WO2004003058A2 - Procede pour produire une resine d'organopolysiloxane - Google Patents

Procede pour produire une resine d'organopolysiloxane Download PDF

Info

Publication number
WO2004003058A2
WO2004003058A2 PCT/JP2003/008251 JP0308251W WO2004003058A2 WO 2004003058 A2 WO2004003058 A2 WO 2004003058A2 JP 0308251 W JP0308251 W JP 0308251W WO 2004003058 A2 WO2004003058 A2 WO 2004003058A2
Authority
WO
WIPO (PCT)
Prior art keywords
component
manufacturing
hydrogen chloride
organopolysiloxane resin
hydrolyzable
Prior art date
Application number
PCT/JP2003/008251
Other languages
English (en)
Other versions
WO2004003058A3 (fr
Inventor
Ryuko Manzouji
Makoto Yoshitake
Original Assignee
Dow Corning Toray Silicone Co.,Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Silicone Co.,Ltd. filed Critical Dow Corning Toray Silicone Co.,Ltd.
Priority to AU2003245039A priority Critical patent/AU2003245039A1/en
Publication of WO2004003058A2 publication Critical patent/WO2004003058A2/fr
Publication of WO2004003058A3 publication Critical patent/WO2004003058A3/fr

Links

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
    • C08G77/08—Preparatory processes characterised by the catalysts used

Definitions

  • the present invention relates to a method for manufacturing an organopolysiloxane resin, and more particularly relates to a method for manufacturing an organopolysiloxane resin having extremely little precipitate, which allows unreacted raw material and by-products to be reused, and which affords excellent productivity.
  • a commonly known method for manufacturing an organopolysiloxane resin is to employ hydrolytic condensation, using an organohalogenosilane as the main raw material.
  • a drawback to this method is that if the reaction proceeds all at once, it is difficult to control the condensation reaction between the silanol groups.
  • a method that has been proposed for solving these problems is to manufacture an organopolysiloxane resin in which a suitable amount of silanol groups or alkoxy groups remain, by controlling the reaction through the use of an alcohol.
  • Japanese Patent Publication S46-41396 (corresponding foreign patent: GB1192506) and Japanese Patent Publication S48-14680 (corresponding foreign patent: GB1294196) discussed methods for stably obtaining an organopolysiloxane resin by using an alcohol and acetone.
  • the drawback to these methods was the low efficiency of the reaction apparatus because such a large quantity of water was used. Recovering, refining, and reusing the organic solvent also posed serious difficulties.
  • Japanese Patent Application Publication(Kokai) S50-77500 proposed a method in which an organohalosilane was reacted with an alcohol and water to undergo alkoxidation, then more alcohol was added to adjust the acidity to between 1 and 300 ppm, and then water was added to effect hydrolysis.
  • One drawback to this method was that the manufacturing process was complicated and it took a long time to remove the hydrogen halide, resulting in low manufacturing efficiency.
  • Another drawback was that when the methylpolysiloxane resin was produced a large quantity of precipitate also resulted.
  • One object of the present invention to provide a method for manufacturing an organopolysiloxane resin having extremely little precipitate, which allows unreacted raw material and by-products to be reused, and which affords excellent productivity.
  • the present invention relates to a method for manufacturing an organopolysiloxane resin(E) having the average compositional formula R a SiO( 4 _ a ) 2 and containing siloxane units having the formula RSi0 3/2 , comprising the steps:
  • step (1) of the present method a hydrolyzable silane (A) or a mixture of the hydrolyzable silane (A) and a hydrolyzable siloxane (B) is hydrolyzed.
  • Component (A) useful in step (1) of the present method consists of at least one hydrolyzable silane including a silane described by the general formula R'SiX 3 .
  • Component (A) can be either a hydrolyzable silane described by the above formula by itself or a mixture of said silane and another hydrolyzable silane.
  • Component (B) useful in step (1) is a mixture of said Component (A) and a hydrolyzable siloxane.
  • Camponent (B) can be a mixture of a silane described by the above formula R SiX 3 and a hydrolyzable siloxane, or a mixture of a silane described by the above formula R'SiX ⁇ another hydrolyzable silane, and a hydrolyzable siloxane.
  • the group R 1 in the above formula R ! SiX 3 is a non- hydrolyzable monovalent organic group, which is exemplified by an unsubstituted monovalent hydrocarbon group, a substituted monovalent hydrocarbon group, and a monovalent organofunctional group of which carbon atom bonds to the silicone atom.
  • non- hydrolyzable monovalent organic group examples include methyl, ethyl, propyl, butyl, hexyl, or other alkyl groups, vinyl, allyl, or other alkenyl group, cyclohexyl or other cycloalkyl group, phenyl or other aryl group, benzyl, styrenyl, or other aralkyl group, or another such unsubstituted monovalent hydrocarbon group; 3,3,3-trifluoropropyl or other perfluoroalkyl groups, chlorophenyl, or other halogen-substituted monovalent hydrocarbon group; 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxy
  • the group X in the above formula R ⁇ iXs is a hydrolyzable group bonded to a silicon atom.
  • X include a chlorine atom, bromine atom, or other halogen atom; methoxy, ethoxy, propoxy, butoxy, or other alkoxy group; an alkenoxy group; an acyloxy group; an amide group; and an oxime group.
  • a halogen atom is preferred, and a chlorine atom is particularly favorable from the standpoint of ready availability, ease of removal in step (2), cost, and so forth.
  • the hydrolyzable groups X in a single molecule may all be the same, or two or more different groups may be used.
  • Examples of hydrolyzable silanes other than the silane expressed by the above formula R'SiXs include silanes described by the formula R ! 2 SiX 2 , silanes described by the formula SLX 4 , and silanes described by the formula R ! 3 SiX where R 1 and X are as defined above.
  • component (A) is generally a silane described by the formula R'SiXs by itself, or a mixture of a silane described by the formula R ⁇ iXs and a silane described by the formula R ! 2 SiX 2 , but a silane described by the formula S1X 4 or a silane described by the formula R ! 3 SiX may also be used together with the above.
  • the hydrolyzable siloxane (B) is a siloxane containing a hydrolyzable group bonded to a silicon atom. From a siloxane oligomer with low molecular weight to a liner organopolysiloxane with high molecular weight can be used as component (B). Of these, a liner, cyclic, or branched liner siloxane oligomer is preferred. Examples of this hydrolyzable group are the same as those listed above for X. Examples of the group bonded to a silicon atom other than a hydrolyzable group are the same as those listed above for R 1 . This hydrolyzable siloxane may also be a partially hydrolyzed condensate of component (A).
  • component (B) examples include hexamethoxydisiloxane, hexaethoxydisiloxane, dimethyltetraethoxydisiloxane, tris(methoxydimethylsiloxy)silane, and ethylpolysilicate.
  • Component (C) serves to suppress the generation of gelled substances and microcrystalline precipitate, and is described by the general formula R 2 OH.
  • R 2 in the formula is a Ci to C 8 alkyl group or alkyloxyethyl group. It has been found that if there are more than eight carbon atoms, reactivity will decrease during hydrolysis, and the substance will become a solid and more difficult to handle.
  • component (C) examples include methanol, ethanol, isopropanol, n-butanol, isobutanol, and other monovalent unsubstituted alcohols; and methoxyethanol, ethoxyethanol, butoxyethanol, and other ether alcohols. These may be used singly or in mixtures of two or more types. Of these, methanol, ethanol, and isopropanol are preferred because the reactivity of the hydrolyzate is better, a suitable reflux temperature is obtained in steps (2) to (4), and the substance is very easy to handle.
  • Component (D) which is a hydrogen chloride aqueous solution is one of the characteristic features of the present invention, and serves to hydrolyze component (A) and component (B).
  • the hydrogen chloride concentration in component (D) is not restricted, but greater than 20 wt% is preferable, and 25 wt% or greater is even better.
  • a saturated hydrogen chloride aqueous solution (at least 35 wt%) is generally used because of its ready availability.
  • step (1) component (C) and component (D) are used in amounts such that the ratio of the combined gram equivalents of component (C) and the water in component (D) to the gram equivalents of component (A) or component (B) is 0.9 to 2.0, preferably 1.0 to 1.5, and even more preferably 1.0 to 1.3. It has been found that if the ratio is below this range, many hydrolyzable groups will remain unreacted and it will be difficult to control the reaction during the hydrolytic condensation in step (3), but if the ratio is over the above range, the reaction will be difficult to control and manufacturing efficiency will decrease.
  • the ratio of the gram equivalents of water in component (D) to the gram equivalents of component (A) or component (B) is between 0.3 and 0.95, and preferably between 0.5 and 0.9. This is because if the ratio is below this range, a great deal of gelled substance or microcrystalline precipitate will be generated, but if the ratio is too high, there will be a decrease in manufacturing efficiency.
  • the gram equivalents are calculated by dividing the amount used (grams) by the chemical equivalent. Table 1 below lists the chemical equivalents for compounds typical of the various components, and shows how to calculate the gram equivalent.
  • the hydrolysis is generally accomplished by a method in which component (A) or component (B) is added dropwise to a mixture of component (C) and component (D), but component (C) and component (D) may instead be added dropwise to component (A) or component (B).
  • component (C) and component (D) may instead be added dropwise to component (A) or component (B).
  • the water contained in component (C) and the water produced by the reaction between component (C) and the by-product hydrogen halide sometimes participates in the hydrolysis in step (1), but does not hinder the progress of the present invention in any way.
  • component (D) may be added in two batches here. In this case, it is preferred for the entire amount of component (C) be used during the mixing of the first batch of component (D).
  • the proportions of the first and second batches of component (D) may be varied as desired.
  • the hydrogen chloride concentration of component (D) added in the second batch it is preferable for the hydrogen chloride concentration of component (D) added in the second batch be greater than 20 wt%, and a saturated hydrogen chloride aqueous solution is generally used, as mentioned above.
  • a saturated hydrogen chloride aqueous solution may be used for the first batch of component (D), but the mixture of hydrogen chloride and water present in the azeotropic component removed in step (4) may also be utilized.
  • the proportion of hydrogen chloride versus the combined amount of water and hydrogen chloride here is preferably greater than 20 wt%.
  • component (F) an organic solvent that is inert with respect to the hydrolysis reaction in order to control the reaction.
  • An inert organic solvent is one that is substantially immiscible with water.
  • inert organic solvents include benzene, toluene, xylene, petroleum ether, petroleum benzine, gasoline, naphtha, cyclohexane, and other hydrocarbon-based solvents; trichloroethylene, tetrachloroethylene, chlorobenzene, and other halogenated hydrocarbon-based solvents; ethyl acetate, butyl acetate, and other ester-based solvents; and mixtures of these.
  • the amount in which this solvent is used should be 50 to 500 weight parts, and preferably 100 to 300 weight parts, in each case per 100 weight parts component (A) or component (B).
  • An example of a specific method is to mix component (A) or (B) with component (F), mix this mixture with a mixture of components (C), (D), and (F), and then add more component (D).
  • Step (2) involves removing the hydrogen chloride by heating.
  • This step controls the reaction by lowering the acid concentration in the reaction system.
  • the heating temperature There are no particular restrictions on the heating temperature, but 40°C or higher is preferable, and 60°C or higher is even more preferable. When manufacturing efficiency is taken into account, the heating should last no longer than 120 minutes.
  • This step should be carried out under reflux conditions until the acid concentration in the reaction system reaches 1/10 or lower, and bubbling, reduced pressure, or another such means may be employed to shorten the time this takes. Any volatile components removed along with the hydrogen chloride in this step should be returned to the system by cooling.
  • An inert organic solvent can be added after step (2) but before step (3) to adjust the acid concentration in the reaction system and control the reaction in step (3), thereby further suppressing precipitation.
  • this inert organic solvent are the same as those listed for component (F), which may be used singly or in mixtures.
  • the solvent may be the same as that used for component (F) in step (1), or different solvents may be used.
  • the amount used may be varied as desired, but in general, the greater the amount, the easier it will be to control the hydrolytic condensation reaction.
  • the amount is preferably at least 5 weight parts, and even more preferably at least 50 weight parts, in each case per 100 weight parts of the reaction mixture.
  • step (3) water or a hydrogen chloride aqueous solution is added to bring about a hydrolytic condensation reaction.
  • a hydrogen chloride aqueous solution for this step, a hydrogen chloride aqueous solution, water, or a mixture of these can be used.
  • the hydrogen chloride concentration of the hydrogen chloride aqueous solution may be varied as desired, but generally should be greater than 20 wt% and preferably greater than 25 wt%.
  • a saturated hydrogen chloride aqueous solution (at least 35 wt%) is generally used because of its ready availability.
  • This hydrolytic condensation reaction is generally conducted by a method in which the hydrolyzed product obtained from steps (1) and (2) is heated and stirred while water or a hydrogen chloride aqueous solution is added dropwise thereto, but the hydrolyzed product may instead be added to the water or hydrogen chloride aqueous solution.
  • the addition time, reaction time, and reaction temperature here are suitably selected so as to obtain the desired organopolysiloxane resin, but it is preferable for the reaction to be conducted under heating so as to shorten the time it takes.
  • step (4) the by-product alcohol and the hydrogen chloride, water, and organic solvent are removed as an azeotropic composition to outside the system by heating.
  • the heating temperature is preferably close to the reflux temperature of the reaction mixture, and when manufacturing efficiency is taken into account, the heating time should be 5 hours or less.
  • the acid concentration (hydrogen chloride concentration) in the reaction system should be reduced to 300 ppm or less, and to facilitate after-treatment, 50 ppm or less is preferred. If the acid concentration does not drop as much as desired, it can be further lowered by adding and distilling off alcohol or water or washing the system with water.
  • the organic solvent being used has a higher boiling point than water or the alcohol
  • the difference in boiling points of the azeotropic component can be utilized to obtain two types of fraction. Specifically, the first fraction can be obtained by continuing the heating after the alcohol, hydrogen chloride, water, and small amount of organic solvent have been distilled off, while the second fraction can be obtained by distilling off the organic solvent.
  • the first fraction can be reused as the mixture of component (C) and component (D) in step (1), while the second fraction can be reused as the organic solvent added in between step (2) and step (3).
  • the method of the present invention comprises the above steps (1) to (4) and they make progress in numerical order, but the obtained reaction product may also be neutralized or filtered as needed.
  • An ordinary neutralizer can be used for this neutralization, examples of which include ammonia gas, activated carbon, and magnesium oxide, as well as salts such as sodium carbonate and calcium carbonate.
  • the organopolysiloxane resin (E) obtained by the method of the present invention is expressed by the average compositional formula R a SiO ⁇ y ⁇ , and contains siloxane units expressed by the formula RSi0 3/2 as essential constituent units.
  • R is a monovalent organic group, and examples of R are.the same as listed above R 1 , including methoxy, ethoxy, isopropoxy, n-butoxy, isobutoxy, methoxyethoxy, or other such alkoxy group.
  • a part of R in the molecule can be substituted by hydroxyl groups.
  • siloxane units other than the siloxane unit expressed by the above formula RSi0 3 / 2 include siloxane units expressed by the formulas R 2 Si0 2 / 2 , Si0 4 / 2 , and R 3 SiO ⁇ /2 .
  • the proportion of siloxane units expressed by RSi0 3/2 in this organopolysiloxane resin is preferably at least 50 mol%, with 70 mol% or higher being more preferable.
  • the molecular structure thereof can be network, three dimensional, or branched liner.
  • the weight average molecular weight thereof is preferably between 300 and 1 ,000,000, with a range of 500 to 100,000 being more preferable, with a range of 700 to 50,000 being the most preferable.
  • This resin is in the form of a liquid or a solid at room temperature.
  • organopolysiloxane resin examples include methylpolysiloxane resin, methylpropylpolysiloxane resin, methylphenylpolysiloxane resin, phenylpolysiloxane resin, methylvinylpolysiloxane resin, vinylpolysiloxane resin, epoxy group-containing polysiloxane resin, acryl group-containing polysiloxane resin, and methacryl group-containing polysiloxane resin.
  • the above-mentioned manufacturing method of the present invention is characterized in that a hydrolyzable silane or a mixture of this hydrolyzable silane and a hydrolyzable siloxane is hydrolyzed with a hydrogen chloride aqueous solution in the presence of an alcohol, after which the acid concentration in the reaction system is reduced and condensation is then performed, so there is extremely little generation of gelled substance or microcrystalline precipitate. Accordingly, the advantages to this are that the system does not have to be allowed to stand, the filtration step takes much less time, and there is extremely little loss of yield. Furthermore, with the present invention, the alcohol, hydrogen chloride, and organic solvent removed in step (4) can be used again, which lowers manufacturing cost.
  • the manufacturing method of the present invention is favorable for the industrial production of organopolysiloxane resins, and is particularly favorable for the industrial production of methylpolysiloxane resins. Furthermore, the manufacturing method of the present invention can be applied to either a batch or continuous process.
  • the hydrogen chloride concentration in the saturated hydrogen chloride aqueous solution is 36 wt%.
  • the acid value is the number of moles of KOH required to neutralize the resin solution per unit of weight, and the acid concentration is found by measuring the amount of characteristics in the reaction system.
  • Example 1 159 g methyltrichlorosilane, 24 g dimethyldichlorosilane, and
  • the ratio of the combined gram equivalents of isopropyl alcohol and water in saturated hydrogen chloride aqueous solution to the combined gram equivalents of chlorosilanes was 1.2.
  • the system was then heated to 75°C while being bubbled with nitrogen gas at a flux of 0.3 L/min to remove the hydrogen chloride.
  • the acid value of the reaction system was thereby lowered from 4.72 mol/kg to 0.19 mol/kg.
  • 300 g toluene was then added, the temperature was brought back up to 75°C, 12.3 g of water was added dropwise, and the system was heated and refluxed for 30 minutes. After this heating and reflux, the system was heated under normal pressure to distill off 195 g of low-boiling fraction.
  • the system was then heated under normal pressure while being bubbled with nitrogen gas at a flux of 0.3 L/min to distill off another 363 g of low-boiling fraction.
  • the acid value of the resulting reaction product was 29 ppm, and the non- volatile component accounted for 49.9 wt%.
  • Example 2 82 g isopropyl alcohol, 13.7 of saturated hydrogen chloride aqueous solution, and 192 g toluene were put into a 1 L four-neck flask equipped with a stirrer, a thermometer, a condenser pipe, and a dropping funnel.
  • the acid value of the reaction system was thereby lowered from 4.84 mol/kg to 0.3 mol/kg.
  • 300 g of toluene was then added, the temperature was brought back up to 75°C, a mixture of 10.8 g of water and 2.3 g of saturated hydrogen chloride aqueous solution was added dropwise, and the system was heated and refluxed for 30 minutes. After this heating and reflux, the system was heated under normal pressure to distill off 218 g of low-boiling fraction (first fraction). The system was then heated under normal pressure while being bubbled with nitrogen gas at a flux of 0.3 L/min to distill off another 350 g of low-boiling fraction (second fraction).
  • the acid value of the resulting reaction product was 32 ppm, and the non- volatile component accounted for 50.2 wt%. Also, the fractions obtained here were analyzed by gas chromatography, coulometric titration, and neutralization titration, which showed them to comprise the following components, described in Table 2 .
  • Second fraction (350 g) hydrogen chloride 2.8 wt% toluene 99.8 wt% isopropyl alcohol 33.1 wt% isopropyl alcohol 0.2 wt% water 2.2 wt% toluene 61.4 wt% other by-products 0.5 wt%
  • Example 3 Isopropyl alcohol and water were added to the 218 g of the first fraction recovered in Example 2 so as to adjust an amount of isopropyl alcohol to 82 g and an amount of water to 8.8 g, after which the entire amount was put into a 1 L four-neck flask equipped with a stirrer, a thermometer, a condenser pipe, and a dropping funnel. A mixture of 174 g methyltrichlorosilane, 26 g dimethyldichlorosilane, and 109 g toluene was added dropwise to this flask under cooling that kept the reaction temperature from exceeding 40°C.
  • Example 2 300 g of the second fraction recovered in Example 2 was then added, the temperature was raised to 75°C, 12.3 g of water was added dropwise, and the system was heated and refluxed for 30 minutes. After this heating and reflux, the system was heated under normal pressure to distill off 208 g of low-boiling fraction. The system was then heated under normal pressure while being bubbled with nitrogen gas at a flux of 0.3 L/min to distill off another 358 g of low-boiling fraction. The acid value of the resulting reaction product was 25 ppm, and the non-volatile component accounted for 50.1 wt%.
  • Comparative Example 1 82 g isopropyl alcohol, 8.8 g water, and 192 g toluene were put into a 1 L four-neck flask equipped with a stirrer, a thermometer, a condenser pipe, and a dropping funnel. A mixture of 174 g methyltrichlorosilane, 26 g dimethyldichlorosilane, and 109 g toluene was added dropwise to this flask under cooling that kept the reaction temperature from exceeding 40°C. Upon completion of the addition, the contents were stirred for 10 minutes, 17.5 g of water was added dropwise, and the system was stirred for 10 minutes.
  • the ratio of the combined gram equivalents of isopropyl alcohol and water to the combined gram equivalents of chlorosilanes was 1.1.
  • the system was then heated to 71°C while being bubbled with nitrogen gas at a flux of 0.3 L/min to remove the hydrogen chloride.
  • the acid value of the reaction system was thereby lowered from 4.77 mol/kg to 0.3 mol/kg.
  • 300 g toluene was then added, the temperature was brought back up to 75°C, 12.3 g of water was added dropwise, and the system was heated and refluxed for 30 minutes. After this heating and reflux, the system was heated under normal pressure to distill off 195 g of low-boiling fraction.
  • the system was then heated under normal pressure while being bubbled with nitrogen gas at a flux of 0.3 L/min to distill off another 220 g of low-boiling fraction.
  • the system was further heated under normal pressure while being bubbled with nitrogen gas at a flux of 0.3 L/min to distill off another 350 g of low-boiling fraction.
  • the acid value of the resulting reaction product was 32 ppm, and the non-volatile component accounted for 50 wt%.
  • Comparative Example 2 70 g isopropyl alcohol, 134 g water, and 211 g toluene were put into a 1 L four-neck flask equipped with a stirrer, a thermometer, a condenser pipe, and a dropping funnel. A mixture of 184 g methyltrichlorosilane, 22 g dimethyldichlorosilane, and 73 g toluene was added dropwise to this flask under cooling that kept the reaction temperature from exceeding 40°C. Upon completion of the addition, the contents were stirred for 1 hour at room temperature, then heated to 80°C and heated and refluxed for 30 minutes.
  • the manufacturing method of the present invention produces the organopolysiloxane resin very efficiently, with extremely little generation of gelled substance or microcrystalline precipitate.
  • the water washing process can be substantially omitted, and unreacted raw material and by-products can be reused after the reaction, so this method is safer for the environment and less expensive, and as such is favorable for industrial production.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un procédé pour produire une résine d'organopolysiloxane, notamment une résine d'organopolysiloxane qui présente un précipité extrêmement faible, ce qui permet de réutiliser la matière brute qui n'a pas réagi et les sous-produits, conduisant ainsi à une productivité très satisfaisante.
PCT/JP2003/008251 2002-06-27 2003-06-27 Procede pour produire une resine d'organopolysiloxane WO2004003058A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003245039A AU2003245039A1 (en) 2002-06-27 2003-06-27 Method for manufacturing organopolysiloxane resin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-188773 2002-06-27
JP2002188773 2002-06-27

Publications (2)

Publication Number Publication Date
WO2004003058A2 true WO2004003058A2 (fr) 2004-01-08
WO2004003058A3 WO2004003058A3 (fr) 2004-04-01

Family

ID=29996829

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/008251 WO2004003058A2 (fr) 2002-06-27 2003-06-27 Procede pour produire une resine d'organopolysiloxane

Country Status (2)

Country Link
AU (1) AU2003245039A1 (fr)
WO (1) WO2004003058A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8076438B2 (en) * 2005-10-04 2011-12-13 Wacker Chemie Ag Method for producing organopolysiloxanes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846358A (en) * 1973-09-20 1974-11-05 Gen Electric Process for producing silicone resins

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06136124A (ja) * 1992-10-22 1994-05-17 Hitachi Chem Co Ltd シリカ系被膜形成用塗布液の製造法、シリカ系被膜の製造法、シリカ系被膜および半導体デバイス
JPH06179751A (ja) * 1992-12-14 1994-06-28 Tokuyama Soda Co Ltd ポリオルガノシルセスキオキサンの製法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846358A (en) * 1973-09-20 1974-11-05 Gen Electric Process for producing silicone resins

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NOLL WALTER: "CHEMISTRY AND TECHNOLOGY OF SILICONES" , ACADEMIC PRESS , NEW YORK XP002255330 paragraph [5.1.1] *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 443 (C-1239), 18 August 1994 (1994-08-18) & JP 06 136124 A (HITACHI CHEM CO LTD), 17 May 1994 (1994-05-17) *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 520 (C-1255), 30 September 1994 (1994-09-30) & JP 06 179751 A (TOKUYAMA SODA CO LTD), 28 June 1994 (1994-06-28) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8076438B2 (en) * 2005-10-04 2011-12-13 Wacker Chemie Ag Method for producing organopolysiloxanes

Also Published As

Publication number Publication date
AU2003245039A1 (en) 2004-01-19
AU2003245039A8 (en) 2004-01-19
WO2004003058A3 (fr) 2004-04-01

Similar Documents

Publication Publication Date Title
US6284858B1 (en) Silicone compounds and process for producing the same
US5262558A (en) Method of making organo-silicon polymers having mono- and tetra-functional siloxane units
US3846358A (en) Process for producing silicone resins
GB2108984A (en) Hydrolysis of alkoxysilanes
JPH0632906A (ja) エポキシシリコーンの合成法
JP5356604B2 (ja) オルガノポリシロキサンの製造法
JPH0718077A (ja) カルビノール・官能シロキサンの製造法
JPH11255899A (ja) 一官能価単位および四官能価単位を含有するポリオルガノシロキサン樹脂の製造法
JP6490816B2 (ja) オルガノポリシロキサンの調製方法
JP4149885B2 (ja) オルガノポリシロキサン樹脂の製造方法
JPH0633335B2 (ja) オルガノポリシロキサンの製造方法
JP3263177B2 (ja) エポキシ基含有シリコーンレジンおよびその製造方法
JP2830731B2 (ja) シラノール基を有するオルガノシランの製造方法
US5576408A (en) Process for preparing low molecular weight organosiloxane terminated with silanol group
JP3410486B2 (ja) アルコキシ基含有シリコーンレジンの製造方法
CN105339417B (zh) 制备含SiOH官能团的聚硅氧烷的方法
CA1121369A (fr) Polysiloxanes hydro-carbonoxyles, prepares par un procede de reflux en continu
JP5821971B2 (ja) ポリシロキサンの製造方法
EP0645395B1 (fr) Composés organosilicique contenant des groupes vinyl et alkoxy, et leur préparation
WO2004003058A2 (fr) Procede pour produire une resine d'organopolysiloxane
JP3218872B2 (ja) 有機ケイ素樹脂の製造方法
JP2004083883A (ja) オルガノポリシロキサンレジンの製造方法
US6448360B2 (en) Process for the production of cyclic siloxane
US5405928A (en) Method of preparing (meth)acryl group-containing organosiloxanes
JPH0717752B2 (ja) アルコキシ官能性オルガノポリシロキサンの製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase