TW581778B - Process for synthesis of silicone resin - Google Patents

Abstract

A method is disclosed for hydrolyzing chlorosilanes having at least three chlorine atoms bonded to each silicon atom to form silicone resins. The method comprises adding at least one of hydridotrichlorosilane, tetrachlorosilane, or organotrichlorosilane to a two-phase mixture comprising a non-polar organic solvent, an aqueous phase comprising 0 to 43 weight percent hydrochloric acid and a surface active compound described by formula R2SO3H and alkali metal salts thereof, where R2 is an alkyl group having 4 to 16 carbon atoms and alkylphenyl groups having 7 to 22 carbon atoms.

Description

581778 A7

The present invention is a kind of chlorine that hydrolyzes one-per-Xiyuan atom, and forms oxygen tree :: 乂 Three chlorine: Including the addition of at least one kind of nitrogenous three-gas crushing and four-gas-core organic: " Agent,-: two ::: two-phase mixture system comprising-non-polar hydrate, "J, one hundred water phase, and-selected from the group consisting of alkanoic acid k-based bismuth alkali alkali metal salt, arylsulfonic acid hydrate和 芳 美 # ::: Surface active compounds of metal salts. It is known in the prior art: ^ In the presence of water, it will turn quickly, and it will be condensed to form polystearyl alcohols. "Progressively" It is also known in the prior art that "money contains two or more self-atoms, These two methods are carried out almost at the same time. The result of this rapid hydrolysis and condensation is to produce an insoluble gum with little practical value. See, for example, US Patent No. 2,091,46. The industry has suggested many of the above problems. The solution, for example, Boldebuck, supra describes the use of a hydrolysing medium containing tetrahydrofuran and water to slow gelation. U.S. Patent No. 3,615,272 describes a method of forming hydrogen silsesquioxane trees, which includes making a The mash is reacted with sulfuric acid and aromatic hydrocarbons in the presence of a hydrocarbon solvent, the reaction mixture is washed with water and sulfuric acid until it becomes neutral, and then the product is recovered by evaporation of the solvent. US Patent No. 5,010,159 Teach a method for hydrolyzing a hydrogenated silane having two or more hydrolyzable groups, comprising forming a reaction medium containing an arylsulfonic acid hydrate, and adding silane to the reaction medium Hydrolyze silanes to form polyesters and recover polymers. Bank et al. Teach that the reaction medium containing the arylsulfonic acid hydrate can be formed by dissolving an arylsulfonic acid hydrate in a solvent, or Comparison of the reaction between aromatic hydrocarbons and concentrated sulfuric acid -4- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) binding

581778 A7 B7 V. Description of the invention (2) The best way to produce it.

Ezerets et al., SU (11) 1, 47723 teach a method for hydrolyzing a methyl chloride fragment having a functionality of 2.9 to 3 in a mixture of an aromatic hydrocarbon solvent and a water-miscible lotion, or Method for co-hydrolysis with diorganodichlorosilane or organotrichlorosilane, the method is characterized in that the water-miscible solvent contains acetic acid and concentrated hydrochloric acid, and there is a water-soluble cationic surfactant, and the water-soluble cationic surfactant It is described as hydrogen chloride amines, quaternary amine salts and protonated carboxylic acid salts containing 6 to 20 carbon atoms.

Hacker et al., In WO 98/47941, describe a method for preparing hydrogenated siloxanes and organic hydrogenated oxyhydrogen resins. The method involves the use of a wheat-fired monomer and a phase transfer catalyst in a non-polar solvent and a polar solvent. The step of contacting in the presence of the reaction mixture, Hacker et al. Mentioned that the phase transfer catalyst is a quaternary ammonium salt.

Shkolnik et al. In SU (1 1) 1666469 describe a method for the preparation of oligomeric organic hydrates, siloxane, which includes the pentyl trichloride in the presence of diethylstilbene and styrene-acrylic acidification copolymers. Acidic hydrolysis of a mixture of silane or vinyltrichlorohydrin monomethyl-chlorochlorine and hexamethyldichlorobenzene. It is also known that non-ionic active agents can affect the hydrolysis of diorganochlorosilanes. For example, Williams taught in US Patent No. 4,412,080 that cyclic dimethylpolysiloxanes can be prepared in the following manner: Hydrolysis of dimethyldichlorosilane and hydrochloric acid aqueous solution in the presence of a carboxylic acid <, to obtain a cyclic polysiloxane with good yield. The present invention relates to a method for producing high-yield soluble non-polar solvents in a high yield. This paper is applicable to Chinese standards (cns) A 视 格 ⑽ 心 7 公 董) 3 V. Description of the invention Shuyue said "Wanfa" This method has the following advantages: · No need to use hands: neutralization when the solvent reacts with sulfuric acid to form an arylsulfonic acid hydrate as a reactant 'so the method is easy to control, ( 3) Anhydrous gas of hydrolyzation of chloroform separated from the mixture by ^ 1, q-type hydrogen hydride, which can be recycled back to the method or open :: ⑷The water layer containing chlorine chloride and surfactant can be directly Recycling = The resin prepared by the method of the present invention is quite unique: a content: the predetermined monomer distribution, compared to other procedures =; ... 'it appears to be easier to carry out the out-molecular cyclization of the mature resin prepared by the Ming method The film has high resistance to = pressure cracking. «The polymer prepared by the method of the present invention is cured to its ceramic state or ceramic-like state 2, and has coating properties and sealing properties. These polymers are used for example in coating Cover electronics to form a protective barrier It has practicality. Β The present invention provides a method for hydrolyzing chlorins with at least three chlorine atoms bonded to each dream atom to form a polyoxygen resin, which method comprises adding at least one hydrogenated trichloride Dichloromethane, tetrachloromethane, or organic trichloromethane in a two-phase mixture comprising a non-polar solvent, an aqueous phase containing 0 to 43 weight percent hydrochloric acid, and a table of formula r2s〇3H Surface-active compounds and metal detection salts thereof, in which r2 is a fluorenyl group having 3 carbon atoms and an alkylphenyl group having 7 to 22 carbon atoms. The method for preparing a polysiloxane resin according to the present invention includes adding at least A table is the formula "In the two-phase mixture of chlorine and chlorine, the two phases are mixed 581778 A7 —____ B7 V. Description of the invention (4) The system contains a non-polar solvent, a water containing 0 to 43 weight percent hydrochloric acid Phase 'and a table are surface-active compounds of formula R2S0sH and their alkali metal salts. Among them, R is hydrogen or a monovalent hydrocarbon radical. R2 is an alkyl group having 4 to 16 carbon atoms or 7 to 22 carbon atoms. Alkyl phenyl of carbon atom, and Chlorosilane can be a mixture of hydrogenated trichlorosilane, tetrachlorosilane, and organic trichlorosilane. In formula (1), ... can be hydrogen or a single k-fe radical, which is exemplified by an alkyl group such as methyl Alkyl, ethyl, propyl, octyl, dodecyl and octadecyl; cycloalkyl, such as cyclopentyl or cyclohexyl; cycloalkenyl, such as cyclopentenyl or cyclohexenyl; aryl , Such as phenyl, fluorenyl, and naphthyl; alkenyl, such as ethylenyl, allyl, and pentenyl; aralkyl, such as benzyl, and tolylpropyl; and substituted hydrocarbyl radicals such as murine Radical, 3,3,3-difluoropropyl and pentafluoropropyl. It is preferred when R1 is hydrogen and a hydrocarbyl radical containing 1 to 20 carbon atoms. Chlorosilane is preferred for use in the method of the present invention. Trichlorosilane and methyltrichlorosilane. The gas pulverization shown in the formula (1) can be hydrolyzed alone or in the form of two or more mixtures. In addition, it can be hydrolyzed together with the two organic disilanes shown in SR12SCU, where R1 is as defined above. Chlorosilanes are used in liquid form. This liquid can contain chlorosilanes in liquid form, or chlorosilanes mixed with a non-polar organic solvent to form a solution. If a solvent is used, the solvent may be any non-polar hydrocarbon or water-insoluble carbon chloride that can be used as a solvent for chlorosilanes. Examples of such solvents are saturated aliphatics such as dodecane, n-pentane, n-hexane Alkane, n-heptane and isooctane are aromatic, such as benzene, toluene and xylene; cyclic aliphatics, such as cyclohexane; halogenated aliphatics, such as trichloroethylene, perchloroethylene, and 3-propane ; And halogen A7 ---__ B7 V. Description of the invention (5 ~ J 一 ~-*-: Drake family, such as brominated benzene and chlorinated benzene. In addition, the combination of the above solvents can also be used as a co-chlorosilane Solvents. Preferred non-polar organic solvents are aromatic compounds. Among these compounds, toluene is the best. To obtain good product yields from the process of the present invention, chlorophosphonium is preferably diluted with polar organic solvents. Benzene is the best solvent. Dilution of chlorosilane in a non-polar organic solvent before adding the present invention; 7 can give a better dispersion of chlorochlorosilane in a two-phase mixture, Thus minus formation of < and improved yields. The chlorosilanes may contain 10 to The amount of chlorosilane and non-polar organic solvent mixture, preferably, the $ may include 20 to 60 weight percent of chlorophosphonium and non-polar organic solvent mixture. The perchlorosilane can be used in any technique to hydrolyze these chlorines. Standard methods of silanes are added to the method of the present invention. However, in order to maximize the yield, the f-family will add chloroweiline to ensure that the chlorine will be quickly added to the two-phase mixture. `` These methods can include Chlorosilane is slowly added to the fluid below the liquid mixture under vigorous stirring. In a preferred method, the chlorosilane in the non-polar organic solvent is added to-rapid mixing, contains a non-polar solvent, A two-phase mixture of an aqueous solution of hydrochloric acid and a surface-active compound. The term "two-phase" mixture ~, a mixture containing an organic phase and an aqueous phase. The non-polar organic solvent phase of the two-phase mixture can be any of the above. The non-polar organic solvents used to dilute chlorosilanes can be the same as those used to dilute chlorosilanes before adding the method of the present invention (any non-polar organic solvents or Different, preferably the two-phase mixture < non-polar organic solvent component and any solvent used to dilute the gas silane -8-

Fives

Description of the invention (6 series belong to the same, and A! T winter series is a better solvent.

Contains 0 to 43 V 4ρτ, which is the second phase of the two-phase mixture of the aqueous phase than hydrochloric acid. It should have at least 7 Preferably, it is a chemical excess. In general, the range between 30 and 100 mole percentages is better, while the amount of excess water is between 250 and 800 mole percentages. Pull, 4 is the better. The aqueous phase contains 0 to 43% by weight of hydrochloric acid, and the light phase M,, and ground are considered. The aqueous phase contains 15 to 37% by weight of hydrochloric acid. The advantage of the method is that the nitrogen chloride formed by the hydrolysis reaction can be released in the form of anhydrous hydrogen chloride gas when the aqueous phase is saturated with hydrogen chloride. Therefore, it is preferable that the aqueous phase contains at least about 35% by weight Hydrogen chloride, the released hydrogen chloride can be recovered in the form of gas and recycled back to the method or the user or other application towels. The hydrogen chloride present in the water phase can be added to the process as a separate aqueous solution or produced in situ by hydrolysis of chlorosilane. In the method of the present invention, it is necessary to have a formula of the formula R2s03H < surface-active compounds and alkali metal salts thereof, in which R2 is an alkyl group having 4 to 6 carbon atoms and 7 to 22 carbon atoms. The phenyl group is preferably one having 6 to 12 carbon atoms, and the alkylphenyl group having R2 is 9 to 18 carbon atoms. The surface-active compound may be, for example, and

Eight a Lnn (2n + "b (j3H) alkylsulfonic acid hydrate, wherein η is 4 to 16, the alkylsulfonic acid hydrate may be 'for example, C4H9S03H, C6H13S03H, C8H17S03H, C0H2lSO3H,. The The surface-active compound may be a relevant metal test salt of the burnt acid hydrate, wherein the metal test may be, for example, bell or sodium. The alkali metal salt of the alkylsulfonic acid hydrate may be, for example, -9- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) " -------- 581778 A7 B7 V. Description of the invention (7) C6HuS〇3 Na, C8H17S03'Na +, C1 ( ) H21SCVNa +, C12H25S〇3-Na +, C16H33S〇3-Na + and C8H17S03-K +. The surface-active compound may be an aryl transverse acid hydrate and its related metal test salt, for example, benzoic acid hydrate and toluenesulfonic acid Potassium salt of hydrate. The preferred surface-active compound used in the method of the present invention is selected from the group consisting of n-octane sulfonic acid hydrate, p-toluene% acid hydrate, benzoic acid hydrate, and ethanoic acid hydrate , N-butanesulfonic acid hydrate and sodium n-dodecanesulfonate. Surface active compounds in the water phase of a two-phase mixture Concentration, based on the weight of water added in the method, can be in the range between ⑺ 丨 and ㈧ weight percent. Generally, preferably, the concentration of the surface-active compound is added to the method by 0.05 to 2 weight percent. The temperature at which the method of the present invention can be performed is not limited, but may be in the range of 0 ° to 100 ° C, and the temperature range of 1 (rc to 3 (rc) is the better. In the method of the present invention, if necessary, the residual hydroxyl groups on the silicon atom of the resin can be reacted with an organic silane terminal capping agent. For example, the formula is represented by the formula hSici1 where R is a monovalent hydrocarbon group as described previously, preferably the terminal The alkyl chlorosilane is capped, and even more preferably, the terminal capping agent is trimethylchlorosilane. After the hydrolysis reaction of the method of the present invention is completed and a polysiloxane resin is formed, the two-phase mixture may be subjected to, for example, a sedimentation method. The "separation" method can be achieved by, for example, directly stopping the stirring of the hydrolysis mixture and then performing simultaneous separation of the non-mixing layers in the reactor. The formed layer is an organic layer containing a polysiloxane resin and a solvent, and hydrogen chloride and The aqueous layer of this blade surface active compound from step < before, during, or after, the organic layer was allowed to stand allows a period of time, to provide a resin with a stone Xi residual chlorine atom on the broken atom -10-

581778 A7 B7 V. Description of the invention (8) The further condensation reaction between the bonded hydroxyl groups results in an increase in the structure and / or molecular weight of the silicone resin. Generally, if thickening is desired, it is preferred that the thickening method be performed before the two phases are separated. In order to impart stability to the silicone resin prepared by the method of the present invention, it is useful to use a cleaning method with or without a neutralizing system. If the organic layer is to be cleaned, only water may be used, but the cleaning liquid is preferably a sulfuric acid aqueous solution. Generally, a cleaning liquid containing more than 5% sulfuric acid is more useful. The organic layer can be contacted with a neutralizer, whether cleaned or unwashed, preferably in the presence of water, which can promote the hydrolysis of the remaining atoms. The neutralizer should be sufficiently basic to neutralize any residual acids, such as sulfuric acid, hydrochloric acid, and organic acids, without causing the chemical rearrangement of the silicone resin or the reaction between hard-bonded hydrogen and water. Appropriate tests may include, for example, carbonic acid carbonate, carbonic acid steel, dicarbonate, sodium carbonate, ammonia, calcium hydroxide and calcium hydroxide. Preferably, the neutralizing agent is a solid, and this organic: the separation is relatively easy. And, preferably, after washing and reaction, the organic should be dried accordingly, if necessary, it should be dried to remove any water-insoluble salts or be aware of other insoluble sinks. Any suitable 22 ~ Fat sealing properties or eight early ~ ... Tian "Dry grade agents such as magnesium sulfate, sodium sulfate In addition, water can be removed by Weishi evaporation method. Polysilicone prepared from the method of the present invention: the dissolving formula in the agent, or if the q material is required to be present in the reaction solution a, it can be carried out by adding a second solvent -Simple solution exchange. Or: It is composed of a silicone resin in a standard method such as a zeolite distillation method. / Multiple solids can be recovered by the method of the present invention / Siliceous resin is based on the chlorine and chlorine catalysis and solvent tangible silicon-11-G-scale-applicable x 297 mm ) 581778 A7 B7 V. Description of the invention (9) It changes with firing, however, the following list is not specifically limited to the possibility of hydrolysis and co-hydrolysis are particularly expected: resins that are fully and almost completely condensed include, (HSi〇3 / 2) m ,, (HSiO ^^ RiSiOwh, (HSiO ^ MR'SiC ^ y and (RiSiC ^ / ^ xCR'SiCOy; related partial condensation and silanol-containing resins are described by the formula (HSi〇3 / 2 ) x (H (HO) SiO) y, formula (R1Si03 / 2) x (Rl (H0) Si0) y, formula (HSi03 / 2) w (H (H0) Si0) x (R1Si03 / 2) y (R1 (H0) Si0) z, formula (HSi03 / 2) w (H (H0) Si0) x (R12Si0) y (R12 (H0) Si0) z, formula (RlSi03 / 2) w (Rl (H0) Si0) x (R12Si0) y (R12 (H0) Si0) z, (RSSiO ^ KSiOOyiXHCOSiOs / dz; the related triorganosilyl terminal resin system is described as formula (R'SiOm ^ HSiOwh, formula (R13Si01 / 2) x (RlSi03 / 2 ) y, formula (R13Si01 / 2) x (HSi〇3 / 2) y (R1Si〇3 / 2) z, formula (R13Si01 / 2) x (HSi03 / 2) y (R12Si0) z, formula (R ^ SiOwAWsiOw ^ R ^ SiO) ,, (RSsiOwW SiOJy, the formula (R13Si0l / 2) w (HSi03 / 2) x (R12Si0) y (Si02) 2, and the formula (RSSiOwdJRisiOw ^ R'SiO ^ SiOdz; where Ri is as previously described, and each R1 may be the same or Different, m is 8 or more, and the Mohr fraction w + x + y + z = l of the above polymer polyoxygenated resin. The following examples are intended to illustrate the present invention, but these examples are not intended to limit the present invention. The range defined by the scope of patent application in China. Example 1 -1 In Example 1, in a 1 liter flask equipped with a stirrer and an addition funnel, add 15 1.5 g of 35% by weight HC and 50.5 g of toluenesulfonic acid single Hydrate-12- This paper size is in accordance with China National Standards (CNS) A4 specifications (21 × 297 public love) --- 581778 A7 B7 V. Description of the invention (10 and 334 grams of Jiaben, one + one 3, 3 g of trichlorosilane in 55.6 g of toluene, i-^^ v ^, + :. Under stirring, the trichlorosilane solution was added at a time of 45 minutes for 1 minute, and ^ m 41, t door into 1 watt. After the addition is complete, the contents of the flask are agitated to remove the other two babies. When μ ^ is stopped, the stirring is stopped and the contents of the flask are separated into an aqueous phase and an organic phase. A 47% S in 100 ml portion was neutralized with 25 g of solid calcium carbonate, dried with 50 g of magnesium sulfate, and pre-treated. After the toluene was removed from the organic phase, 7.5: solid was obtained and a yield based on the total amount of trichlorosilane added to the boiled tile was provided. Example 2 16 α, — 垔 is% mole. Change the amount of reagents listed in Table 1 to it. Ding, Ran table

-13-Show thousands of examples 2-16 in a similar way to example i This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 581778 5 Description of the invention (

11 1 ~-H2.5 ------- 37.5 ---- 50.1 33 3.6 47.4 50 2 80.5 12 37 ^ 5 J13 50.2 332.2 50.2 50 2 5.6 13 37 ^ 5 0 12.5 333.4 48 50 2 69.2 14 — --- ^! S. 8 0 6.3_ 333.5 48.3 50 2 46.5 15 '----- 15 ^ 3 0 50 83 47.9 50 2 59 16 150 〇 0 50 42 50.5 50 2 33 ----, everyone ^ 1117 ^ 330,000; Example 17 tb, person ^, in the 'in a 1 liter flask equipped with a stirrer and an addition funnel' Tianlikou 19Qgu + 1C '克 之 甲 # see heart 35 wt% 1 * 1 ( : 1 '1.0 grams of sodium octyl sulfonate and 333 are added to the core. A solution containing 47.3 grams of trichlorosilane in 55 grams of toluene is placed in a Γ funnel for one minute. The trichlorosilane solution is added for more than one stage with stirring. Add 50% to the flask and add to the flask. After the addition is complete, the contents of the flask are stirred; for 5 hours and 2 hours, then stop stirring and separate the contents of the flask into water from the organic phase. The organic phase is water. Washed, dried with magnesium sulfate and filtered. After removing toluene from it, 16.3 g of a white solid was obtained, and the yield was provided. Strength: The total weight of trichlorosilane in the soil flask was 87.9 mole percent. 1 8- 3 6 or more The similar formula described above is ^ ^ The pain is similar, but the amount of military agent listed in Table 2 is used instead. Π τ, -14- 581778 A7 B7 V. Description of the invention (12) Table 2 Examples of feeds added to the reactor Surfactant solvent HCla Solvent surfactant HSi03 Solvent yield (g) (g) (g) (g) (g)% 18 PhMec 200 334 0 47.1 55.7 10 19 BSAb PhMe 196 334 4 47.1 55.7 38 20 BSA octane 151 271 50.5 46.9 45.1 22 21 BSA 2-ClPrd 150 333 50 59.8 55.0 51 22 C2H5SO3H PhMe 196 333 4 50.4 55.6 16 23 C2H5S〇3H PhMe 180 334 20 48.9 55.5 35 24 c2h5so3h PhMe 150 333 50 49.4 55.5 63 25 C4H9SO3H PhMe 196 333 4 49.1 55.5 42 26 c4h9so3h PhMe 190 333 10 50 55.5 43 27 c6h13so3h PhMe 196 333 4 48.4 55.4 89 28 c6h13so3h PhMe 199 334 1 49 55.5 56 29 C8H17S03Na0.25 MeMe 81.2 30 C8H17S〇3Na PhMe 199 333 1 47.3 55.5 87.9 31 C8Hl7S03Na PhMe 196 334 4 50.2 55.7 48 32 C8H17S03Na Octane 196 270 4 48.2 45.0 65 33 C8H17S〇3Na PhMe 180 334 20 48.3 55.5 29 a = 35 wt% HC1 aqueous solution c = toluene b = benzoic acid hydrate d = 2-chloropropane -15- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 581778

f Example 37-3Q

Fill in Example 37. In a 1 liter flask equipped with a stirrer and an addition funnel, add 50,000 grams of benzenesulfonic acid hydrate, 150 grams of 35% by weight HC1, and 3 33.6 grams of toluene at 600 rpm. A solution containing 50.5 g of methyltrichlorosilane in 55.5 g of toluene was added to the mixture over a period of 65 minutes while stirring at a speed. After the addition was completed, the contents of the flask were mixed for another 2 hours, and then the material was stopped and the flask contents were separated into an aqueous phase and an organic phase. The organic phase was washed with 47% sulfuric acid twice in 1000 ml portions, and 25 grams of solid calcium carbonate was neutralized and dried over 50 grams of magnesium sulfate and filtered. After the toluene was removed from the organic phase, 165 grams of a white solid was obtained and a yield based on the total weight of trichlorosilane added to the flask was 735 mole percent. Examples 38 and 39 were performed in a similar manner, except that the amounts of reagents listed in Table 3 were changed. Table 3 Initial S & reactor feed added to reactor feed ----- Example Toluene HC1 h2o PhS03 Toluene MgSiCl3 Rate Yield (g) (g) (g)） (g) (g) (g) ( Ml / min) (%) (g) 38 333.6 75 75 50 55.5 50 2 39 333.2 0 150 50 55.2 50 2 \ j ^ 44 Session 40-47 — The methyl silsesquioxane system is obtained by: A solution of the methyl trichloride in toluene was added to a flask containing concentrated hydrochloric acid (36% by weight in water), toluene, and sodium octylsulfonate. The concentrations are shown in Table 4. Methyl

Line-16- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 581778 Five invention description (14 The addition rate of triclosan is based on borrowing, and & $, ^ ΤΜ, refined It is controlled by the / Kingjet pump, and the feed is added through a TeflonTM test tube. The q ^ germline l This tritium tube is hidden in the flask. In the table,

The title "Initial reactor feed, injury button a, > 丄, | T" refers to the material added to the flask in private.

Grams' The title "Feed Weight" refers to the total weight of the toluene and trichlorosilane mixture added to the reactor at the stated rate. The title "Reaction Number" refers to the amount of The number of the method for processing the sample is' The operation method is listed below as methods 丨, 2 and 3, and the title "Yield%" refers to the product yield based on the total weight of fluorenyltrichlorosilane added to the flask. rate. Table 4 Examples of initial reactor feeds added to the reactor Feed benzene HC1 η2ο PhS03H toluene MgSiCl3 Rate reaction number Yield (g) (g) (g) (g) (g) (g) (ml / min) (%) 40 330 199 0 1 55 51.9 2 1 86 41 330 199 0 1 55 51.9 2 2 99 42 330 199 0 1 155 51.9 1.8 2 100 43 330 199 0 1 155 51.9 1.8 2 100 44 333.8 199 0 1 55.5 50 1.8 3 '' 100 45 333.5 199 0 1 55.5 50 1.8 3 97 46 333.5 99.5 99.5 1 55.5 50 1.8 3 86 47 333.5 0 199 1 55.5 50 1.8 3 61 Reaction No. 1-After 2 hours of feed addition, take 64 grams Organic binding-17- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 581778 A7 B7 V. Description of the invention (15) Phase sample, 100 ml whole deionized, main, soil Although A 4 was washed 6 times in water, the sample was dried by zeolite retort at 55 ° C and vacuum. Reaction No. 2-Samples 41 and 42 were processed for 19 hours after feed addition. Sample 19 was processed immediately after feed addition was completed. For each sample, the organic phase was separated, and then an equivalent of MesSiCl was added to the organic phase, and the organic phase was stirred at room temperature for 3 hours. Then take a 64 g sample of the organic phase and process it in the following steps: (ι) 2 × 2⑻ liters of 50% by weight H2SO4, 10 minutes, (2) χ 200 ml of deionized water, (3) 1 X 200 ml of a 5% by weight 1 ^! ^ 03 solution, and (4) 2 × 200 ml of deionized water. The resulting washed and neutralized organic phase was dried by zeolite distillation at 55 ° C and under vacuum. Reaction No. 3-Pour the reaction mixture into a separatory funnel and remove the acid layer. Place the organic layer in a three-necked flask with a bottom drain hole. Then, add 100 ml of 47% sulfuric acid and stir the mixture. The obtained organic layer was washed 3 times with 5% disodium diacid, and then with! Wash 2 times with 00 ml of deionized water. The organic layer was then treated with 25 g of calcium carbonate with stirring for 0 minutes, and magnesium sulfate was added. The organic layer was filtered and the solvent was removed under vacuum to give a resin as a white solid. The selected samples as described above were analyzed using 29Si NMR, GPC, and a control polystyrene standard. The results are shown in Table 5. In Table 5, the mole percentage of silicon atoms with a degree of hydroxyl substitution is labeled "SiOH" and the mole percentage of broken atoms with a degree of chlorine substitution is labeled "SiCl". -18- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Binding

And invention description (16 A7 B7

Example 4S-S1 Bookbinding Midnight Permanent Oxygen Resin was prepared by the co-decomposition of different chlorine crushing as described in Table 6, and the hydrolysis was provided by providing a Winter, weight: S% hydrochloric acid and octyl acetic acid are used as starting materials. The mixture of chlorosilanes in toluene as described in Table 6 is fed into the reactor at the listed rates. After the addition is complete, the samples are processed. The product yield series based on the mole% total weight of chlorosilane added to the reactor is shown in Table 6. Table 6 Example of initial reactor feed added to the reactor aTol. HC1 OctS〇3H (toluene silane (g) (g) (g) (g) (g) 48 330 199 1 100 bprfSiCl3 HSiCl3 (40.2 g) (23.5 g) 49 330 199 1 60.6 MeSiCl3 Me2SiCl2

19- This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 Public Love 1 ^ '------ 581778 A7 B7 V. Description of the invention (17) (44.2 g) (6.7 g) 50 330c 199 1 80 SiCl4 (30 g) Me3SiCl (38.4 g) 2.0 5 90 51 330 199 1 155 MeSiCls (25.9 g) Me2SiCl2 (23 · 5 g) 2.5 6-Toluene b = trifluoropropane firing also contains Me3SiCl initial reaction Feed Reaction No. 4-After 12 hours of feed addition, take a sample of 64 grams of organic phase and wash it twice with 200 ml of 50% by weight 112304. This sample is further washed with 200 ml of a 5% by weight NaH2S03 solution. Here The sample is gelatinous. Reaction No. 5-After the feed of sample 22 and sample 23 are added, the organic phase samples 41 and 42 are processed for 21 hours by the following operations, and 64 grams of each organic phase sample is below Steps of processing: (i) 50% by weight of 2 × 200 ml of 1 ^ 800, 10 minutes, (2) 1 × 200 ml of 5% by weight NaHS〇3 solution, and (3) 1 × 200 ml of Ionized water, 10 minutes. The obtained washed and neutralized organic phase was zeolite distilled at 55. (: and vacuum Dry. Reaction No. 6-The organic phase sample is treated with an excess of bis (trimethylsilyl) trifluoroacetamide in methyl isobutyl ketone / toluene solution and capped. Reaction sample numbers 49 and 50 are used. 29Si NMR, GPC, and control polystyrene standards were analyzed. The results and experimental formula series are shown in Table 7. In these chemical formulas, M, D, T, and Q represent monofunctional and bifunctional -20- Paper Standards CNS A4 Specification (21GX 297 male) "-581778 A7 B7 V. Description of the Invention (18) Properties, trifunctional and tetrafunctional siloxane units. Table 7 Example Mn Mw Experimental formula 49 1463 73330 ((OH) Me2Si03 / 2) 0.95 (Me2SiO) 17 (OSiMeOH) 5.7 (〇3 / 2SiMe) 76.4 50 2570 6547 M47.7T (〇H) 3.2Q49.1 Example 52 in a configuration In a 1-liter flask with a stirrer and an addition funnel, 199 grams of 35% by weight HC1 and 333.5 grams of toluene were added. At a stirring speed of 500 rpm, a solution containing 50.0 grams of phenyltrichlorosilane in 55.5 grams of toluene was added in one stage. Add dropwise over 150 minutes. After the addition, the contents of the flask are stirred for another 70 hours. , Then stop stirring and separate the contents of the flask into an aqueous phase and an organic phase, wash the organic phase twice with 100 ml of 47% sulfuric acid, wash 100 times with 100 ml of a 5% disodium carbonate solution, and Wash three times with 100 ml of deionized water, then neutralize with 25 g of solid calcium carbonate, dry with 50 g of solid magnesium sulfate, and filter. After removing the solvent from the organic phase, 3 1.0 g of a white solid is produced, and A yield of 102 mole percent based on the total trichlorosilane weight added to the flask was provided. Examples 53-55 In a 9-liter baffled reactor, 1.5 kg of 37% hydrochloric acid, 0.010 kg of sodium octyl sulfate, and the amount of toluene as described in Table 8 were placed. The stirrer was set to 900 rpm, and then 0.50 kg of methyltrichlorosilane dissolved in 0.50 kg of toluene was added to the reactor at a rate of 12 ml / min at room temperature. After the addition, the mixture was allowed to stand in the chamber. Stir at temperature for 14 hours. Stop stirring, -21-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Λ Binding

581778 A7 B7 V. Description of the invention (19: Guanger I organic phase is washed with 1 liter of deionized water ... / person ’until the pH value of the direct washing water reaches 4, and the organic phase" 50 grams of

Mg! 〇4, and vacuum filtration with filter paper. The organic solution is used for rotation: concentrated under the benefit of thieves, and the dried resin is placed under direct air to: volts to remove residual solvents. The product obtained from the above operation was ㈣kg ... solid. The absolute molecular weight data are obtained by light scanning third degree measurement. The molecular weight data series obtained for these different substances are listed in the table below. > Table 8 Examples of toluene (kg) Mn Μ 53 1.0 -------- ~ --_ 7,220 -------- 丄 YA W 303,900 54 2.0 6,920 " --- ~ -------. 27 300 55 3.0 2,240 9,490 Example 56 In a 1-liter flask equipped with a concentrator, a nitrogen inlet, a mechanical stirrer, an addition funnel, and a temperature probe, 152.37 g of 37% by weight hydrochloric acid and 0.9908 g of octylsulfonate were added. Sodium. After sodium octyl sulfonate was dissolved, 335.34 grams of toluene was added. A solution containing 34.57 grams of octadecyltrichlorosilane, 52.97 grams of methyltrichlorosilane, and 87.37 grams of toluene was prepared. This feed solution was added dropwise over a period of more than 1 hour, and the obtained The mixture was stirred at room temperature until overnight. After the stirring was stopped, the mixture was separated into an organic phase and an aqueous phase, the aqueous phase was removed, and then the organic phase was washed 4 times with 3 ⑻mL of deionized water at 55 ° C. The organic phase was then dried over magnesium sulfate and vacuumed. Medium > Chen Shrink, yielding 37.89 g (74% yield) of silane resin with 9,68〇-22-This paper size is applicable to China® Home Fresh (CNS) M specification (21ϋχ tear public love) 581778 A7 B7

V. Description of the invention (20) Mn and 66,800 MW.

Example U In an i-liter flask configured as described in Example 56, 1527 grams of 37% by weight hydrochloric acid and 335.14 grams of toluene were added. Preparation—a solution containing μ "gram of octadecyltrigassilane, 52.74 grams of methyltrigassilane and S 702 grams of toluene, this feed solution was added dropwise over a period of i hours, and the resulting The mixture was stirred at room temperature until overnight. After stirring was stopped = the mixture was separated into an organic phase and an aqueous phase. The aqueous phase was removed, and then the organic phase was washed 4 times with 300 ml of deionized water under hunger. Drying with magnesium sulfate in vacuo and preconcentration yielded 27.91 g (55% yield) of a silane resin with a Mw of 1,650 and a Mw of 105,650. Example 5 8 In a configuration as described in Example 56 丨In a 1-liter flask, add 5 μg of 37% by weight hydrochloric acid and 0.9967 g of sodium octyl sulfonate. After the sodium octyl sulfonate is dissolved, add 200.88 g of toluene. Prepare an octadecyl disulfite containing 43.55 g , 48.55 grams of methyl trichloride and 8850 grams of toluene solution, this feed solution was added dropwise over a period of more than 36 minutes, and the resulting mixture was stirred at room temperature overnight. Stop stirring After that, the mixture is separated into an organic phase and an aqueous phase ' The aqueous phase was removed, then the organic phase was washed 4 times with 300 liters of deionized water at 65 C. The organic phase was then dried over ferric sulfate and concentrated in vacuo to a solid. This solid was dissolved in 2 ° C. 0 ml of THF, and 10 ml of deionized water was added. After stirring for 1 hour, the mixture was stripped in vacuo to obtain a solid, yielding 60.54 g (108% yield) of a silane resin. , Which has a Mη of 7,260 and a M of 51,000. -23- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm)

Binding 581778 V. Description of the invention (a Example 5 9 In a 1 liter flask configured as described in Example 56, soil, ~ ,, and strength 1 < g < 37% by weight hydrochloric acid and 0.999 u of octyl Sodium sulfonate, after octanoate 0.58.83 sodium is dissolved, 200.28 grams of toluene is added. Prepare a stupid solution containing μ% sulfenyl trichlorosilane, 34.01 grams of methyltrichlorosilane, and 8715 grams of methyl chlorosilane. The material solution is dropped dropwise over a period of more than 45 minutes, and the resulting mixture is allowed to stir at room temperature until overnight. After stopping the mixing and mixing, the mixture is separated into an organic phase and an aqueous phase and removed. The aqueous phase was then washed 4 times with 3⑽ Φ liters of deionized water. The organic phase was then dried over magnesium sulfate in a vacuum and concentrated to yield 41.88 g (83% yield) of a silane resin with 9,300 Mn and Mw of 204,500. -24- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

A B c D Wai Fan-ΙΠΊ Specially invited to 六 581778 7 Progression between mouse atoms _ step condensation reaction. • The method according to item 1 of the scope of patent application, wherein the two-phase mixture is knifed off into an organic phase containing silicone resin and an aqueous phase, and the organic phase is washed with water to reduce the residual chlorine content. 8. The method according to item 1 of the scope of patent application, wherein the two-phase mixture is separated into an organic phase containing a silicone resin and an aqueous phase, and the organic phase is in contact with a neutralizing agent. 9. A method for preparing a polysiloxane resin, which comprises (A) adding at least one chlorimone appearance represented by the formula R xSiCl4_x to a two-phase mixture, the two-phase mixture containing a non-polar solvent, and containing 0 to 43% by weight of the aqueous phase of hydrochloric acid 'and a surface-active compound of the formula r2SO3H and its alkali metal salts' and (B) the two-phase mixture is separated into an organic phase containing polyoxygenated resin and a Aqueous phase, in which the polysiloxane resin is selected from the group consisting of the following resins: Fully condensed resins, the formula is (HSi〇3 / 2) m, (R Si〇3 / 2) m J (HSi03 / 2) x (RlSi〇3 / 2) y > (HSi03 / 2) x (Rl2Si〇) y and (R Si〇3 / 2) x (Rl2SiO) y; partially condensed resin containing crushed alcohol, table It is the formula (HSi03 / 2) x (H (H0) Si0) y, chemical formula 4〇3 / 2) 1 (rib) with 0, (HSi03 / 2) w (H (HO) SiO) x (R1Si). 3/2) y (R1 (HO) SiO) z, (HSi03 / 2) w (H (H0) Si0) x (R12Si0) y (R12 (H0) Si0) z, (R1Si〇3 / 2) w ( R1 (HO) SiO) x (R12SiO) y (R12 (H〇) Si〇) z and (R ^ SiOwMSiC ^ yUHCOSiC ^ / Jz; and three organic ground-burning terminal resins, the formula is (Rl3Si0W2) x (HSi03 / 2) y, (R13Si01 / 2) x (R1Si〇3 / 2) y, -2-This paper is suitable for standard paper ® ® Home Standard (CNS) A4 size_X 297mm) "-~ 581778 8 8 8 8 AB c D Patent application scope (R13Si01 / 2) x (HSi〇3 / 2) y (R1Si〇3 / 2) z, (Rl3Si01 / 2) x (HSi〇3 / 2) y (R12SiO ) z, (R13Si01 / 2) x (R1Si03 / 2) y (R12Si0) z ^ (R13Si01 / 2) x (Si02) y ^ (R13Si01 / 2) w (HSi〇3 / 2) x (R12SiO) y ( Si02) z and (RSSiOwJJRiSiOwMRSSiCO / SiOdz; where each R1 is a hydrogen or a monovalent hydrocarbon radical, R2 is an alkyl group having 4 to 16 carbon atoms or an alkylphenyl group having 7 to 22 carbon atoms, X is 0 or 1, m is 8 or more, and the mole fraction of w + x + y + z = l. 3- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 填 Filled by this bureau). Η \ 7β A4 ~ C4 --- .. I. Daming's new type of stone bait Chinese --- ----.-English ------ Name Nationality II, Inventor Creation A Name of residence and residence (name? Nationality III. Applicant% ί ^) Name of representative 1. Gaikoli Scottbeck 2. Russel Keskin 3. Dono Tetsuya 4 Resley Ilkabon Special 1. United States 2. United States 3. Japan's American Commercial Dow Corning Co., Ltd. Rob L. McCaller, Michigan, Michigan, USA, invented a Chinese manual replacement (January 1993) 581778 Patent Specification Polysilicone PROCESS FOR SYNTHESIS OF SILICONE RESIN 5. Eric Scott Moore 6. Clegellin Yeker II 4. United States 5. United States 6. United States 1. United States Michigan State No. 3347, Douglas Road, Buddhism City 2. No. 433 South Kexian Road, Midland City, Michigan, USA 3. 3_44, Numadai-Shin, Qino City, Kanagawa Prefecture, United States 4 · 3823 Ted Street, Midland, Michigan, USA 5 · United States No. 4500 Andrew Street, Michigan City, Michigan6. Binding Line, 181 Yande Road, Michigan City, Michigan, USA This paper size is applicable in B @ 家 scale (CNS) A4 specifications (21 ()) The scope of this application for patent A8 1. A method for preparing a polysilicone resin, and ^ /, comprising adding at least one kind of smashed atomic bond, the formula is β, χ Η rat stone is burned in a two-phase ~ compound, The two-phase mixture contains (I) a non-polar solvent, (II) an aqueous phase containing (0 may contain at least a stoichiometric amount of water about the fragmentation of the chlorine atom bonded to the chlorine atom, and (11) one containing 0 To 43% by weight of hydrochloric acid 'based on the water phase and (iH) —surface-active compounds of the formula R2S03H and their alkali metal salts, where R1 is hydrogen or a monovalent hydrocarbon group and r2 is 4 to 16 carbons Atomic alkyl group or alkylphenyl group having 7 to 22 carbon atoms, and \ is 0 or ^ 2 according to the method of claim η, wherein the chlorophosphonium is added to the method before Non-polar organic solvent dilution. 3. The method according to item 丨 of the patent application scope, wherein the aqueous hydrochloric acid provides a stoichiometric excess of 30 to 100 mol% of water in the method. 4. According to the patent application scope 丨Item, wherein the aqueous phase contains from $ 37 to about 37 weight percent hydrochloric acid. The method according to item 丨 of the scope of patent application, wherein the concentration of the surface-active compound is based on the weight of water added to the method, and ranges from 0.1 to 10% by weight. The method of item 1, wherein the two-phase mixture is separated into an organic phase containing polysiloxane and an aqueous phase, and the organic phase is left to stand for a sufficient time to provide a residual silicon-bonded hydroxyl group and This paper size applies to China National Standard (CNS) A4 specifications (210X297 public directors)