CN114130345A - Preparation method of polydimethylsilane - Google Patents
Preparation method of polydimethylsilane Download PDFInfo
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- CN114130345A CN114130345A CN202111524415.5A CN202111524415A CN114130345A CN 114130345 A CN114130345 A CN 114130345A CN 202111524415 A CN202111524415 A CN 202111524415A CN 114130345 A CN114130345 A CN 114130345A
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- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000005406 washing Methods 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 230000029087 digestion Effects 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 239000002699 waste material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 238000005086 pumping Methods 0.000 claims description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 13
- 239000008096 xylene Substances 0.000 claims description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 11
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 230000001133 acceleration Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- -1 polydimethylsiloxane Polymers 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ULCJKUYYIXMTBS-UHFFFAOYSA-N [Si].C[Si](C)(C)Cl Chemical compound [Si].C[Si](C)(C)Cl ULCJKUYYIXMTBS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
Abstract
The invention provides a preparation method of polydimethylsilane, which has simple structure and low production cost and improves the productivity, and comprises the following steps: s1, adding methanol into the first reaction kettle, filling inert gas, dropwise adding a hydrochloric acid solution, and keeping stirring; s2, introducing the mixture into a second reaction kettle, and adding silicon powder, a catalyst and an auxiliary agent for reaction; s3, introducing the mixture into a dissolving kettle, and adding sodium to react; s4, introducing into a digestion kettle, adding an absolute ethyl alcohol solution, and stirring; s5, carrying out secondary washing; and S6, drying under reduced pressure to obtain the finished product of the polydimethylsilane.
Description
Technical Field
The invention relates to the technical field of polydimethylsiloxane production, and particularly relates to a preparation method of polydimethylsiloxane.
Background
The method is characterized in that the polydimethylsilane is a raw material of a special ceramic material precursor and is one of main raw materials for preparing polycarbosilane, the existing process for preparing the polydimethylsilane is mainly characterized in that metal sodium and chlorosilane are subjected to Wutz reaction, and the reaction conditions are controlled, but the raw material price is high, the preparation yield is about 92-95%, and the yield of a finished product is not high, so that a large amount of raw materials are required, the production cost is increased, and the long-term development is not facilitated.
Disclosure of Invention
Therefore, aiming at the problems, the invention provides a preparation method of polydimethylsilane, which has the advantages of simple structure, low production cost and capability of improving the productivity.
In order to realize the technical problem, the solution scheme adopted by the invention is as follows: a preparation method of polydimethylsilane comprises the following steps:
s1, adding methanol into a first reaction kettle, controlling the temperature in the first reaction kettle to be 5-10 ℃, vacuumizing the first reaction kettle, filling inert gas into the first reaction kettle, dropwise adding a hydrochloric acid solution, wherein the molar ratio of the methanol to the hydrochloric acid solution is 1: 1.05-1: 1.2, and keeping stirring while dropwise adding the hydrochloric acid solution to prepare a first mixed solution;
s2, introducing the first mixed solution into a second reaction kettle, adding silicon powder into the second reaction kettle, wherein the molar ratio of the silicon powder to gasified chloromethane is 1: 2-1: 3, adding a catalyst and an auxiliary agent while adding the silicon powder, and fully reacting to obtain a second mixed solution;
s3, adding metal sodium into a dissolving kettle protected by inert gas, wherein the molar ratio of the metal sodium to the dimethyl dichlorosilane is 1: 1.05-1: 1.1, adding a xylene solvent, heating the dissolving kettle, keeping the temperature for 1-2 hours when the temperature reaches 80-90 ℃, dropwise adding the second mixed solution into the dissolving kettle to obtain a third mixed solution, and performing suction filtration on the third mixed solution to obtain a first material;
s4, introducing the first material into a digestion kettle, quantitatively adding an absolute ethyl alcohol solution into the first material of the digestion kettle, and stirring;
s5, washing the first material;
and S6, introducing the washed first material into a double-cone drying kettle for reduced pressure drying to obtain the finished product of polydimethylsilane.
The further improvement is that: the washing step in the S5 step includes:
s5-1, pumping and filtering the first material into a first washing kettle, keeping the first washing kettle vacuum, pre-holding a xylene solvent in the first washing kettle, adding the first material, stirring, and after stirring, pumping out waste liquid in the first washing kettle under the condition of keeping the interior of the first washing kettle vacuum;
s5-2, adding absolute ethyl alcohol into the first washing kettle for cleaning, stirring, and after stirring is completed, extracting waste liquid in the first washing kettle;
s5-3, adding deionized water into the first washing kettle for cleaning, stirring, keeping the first washing kettle vacuum in the whole process, pumping out waste liquid after stirring is finished,
s5-4, pumping and filtering the first material into a second washing kettle, adding a xylene solvent, stirring, and pumping out waste liquid; adding into absolute ethanol solvent, stirring, and extracting waste liquid; adding deionized water, stirring, and pumping out waste liquid.
The further improvement is that: in the step S5-1, the stirring speed is 10-20Hz, the stirring time is 5-6h, and in the step process, the vacuum degree of the first washing kettle is kept between-0.05 and-0.09 Mpa.
The further improvement is that: in the step S5-2, the stirring speed is 10-20Hz, and the stirring time is 3-5 h.
The further improvement is that: the stirring speed in the step S5-3 is 10-20Hz, the stirring time is 2-4h, and the vacuum degree is-0.06-0.095 Mpa.
The further improvement is that: s5-4, adding dimethylbenzene, wherein the stirring speed is 10-20Hz, and the stirring time is 3-5 h; adding anhydrous alcohol solvent, stirring at 10-20Hz for 2-4 h.
The further improvement is that: in the step S1, the dropping speed of the hydrochloric acid solution is 5-10rpm, the stirring speed is 20-35Hz, the temperature in the first reaction kettle is controlled to be 100-120 ℃, and the heat preservation time is 2-5 h.
The further improvement is that: the adding speed of the silicon powder in S2 is 2G/MIN-3G/MIN, the reaction temperature in the second reaction kettle is controlled to be 250-350 ℃, and the heat preservation time is 10-15 h.
The further improvement is that: in the step S3, the heating rate is 5-10 ℃/h, the second mixed liquid drop acceleration rate is 1g/min-2g/min, when the second mixed liquid drop is added into the dissolving kettle, the temperature in the dissolving kettle is controlled to be 80-90 ℃, the temperature is controlled for 2-3 hours, the second mixed liquid drop is kept, the temperature is increased to 108-118 ℃ within 2-3 hours, and the heat preservation time is 10-15 hours.
The further improvement is that: in the step S4, the dropping speed of the absolute ethyl alcohol solution is 1.5-1.8kg/min, the temperature is controlled to be 20-35 ℃, the stirring speed is 30-40Hz, and the heat preservation time is 3-5 h.
The further improvement is that: in the step S6, the temperature of the double-cone drying kettle is controlled to be 90-98 ℃, the heat preservation time is 10-18H, and the pressure in the double-cone drying kettle is-0.01-0.02 Mpa.
By adopting the technical scheme, the invention has the beneficial effects that: 1. the invention discloses a new method for preparing polydimethylsilane, which comprises the following reaction principle, utilizing methanol and hydrochloric acid to generate chemical reaction to prepare methyl chloride,
the reaction of methyl chloride and metallic silicon is used to prepare the mixed product of methyl chlorosilane, CH3Cl+Si→(CH3)2SiCl2+(CH3)3Refining and separating SiCl to obtain products of dimethyldichlorosilane and trimethylchlorosilane silicon, and reacting the obtained products with sodium powder, (CH3)2SiCl2+ (CH3)3SiCl + Na → NaCl + (CH3)3)2Si to obtain the crude product of the polydimethyl silane.
The polydimethylsilane with the yield of 96 percent and the oxygen content of less than 0.3 percent is finally prepared by the preparation processes of impurity removal, washing, drying and the like, and the production efficiency and the yield are improved.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing polydimethylsilane according to an embodiment of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and specific embodiments.
The first embodiment is as follows:
the embodiment of the invention discloses a preparation method of polydimethylsilane, which comprises the following steps:
s1, adding methanol into a first reaction kettle 1, controlling the temperature in the first reaction kettle 1 to be 10 ℃, vacuumizing the first reaction kettle 1, filling nitrogen, dropwise adding a hydrochloric acid solution at a dropwise adding speed of 10rpm, wherein the molar ratio of the methanol to the hydrochloric acid solution is 1: 1.05, controlling the temperature in the first reaction kettle 1 to be 120 ℃ and keeping stirring when the hydrochloric acid solution is dropwise added, wherein the stirring speed is 20Hz, and the heat preservation time is 2H, so as to prepare a first mixed solution;
the device is also provided with a condenser 11, the feeding end and the discharging end of the condenser 11 are both communicated with the first reaction kettle 1 through pipelines, gaseous substances in the first reaction kettle 1 enter the condenser 11 through the pipelines to be condensed and then flow back to the first reaction kettle 1, and the temperature of the condenser 11 is controlled by 20 ℃;
the condensing device is adopted, so that the volatilization of reactants can be avoided, and the loss of methanol and hydrochloric acid is reduced, thereby increasing the amount of reaction products; and a part of excessive hydrochloric acid solution ensures the full reaction of the methanol.
S2, introducing the first mixed solution into a second reaction kettle 2, adding silicon powder into the second reaction kettle 2 at the adding speed of 2G/MIN, wherein the molar ratio of the silicon powder to gasified chloromethane is 1: 3, controlling the reaction temperature to be 250 ℃ and keeping the temperature for 10 hours;
the further improvement is that: the particle size range of the silicon powder is 45-300 mu m;
adding a catalyst cuprous chloride powder while adding silicon powder, and adding an auxiliary agent zinc powder to obtain a second mixed solution (the second mixed solution contains methyltrichlorosilane, dimethyldichlorosilane and 1% trimethylchlorosilane);
the cuprous chloride powder is used as a catalyst to promote the reaction progress, the zinc powder improves the catalytic capability of the copper powder, the activity of a catalytic system of the cuprous chloride-zinc powder is very high, and the yield of the product dimethyldichlorosilane can be further improved by selecting the reaction temperature of 250-350 ℃.
S3, adding sodium metal into a nitrogen-protected dissolving kettle 3, adding a xylene solvent, heating the dissolving kettle 3 at a heating rate of 5 ℃/h when the molar ratio of the sodium metal to the dimethyldichlorosilane is 1: 1.05, keeping the temperature for 2h when the temperature reaches 80 ℃, dripping a second mixed liquid into the dissolving kettle 3 at an acceleration rate of 1g/min, controlling the temperature to 65 ℃, controlling the temperature for 2h, keeping the second mixed liquid dripped, heating the second mixed liquid to 108 ℃ within 3h, keeping the temperature for 15h to obtain a third mixed liquid, and carrying out suction filtration on the third mixed liquid to obtain a first material;
the second mixed solution contains a small amount of trimethylchlorosilane which can be used as an end-capping agent; avoiding the problems that the molecular chain of the reaction product is too long, the molecular weight is too large, and the reaction product is difficult to process in subsequent use.
In the prior art, almost 100% of dimethyldichlorosilane is used as a reaction product, the molecular weight of the obtained crude polydimethylsiloxane product is between 2800-3500, the molecular weight of the polydimethylsilane prepared by the method is between 2000-2700, and the more PDMS with small molecular weight, the more thorough the subsequent cracking is under the premise of not reducing the yield.
S4, introducing the first material into a digestion kettle 4, quantitatively adding an absolute ethyl alcohol solution into the first material of the digestion kettle 4, wherein the dropping rate of the absolute ethyl alcohol solution is 1.5kg/min, controlling the temperature to be 20 ℃, stirring at the stirring rate of 30Hz, and keeping the temperature for 5 hours;
the dropping rate is controlled to reduce the heat generated by the reaction, reduce the occurrence of side reaction and control the reaction process more easily.
S5-1, keeping the vacuum degree of the first washing kettle 5 at-0.05 Mpa, carrying out suction filtration on a first material to the first washing kettle 5, keeping the first washing kettle 5 in vacuum, pre-containing a xylene solvent in the first washing kettle 5, adding the first material, stirring at the stirring speed of 10Hz for 6h, and after stirring, extracting waste liquid in the first washing kettle 5 under the condition of keeping the vacuum inside the first washing kettle 5;
s5-2, adding absolute ethyl alcohol into the first washing kettle 5 for cleaning, stirring at a stirring speed of 10Hz for 5 hours, and after stirring is completed, pumping out waste liquid in the first washing kettle 5;
s5-3, keeping the first washing kettle 5 vacuum at a vacuum degree of-0.06 Mpa, adding deionized water into the first washing kettle 5 for cleaning, stirring at a stirring speed of 10Hz for 4 hours, and after the stirring is finished, pumping out the waste liquid;
s5-4, pumping and filtering the first material into a second washing kettle 6, adding a xylene solvent, stirring at a stirring speed of 20Hz for 3 h; after completion, the waste liquid is extracted; adding the mixture into an absolute ethyl alcohol solvent, and stirring for 2 hours at a stirring speed of 20 Hz; extracting waste liquid; adding deionized water, and stirring at a stirring speed of 20Hz for 2 h; after stirring, extracting waste liquid;
removing excessive inorganic salts dissolved in water, absolute ethyl alcohol solvent and the like through the steps from S5-1 to S5-4;
s6, introducing the washed first material into a double-cone drying kettle 7 for reduced pressure drying, controlling the temperature to be 90-98 ℃, keeping the temperature for 10H, and controlling the pressure in the double-cone drying kettle 7 to be 0.01Mpa to obtain the finished product of the polydimethylsilane.
The conventional drying time of the prior art is about 24-36h, and the drying time of the technology is 10-18 h. The same drying effect can be realized in a shorter time, and the production efficiency is improved.
Example two:
the invention discloses a preparation method of polydimethylsilane, which comprises the following steps:
s1, adding methanol into a first reaction kettle 1, controlling the temperature in the first reaction kettle 1 to be 5 ℃, vacuumizing the first reaction kettle 1, filling nitrogen, dropwise adding a hydrochloric acid solution at a dropwise adding speed of 5rpm, wherein the molar ratio of the methanol to the hydrochloric acid solution is 1: 1.2, controlling the temperature in the first reaction kettle 1 to be 100 ℃ and keeping stirring when the hydrochloric acid solution is dropwise added, wherein the stirring speed is 35Hz, and keeping the temperature for 5 hours to prepare a first mixed solution;
the device is also provided with a condenser 11, the feeding end and the discharging end of the condenser 11 are both communicated with the first reaction kettle 1 through pipelines, gaseous substances in the first reaction kettle 1 enter the condenser 11 through the pipelines to be condensed and then flow back to the first reaction kettle 1, and the temperature of the condenser 11 is controlled by 20 ℃;
s2, introducing the first mixed solution into a second reaction kettle 2, adding silicon powder into the second reaction kettle 2 at the speed of 3G/MIN, wherein the molar ratio of the silicon powder to gasified chloromethane is 1: 2, the reaction temperature is 350 ℃, the heat preservation time is 15 hours,
adding silicon powder, simultaneously adding a catalyst cuprous chloride and an auxiliary agent zinc powder, and fully reacting to obtain a second mixed solution (the second mixed solution contains methyltrichlorosilane, dimethyldichlorosilane and 10% trimethylchlorosilane);
s3, adding metal sodium into a nitrogen-protected dissolving kettle 3, wherein the molar ratio of the metal sodium to dimethyldichlorosilane in a second mixed solution is 1: 1.1, adding a xylene solvent, heating the dissolving kettle 3 at a temperature rate of 10 ℃/h, keeping the temperature for 1h when the temperature reaches 90 ℃, dripping the second mixed solution into the dissolving kettle 3 at a speed of 2g/min, controlling the temperature to be 40 ℃, controlling the temperature for 3h, keeping the second mixed solution dripped, heating the second mixed solution to 118 ℃ within 2h, keeping the temperature for 10h to obtain a third mixed solution, and carrying out suction filtration on the third mixed solution to obtain a first material;
s4, introducing the first material into a digestion kettle 4, quantitatively adding an absolute ethyl alcohol solution into the first material of the digestion kettle 4, wherein the dropping rate of the absolute ethyl alcohol solution is 1.8kg/min, the temperature is controlled to be 35 ℃, stirring is carried out, the stirring rate is 40Hz, and the heat preservation time is 3 hours;
s5-1, keeping the vacuum degree of the first washing kettle 5 at-0.09 Mpa, carrying out suction filtration on a first material to the first washing kettle 5, keeping the first washing kettle 5 in vacuum, pre-containing a xylene solvent in the first washing kettle 5, adding the first material, stirring at the stirring speed of 30Hz for 5 hours, and after stirring, keeping the vacuum inside the first washing kettle 5, and extracting waste liquid in the first washing kettle 5;
s5-2, adding absolute ethyl alcohol into the first washing kettle 5 for cleaning, stirring at a stirring speed of 20Hz for 3 hours, and after stirring is completed, pumping out waste liquid in the first washing kettle 5;
s5-3, keeping the first washing kettle 5 vacuum at a vacuum degree of-0.095 Mpa, adding deionized water into the first washing kettle 5 for cleaning, stirring at a stirring speed of 20Hz for 2 hours, and after the stirring is finished, extracting waste liquid;
s5-4, pumping and filtering the first material into a second washing kettle 6, adding a xylene solvent, stirring at a stirring speed of 10Hz for 5 h; after completion, the waste liquid is extracted; adding the mixture into an absolute ethyl alcohol solvent, and stirring for 4 hours at a stirring speed of 10 Hz; extracting waste liquid; adding deionized water, and stirring at a stirring speed of 10Hz for 4 h; after stirring, extracting waste liquid;
s6, introducing the washed first material into a double-cone drying kettle 7 for reduced pressure drying, controlling the temperature at 90 ℃, keeping the temperature for 18 hours, and controlling the pressure in the double-cone drying kettle 7 to be 0.02Mpa to obtain the finished product of the polydimethylsilane.
EXAMPLE III
Based on the scheme, the adding speed of the silicon powder in the S2 step is preferably 2.5G/MIN; the dropping speed of the second mixed solution in S3 is: 1.58g/min
Modifications and variations of the present invention are within the scope of the claims and are not limited by the disclosure of the embodiments.
Claims (11)
1. A method for preparing polydimethylsilane is characterized in that: the method comprises the following steps:
s1, adding methanol into a first reaction kettle, controlling the temperature in the first reaction kettle to be 5-10 ℃, vacuumizing the first reaction kettle, filling inert gas into the first reaction kettle, dropwise adding a hydrochloric acid solution, wherein the molar ratio of the methanol to the hydrochloric acid solution is 1: 1.05-1: 1.2, and keeping stirring while dropwise adding the hydrochloric acid solution to prepare a first mixed solution;
s2, introducing the first mixed solution into a second reaction kettle, adding silicon powder into the second reaction kettle, wherein the molar ratio of the silicon powder to gasified chloromethane is 1: 2-1: 3, adding a catalyst and an auxiliary agent while adding the silicon powder, and fully reacting to obtain a second mixed solution;
s3, adding metal sodium into a dissolving kettle protected by inert gas, wherein the molar ratio of the metal sodium to the dimethyl dichlorosilane is 1: 1.05-1: 1.1, adding a xylene solvent, heating the dissolving kettle, keeping the temperature for 1-2 hours when the temperature reaches 80-90 ℃, dropwise adding the second mixed solution into the dissolving kettle to obtain a third mixed solution, and performing suction filtration on the third mixed solution to obtain a first material;
s4, introducing the first material into a digestion kettle, quantitatively adding an absolute ethyl alcohol solution into the first material of the digestion kettle, and stirring;
s5, washing the first material;
and S6, introducing the washed first material into a double-cone drying kettle for reduced pressure drying to obtain the finished product of polydimethylsilane.
2. The method for preparing polydimethylsilane according to claim 1, wherein: the washing step in the S5 step includes:
s5-1, pumping and filtering the first material into a first washing kettle, keeping the first washing kettle vacuum, pre-holding a xylene solvent in the first washing kettle, adding the first material, stirring, and after stirring, pumping out waste liquid in the first washing kettle under the condition of keeping the interior of the first washing kettle vacuum;
s5-2, adding absolute ethyl alcohol into the first washing kettle for cleaning, stirring, and after stirring is completed, extracting waste liquid in the first washing kettle;
s5-3, adding deionized water into the first washing kettle for cleaning, stirring, keeping the first washing kettle vacuum in the whole process, pumping out waste liquid after stirring is finished,
s5-4, pumping and filtering the first material into a second washing kettle, adding a xylene solvent, stirring, and pumping out waste liquid; adding into absolute ethanol solvent, stirring, and extracting waste liquid; adding deionized water, stirring, and pumping out waste liquid.
3. The method for preparing polydimethylsilane according to claim 2, wherein: in the step S5-1, the stirring speed is 10-20Hz, the stirring time is 5-6h, and in the step process, the vacuum degree of the first washing kettle is kept between-0.05 and-0.09 Mpa.
4. The method for preparing polydimethylsilane according to claim 2, wherein: in the step S5-2, the stirring speed is 10-20Hz, and the stirring time is 3-5 h.
5. The method for preparing polydimethylsilane according to claim 2, wherein: the stirring speed in the step S5-3 is 10-20Hz, the stirring time is 2-4h, and the vacuum degree is-0.06-0.095 Mpa.
6. The method for preparing polydimethylsilane according to claim 2, wherein: s5-4, adding dimethylbenzene, wherein the stirring speed is 10-20Hz, and the stirring time is 3-5 h; adding anhydrous alcohol solvent, stirring at 10-20Hz for 2-4 h.
7. The method for preparing polydimethylsilane according to claim 1, wherein: in the step S1, the dropping speed of the hydrochloric acid solution is 5-10rpm, the stirring speed is 20-35Hz, the temperature in the first reaction kettle is controlled to be 100-120 ℃, and the heat preservation time is 2-5 h.
8. The method for preparing polydimethylsilane according to claim 1, wherein: the adding speed of the silicon powder in S2 is 2G/MIN-3G/MIN, the reaction temperature in the second reaction kettle is controlled to be 250-350 ℃, and the heat preservation time is 10-15 h.
9. The method for preparing polydimethylsilane according to claim 1, wherein: in the step S3, the heating rate is 5-10 ℃/h, the second mixed liquid drop acceleration rate is 1g/min-2g/min, when the second mixed liquid drop is added into the dissolving kettle, the temperature in the dissolving kettle is controlled to be 80-90 ℃, the temperature is controlled for 2-3 hours, the second mixed liquid drop is kept, the temperature is increased to 108-118 ℃ within 2-3 hours, and the heat preservation time is 10-15 hours.
10. The method for preparing polydimethylsilane according to claim 1, wherein: in the step S4, the dropping speed of the absolute ethyl alcohol solution is 1.5-1.8kg/min, the temperature is controlled to be 20-35 ℃, the stirring speed is 30-40Hz, and the heat preservation time is 3-5 h.
11. The method for preparing polydimethylsilane according to claim 1, wherein: in the step S6, the temperature of the double-cone drying kettle is controlled to be 90-98 ℃, the heat preservation time is 10-18H, and the pressure in the double-cone drying kettle is-0.01-0.02 Mpa.
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