CN103408579B - The synthetic method of a kind of ��-chloropropyl trichloro-silane - Google Patents
The synthetic method of a kind of ��-chloropropyl trichloro-silane Download PDFInfo
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- CN103408579B CN103408579B CN201310392541.9A CN201310392541A CN103408579B CN 103408579 B CN103408579 B CN 103408579B CN 201310392541 A CN201310392541 A CN 201310392541A CN 103408579 B CN103408579 B CN 103408579B
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- thiodiphenylamine
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 150000001412 amines Chemical class 0.000 claims abstract description 29
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 25
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000009413 insulation Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- -1 chloropropyl Chemical group 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RTPJPWAZISRJEM-UHFFFAOYSA-N C[Si](C)(C)O[Si](C)(C=C)C=C.Cl Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C.Cl RTPJPWAZISRJEM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The present invention discloses the synthetic method of a kind of ��-chloropropyl trichloro-silane, and it is taking trichlorosilane and propenyl chloride as raw material, and have employed Platinic chloride-thiodiphenylamine-organic amine complex compound is catalyzer; Building-up process is: first add in pressure reaction still by described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, under 100-180 DEG C of temperature of reaction, drip in pressure reaction still by header tank and add trichlorosilane and propenyl chloride two kinds of reaction masses, after insulation reaction 10-60 minute, complete the synthesis of ��-chloropropyl trichloro-silane; It is 1.5-2.5 hour that the dripping of described trichlorosilane and propenyl chloride adds the time; Described reacting kettle inner pressure is 0.3-1.1MPa. The synthetic method of the ��-chloropropyl trichloro-silane of the present invention, has that the reaction times is short, production efficiency height, makes the features such as loss of material is few, product yield height.
Description
Technical field
The present invention relates to the synthetic method of a kind of ��-chloropropyl trichloro-silane, belong to chemosynthesis technical field.
Background technology
��-chloropropyl trichloro-silane (Cl (CH2)3SiCl3) it is one of intermediate the most important in silane coupling agent products production, the silane coupling agent products such as chloropropyl three second (first) oxygen base silane, aminopropyl three second (first) oxygen base silane, two (triethoxysilylpropyl) tetrasulfide can be produced taking it as main raw material, it is auxiliary agent important in rubber item, glass fibre reinforcement.
The synthesis of ��-chloropropyl trichloro-silane carries out addition reaction of silicon with hydrogen and obtain with trichlorosilane and propenyl chloride under the precious metal chemical complexs such as platinum, rhodium, palladium or complex compound catalyst effect, by the fractionation by distillation to reaction product, the ��-chloropropyl trichloro-silane of technical grade can be obtained. Current existing production method is mainly dripped the mixture adding propenyl chloride and trichlorosilane at ambient pressure and is reacted. " production method of a kind of ��-chloropropyl trichloro-silane " patent documentation (publication number: CN102321111) as disclosed in 18 days January in 2012 of State Intellectual Property Office; the production method of the ��-chloropropyl trichloro-silane described; adopt Platinic chloride-divinyl tetramethyl disiloxane to be catalyzer, evenly dripped in enamel still from high level tank with 14-16 hour under nitrogen protection and add raw material trichlorosilane and propenyl chloride compound reacts. " a kind of method of preparing gamma-chloropropyl trichlorosilane by multicomponent compound catalysis " patent documentation (publication number: CN101624398) disclosed in 13 days January in 2010 of State Intellectual Property Office in addition, employing isopropyl alcohol solution of chloroplatinic acid is Primary Catalysts, the aqueous isopropanol of mphenylenediamine, Tributylamine is promotor, 2000L still adds 750Kg trichlorosilane and 550kg propenyl chloride, react 4.5 hours in 50-55 DEG C, then with 5.5 hours, temperature is raised to 81-84 DEG C of insulation reaction and prepares ��-chloropropyl trichloro-silane.
Above-mentioned ��-chloropropyl trichloro-silane preparation method mainly has the following disadvantages: (1) reactant drips that to add the time long, and the production cycle is long, is not suitable for scale operation; (2) temperature of reaction is low, and catalyst activity is low, it is necessary to long-time inductive phase;(3) synthesis under normal pressure makes loss of material amount big, and product yield is low; (4) raw material boiling point is low, and reflux exchanger cold consumption is big, energy consumption height.
Summary of the invention
For above-mentioned situation, the problem that quasi-solution of the present invention is determined is to provide that a kind of reaction times is short, production efficiency height, the synthetic method of the ��-chloropropyl trichloro-silane of catalyst activity height, active duration length, to reduce loss of material, to improve product yield, simultaneously, can make to be cooled with circulating water, reduce reflux exchanger cold and consume, reduce energy consumption.
For achieving the above object, the present invention by the following technical solutions: the synthetic method of a kind of ��-chloropropyl trichloro-silane, it is taking trichlorosilane and propenyl chloride as raw material, and the mol ratio of described trichlorosilane and propenyl chloride is 0.95-1.25:1; It has employed Platinic chloride-thiodiphenylamine-organic amine complex compound is catalyzer, and the consumption of described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst is: in Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, Platinic chloride quality is the 5-50PPm of reaction raw materials total mass; Building-up process is: first add in pressure reaction still by described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, under 100-180 DEG C of temperature of reaction, drip in pressure reaction still by header tank and add trichlorosilane and propenyl chloride two kinds of reaction masses, after insulation reaction 10-60 minute, complete the synthesis of ��-chloropropyl trichloro-silane; It is 1.5-2.5 hour that the dripping of described trichlorosilane and propenyl chloride adds the time; Described reacting kettle inner pressure is 0.3-1.1MPa.
In described pressure reaction still, leaving the bed material of last batch reaction mass as this batch of reaction before the reaction, the quality of described bed material is this batch of trichlorosilane and the 10-30% of propenyl chloride raw materials quality sum.
Described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst is Platinic chloride-thiodiphenylamine-Tri-n-Propylamine complex compound or Platinic chloride-thiodiphenylamine-tri-n-butylamine complex compound or Platinic chloride-thiodiphenylamine-tri-isobutylamine complex compound.
In described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, the mol ratio of Platinic chloride, thiodiphenylamine, organic amine complex compound is 1:20-40:10-50.
The synthetic method of the ��-chloropropyl trichloro-silane of the present invention, owing to have employed the pressure condition of 0.3-1.1MPa, temperature of reaction brings up to 100-180 DEG C, substantially reduces the reaction times, improves the efficiency of production, adopt confined reaction simultaneously, makes that loss of material is few, product yield height.
In addition, owing to have employed Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, compared with the Platinic chloride of prior art-organic amine complex compound, improve platinum catalyst stability at high temperature, make it still to have good catalytic activity under the temperature of reaction of 180 DEG C, raw material reaction speed is accelerated, and significantly shortens reaction time. Owing to reacting under the pressure of 0.3-1.1MPa, raw material boiling point raises, vapor condensation available cycles water, compared with tradition atmospheric low-temperature technique, can cancel the use of refrigerating fulid, save a large amount of energy.
Experiment proves, the synthetic method of the ��-chloropropyl trichloro-silane of the present invention, product yield can reach more than 75%, compared with synthesizing ��-chloropropyl trichloro-silane with prior art under 81-84 DEG C of environment, can improving receipts rate more than 10%, the reaction times only needs the 20-30% of existing ��-chloropropyl trichloro-silane synthetic method.
Embodiment
The synthetic method of the ��-chloropropyl trichloro-silane of the present invention compared with the prior art, have employed identical reaction raw materials, and two main differences are the change of reaction process and the adjustment of catalyzer.
First carry out describing to the concrete enforcement of catalyzer below: the present invention is taking Platinic chloride-thiodiphenylamine-organic amine complex compound as catalyzer, in described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, the mol ratio of Platinic chloride, thiodiphenylamine, organic amine complex compound is 1:20-40:10-50.
Described Platinic chloride-thiodiphenylamine-organic amine complex compound to be catalyzer can be Platinic chloride-thiodiphenylamine-Tri-n-Propylamine complex compound or Platinic chloride-thiodiphenylamine-tri-n-butylamine complex compound or Platinic chloride-thiodiphenylamine-tri-isobutylamine complex compound.
Its building-up process is: first add a small amount of trichlorosilane and propenyl chloride raw mixture in reactor, again described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst is added in pressure reaction still, under 100-180 DEG C of temperature of reaction, drip in pressure reaction still by header tank and add remaining trichlorosilane and propenyl chloride two kinds of reaction masses, after insulation reaction 10-60 minute, complete the synthesis of ��-chloropropyl trichloro-silane; It is 1.5-2.5 hour that the dripping of described trichlorosilane and propenyl chloride adds the time; Described reacting kettle inner pressure is 0.3-1.1MPa.
The mol ratio of described trichlorosilane and propenyl chloride is 0.95-1.25:1; The consumption of described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst is: in Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, platinum element quality is the 20-50PPm of reaction raw materials.
As preferably, in described reactor, leaving the bed material of last batch reaction mass as this batch of reaction before the reaction, described last batch reaction mass is this batch of trichlorosilane and the 10-30% of propenyl chloride raw materials quality sum.
Providing some embodiments below, the invention will be further described, and following embodiment is explanation property, is not limited, can not limit protection scope of the present invention with following embodiment.
One, the preparation of catalyzer
Platinic chloride-the thiodiphenylamine of the present invention-concrete compound method of organic amine complex compound catalyst is:
Being dissolved in Virahol by Platinic chloride, then tri-n-butylamine and thiodiphenylamine are added in above-mentioned solution mixed even, obtaining Platinic chloride-thiodiphenylamine-organic amine complex compound is catalyzer.
Following table is Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst formulation and formulation content
Two, the synthesis of ��-chloropropyl trichloro-silane
Select and it is furnished with condenser and drips the 2000L steel pressure reactor adding header tank, elder generation adds, from header tank, the trichlorosilane prepared in advance in reactor and propenyl chloride raw material is about 50Kg, it is that catalyzer adds in reactor by the Platinic chloride-thiodiphenylamine-organic amine complex compound prepared again, open steam and it is warming up to 120 DEG C, open cold condenser cooling water intakeoutfall valve, trichlorosilane remaining in header tank and propenyl chloride were dropped to reactor in 1.5-2.5 hour react, drip that to add process reacting kettle inner pressure be 0.3-1.1MPa, control temperature is within the scope of 120-160 DEG C, drip latter insulation reaction 10-60 minute (can be 10 minutes or 60 minutes or 30 minutes or 20 minutes or 40 minutes), after reaction terminates, open reactor cooling water temperature, discharging.
Product samples, and through gas chromatographic detection, in crude product, ��-chloropropyl trichloro-silane content is 70-80%, and through calculating, ��-chloropropyl trichloro-silane receipts rate is 80-87%.
Following table is each parameter value in building-up process
Three, the preferred synthetic method of ��-chloropropyl trichloro-silane
Before the synthesis of ��-chloropropyl trichloro-silane, to the ��-chloropropyl trichloro-silane being furnished with in the 2000L steel pressure reactor of condenser to add last batch reaction as bed material, described last batch reaction mass is the 10-30%(of this batch of trichlorosilane and propenyl chloride raw materials quality sum can be 10% or 15% or 20% or 25% or 30%).Then operate according to the synthesis of previously described ��-chloropropyl trichloro-silane.
Claims (3)
1. a synthetic method for ��-chloropropyl trichloro-silane, it is taking trichlorosilane and propenyl chloride as raw material, and the mol ratio of described trichlorosilane and propenyl chloride is 0.95-1.25:1; It is characterized in that it have employed Platinic chloride-thiodiphenylamine-organic amine complex compound is catalyzer, and the consumption of described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst is: in Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, Platinic chloride quality is the 5-50PPm of reaction raw materials total mass; Building-up process is: first add in pressure reaction still by described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, under 100-180 DEG C of temperature of reaction, drip in pressure reaction still by header tank and add trichlorosilane and propenyl chloride two kinds of reaction masses, after insulation reaction 10-60 minute, complete the synthesis of ��-chloropropyl trichloro-silane; It is 1.5-2.5 hour that the dripping of described trichlorosilane and propenyl chloride adds the time; Described reacting kettle inner pressure is 0.3-1.1MPa; Described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst is Platinic chloride-thiodiphenylamine-Tri-n-Propylamine complex compound or Platinic chloride-thiodiphenylamine-tri-n-butylamine complex compound or Platinic chloride-thiodiphenylamine-tri-isobutylamine complex compound.
2. the synthetic method of ��-chloropropyl trichloro-silane according to claim 1, it is characterized in that in described pressure reaction still, leaving the bed material of last batch reaction mass as this batch of reaction before the reaction, the quality of described bed material is this batch of trichlorosilane and the 10-30% of propenyl chloride raw materials quality sum.
3. the synthetic method of ��-chloropropyl trichloro-silane according to claim 1, it is characterised in that in described Platinic chloride-thiodiphenylamine-organic amine complex compound catalyst, the mol ratio of Platinic chloride, thiodiphenylamine, organic amine complex compound is 1:20-40:10-50.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4292433A (en) * | 1980-10-31 | 1981-09-29 | Chisso Corporation | Method for producing 3-chloropropyltrichlorosilane |
| CN1056881A (en) * | 1990-05-28 | 1991-12-11 | 珠海经济特区华大医药发展有限公司研究所 | The preparation technology of r-chloropropyl trichloro-silane |
| CN1123283A (en) * | 1994-11-21 | 1996-05-29 | 中国科学院化学研究所 | Method for preparation of 3-chloropropyl trichloro-silane |
| CN102260285A (en) * | 2011-07-10 | 2011-11-30 | 天津市圣滨化工有限公司 | Production method of gamma-methacrylic acyloxy propyl trimethoxy silane |
-
2013
- 2013-09-03 CN CN201310392541.9A patent/CN103408579B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4292433A (en) * | 1980-10-31 | 1981-09-29 | Chisso Corporation | Method for producing 3-chloropropyltrichlorosilane |
| CN1056881A (en) * | 1990-05-28 | 1991-12-11 | 珠海经济特区华大医药发展有限公司研究所 | The preparation technology of r-chloropropyl trichloro-silane |
| CN1123283A (en) * | 1994-11-21 | 1996-05-29 | 中国科学院化学研究所 | Method for preparation of 3-chloropropyl trichloro-silane |
| CN102260285A (en) * | 2011-07-10 | 2011-11-30 | 天津市圣滨化工有限公司 | Production method of gamma-methacrylic acyloxy propyl trimethoxy silane |
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