CN104004011A - Method for chlorination of diphenyl dichlorosilane - Google Patents
Method for chlorination of diphenyl dichlorosilane Download PDFInfo
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- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 49
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 abstract description 24
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- 125000000068 chlorophenyl group Chemical group 0.000 description 7
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- 150000008422 chlorobenzenes Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004188 dichlorophenyl group Chemical group 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 2
- -1 trichlorophenyl Chemical group 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- XNAFLNBULDHNJS-UHFFFAOYSA-N dichloro(phenyl)silicon Chemical class Cl[Si](Cl)C1=CC=CC=C1 XNAFLNBULDHNJS-UHFFFAOYSA-N 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及二苯基二氯硅烷氯化的一种方法，具体是指使用Cl2为氯化剂，采用催化剂催化二苯基二氯硅烷氯化，属于有机硅材料技术领域。向二苯基二氯硅烷中加入ZnCl2、SnCl4、ZnCl2与SbCl5按摩尔比为1:1的混合物、SnCl4与SbCl5按摩尔比为1:1的混合物或FeCl3与SbCl5按摩尔比为1:1的混合物作为催化剂，搅拌使其分散均匀；然后通入氯气，在一定氯化反应温度下反应一定时间，尾气冷凝后经NaOH溶液吸收除去HCl。该方法反应条件温和，催化剂来源广、用量少，反应工艺简单、环保，易于工业化。The invention relates to a method for chlorination of diphenyldichlorosilane, specifically refers to using Cl2 as a chlorination agent and adopting a catalyst to catalyze the chlorination of diphenyldichlorosilane, which belongs to the technical field of organosilicon materials. Add ZnCl 2 , SnCl 4 , a mixture of ZnCl 2 and SbCl 5 in a molar ratio of 1:1, a mixture of SnCl 4 and SbCl 5 in a molar ratio of 1:1 or FeCl 3 and SbCl 5 to diphenyldichlorosilane Use a mixture with a molar ratio of 1:1 as a catalyst, stir to disperse evenly; then pass in chlorine gas, react for a certain period of time at a certain chlorination reaction temperature, and remove HCl by absorbing NaOH solution after the tail gas is condensed. The method has mild reaction conditions, wide source of catalyst, less dosage, simple reaction process, environmental protection and easy industrialization.
Description
技术领域 technical field
本发明涉及二苯基二氯硅烷氯化的一种方法，具体是指使用Cl2为氯化剂，采用催化剂催化二苯基二氯硅烷氯化，属于有机硅材料技术领域。 The invention relates to a method for chlorination of diphenyldichlorosilane, specifically refers to using Cl2 as a chlorination agent and adopting a catalyst to catalyze the chlorination of diphenyldichlorosilane, which belongs to the technical field of organosilicon materials.
背景技术 Background technique
航空航天用三大油料包括喷气燃料、航空润滑油和航空液压油，属于飞机用类功能材料；气燃料用于燃气涡轮发动机，航空润滑油用于发动机润滑系统，航空液压油用于飞机液压系统，正确合理地选用这些材料对保障飞机总体设计的先进性以及航空工作的可靠性有着重要意义。 The three major oils used in aerospace include jet fuel, aviation lubricating oil and aviation hydraulic oil, which belong to aircraft functional materials; gas fuel is used in gas turbine engines, aviation lubricating oil is used in engine lubrication systems, and aviation hydraulic oil is used in aircraft hydraulic systems The correct and reasonable selection of these materials is of great significance to ensure the advancement of the overall design of the aircraft and the reliability of aviation work. the
二苯基二氯硅烷是一种常见的有机硅单体，对其进行氯化后，会生成多种氯代产物；以氯代苯基二氯硅烷及其它有机氯硅烷单体为原料合成的油、脂使用温度范围广，黏度指数变化小，润滑性、耐氧化性和耐高低温性能好，具有良好的抗磨性能；该油、脂不论是否加入添加剂改性均可用于航空航天发动机，较合成酯类油性能更加优异，是一类高附加值的有机硅产品。 Diphenyldichlorosilane is a common organosilicon monomer. After chlorination, it will generate a variety of chlorinated products; it is synthesized from chlorophenyldichlorosilane and other organochlorosilane monomers. Oils and greases have a wide temperature range, small changes in viscosity index, good lubricity, oxidation resistance, high and low temperature resistance, and good anti-wear performance; the oils and greases can be used in aerospace engines regardless of whether they are modified with additives. Compared with synthetic ester oil, it has better performance and is a kind of silicone product with high added value. the
本发明的主要目的是研究开发一条二苯基二氯硅烷氯代的新工艺，为研究开发耐高、低温航空航天发动机用硅油奠定基础，打破我国耐高、低温润滑油研究开发技术落后的局面，具有良好的经济和社会效益。 The main purpose of the present invention is to research and develop a new process of diphenyl dichlorosilane chlorination, to lay the foundation for the research and development of silicone oil for high and low temperature resistant aerospace engines, and to break the backward situation of my country's high and low temperature resistant lubricating oil research and development technology , has good economic and social benefits. the
发明内容 Contents of the invention
在前期研究的基础上，本发明采用ZnCl2、SnCl4、ZnCl2与SbCl5的混合物、SnCl4与SbCl5的混合物或FeCl3与SbCl5的混合物催化二苯基二氯硅烷氯化制备氯代苯基二氯硅烷；该方法反应条件温和，催化剂来源广、用量少，反应工艺简单、环保，易于工业化。 On the basis of previous studies, the present invention uses ZnCl 2 , SnCl 4 , a mixture of ZnCl 2 and SbCl 5 , a mixture of SnCl 4 and SbCl 5 or a mixture of FeCl 3 and SbCl 5 to catalyze the chlorination of diphenyldichlorosilane to prepare chlorine Substituted phenyl dichlorosilane; the method has mild reaction conditions, wide source of catalyst, less consumption, simple reaction process, environmental protection and easy industrialization.
一种二苯基二氯硅烷氯化的方法，其特征是按下述步骤进行的： A method for diphenyl dichlorosilane chlorination is characterized in that it is carried out in the following steps:
向二苯基二氯硅烷中加入ZnCl2、SnCl4、ZnCl2与SbCl5按摩尔比为1∶1的混合物、SnCl4与SbCl5按摩尔比为1∶1的混合物或FeCl3与SbCl5按摩尔比为1∶1的混合物，搅拌使其分散均匀；然后通入氯气，在一定氯化反应温度下反应一定时间，尾气冷凝后经NaOH溶液吸收除去HCl。 Add ZnCl 2 , SnCl 4 , a mixture of ZnCl 2 and SbCl 5 with a molar ratio of 1:1, a mixture of SnCl 4 and SbCl 5 with a molar ratio of 1:1 or FeCl 3 and SbCl 5 to diphenyldichlorosilane Stir the mixture with a molar ratio of 1:1 to disperse it evenly; then pass in chlorine gas and react for a certain period of time at a certain chlorination reaction temperature. After the tail gas is condensed, it is absorbed by NaOH solution to remove HCl.
其中所述的总的催化剂用量为二苯基二氯硅烷摩尔数的0.1％～10％，其中优选0.5％～5％。 The total amount of catalyst used is 0.1%-10% of the moles of diphenyldichlorosilane, preferably 0.5%-5%. the
其中所述的氯气是经浓硫酸干燥的氯气，氯气流量为10～25mL/min，其中优选15～ 20mL/min。 Wherein said chlorine is chlorine gas dried through concentrated sulfuric acid, and the flow rate of chlorine gas is 10～25mL/min, preferably 15～20mL/min. the
其中氯化反应温度为20～100℃，其中优选80～100℃。 Wherein the chlorination reaction temperature is 20-100°C, preferably 80-100°C. the
其中所述的氯化反应时间为4h～18h，其中优选10h～14h。 The chlorination reaction time described therein is 4h-18h, preferably 10h-14h. the
本发明的优点在于： The advantages of the present invention are:
1.本发明中使用的催化剂来源广、价格低廉、用量少，有利于该反应的工业化应用。 1. The catalyst used in the present invention has wide sources, low price and low consumption, which is beneficial to the industrial application of this reaction. the
2.本发明采用连续的气液催化反应，工艺流程简单、易于控制、反应条件温和。 2. The present invention adopts continuous gas-liquid catalytic reaction, has simple technological process, is easy to control, and has mild reaction conditions. the
3.本发明二苯基二氯硅烷氯化方法使用价格低廉的氯气，原料转化率高，氯代苯基产物收率高。 3. The diphenyldichlorosilane chlorination method of the present invention uses inexpensive chlorine gas, has high conversion rate of raw materials, and high yield of chlorophenyl products. the
4.本发明制备的氯代苯基二氯硅烷可与其他有机硅单体一起制备耐高温、润滑性好的硅油，应用前景广阔。 4. The chlorophenyldichlorosilane prepared by the present invention can be used together with other organosilicon monomers to prepare silicone oil with high temperature resistance and good lubricity, and has broad application prospects. the
具体实施方式 Detailed ways
以下为本发明的较佳实施例，能够更好地理解本发明，但本发明的实施例不限于此，同时其所示数据不代表对本发明特征范围的限制。 The following are preferred embodiments of the present invention, which can better understand the present invention, but the embodiments of the present invention are not limited thereto, and the data shown therein do not represent limitations to the scope of the present invention. the
实施例1 Example 1
在100mL的四口烧瓶中加入0.5mol二苯基二氯硅烷，再加入0.0125mol的无水FeCl3和0.0125mol的无水SbCl5，搅拌使其分散均匀；然后向系统中通入经浓硫酸干燥的氯气，其流量为20mL/min，在80℃下反应14h，尾气冷凝后经NaOH溶液吸收除去HCl；产物通过气相-质谱联用仪(Agilent GC(7890A)-MS(5975C))定性分析，气相色谱(GC7890，毛细管柱为SE-54)定量分析。 Add 0.5mol diphenyldichlorosilane to a 100mL four-neck flask, then add 0.0125mol anhydrous FeCl 3 and 0.0125mol anhydrous SbCl 5 , stir to disperse evenly; then pass concentrated sulfuric acid into the system Dry chlorine gas with a flow rate of 20mL/min was reacted at 80°C for 14h. After the tail gas was condensed, it was absorbed by NaOH solution to remove HCl; the product was qualitatively analyzed by gas chromatography-mass spectrometry (Agilent GC (7890A)-MS (5975C)) , gas chromatography (GC7890, capillary column is SE-54) quantitative analysis.
固定总的催化剂用量，改变氯化反应中催化剂的组合，具体数据与实验结果如表1所示： Fix the total catalyst consumption and change the combination of catalyst in the chlorination reaction. The specific data and experimental results are shown in Table 1:
表1复合催化剂对二苯基二氯硅烷氯化反应的影响 The influence of table 1 composite catalyst on the chlorination reaction of diphenyldichlorosilane
实验条件：甲基苯基二氯硅烷用量：0.5mol；总催化剂用量(占原料摩尔比)：5％；氯气流量：20mL/min；反应温度：80℃；反应时间：14h。 Experimental conditions: methylphenyldichlorosilane dosage: 0.5mol; total catalyst dosage (accounting for raw material molar ratio): 5%; chlorine gas flow rate: 20mL/min; reaction temperature: 80°C; reaction time: 14h. the
表1展示了以ZnCl2、SnCl4或FeCl3与SbCl5按摩尔比为1∶1的混合物催化该氯化反应的实验结果，从表中可以看出，在三种组合催化剂中，FeCl3与SbCl5复合的催化剂最利于该反应的进行，氯代苯基产物的收率可以达到79％。 Table 1 shows the experimental results of this chlorination reaction catalyzed by a mixture of ZnCl 2 , SnCl 4 or FeCl 3 and SbCl 5 in a molar ratio of 1: 1. As can be seen from the table, among the three combined catalysts, FeCl 3 The catalyst compounded with SbCl 5 is the most favorable for the reaction, and the yield of chlorophenyl product can reach 79%.
实施例2 Example 2
在100mL的四口烧瓶中加入0.5mol二苯基二氯硅烷，再加入0.0125mol的无水FeCl3和0.0125mol的无水SbCl5，搅拌使其分散均匀；然后向系统中通入经浓硫酸干燥的氯气，其流量为20mL/min，在80℃下反应14h，尾气冷凝后经NaOH溶液吸收除去HCl，产物通过气相-质谱联用仪(Agilent GC(7890A)-MS(5975C))定性分析，气相色谱(GC7890，毛细管柱为SE-54)定量分析。 Add 0.5mol diphenyldichlorosilane to a 100mL four-neck flask, then add 0.0125mol anhydrous FeCl 3 and 0.0125mol anhydrous SbCl 5 , stir to disperse evenly; then pass concentrated sulfuric acid into the system Dry chlorine gas with a flow rate of 20mL/min was reacted at 80°C for 14h. After the tail gas was condensed, it was absorbed by NaOH solution to remove HCl. The product was qualitatively analyzed by gas chromatography-mass spectrometry (Agilent GC (7890A)-MS (5975C)) , gas chromatography (GC7890, capillary column is SE-54) quantitative analysis.
固定氯化反应催化剂中FeCl3和SbCl5的比例，将复合催化剂的总用量(占甲基苯基二氯硅烷摩尔数)5％改变为0.1％、0.5％和10％，实验结果如表2所示： Fix the ratio of FeCl3 and SbCl5 in the chlorination reaction catalyst, change the total consumption (accounting for methylphenyldichlorosilane mol number) 5% of the composite catalyst to 0.1%, 0.5% and 10%, the experimental results are shown in Table 2 Shown:
表2催化剂用量对二苯基二氯硅烷氯化反应的影响 The impact of table 2 catalyst dosage on diphenyl dichlorosilane chlorination reaction
实验条件：甲基苯基二氯硅烷用量：0.5mol；催化剂为FeCl3-SbCl5；氯气流量：20mL/min；反应温度：80℃；反应时间：14h。 Experimental conditions: dosage of methylphenyldichlorosilane: 0.5mol; catalyst: FeCl 3 -SbCl 5 ; chlorine gas flow rate: 20mL/min; reaction temperature: 80°C; reaction time: 14h.
随着催化剂用量的增加，反应速率有增加的趋势，氯代苯基产物的总收率先增加后减小，而副产物氯苯类收率显著增加。其中，当催化剂用量为5％时，氯代苯基产物的总收率可以达到79％。 With the increase of the amount of catalyst, the reaction rate tends to increase, the total yield of chlorophenyl products first increases and then decreases, while the yield of by-product chlorobenzenes increases significantly. Wherein, when the catalyst dosage is 5%, the total yield of chlorophenyl products can reach 79%. the
实施例3 Example 3
在100mL的四口烧瓶中加入0.5mol二苯基二氯硅烷，再加入0.0125mol的无水FeCl3和0.0125mol的无水AlCl3，搅拌使其分散均匀；然后向系统中通入经浓硫酸干燥的氯气，其流量为10mL/min，在80℃下反应14h，尾气冷凝后经NaOH溶液吸收除去HCl，产物通过气相-质谱联用仪(Agilent GC(7890A)-MS(5975C))定性分析，气相色谱(GC7890，毛细管柱为SE-54)定量分析。 Add 0.5mol diphenyldichlorosilane to a 100mL four-necked flask, then add 0.0125mol anhydrous FeCl 3 and 0.0125mol anhydrous AlCl 3 , stir to disperse evenly; then pass concentrated sulfuric acid into the system Dry chlorine gas with a flow rate of 10mL/min was reacted at 80°C for 14h. After the tail gas was condensed, it was absorbed by NaOH solution to remove HCl, and the product was qualitatively analyzed by gas chromatography-mass spectrometry (Agilent GC (7890A)-MS (5975C)) , gas chromatography (GC7890, capillary column is SE-54) quantitative analysis.
改变氯化反应中氯气的流量分别为15mL/min、20mL/min和25mL/min，实验结果如表3所示： Change the flow rate of chlorine in the chlorination reaction to be 15mL/min, 20mL/min and 25mL/min respectively, and the experimental results are shown in Table 3:
表3氯气流量对二苯基二氯硅烷氯化反应的影响 The impact of table 3 chlorine gas flow on the chlorination reaction of diphenyldichlorosilane
实验条件：甲基苯基二氯硅烷用量：0.5mol；催化剂：FeCl3-SbCl5；总催化剂用量(占原料 摩尔比)：5％；；反应温度：80℃；反应时间：14h。 Experimental conditions: methylphenyldichlorosilane dosage: 0.5mol; catalyst: FeCl 3 -SbCl 5 ; total catalyst dosage (accounting for raw material molar ratio): 5%; reaction temperature: 80°C; reaction time: 14h.
从表3可以看出，氯气流量对反应速率以及反应产物的分布都有较大的影响，随着氯气流量的增加，反应速率增加，一氯代苯基产物收率降低，而二氯代和三氯代苯基产物收率增加，副产物氯苯类收率显著增加；其中，当氯气流量在15～20mL/min范围内时，氯代苯基产物的收率均大于77％。 As can be seen from Table 3, the chlorine gas flow rate has a greater impact on the distribution of the reaction rate and the reaction product. With the increase of the chlorine gas flow rate, the reaction rate increases, and the yield of a chlorophenyl product decreases. The yield of trichlorophenyl products increased, and the yield of by-products chlorobenzenes increased significantly; among them, when the flow of chlorine gas was in the range of 15-20mL/min, the yields of chlorophenyl products were all greater than 77%. the
实施例4 Example 4
在100mL的四口烧瓶中加入0.5mol二苯基二氯硅烷，再加入0.0125mol的无水FeCl3和0.0125mol的无水AlCl3，搅拌使其分散均匀；然后向系统中通入经浓硫酸干燥的氯气，其流量为20mL/min，在20℃下反应14h，尾气冷凝后经NaOH溶液吸收除去HCl；产物通过气相-质谱联用仪(Agilent GC(7890A)-MS(5975C))定性分析，气相色谱(GC7890，毛细管柱为SE-54)定量分析。 Add 0.5mol diphenyldichlorosilane to a 100mL four-necked flask, then add 0.0125mol anhydrous FeCl 3 and 0.0125mol anhydrous AlCl 3 , stir to disperse evenly; then pass concentrated sulfuric acid into the system Dry chlorine gas with a flow rate of 20mL/min was reacted at 20°C for 14h. After the tail gas was condensed, it was absorbed by NaOH solution to remove HCl; the product was qualitatively analyzed by gas chromatography-mass spectrometry (Agilent GC (7890A)-MS (5975C)) , gas chromatography (GC7890, capillary column is SE-54) quantitative analysis.
改变氯化反应中温度分别为60℃、80℃和100℃，实验结果如表4所示： Change the temperature in the chlorination reaction to 60°C, 80°C and 100°C respectively, and the experimental results are shown in Table 4:
表4反应温度对二苯基二氯硅烷氯化反应的影响 The influence of table 4 reaction temperature on diphenyl dichlorosilane chlorination reaction
实验条件：甲基苯基二氯硅烷用量：0.5mol；催化剂：FeCl3-SbCl5；总催化剂用量(占原料摩尔比)：5％；氯气流量：20mL/min；反应时间：14h。 Experimental conditions: methylphenyldichlorosilane dosage: 0.5 mol; catalyst: FeCl 3 -SbCl 5 ; total catalyst dosage (accounting for raw material molar ratio): 5%; chlorine gas flow rate: 20 mL/min; reaction time: 14 h.
从表4可以看出，反应温度对反应速率以及反应产物的分布都有较大的影响，随着反应温度的增加，反应速率增加，一氯代和二氯代苯基产物收率先增加后降低，这是因为该产物在较高温度下更容易继续氯化生成多氯代产物以及副产物氯苯；因此，三氯代苯基产物和副产物氯苯类收率均随着反应温度增加而显著增加。其中，当反应温度为80～100℃范围内，氯代苯基产物的总收率均大于74％。 As can be seen from Table 4, the reaction temperature has a greater impact on the reaction rate and the distribution of the reaction product. As the reaction temperature increases, the reaction rate increases, and the yield of monochloro and dichlorophenyl products increases first and then decreases. , this is because the product is more likely to continue to be chlorinated at a higher temperature to generate polychlorinated products and by-product chlorobenzenes; A significant increase. Wherein, when the reaction temperature is in the range of 80-100° C., the total yield of chlorophenyl products is greater than 74%. the
实施例5 Example 5
在100mL的四口烧瓶中加入0.5mol二苯基二氯硅烷，再加入0.0125mol的无水FeCl3和0.0125mol的无水AlCl3，搅拌使其分散均匀；然后向系统中通入经浓硫酸干燥的氯气，其流量为20mL/min，在80℃下反应4h，尾气冷凝后经NaOH溶液吸收除去HCl；产物通过气相-质谱联用仪(Agilent GC(7890A)-MS(5975C))定性分析，气相色谱(GC7890，毛细管柱为SE-54)定量分析。 Add 0.5mol diphenyldichlorosilane to a 100mL four-necked flask, then add 0.0125mol anhydrous FeCl 3 and 0.0125mol anhydrous AlCl 3 , stir to disperse evenly; then pass concentrated sulfuric acid into the system Dry chlorine gas with a flow rate of 20mL/min was reacted at 80°C for 4h. After the tail gas was condensed, it was absorbed by NaOH solution to remove HCl; the product was qualitatively analyzed by gas chromatography-mass spectrometry (Agilent GC (7890A)-MS (5975C)) , gas chromatography (GC7890, capillary column is SE-54) quantitative analysis.
改变氯化反应中氯化时间分别为10h、14h和18h，实验结果如表5所示： Change the chlorination time in the chlorination reaction to be 10h, 14h and 18h respectively, and the experimental results are as shown in table 5:
表5反应时间对二苯基二氯硅烷氯化反应的影响 The influence of table 5 reaction time on diphenyl dichlorosilane chlorination reaction
实验条件：甲基苯基二氯硅烷用量：0.5mol；催化剂：FeCl3-SbCl5；总催化剂用量(占原料摩尔比)：5％；氯气流量：20mL/min；反应温度：80℃。 Experimental conditions: methylphenyldichlorosilane dosage: 0.5mol; catalyst: FeCl 3 -SbCl 5 ; total catalyst dosage (mole ratio of raw materials): 5%; chlorine gas flow rate: 20mL/min; reaction temperature: 80°C.
随着反应时间的增加，原料转化率增加，一氯代和二氯代苯基产物收率先增加后降低，这是因为该产物继续氯化生成多氯代产物以及副产物氯苯，三氯代苯基产物和副产物氯苯类收率均随着反应温度增加而显著增加。 As the reaction time increases, the conversion rate of raw materials increases, and the yield of monochloro and dichlorophenyl products first increases and then decreases, because the product continues to be chlorinated to generate polychlorinated products and by-products chlorobenzene, trichlorophenyl The yields of phenyl products and by-product chlorobenzenes both increased significantly with the increase of reaction temperature. the
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| US2803638A (en) * | 1954-08-18 | 1957-08-20 | Gen Electric | Method for preparing chlorophenylchlorosilanes |
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| CN102659828A (en) * | 2012-04-26 | 2012-09-12 | 江苏大学 | Method for chlorinating methyl phenyl dichloro-silane |
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| US2803638A (en) * | 1954-08-18 | 1957-08-20 | Gen Electric | Method for preparing chlorophenylchlorosilanes |
| US2887503A (en) * | 1957-08-19 | 1959-05-19 | Gen Electric | Method for preparing chlorophenylchlorosilanes |
| CN102659828A (en) * | 2012-04-26 | 2012-09-12 | 江苏大学 | Method for chlorinating methyl phenyl dichloro-silane |
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