1所示，预先将回流冷凝器的冷却系统打开，回流冷凝器采用冰冻盐水介质即可，气相反应器不需要冷却介质。将400ml三甲基氯硅烷注入上述反应器(瓶)中，通高纯N2置换反应系统中的氧气，然后开启电磁搅拌，加热，待体系回流稳定时，此时反应瓶液相温度T1为70-72℃，气相温度T2为72℃，慢慢打开氯气阀，此时氯化反应即迅速进行，同时气相反应器的器壁上有油状物出现，并且尾气呈酸性。控制加热速度，使回流适中，同时应控制氯气流量，使反应速度不要过于剧烈。随着氯化反应的进行，反应瓶内温度T1会不断升高，待釜内温度升至110℃时停止反应。取样送GC分析，反应液中各组份含量如表1所示。Prepare the gas-phase chlorination reaction device as shown in Figure 1. The cooling system of the reflux condenser is opened in advance, and the reflux condenser can use frozen brine as a medium, and the gas-phase reactor does not need a cooling medium. Inject 400ml of trimethylchlorosilane into the above-mentioned reactor (bottle), pass high-purity N Oxygen in the replacement reaction system, then turn on electromagnetic stirring, heat, when the reflux of the system is stable, the liquid phase temperature T1 of the reaction bottle is 70-72°C, the gas phase temperature T2 is 72°C, slowly open the chlorine valve, at this time the chlorination reaction proceeds rapidly, and at the same time, there are oily substances on the wall of the gas phase reactor, and the tail gas is acidic. Control the heating rate so that the reflux is moderate, and at the same time control the flow of chlorine gas so that the reaction rate is not too violent. As the chlorination reaction proceeds, the temperature T1 in the reaction flask will continue to rise, and the reaction will stop when the temperature in the kettle rises to 110°C. Sampling was sent to GC analysis, and the contents of each component in the reaction solution are shown in Table 1.
常压精馏，小于120度馏份回收套用；收集120-121℃馏份为产品甲基氯甲基硅烷，GC分析纯度为97.8％；大于121度馏份为多氯代副产物。Atmospheric distillation, recovery of fractions less than 120°C; collection of fractions at 120-121°C is the product methylchloromethylsilane, GC analysis purity is 97.8%; fractions greater than 121°C are polychlorinated by-products.
实施例4以甲基三氯硅烷为原料通过气相氯化反应制备氯甲基三氯硅烷的方法Embodiment 4 is the method for preparing chloromethyltrichlorosilane by gas phase chlorination reaction using methyltrichlorosilane as raw material
准备气相氯化反应装置如图1所示，预先将回流冷凝区的冷却系统打开，回流冷凝器采用冰冻盐水介质即可，气相反应器不需要冷却介质。将400ml三甲基氯硅烷注入上述反应器(瓶)中，通高纯N2置换反应系统中的氧气，然后开启电磁搅拌，加热，待体系回流稳定时，此时反应瓶液相温度T1为66-68℃，气相温度T2为67℃，慢慢打开氯气阀，此时氯化反应即迅速进行，同时气相反应器的器壁上有油状物出现，并且尾气呈酸性。控制加热速度，使回流适中，同时应控制氯气流量，使反应速度不要过于剧烈。随着氯化反应的进行，反应器内的温度T1会不断升高，待釜内温度升至108℃时停止反应。取样送GC分析，反应液中各组份含量如表1所示。Prepare the gas-phase chlorination reaction device as shown in Figure 1. The cooling system in the reflux condensation zone is opened in advance, and the reflux condenser can use frozen brine as a medium, and the gas-phase reactor does not need a cooling medium. Inject 400ml of trimethylchlorosilane into the above-mentioned reactor (bottle), pass high-purity N Oxygen in the replacement reaction system, then turn on electromagnetic stirring, heat, when the reflux of the system is stable, the liquid phase temperature T1 of the reaction bottle is 66-68°C, the gas phase temperature T2 is 67°C, slowly open the chlorine valve, at this time the chlorination reaction proceeds rapidly, and at the same time, there are oily substances on the wall of the gas phase reactor, and the tail gas is acidic. Control the heating rate so that the reflux is moderate, and at the same time control the flow of chlorine gas so that the reaction rate is not too violent. As the chlorination reaction proceeds, the temperature T1 in the reactor will continue to rise, and the reaction will stop when the temperature in the kettle rises to 108°C. Sampling was sent to GC analysis, and the contents of each component in the reaction solution are shown in Table 1.
常压蒸馏，小于117℃馏份回收套用；收集117-118.5℃馏份为产品氯甲基三氯硅烷，GC分析纯度为97.2％；大于118.5℃馏份为多氯代副产物。Atmospheric distillation, the fraction below 117°C is recovered and applied mechanically; the fraction at 117-118.5°C is collected as the product chloromethyltrichlorosilane, and the purity of GC analysis is 97.2%; the fraction above 118.5°C is polychlorinated by-products.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445289C (en) * | 2006-11-21 | 2008-12-24 | 上海试四赫维化工有限公司 | Process for preparing chloromethylmethyldichlorsilane |
| CN104558003A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Method for preparing chloromethyl trichlorosilane by using liquid-phase chlorination reaction |
| CN104804031A (en) * | 2015-04-08 | 2015-07-29 | 湖北晶星科技股份有限公司 | Method for preparing chloromethyl chlorosilane through light chlorination process |
| CN105198913A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Method for preparing chloromethyl trichlorosilane |
| CN105198914A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Device for preparing chloromethyl trichlorosilane |
| CN106543217A (en) * | 2016-06-28 | 2017-03-29 | 宁夏海诚电化信息科技有限公司 | A kind of CMDMCS chloromethyl dimethyl chlorosilane production technology |
| CN106957330A (en) * | 2016-01-08 | 2017-07-18 | 溧阳市智行新材料有限公司 | A kind of method that chlorination rectification process prepares chloromethyl trichlorosilane |
| CN113234101A (en) * | 2021-06-23 | 2021-08-10 | 唐山三孚新材料有限公司 | Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyltrichlorosilane |
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2001
- 2001-03-16 CN CNB011056908A patent/CN1181079C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445289C (en) * | 2006-11-21 | 2008-12-24 | 上海试四赫维化工有限公司 | Process for preparing chloromethylmethyldichlorsilane |
| CN104558003B (en) * | 2015-01-27 | 2017-08-29 | 荆州市江汉精细化工有限公司 | A kind of method that liquid phase chlorination reaction prepares Chloromethyltrichlorosilane |
| CN104558003A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Method for preparing chloromethyl trichlorosilane by using liquid-phase chlorination reaction |
| CN104804031A (en) * | 2015-04-08 | 2015-07-29 | 湖北晶星科技股份有限公司 | Method for preparing chloromethyl chlorosilane through light chlorination process |
| CN105198914B (en) * | 2015-10-14 | 2018-03-13 | 济南大学 | Device for preparing chloromethyl trichlorosilane |
| CN105198914A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Device for preparing chloromethyl trichlorosilane |
| CN105198913B (en) * | 2015-10-14 | 2018-03-06 | 济南大学 | Method for preparing chloromethyl trichlorosilane |
| CN105198913A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Method for preparing chloromethyl trichlorosilane |
| CN106957330A (en) * | 2016-01-08 | 2017-07-18 | 溧阳市智行新材料有限公司 | A kind of method that chlorination rectification process prepares chloromethyl trichlorosilane |
| CN106957330B (en) * | 2016-01-08 | 2019-01-22 | 溧阳市智行新材料有限公司 | A kind of method that chlorination rectification process prepares chloromethyl trichlorosilane |
| CN106543217A (en) * | 2016-06-28 | 2017-03-29 | 宁夏海诚电化信息科技有限公司 | A kind of CMDMCS chloromethyl dimethyl chlorosilane production technology |
| CN113234101A (en) * | 2021-06-23 | 2021-08-10 | 唐山三孚新材料有限公司 | Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyltrichlorosilane |
| CN113234101B (en) * | 2021-06-23 | 2023-08-22 | 唐山三孚新材料有限公司 | Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyl trichlorosilane |
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