GB2112407A - Method of hydrolyzing chlorosilanes - Google Patents
Method of hydrolyzing chlorosilanes Download PDFInfo
- Publication number
- GB2112407A GB2112407A GB08233095A GB8233095A GB2112407A GB 2112407 A GB2112407 A GB 2112407A GB 08233095 A GB08233095 A GB 08233095A GB 8233095 A GB8233095 A GB 8233095A GB 2112407 A GB2112407 A GB 2112407A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydrogen chloride
- hydrolysis
- water
- chlorosilane
- saturated aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 16
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 15
- 230000003301 hydrolyzing effect Effects 0.000 title description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000007062 hydrolysis Effects 0.000 claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 23
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- -1 polysiloxane Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract description 7
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 abstract description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
Hydrolysis of chlorosilanes, for example, dimethyldichlorosilane, to produce dimethylpolysiloxane, is effected in the presence of a substantially stoichiometric equivalence of water which results in the direct generation of anhydrous hydrogen chloride and a saturated aqueous hydrogen chloride solution. The saturated aqueous solution of hydrogen chloride can be recycled to the chlorosilane hydrolysis step.
Description
SPECIFICATION
Method of hydrolyzing chlorosilanes
The present invention relates to the hydrolysis of chlorosilanes including organochlorosilanes in a stoichiometric amount of water to produce a polysiloxane hydrolyzate and anhydrous hydrogen chloride. More particularly, the present invention relates to the hydrolysis of dimethyldichloro- silane resulting in the production of dimethylpolysiloxane hydrolyzate, anhydrous hydrogen chloride and a saturated aqueous hydrogen chloride solution which can be recycled.
Prior to the present invention, dimethyldichiorosilane was hydrolyzed in the presence of an excess amount of water to produce a dimethylpolysiloxane hydrolyzate consisting essentially of a major amount of dimethylcyclopolysiloxane and a substantially linear silanol terminated dimethylpolysiloxane. An aqueous solution of hydrogen chloride was also formed which contained a significant amount of salvageable hydrogen chloride which could be used to convert methanol to methyl chloride used in the direct method for making dimethyidichlorosilane.
One procedure for recovering the hydrogen chloride from the aqueous hydrochloric acid was to distill the mixture to produce a constant boiling HCl-H2O azeotrope along with anhydrous hydrogen chloride. A significant amount of energy is required in the distillation to salvage as much of the available hydrogen chloride from the dimethyldichlorosilane hydrolysis. In An
Introduction to the Chemistry of the Silicones, 2nd Edition, (1951), John Wiley 8 Sons, Inc.,
New York, E. G. Rochow indicate that, if insufficient water is supplied without a mutual solvent, part of the dimethyldichlorosilane is hydrolyzed completely to dimethylpolysiloxane and part does not react at all, or end up as linear polysiloxane with terminal halogen atoms.In addition, if hydrolysis is conducted in the presence of excess water, significant amounts of heat are generated exothermically which can result in processing problems in particular situations.
The present invention is based on the discovery that if substantially stoichiometric amounts of water are utilized to hydrolyze dimethyldichloro- silane, that anhydrous hydrogen chloride is generated directly along with a saturated solution of hydrogen chloride and water. It has been further found that additional benefits are achieved if the aqueous saturated hydrogen chloride solution is recycled to the hydrolysis reactor. In addition, it has been found that the resulting dimethylpolysiloxane is substantially the same dimethylpolysiloxane hydrolyzate produced by the
procedure of the prior art utilizing excess water.
Further, the method of the present invention
provides anhydrous hydrogen chloride which
separates from the hydrolysis mixture as it is
formed during the reaction. In essence, the
reactor is used as both a theoretical distillation
plate and chlorosilane hydrolysis reactor.
In a chlorosilanes hydrolysis method comprising hydrolyzing chlorosilane in a stoichiometric excess of water to produce a polysiloxane hydrolyzate and an aqueous hydrogen chloride solution, whereby hydrogen chloride is recycled by heating the resulting aqueous hydrogen chloride solution obtained from the hydrolysis to form a constant boiling HCI-water azeotrope and anhydrous hydrogen chloride requiring a major amount of input energy, the improvement which comprises hydrolyzing the chlorosilane with a substantially stoichiometric equivalence of water to produce substantially the same polysiloxane hydrolyzate, anhydrous hydrogen chloride and a saturated aqueous solution of hydrogen chloride, whereby the requirement of a major amount of input energy is avoided.
In order that those skiiled in the art will be better able to understand the practice of the invention reference is made to the drawing. There is shown at 10 a hydrolysis reactor which feeds into a phase separator at 20 and a storage tank at 30 which can provide for the recycling of concentrated aqueous hydrogen chloride to the aqueous feed. Multiple storage tanks, not shown, may also be used.
More particularly, water is introduced into the hydrolysis reactor at 12 and chlorosilane is introduced into the hydrolysis reactor at 11 at rates sufficient to maintain about a stoichiometric equivalence between the respective feeds.
For example, a mole ratio of
D
< 1/2
H20 can be maintained in the feed mixture, where D is dimethyldichorosilane. The chlorosilane which can be used in the practice of the invention can be represented by the following formula (R)a(H)bSiX4(a+b)t where R is a Cft~6} hydrocarbon radical selected from an alkyl to aryl, a is an integer equal to 1 to 3 inciusive, b is a whole number equal to 0 to 2 inclusive and the sum of a+b is equal to 3.
Radicals included within R are, for example, methyl, ethyl, propyl, phenyl, etc., which can be the same or different when a is greater than one.
There is immediate reaction upon contact between the chlorosilane and water. However, a temperature in the range of about 250C to 650C can be used while residence time with agitation, such as stirring, etc., can vary from 0.1 to 20 minutes. Higher or lower reaction times can be used if desired. Polysiloxane hydrolyzate is recovered at 21, and aqueous saturated hydrogen chloride solution is separated at 22 and fed into the storage tank at 30. In instances where the saturated aqueous hydrogen chloride solution is recycled, it is fed from 31 to the aqueous feed which is fed into the hydrolysis reactor.
Anhydrous HCI may be drawn off at 14 and also at 23 and 32 for subsequent processing.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of iliustration and not by way of limitation.
Example 1 Dimethyldichiorosilane or "D" and water were fed into a continuous hydrolysis reactor
maintained at about 250C. With a mean liquid
residence time of about 5 minutes and a constant
D to water molar feed ratio of 1 :2, the steady
state composition of the hydrolyzate gave about
51.1% octamethyltetracyclosiloxane (D4) and
about 64.4% total cyclic polysiloxanes. During the
same run, about 66.2% of the total chloride of the
D was evolved as anhydrous HCI, with 27.6%
going out as aqueous HCI which could be
recovered by recycling this aqueous stream back
to the hydrolysis reactor.
Example 2
In a similar run as Example 1, but with
temperature maintained at about 600C and a
mean liquid residence time of about 1 5 minutes,
about 87% of the total chloride of the D was
evolved as anhydrous HCI with about 12. 5%
going out as aqueous HCI. The steady state
hydrolyzate composition showed about 40% and 50% total cyclic polysiloxanes.
Example 3
In this run, dimethyldichlorosilane and a 37 weight percent HCI stream were fed into a continuous hydrolysis reactor maintained at about 600C. With a mean liquid residence time of about
12 minutes and D to water molar ratio in the inlet feed maintained at 1:4, a hydrolyzate of 52% D4 and 73% total cyclics was obtained. At the same time, nearly 66% of the total chloride of the D fed was evolved as anhydrous HCI.
Although the above examples are directed to only a few of the very many variables in the method of the present invention, it should be understood that the present invention is directed to the hydrolysis of a much broader variety of chlorosilanes and conditions used in such hydrolysis mixtures as shown in the description preceding these examples.
Claims (6)
1. A chlorosilane hydrolysis method which method comprises hydroiyzing the chlorosilane in substantially a stoichiometric equivalence of water to produce substantially the same polysiloxane hydrolyzate as obtained with excess water, anhydrous hydrogen chloride and a saturated aqueous solution of hydrogen chloride, whereby the requirement of a major amount of input energy is avoided.
2. A method as claimed in claim 1, where saturated aqueous hydrogen chloride is recycled to the hydrolysis reactor.
3. A method as claimed in claim 1 or claim 2, where anhydrous hydrogen chloride is recovered from the hydrolysis mixture.
4. A method as claimed in any one of the preceding claims, wherein the chlorosilane is dimethyldicorosilane.
5. A method as claimed in claim 1 substantially as hereinbefore described in any one of the examples.
6. Polysiloxane hydrolyzate when produced by a method as claimed in any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33034781A | 1981-12-14 | 1981-12-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2112407A true GB2112407A (en) | 1983-07-20 |
| GB2112407B GB2112407B (en) | 1985-06-19 |
Family
ID=23289362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08233095A Expired GB2112407B (en) | 1981-12-14 | 1982-11-19 | Method of hydrolyzing chlorosilanes |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS58126893A (en) |
| DE (1) | DE3244500A1 (en) |
| FR (1) | FR2518099A1 (en) |
| GB (1) | GB2112407B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0658588A1 (en) * | 1993-12-16 | 1995-06-21 | Wacker-Chemie GmbH | Process for preparing polydimethylsiloxanes |
| US7479567B2 (en) | 2005-03-29 | 2009-01-20 | Dow Corning Corporation | Reactive distillation of chlorosilanes |
| US9422316B2 (en) | 2012-10-16 | 2016-08-23 | Dow Corning Corporation | Method of preparing halogenated silahydrocarbylenes |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4497942A (en) * | 1983-12-14 | 1985-02-05 | General Electric Company | Process for hydrolyzing chlorosilanes |
| JPH028223A (en) * | 1988-06-27 | 1990-01-11 | Toshiba Silicone Co Ltd | Hydrolysis of organochlorosilane |
| US5191053A (en) * | 1990-11-14 | 1993-03-02 | Dow Corning Corporation | Preparation of polyorganosiloxanes with controlled low-levels of hydroxy substitution |
| EP0561554A1 (en) * | 1992-03-17 | 1993-09-22 | General Electric Company | Hydrogen chloride recovery process |
| JP3644703B2 (en) * | 1993-08-18 | 2005-05-11 | 信越化学工業株式会社 | Method for producing cyclic dimethylpolysiloxane |
| JP3436075B2 (en) | 1997-05-28 | 2003-08-11 | 信越化学工業株式会社 | Method for continuous hydrolysis of organochlorosilane |
| DE10146390B4 (en) * | 2001-09-20 | 2006-08-10 | Wacker Chemie Ag | Wastewater-free production of polyorganosiloxanes |
| DE10340887B4 (en) * | 2003-09-04 | 2005-01-05 | Wacker-Chemie Gmbh | Process for the preparation of disiloxanes |
| US7306504B2 (en) | 2004-07-12 | 2007-12-11 | Spin Master, Ltd. | Transformable toy |
| JP4859206B2 (en) | 2006-02-20 | 2012-01-25 | 株式会社セガ トイズ | toy |
| BR112013014581A2 (en) * | 2010-12-17 | 2019-09-24 | Dow Corning | method for the manufacture of a diorgano-dihalosilane |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2381366A (en) * | 1942-10-29 | 1945-08-07 | Gen Electric | Organo-dihalogenosiloxanes |
| US2483963A (en) * | 1948-11-24 | 1949-10-04 | Dow Corning | Production of organosiloxanes |
| US2758124A (en) * | 1952-04-11 | 1956-08-07 | Gen Electric | Continuous hydrolysis of organohalogenosilanes |
| FR1077230A (en) * | 1952-04-11 | 1954-11-05 | Thomson Houston Comp Francaise | Hydrolysis of organohalosilanes in continuous operation |
| US2901460A (en) * | 1956-02-07 | 1959-08-25 | Gen Electric | Halosilane hydrolysis with tetrahydrofuran and water |
| US3763212A (en) * | 1972-02-04 | 1973-10-02 | Gen Electric | Hydrolysis of alkylalkenyldichlorosilane |
| US3983148A (en) * | 1975-08-29 | 1976-09-28 | Union Carbide Corporation | Process for producing cyclic siloxanes |
| US4221691A (en) * | 1979-02-16 | 1980-09-09 | Dow Corning Corporation | Method of hydrolyzing chlorosilanes |
-
1982
- 1982-11-19 GB GB08233095A patent/GB2112407B/en not_active Expired
- 1982-12-02 DE DE19823244500 patent/DE3244500A1/en not_active Withdrawn
- 1982-12-13 JP JP21712082A patent/JPS58126893A/en active Granted
- 1982-12-14 FR FR8220922A patent/FR2518099A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0658588A1 (en) * | 1993-12-16 | 1995-06-21 | Wacker-Chemie GmbH | Process for preparing polydimethylsiloxanes |
| US5476916A (en) * | 1993-12-16 | 1995-12-19 | Wacker-Chemie Gmbh | Process for preparing polydimethylsiloxanes |
| US7479567B2 (en) | 2005-03-29 | 2009-01-20 | Dow Corning Corporation | Reactive distillation of chlorosilanes |
| US9422316B2 (en) | 2012-10-16 | 2016-08-23 | Dow Corning Corporation | Method of preparing halogenated silahydrocarbylenes |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2518099A1 (en) | 1983-06-17 |
| DE3244500A1 (en) | 1983-06-23 |
| JPS58126893A (en) | 1983-07-28 |
| JPS6332357B2 (en) | 1988-06-29 |
| GB2112407B (en) | 1985-06-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |