US20020099233A1 - Process for making silanol stopped oligomeric materials - Google Patents
Process for making silanol stopped oligomeric materials Download PDFInfo
- Publication number
- US20020099233A1 US20020099233A1 US10/055,199 US5519902A US2002099233A1 US 20020099233 A1 US20020099233 A1 US 20020099233A1 US 5519902 A US5519902 A US 5519902A US 2002099233 A1 US2002099233 A1 US 2002099233A1
- Authority
- US
- United States
- Prior art keywords
- partially neutralized
- polybasic acid
- salt
- strong base
- solvent
- 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
Classifications
-
- 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 System
- 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
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
-
- 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
Definitions
- This invention relates to a process for the production of low molecular weight silanol-stopped materials by reacting hexaorganocyclotrisiloxanes with water in the presence of catalytic amounts of a strong base.
- the reaction is preferably run in a water/acetone system.
- silanol stopped oligomeric siloxane materials are made by two processes.
- the first process involves controlled hydrolysis of dichlorodimethylsilane in a water/polar solvent mixture in the presence of a neutralizing agent, such as sodium bicarbonate or ammonia. This process produces a significant amount of waste and about 30% of cyclic oligomers which have to be removed from the final product by vacuum stripping.
- the second process involves ring opening polymerization of hexamethylcyclotrisiloxane in a water/organic solvent mixture in the presence of acid-activated clay, (such as FILTROL-20) as disclosed in U.S. Pat. No. 3,853,932, or the acidic or basic ion exchange resins as described in for instance, U.S. Pat. No. 3,309,390.
- acid-activated clay such as FILTROL-20
- the process requires filtration of the catalyst and high vacuum distillation to remove cyclic oligomers formed during the ring opening polymerization.
- the present invention provides for a process for the production of linear silanol stopped siloxanes comprising:
- R 1 and R 2 are independently selected from the group of one to forty carbon atom monovalent radicals, in a solvent comprising a mixture of water and a volatile polar, aprotic organic solvent in the presence of catalytic amounts of a strong base;
- cyclic oligomer by-product such as octamethylcyclotetrasiloxane, D4, is very low.
- D 3 also preferred to as hexaorganocyclotrisiloxane, is defined as follows:
- R 1 and R 2 are independently selected from the group of one to forty carbon atom monovalent radicals where such radicals may or may not be substituted by other substituents, e.g. halogen atoms.
- substituents e.g. halogen atoms.
- this definition specifically includes, without limitation, fluoro substituted radicals such as 3,3,3-trfluoropropyl as well as perhalo-alkyl radicals and perhalo-aryl radicals.
- the catalyst With respect to neutralization, the catalyst must be neutralized to prevent condensation of the silanols during removal of solvents. It is preferable to be close to a pH 7 after neutralization of the basic catalyst preferably the pH range after neutralization is from about 6.7 to about 7.3, more preferably from about 6.5 to about 7.5 and most preferably from about 6.0 to about 8.0. This may be accomplished by measuring the base content of the reaction and precisely measuring any acid, including hydrochloric, sulfuric, acetic, etc. However, such an approach requires strict control of the concentration of acids, because if any slight excess or absence of such acids from exact stoichiometry would result in a pH which is too high or too low and cause loss of silanol during stripping.
- Useful deactivating agents include carbon dioxide, and acidic salts of polybasic acids. Under some conditions even carbon dioxide can produce deactivated salts which are too high in pH.
- polybasic acids are acids containing more than one neutralizable acid functionality per molecule, which when partially neutralized function as a buffering agent for control of pH. Therefore, most preferred are salts whose aqueous solution are close to pH 7 and which will react with the basic catalyst to produce deactivation salts which are also in the range of pH 6 to pH 8.
- Preferred are the monobasic salts of di- or tri-basic acids (a subset of polybasic acids). Such salts would include the partially neutralized alkali metal salts of such polybasic acids, e.g.
- sodium or potassium hydrogen sulfate mono sodium or potassium oxalate and other dibasic organic acids, e.g. mono sodium or potassium dilhydrogenphosphate. Most preferred is the mono sodium or potassium dihydrogenphosphate.
- alkali metal includes lithium, sodium, potassium, rubidium and cesium.
- the process of the present invention produces linear siloxanes in excess of 90% yield and preferably in excess of 93% yield, more preferably in excess of 95% yield and most preferably in excess of 97% yield.
- the process of the present invention allows the production of linear silanol-stopped oligomers with a higher yield than known processes.
- the process of the present invention provides a faster rate of reaction, and the filtration step required in the prior art is eliminated by the use of a homogenous catalyst system.
- the process of the present invention produces less cyclic byproduct than the prior art, thereby eliminating the need for a high vacuum distillation.
- the silanol content was determined by placing a thin layer of the sample in a cup, evaporating the residual acetone, then performing an FTIR.
- the D3+D4 content after four hours of reaction was determined to be 5.67% and the silanol content to be 7.14%.
- the D3+D4 content after six hours of reaction was determined to be 5.66% and the silanol content to be about 6.95%.
Abstract
A process for the production of linear silanol stopped siloxanes comprising: a) conducting a ring opening polymerization of a hexaorganocyclotrisiloxane having the formula:
D3=(R1R2SiO)3
where R1 and R2 are independently selected from the group of one to forty carbon atom monovalent radicals, in a solvent comprising a mixture of water and a volatile polar aprotic organic solvent in the presence of catalytic amounts of a strong base; b) neutralizing the catalytic amount of the strong base with a partially neutralized salt of a polybasic acid wherein the pH ranges from about 6 to about 8; and c) washing with water.
Description
- This application claims priority to U.S. application Ser. No. 60/263,911, filed Jan. 24, 2001, which is incorporated by reference in its entirety.
- This invention relates to a process for the production of low molecular weight silanol-stopped materials by reacting hexaorganocyclotrisiloxanes with water in the presence of catalytic amounts of a strong base. The reaction is preferably run in a water/acetone system.
- 1. Brief Description of the Related Art
- Currently, silanol stopped oligomeric siloxane materials are made by two processes. The first process involves controlled hydrolysis of dichlorodimethylsilane in a water/polar solvent mixture in the presence of a neutralizing agent, such as sodium bicarbonate or ammonia. This process produces a significant amount of waste and about 30% of cyclic oligomers which have to be removed from the final product by vacuum stripping.
- The second process involves ring opening polymerization of hexamethylcyclotrisiloxane in a water/organic solvent mixture in the presence of acid-activated clay, (such as FILTROL-20) as disclosed in U.S. Pat. No. 3,853,932, or the acidic or basic ion exchange resins as described in for instance, U.S. Pat. No. 3,309,390. The process requires filtration of the catalyst and high vacuum distillation to remove cyclic oligomers formed during the ring opening polymerization.
- 2. Summary of the Invention
- Broadly conceived the present invention provides for a process for the production of linear silanol stopped siloxanes comprising:
- a) conducting a ring opening polymerization of a hexaorganocyclotrisiloxane having the formula:
- D3=(R1R2SiO)3
- where R 1 and R2 are independently selected from the group of one to forty carbon atom monovalent radicals, in a solvent comprising a mixture of water and a volatile polar, aprotic organic solvent in the presence of catalytic amounts of a strong base;
- b) neutralizing the catalytic amount of the strong base with a partially neutralized salt of a polybasic acid wherein the pH ranges from about 6 to about 8; and optionally
- c) washing with water to remove salts, or, alternatively, stripping water and acetone from the batch and filtering the neutral salts.
- The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein.
- Before the present compositions of matter and methods are disclosed and described, it is to be understood that this invention is not intended to be limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.
- In the following specification, reference will be made to a number of terms that shall be defined to have the following meanings:
- The singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise.
- “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
- It has been discovered that a ring opening polymerization of hexamethylcyclotrisiloxane, D 3, in water/volatile polar, aprotic organic solvent mixture in the presence of catalytic amounts of a strong base such as LiOH, NaOH, KOH, or a mixture thereof proceeds with a high rate to afford linear oligomeric silanol-stopped siloxanes with a high yield, typically above about 90%. The volatile polar organic solvent used with water to form the solvent of the process must be miscible with water. Non-limiting examples of such volatile polar aprotic organic solvents are low molecular weight ketones, e.g. acetone. The amount of cyclic oligomer by-product, such as octamethylcyclotetrasiloxane, D4, is very low. As used herein D3, also preferred to as hexaorganocyclotrisiloxane, is defined as follows:
- D3=(R1R2SiO)3
- where R 1 and R2 are independently selected from the group of one to forty carbon atom monovalent radicals where such radicals may or may not be substituted by other substituents, e.g. halogen atoms. In addition to the alkyl aralkyl and aryl groups subtended by the phrase “one to forty carbon atom monovalent radicals,” this definition specifically includes, without limitation, fluoro substituted radicals such as 3,3,3-trfluoropropyl as well as perhalo-alkyl radicals and perhalo-aryl radicals.
- After neutralization of the strong base with weak acids, such as carbon dioxide or acidic salts, and a subsequent water wash, the system is stable. The removal of the volatile polar aprotic organic solvent, e.g. acetone, by a simple distillation yields the desired silanol-stopped organosiloxanes with high yield. It was unexpectedly found that the process does not require filtration (because no solis are present after a water wash), and high vacuum distillation (since only small amounts of non functional cyclic siloxanes, such as octamethylcyclotetrasiloxane are formed).
- With respect to neutralization, the catalyst must be neutralized to prevent condensation of the silanols during removal of solvents. It is preferable to be close to a pH 7 after neutralization of the basic catalyst preferably the pH range after neutralization is from about 6.7 to about 7.3, more preferably from about 6.5 to about 7.5 and most preferably from about 6.0 to about 8.0. This may be accomplished by measuring the base content of the reaction and precisely measuring any acid, including hydrochloric, sulfuric, acetic, etc. However, such an approach requires strict control of the concentration of acids, because if any slight excess or absence of such acids from exact stoichiometry would result in a pH which is too high or too low and cause loss of silanol during stripping. Useful deactivating agents include carbon dioxide, and acidic salts of polybasic acids. Under some conditions even carbon dioxide can produce deactivated salts which are too high in pH. As used herein polybasic acids are acids containing more than one neutralizable acid functionality per molecule, which when partially neutralized function as a buffering agent for control of pH. Therefore, most preferred are salts whose aqueous solution are close to pH 7 and which will react with the basic catalyst to produce deactivation salts which are also in the range of pH 6 to pH 8. Preferred are the monobasic salts of di- or tri-basic acids (a subset of polybasic acids). Such salts would include the partially neutralized alkali metal salts of such polybasic acids, e.g. sodium or potassium hydrogen sulfate, mono sodium or potassium oxalate and other dibasic organic acids, e.g. mono sodium or potassium dilhydrogenphosphate. Most preferred is the mono sodium or potassium dihydrogenphosphate. As used herein the term alkali metal includes lithium, sodium, potassium, rubidium and cesium. By varying the molar ratio of this salt to the catalyst, the pH of the deactivated catalyst can easily be maintained near pH 7. Even when the amount of sodium dihydrogeiiphosphate is in excess or shortfall, the pH will remain near pH 7. The most preferred ratio is 2 moles of sodium dihydrogenphosphate per mole of basic catalyst.
- The process of the present invention produces linear siloxanes in excess of 90% yield and preferably in excess of 93% yield, more preferably in excess of 95% yield and most preferably in excess of 97% yield.
- The process of the present invention allows the production of linear silanol-stopped oligomers with a higher yield than known processes. The process of the present invention provides a faster rate of reaction, and the filtration step required in the prior art is eliminated by the use of a homogenous catalyst system. The process of the present invention produces less cyclic byproduct than the prior art, thereby eliminating the need for a high vacuum distillation.
- The following examples are set forth to provide those of ordinary skill in the are with a complete description of how the compositions of matter and methods claimed herein are made and evaluated, and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to insure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are by weight, temperature is in ° C.
- A 1000 ml reactor equipped with condenser, mechanical stirrer and addition funnel was charged with acetone (987 g), water (50 g) and D3 (444 g, 2 mols). The reaction mixture was heated to 7° C. When temperature was stabilized, 0.042 g (0.0018 mol) of lithium hydroxide was added to start the reaction. The conversion of D3 was followed by gas chromotography. The reaction was stopped at the point when conversion of D3 was above 95%. The lithium hydroxide was neutralized by an addition of solid carbon dioxide (2 grams) into the flask. The reaction was cooled to 50° and was washed with 100 grams of water. The water layer was removed from the flask. Subsequently, the vacuum was slowly applied to remove the acetone and residual D3. The resulting silanol-stopped oligosiloxane (yield above 93%) was analyzed by gas chromatography.
- In an experiment, using a 500 ml flask with a condenser and a mechanical stirrer, D3 (150 grams) acetone (36 grams) and water (20 grams) were charged. The reaction mixture was heated to 61.5 to 62° C. After the temperature stabilized, 175 ppm of potassium hydroxide based on total weight was added. Samples were taken periodically to follow the reaction by gas chromatography. Samples were neutralized by the addition of carbon dioxide. The reaction continued for six hours when sodium dihydrogen phosphate monohydrate (0.2 grams) was added to neutralize and buffer the reaction mixture. The reaction was washed three times with water. The silanol content was determined by placing a thin layer of the sample in a cup, evaporating the residual acetone, then performing an FTIR. The D3+D4 content after four hours of reaction was determined to be 5.67% and the silanol content to be 7.14%. The D3+D4 content after six hours of reaction was determined to be 5.66% and the silanol content to be about 6.95%.
- An Example of the Current Art
- Charge 84 g methyl trimer, 43 g of acetone, and 13 g of water into a 500 ml reaction vessel with agitator and condenser. Add 2.5 g of Filtrol 20 as a catalyst. Heat to reflux for 16 hours. G. C. analysis shows less than 5% trimer. Add 0.2 g of magnesium oxide to neutralize the Filtrol 20. Agitate and for two hours. Turn off agitation and let the batch separate for 30 minutes. Separate and discard the aqueous bottom layer. Cool until room temperature. Add 1 g of Celite 545, agitate for 10 minutes. Filter to remove all solids. Return a filtrate to a clean 500 ml flask with agitator and with vacuum capability. Add vacuum slowly until 100 mm Hg. Then heat the batch to 120° C. Vacuum strip until D3 content and D4 content combined is less than 5% by GC. 80 g of product was isolated giving a 93% yield.
- This invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims (20)
1. A process for the production of linear silanol stopped siloxanes comprising:
a) conducting a ring opening polymerization of a hexaorganocyclotrisiloxane having the formula:
D3=(R1R2SiO)3
where R1 and R2 are independently selected from the group of one to forty carbon atom monovalent radicals, in a solvent comprising a mixture of water and a volatile polar, aprotic organic solvent in the presence of catalytic amounts of a strong base; and
b) neutralizing the catalytic amount of the strong base with a partially neutralized salt of a polybasic acid wherein the pH ranges from about 6 to about 8.
2. The process of claim 1 further comprising the step of removing the volatile polar aprotic organic solvent.
3. The process of claim 1 where the volatile polar aprotic solvent is a low molecular weight ketone.
4. The process of claim 3 where the low molecular weight ketone is acetone.
5. The process of claim 4 where the partially neutralized salt of a polybasic acid is an alkali metal salt.
6. The process of claim 5 where the partially neutralized salt of a polybasic acid is a potassium salt.
7. The process of claim 3 where the partially neutralized salt of a polybasic acid is a sodium salt.
8. The process of claim 6 where R is methyl.
9. The process of claim 7 where R1 is methyl.
10. The process of claim 5 where R1 is 3,3,3-trifluoropropyl.
11. A process for the production of linear silanol stopped siloxanes consisting essentially of:
a) conducting a ring opening polymerization of a hexaorganocyclotrisiloxane having the formula:
D3=(R1R2SiO)3
where R1 and R2 are independently selected from the group of one to forty carbon atom monovalent radicals, in a solvent comprising a mixture of water and a volatile polar aprotic organic solvent in the presence of catalytic amounts of a strong base; and
neutralizing the catalytic amount of the strong base with a partially neutralized salt of a polybasic acid wherein the pH ranges from about 6 to about 8; and
12. The process of claim 11 further comprising the step of removing the volatile polar aprotic organic solvent.
13. The process of claim 12 where the volatile polar aprotic solvent is a low molecular weight ketone.
14. The process of claim 13 where the low molecular weight ketone is acetone.
15. The process of claim 14 where the partially neutralized salt of a polybasic acid is an alkali metal salt.
16. The process of claim 15 where the partially neutralized salt of a polybasic acid is a potassium salt.
17. The process of claim 15 where the partially neutralized salt of a polybasic acid is a sodium salt.
18. The process of claim 16 where R1 is methyl.
19. The process of claim 17 where R1 is methyl.
20. The process of claim 15 where R1 is 3,3,3-trifluoropropyl.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2002/022501 WO2002092607A1 (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
| EP02756491A EP1358191B1 (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
| AT02756491T ATE382625T1 (en) | 2001-01-24 | 2002-01-23 | METHOD FOR PRODUCING SILANOL-TERMINATED OLIGOMERS |
| CNB028040090A CN100408585C (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
| ES02756491T ES2296980T3 (en) | 2001-01-24 | 2002-01-23 | PROCEDURE FOR THE PREPARATION OF OLIGOMERIC MATERIALS ENDED IN SILANOL. |
| JP2002589490A JP4147115B2 (en) | 2001-01-24 | 2002-01-23 | Method for producing silanol-terminated oligomeric material |
| US10/055,199 US6433204B1 (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
| KR10-2003-7009716A KR20030094237A (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
| DE60224362T DE60224362T2 (en) | 2001-01-24 | 2002-01-23 | PROCESS FOR PREPARING SILANOL TERMINATED OLIGOMERS |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26391101P | 2001-01-24 | 2001-01-24 | |
| US10/055,199 US6433204B1 (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20020099233A1 true US20020099233A1 (en) | 2002-07-25 |
| US6433204B1 US6433204B1 (en) | 2002-08-13 |
Family
ID=26733955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/055,199 Expired - Fee Related US6433204B1 (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6433204B1 (en) |
| EP (1) | EP1358191B1 (en) |
| JP (1) | JP4147115B2 (en) |
| KR (1) | KR20030094237A (en) |
| CN (1) | CN100408585C (en) |
| AT (1) | ATE382625T1 (en) |
| DE (1) | DE60224362T2 (en) |
| ES (1) | ES2296980T3 (en) |
| WO (1) | WO2002092607A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625241A (en) * | 2020-10-12 | 2021-04-09 | 湖北兴瑞硅材料有限公司 | Synthesis method of low-viscosity hydroxyl silicone oil |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040000940A (en) * | 2002-06-26 | 2004-01-07 | 알비페인트 주식회사 | Method for Manufacturing Infinitesimal Siloxane Reactive Polymer |
| JP2012140391A (en) * | 2011-01-06 | 2012-07-26 | Shin-Etsu Chemical Co Ltd | Method for production of low-molecular weight linear organopolysiloxane having silanol groups at both terminals |
| CN104004009B (en) * | 2014-03-18 | 2016-06-29 | 杭州洛科曼有机硅有限公司 | A kind of synthetic method of poly dimethyl silicon diol |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3309390A (en) | 1963-07-01 | 1967-03-14 | Union Carbide Corp | Preparation of hydroxy-endblocked siloxane fluids |
| US3853932A (en) | 1973-12-28 | 1974-12-10 | Gen Electric | Process for producing silanol end-stopped polymers of low molecular weight |
| US4272624A (en) * | 1974-04-24 | 1981-06-09 | General Electric Company | Process for producing high molecular weight diorganopolysiloxanes for use in heat vulcanizable silicone rubber compositions |
| US4287353A (en) * | 1979-11-09 | 1981-09-01 | General Electric Company | Process for synthesizing silanol chain-stopped fluorosiloxane fluids |
| US4267298A (en) * | 1979-11-09 | 1981-05-12 | General Electric Company | Process for preparing M-stopped silicone fluids from silanol fluids |
| US4281146A (en) * | 1979-12-26 | 1981-07-28 | General Electric Company | Method of neutralizing a halogen silicone compound |
| US4683277A (en) * | 1986-07-02 | 1987-07-28 | Dow Corning Corporation | Method for preparing vinyl terminated fluorine-containing polydiorganosiloxane |
| US4897459A (en) * | 1987-11-25 | 1990-01-30 | General Electric Company | Catalyst for producing fluorosilicone polymers |
| JP2538309B2 (en) * | 1988-04-25 | 1996-09-25 | チッソ株式会社 | Method for producing polysiloxane |
| US5087683A (en) * | 1989-02-07 | 1992-02-11 | Shin-Etsu Chemical Co. Ltd. | Process for producing α, ω-hydroxyfluoroalkylpolysiloxanes |
| JP3155547B2 (en) * | 1990-11-29 | 2001-04-09 | 東レ・ダウコーニング・シリコーン株式会社 | Diphenylsiloxane / dimethylsiloxane copolymer and method for producing the same |
| US5969173A (en) * | 1998-12-01 | 1999-10-19 | Dow Corning Corporation | Method of making dialkali metal silanolates and siloxanolates |
| US6316655B1 (en) * | 2001-02-20 | 2001-11-13 | Dow Corning Corporation | Method of making hydroxy end-terminated linear siloxanes |
-
2002
- 2002-01-23 KR KR10-2003-7009716A patent/KR20030094237A/en active IP Right Grant
- 2002-01-23 DE DE60224362T patent/DE60224362T2/en not_active Expired - Fee Related
- 2002-01-23 JP JP2002589490A patent/JP4147115B2/en not_active Expired - Fee Related
- 2002-01-23 WO PCT/US2002/022501 patent/WO2002092607A1/en active IP Right Grant
- 2002-01-23 EP EP02756491A patent/EP1358191B1/en not_active Expired - Lifetime
- 2002-01-23 AT AT02756491T patent/ATE382625T1/en not_active IP Right Cessation
- 2002-01-23 ES ES02756491T patent/ES2296980T3/en not_active Expired - Lifetime
- 2002-01-23 US US10/055,199 patent/US6433204B1/en not_active Expired - Fee Related
- 2002-01-23 CN CNB028040090A patent/CN100408585C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625241A (en) * | 2020-10-12 | 2021-04-09 | 湖北兴瑞硅材料有限公司 | Synthesis method of low-viscosity hydroxyl silicone oil |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1358191B1 (en) | 2008-01-02 |
| EP1358191A1 (en) | 2003-11-05 |
| CN1487945A (en) | 2004-04-07 |
| JP2004536170A (en) | 2004-12-02 |
| KR20030094237A (en) | 2003-12-11 |
| US6433204B1 (en) | 2002-08-13 |
| DE60224362D1 (en) | 2008-02-14 |
| DE60224362T2 (en) | 2008-12-18 |
| WO2002092607A8 (en) | 2004-07-15 |
| WO2002092607A1 (en) | 2002-11-21 |
| CN100408585C (en) | 2008-08-06 |
| ES2296980T3 (en) | 2008-05-01 |
| ATE382625T1 (en) | 2008-01-15 |
| JP4147115B2 (en) | 2008-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7563917B2 (en) | Silicon compound and a production process for silicon compound | |
| JPH0689006B2 (en) | Method for producing tetramethyldisiloxane diol | |
| US3842110A (en) | Process for producing octaphenyltetracyclosiloxane | |
| US6433204B1 (en) | Process for making silanol stopped oligomeric materials | |
| EP0535947B1 (en) | Inorganic acid catalyzed silylation reactions | |
| EP2473549B1 (en) | Synthesis of fluorocarbofunctional silsesquioxanes | |
| EP0698632A1 (en) | Process for preparing organosiloxane terminated with silanol group | |
| US5532399A (en) | Process for the preparation or organosilicon compounds carrying sulfur-containing organic radicals | |
| US7015296B2 (en) | Preparation of linear organosiloxane polymers | |
| JP5440381B2 (en) | Method for producing low molecular weight linear organopolysiloxane having silanol groups at both ends | |
| AU2002322497A1 (en) | Process for making silanol stopped oligomeric materials | |
| JP3206384B2 (en) | Method for producing alkoxysiloxane | |
| EP1006117A2 (en) | Method of making dialkali metal silanolates and siloxanolates | |
| JP3252642B2 (en) | Method for producing low molecular weight organosilane or siloxane having silanol group | |
| KR101064063B1 (en) | Organic Silicon Resin Having Alcoholic Hydroxyl Group and Method for Producing the Same | |
| JPH07286043A (en) | Production of organopolysiloxane | |
| US3923834A (en) | Siloxanediolate complexes and preparation thereof | |
| EP0922723B1 (en) | Method for preparation of potassium silanolates | |
| US4003917A (en) | Siloxanediolate complexes and preparation thereof | |
| US7915440B2 (en) | Method for preparing solid polyorganosiloxane | |
| US4065482A (en) | Siloxanediolate complexes and preparation thereof | |
| SU757536A1 (en) | Method of preparing orthosilicic acid esters | |
| JP4172342B2 (en) | Cyclic organosilicon compound and method for producing the same | |
| JP2012140391A (en) | Method for production of low-molecular weight linear organopolysiloxane having silanol groups at both terminals | |
| JPH0786114B2 (en) | Method for producing bis (mercaptoalkyl) tetraorganodisiloxane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GOSH, NANCY E.;RAZZANO, JOHN S.;RUBINSZTAJN, SLAWOMIR;REEL/FRAME:012529/0511 Effective date: 20020122 |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| AS | Assignment |
Owner name: JPMORGAN CHASE BANK, N.A. AS ADMINISTRATIVE AGENT, Free format text: SECURITY AGREEMENT;ASSIGNORS:MOMENTIVE PERFORMANCE MATERIALS HOLDINGS INC.;MOMENTIVE PERFORMANCE MATERIALS GMBH & CO. KG;MOMENTIVE PERFORMANCE MATERIALS JAPAN HOLDINGS GK;REEL/FRAME:019511/0166 Effective date: 20070228 |
|
| AS | Assignment |
Owner name: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., A Free format text: SECURITY AGREEMENT;ASSIGNORS:MOMENTIVE PERFORMANCE MATERIALS, INC.;JUNIPER BOND HOLDINGS I LLC;JUNIPER BOND HOLDINGS II LLC;AND OTHERS;REEL/FRAME:022902/0461 Effective date: 20090615 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20100813 |
|
| AS | Assignment |
Owner name: MOMENTIVE PERFORMANCE MATERIALS JAPAN HOLDINGS GK, JAPAN Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:054387/0001 Effective date: 20201102 Owner name: MOMENTIVE PERFORMANCE MATERIALS INC., NEW YORK Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:054387/0001 Effective date: 20201102 Owner name: MOMENTIVE PERFORMANCE MATERIALS GMBH & CO KG, GERMANY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:054387/0001 Effective date: 20201102 |
|
| AS | Assignment |
Owner name: MOMENTIVE PERFORMANCE MATERIALS INC., NEW YORK Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS COLLATERAL AGENT;REEL/FRAME:054883/0855 Effective date: 20201222 |