TW420685B - Process for preparing organosiloxane terminated with silanol group - Google Patents

Abstract

Hydrolysis of an alkoxysiloxane of the formula: R<1>a(R<2>O)bSiO(4-a-b)/2, wherein R1 is a monovalent hydrocarbon group, R2 is an alkyl group having 1 to 4 carbon atoms, letter a = 0 to 2.2, b = 0.2 to 3, 2 <= a + b <= 3, and the number of silicon atoms in a molecule is 2 to 5, is effected in the presence of a cation exchange resin by adding water therereto in an amount of 1 to 10 mol per mol of the alkoxy group in the alkoxysiloxane and agitating the mixture. Low molecular weight, linear organosiloxanes having a silanol terminal group including dimer diol trimer diol are produced in high yields.

Description

A7 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives 1i 〇β8η &quot; 4_Βτ ___ V. Description of the Invention (1) The present invention relates to a simple method for manufacturing a low molecular weight organic polysiloxane having a silanol group at the end. A linear organopolysiloxane with hydroxyl groups at both ends is a highly effective dispersant when producing silicone rubber compounds. Various dispersants are used. The function of the dispersant is proportional to the hydroxyl content. Polysiloxanes with a large hydroxyl content, that is, low-molecular-weight linear organic polysiloxanes with hydroxyl groups at the end groups, can be used in small amounts. Consider polysiloxanes. The rubber compound is more effective in processability, but today the industrial users are more linear organic polysiloxanes than organic tetrasiloxanes. Monomer diols, dimerization Organic silanes or siloxanes with silanols such as biodiols, trimer diols, etc. have not yet been proposed for industrially more advantageous methods. That is, various methods for synthesizing short-chain hydroxysilanes and siloxanes have been studied in the past. It is known in the laboratory scale to use a buffer solution or the like to keep the solution of the alkoxysilane in a neutral state and to hydrolyze it, but this method is difficult to implement industrially. In addition, there is a method of mixing dimethoxysilane in an excessive amount of neutral distilled water to make it reflux, but the yield of the target product has not been significantly improved. Low-molecular-weight linear organic polysiloxanes having a hydroxyl terminal are industrially hydrolyzed with a weakly alkaline aqueous solution and linear organic chlorinated siloxanes having a chlorine atom at the terminal to prevent them from being made into a ring. However, this method is because silanol groups are unstable to acids or bases, and often cause condensation reactions due to HC generated by hydrolysis. In addition to the intended organic polysiloxanes, there will be higher molecular organic polysiloxanes. Or ring-shaped polysiloxane (please read the notes on the back before filling this page) The size of the paper is applicable to China National Standard (CNS) A4 (210 × 297 mm) 42 0685 Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer Cooperatives Indun A7 B7 V. Invention Description (2) Question. Therefore, in this method, it is necessary to strictly maintain the hydrolysis water as neutral, and it is difficult to synthesize the linear organic polysiloxane other than this method. In addition, a method of oxidizing the above organic-based chlorinated polysiloxane with acetic acid and then hydrolyzing the same is also known. However, it cannot be completely hydrolyzed by this method, and fluorene will remain in the product, which is not suitable for use as a dispersant for silicone rubber. On the other hand, U.S. Patent No. 3 9 2 5 2 8 5 describes the reaction of hexamethylphosphonium trisiloxane, methanol, formic acid, and water to synthesize a low residual methoxy group with a silanol end group. Molecular weight linear organic group. The method of polysiloxane, but because of the higher price of hexamethylcyclotrisiloxane, the cost is high, and it is not possible to generate silanes with D units [(CH3) 2SiO] below 3 The low molecular weight linear polyorganosiloxane of the alcohol end group cannot be formed shorter than 1,5-dihydroxytrisiloxane in the reaction, which has the problem of limited hydroxyl content. In addition, U.S. Patent No. 5 0 7 6 40 describes a method of dripping corresponding chlorosiloxane into an epoxy solvent such as propylene oxide and butylene oxide. In addition to the use of higher-priced hexamethylcyclotrisiloxane, those with low boiling point solvents are prone to electrostatic ignition and safety issues. In addition, Japanese Patent Publication No. 6 4-5 6 0 4 describes a method for synthesizing _solid acid of activated white clay: a short-chain silanol that hydrolyzes alkoxysilane, but this method must neutralize the solid acid , So the operation is complicated. In addition, in this method, a mixture of various short-chain silanols is obtained, and the yield of the dimer glycol is only about 50%. In addition, the related monomer diols are as in the example (please read the precautions on the back before filling this page) The paper size is suitable for China's national standard (CN'S Μ4 specification (210 × 297 mm) 4 2 06 85 A7 B7 V. Description of the invention is shown in FIG. 9 as well as the Miko exchange resin method. However, the combination of finished diols of the present invention is simple and convenient. 0 times the high yield of the alcohol group with a low score of 8 4 Mozambique's patent for the hydrolysis of all non-commissioned, the collection system for the purpose of the evaluation of the human exchange for the child, especially above the silicon silyl to the sub-quantity There are 1% pure 3rd oxygen and short chain ratio, etc. Based on the above, it is best to add water to the alkane to achieve resin retention. Polysiloxane based sand can only get a yield below 1Q%. 〇 4 3 1 8 is the development of the use of cationic silanes to produce highly polymerized silanols, especially dimer diols and trimers, and has been developed by developers to provide low yield silanols. The purpose of molecular weight organosilicone has been thoroughly reviewed. The results show that The alkoxy group represented by the following formula (1) has an alkoxy group at the end represented by the following formula (2): The alkoxy group of these alkoxysiloxanes is hydrolyzed by stirring, which can be extremely easy and the dispersant of rubber is extremely easy. It is useful to have a siloxane. (Please read the notes on the back before filling this page)

R]》 (RO) bSiO 印 Printed by the Industrial Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (where R 1 represents the same or different substituted or unsubstituted monovalent hydrocarbon group, and R 2 represents the same or different carbon The number is 1 to 4 alkyl, a is 0 to 2.2, 1? Is 0.2 to 3, 3 + 13 is 2 to 3. However, the number of silicon atoms in the molecule is 2 to 5). This paper scale is applicable to Chinese National Standard (CNS) Λ4 gauge pile (2ΐϋ X 29 &quot;? mm) 420685 A 7 B7 V. Description of the invention (4) R1 RO-fSiO ^ R2 (2) (where R1, R2 are As defined above, η is an integer of 2 to 5.) At this time, it was found that the dialkoxysiloxane of the above formula (2) is in the presence of a cation exchange resin, and is represented by the following formula (3) R ^ S i (OR2 ) (3) (Please read the notes on the back before filling in this page)

1 ~ 1 times Mohr water of the alkoxy group present in the dialkoxysilane molecule of the above formula (3) is added to the dialkylsilane represented by tT, and the first stage of hydrolysis can be performed by mixing. When it is easily obtained and continues to hydrolyze the dialkoxysilane of the formula (2) obtained as described above, a dialkyloxysilane such as a less expensive dimethoxydimethylsilane can be obtained in a simple method. Advantageously, for example, a low molecular weight organic polysiloxane represented by the following formulae (4) and (5) is obtained, and the present invention has been completed. R1 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs HO- ^ SiO) rH R 'R1 HO- (SiO) j-H I R1 (4) (5) (where R 1 is as defined above). Therefore, the present invention is to provide a low-molecular-weight sheet with a silanol group that is applicable to 1 national standard (CNS) specification (2) 0 × 297 Gongkang_ 7 _ 42 0685 printed by the Shellfish Consumer Cooperative of the China Standards Bureau of the Ministry of Economic Affairs A7 _ B7___ V. Description of the invention (5) A method for producing a quantity of organosiloxanes, which is characterized in that the above-mentioned alkane is added to the alkoxysiloxane represented by the above formula (1) in the presence of 1Ϊ ion exchange resin. Water of 1.0 times mole or more of alkoxy group of oxysiloxane, which is hydrolyzed by stirring. At this time, the present invention is provided as a preferred embodiment in the presence of a cation exchange resin, which is added to the dialkyl silane shown in the above formula (3), corresponding to the dialkoxy silane molecule of the above formula (3). 1 ~ 1 times Mohr's water of alkoxy group, and the first-stage hydrolysis is carried out by stirring to form a dialkoxychooxyalkane having an alkoxy group at the end represented by the above formula &lt; 2). In the presence of a cation exchange resin, a low molecular weight linear organic polysiloxane characterized by adding a stoichiometric excess of water to a dialkoxysilane of the above formula (2), and undergoing the second-stage hydrolysis by mixing. Method for producing alkane 0 The present invention will be described in more detail below. The method for producing a low-molecular-weight organic siloxane having a silanol group according to the present invention is to hydrolyze an alkoxysilane as described above in the presence of a cation exchange resin. Method. When the method according to the present invention is used, the condensation reaction of silanol can be inhibited to obtain a cyclic polysiloxane or a polyorganosiloxane having an extended chain length and having a low content, and a low molecular weight organosiloxane having a silanol group. That is, a method of hydrolyzing the alkoxysiloxane of the raw material to produce a corresponding hydroxysiloxane. Herein, the alkoxysiloxane is represented by the following formula (1). R1. (R2Q) bSi〇4-i. ^ (1) (Please read the notes on the back before filling out this page) This paper &amp; degree applies Chinese National Standard (CNS) Λ4 ^ grid (210X2 ^ 7 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 420685 A7 __________ B7 Five 'Invention Description (6) At this time, R1 is a substituted or unsubstituted monovalent hydrocarbon group, preferably a carbon number of 1 to 10, especially 1 to 6. Specifically, it may be methyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and other alkyl groups: alkenyl such as vinyl; aryl groups such as phenyl and tolyl: p-benzene Aralkyl groups such as ethyl: and — groups in which some or all of the argon atoms bonded to the carbon atoms in these hydrocarbons are replaced by a prime atom such as fluorine or a cyano group (such as 3,3,3-trifluoropropane Or ethyl). Among them, methyl, vinyl and phenyl are preferred. In addition, r 2 is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, and a rainer may be present in the molecule at the same time. In addition, a and b are numbers in the above range. The degree of polymerization of alkoxysiloxanes of the formula (1), that is, the number of silicon atoms in one molecule is preferably 2 to 5, especially 2 to 3. These alkoxysiloxanes are represented by the following formula (2 The dialkoxysiloxanes shown in) are most suitable for use. R1 RO- ^ SiO ^ R2 ^ ⑵ (where R1 and R2 are as defined above, and η is an integer of 2 to 5). Specific examples of the above alkoxysiloxanes may be 1,3-dimethoxytetramethyldisilazane, 1,1-dimethoxytetramethyldisilazane, and i-methoxypentamethyldisiloxane. Siloxane, 1,5-dimethoxyhexamethyltrisiloxane, 1,7-dimethoxyoctamethyltetrasiloxane, 3-methoxyheptamethyltrisiloxane, 1, 3— Dimethoxy_1,3-divinyl-1,3-dimethyldisiloxane and so on. These alkoxysiloxanes can be used alone or in combination. However, when a plurality of alkoxysiloxanes are used in combination, since the two papers are used, the paper is suitable for use (CN'S) Λ4 grid Uiox 297 mm) ^^ 1 ^^ 1 ^^ 1 I ^ I &gt; · (Please read the notes on the back before filling out this page}, 1T printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 2 06 85' A7 B7 V. Explanation of the invention (7) The solution speed is different, In some cases, it is not possible to react uniformly, so care must be taken. The alkoxysiloxanes of formula (1) can be reacted with R, C 5 b S i 0C4-ab in the presence of triethylamine, urea, pyridine, etc. according to known methods. / 2 (R1, a, b are as defined above) can be prepared by reacting with alcohols having an alkyl group corresponding to R2, especially the alkoxysiloxane of formula (2) can be Formula (3) Rl2Si (〇R2) 2 (3) (wherein R1,!? 2 is as described above)-the hydrolysis of the dialkoxysilane shown in the presence of a cation exchange resin is more suitable 〇 More detailed description by the formula ( 3) A method of hydrolyzing a dialkoxysilane to obtain a dialkoxysilane of formula (2). Specifically, the formula (3) dialkoxysilane can be, for example, dimethyldimethoxysilane, phenylmethyldimethoxysilane, methylvinyldimethoxysilane, dimethyldiethyl Oxysilane, phenylmethylmethoxyethoxysilane and the like are preferably dimethyldimethoxysilane. These dialkoxysiloxanes may be used alone or in combination. However, when a plurality of alkoxysiloxanes are used in combination, they may not react uniformly due to the different hydrolysis rates of the two, so care must be taken. In addition, it is preferable to use a small amount of a chlorine component for the dialkoxysiloxane based on the formula (3). That is, the short-chain silanols of the target substance of the present invention are unstable under acidic and alkaline conditions. In order to obtain short-chain silanols, they must remain neutral during the reaction and under reduced pressure distillation. Generally, the alkoxysilanes are The Chinese paper standard can be applied from the corresponding paper size {[, milk) 6 4 specifications (210 &gt; &lt; 297 mm) * iU &quot; (Please read the precautions on the back before filling this page) in the Ministry of Economic Affairs Consumption Cooperation of Employees of the Bureau of Substandard Production Du 420685 A7 __B7__ V. Description of the Invention (8) Chlorinated silane is synthesized, so if it contains chlorinated silane, these chlorinated silanes will react with water to form hydrochloric acid, so The reaction system becomes acidic, causing a poor silanol condensation reaction. Therefore, in order to obtain short-chain silanols, it is preferable to use a dialkoxysilane with a small content of chlorinated silane. Therefore, the chlorine component contained in the dialkoxysilane of the formula (3) is preferably 10 P pm or less, and preferably 10 ppm or less. Secondly, the water system used in the hydrolysis of the dialkoxysilane is used to remove Na, Ca, Mg and other ions by ion exchange resin, so that it is a component necessary for hydrolysis at a relatively low temperature and in the state of a large number of silanols, using conductivity. Ion-exchanged water having a rate of 10 1 Q Ω or more, preferably 10 1 2 Ω or more, and more preferably 10 15 Ω or more is most suitable for use. When the conductivity is less than 10 μMΩ, ion exchange resin and ions contained in the hydrolyzed water cause ion exchange, and the hydrolyzed water becomes acidic, which is not suitable. In addition, the cation exchange resin added to the mixture of the dialkoxysilane and ion-exchanged water is a component that keeps the D of the water to be hydrolyzed near neutrality, and gently hydrolyzes the necessary components. Here, the type of the cation exchange resin is preferably a suspension polymerization polymer made of polystyrene or divinylbenzene. The types of the cation exchange resins are gel type and macroporous type. These hollow systems are most suitable when they are measured by a mercury injection method and have a macroporous cation exchange resin having a pore size of 0.1 mm2 / g or more. The acidic group attached to the resin is preferably a sulfonate type such as a sulfonic acid group, an acrylic fluorenyl group, and the sulfonic acid group is more preferable. Ion exchange resins that can satisfy these conditions include, for example, Amberiist 15 (manufactured by Rohm and Haas), Diaion PK-208H, PK-216H, PK-228H (This paper rule applies to China National Standard (CNS) Λ4 gauge pile (2丨 0 X 297 mm) i. (Please read the notes on the back before filling in this page) Order 4 2 06 85 A7 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ________ B7______ 5. Description of the invention (9) The above are manufactured by Mitsubishi Chemical Corporation) Peuro 丨 ite CT — 1 7 5 'CT_ 1 7 1, CT-1 169 (the above are manufactured by Peuro 丨 ite Corporation), etc., especially the PeurolUe CT — 1 7 5 (made by Peuro 丨 ite Corporation) ) Is preferably 0 in the hydrolysis of dialkoxysilanes of the above formula (3), the water used in the hydrolysis of the above formula (3) dialkoxysilanes in the molecule of the alkoxy group is 0.1 times mole ~ 1 times Moore, 0.2 ~ 0. 6 times more than Moore. 〇1. When it is less than 1 mole, the hydrolysis cannot be performed sufficiently, and a large amount of raw material alkoxysilane is not suitable. When it is more than 1 mole, the formula (2) dialkoxysilane cannot be obtained, and it becomes hydroxysilane. The hydroxyalkoxy group cannot efficiently produce a low molecular weight organosiloxane having a silanol group. 01〜1。 Also, the amount of cation exchange resin is added to 100 parts by weight of the above formula (3) dialkoxysilane and the total amount of hydrolyzed water is 0. 0001 ~ 30 parts by weight, especially from 0.01 to 1 Part by weight is preferred. If the amount of the ion exchange resin is more than 30 weight, the generated silanol groups will be promoted to condense, and sometimes short-chain chains cannot be obtained, and it is 0. Ί] 0 0 1 Fully hydrolyzed. In addition, the hydrolysis reaction time of dialkoxysilane can be arbitrary, but when it is too long, the siloxane bond of dialkoxysiloxane generated by hydrolysis will be cut off, and a bad ring will be formed .. . Siloxane with a long chain length, so in order to obtain short-chain dialkoxysiloxanes, a reaction time of less than 50 hours is appropriate. In addition, the reaction temperature can usually be room temperature. When the temperature is too high, the same reaction occurs. The reaction temperature is below 50 ° C, especially below 25. Implementation of this standard &gt; A4 size (2 丨 0X297 common stitching) ~~~ * '~~' • 1 ^---Γ --.------------ Order (please read the precautions on the back first) (Fill in this page again.) Consumption cooperation between employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du Yinze 4 2 06 85 'A7 B7 V. Description of the invention (10) should be 0 The hydrolysis reaction of dialkoxysilanes of formula (3) above is based on dialkane Hydrolyzed by cation exchange resin in the presence of silane and water, the initial stage of hydrolysis is separated into the dialkoxysilane phase and water phase. With the hydrolysis, water is consumed and alcohols are formed to make the system uniform. Ion-exchange resin-based solids cannot be dissolved in solution, and the reaction proceeds on the surface of the solid. Therefore, when the mixture is not sufficiently mixed, a uniform reaction may not be performed. For this reason, the reaction must be performed while stirring and mixing thoroughly. In the presence of an exchange resin, the above formula (.3) dialkoxysilane and When the amount of alkoxy group is from 0.1 to 1 mol of water, a dialkoxysiloxane represented by the above formula (2) having a chain length of 2 to 5 having an alkoxy group at the end can be obtained, and hydrolyzed by A mixture of by-products such as alcohols produced. The above-mentioned mixture can be easily separated into alkoxysiloxanes of the desired chain length by operations such as distillation if necessary. For example, dimethoxydimethyl Silane is used as a raw material, and 0.3 times mole of alkoxy is used. The reaction mixture obtained by the present invention is different due to reaction conditions, and usually contains 50% 1, 3-dimethoxytetramethyldisilazane. Oxane, 2 5% 1, 5-dimethoxyhexamethyltrisiloxane, 6% 1, 7-dimethoxyoctamethyltetrasiloxane, 2% 1, 9 _dimethyldeca Methylpentasiloxane. The rest are unreacted dimethoxydimethylsilane. These dimethoxysiloxanes with different chain lengths can be separated by distillation. In addition, after the reaction is completed, the catalyst is hydrolyzed. The cation exchange resin can be easily removed by filtering. This paper size is applicable to the Chinese standard (CNS) A4 (210χ2 &lt; ^ 7mm) ) _ Η-— (Please read the notes on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 420685, A7 ____B7_V. Description of the invention (11) Therefore, the present invention is based on ion exchange resin In the presence, hydrolyze the alkoxysiloxane represented by the formula (1) of the dialkoxysiloxane of the formula (2) obtained above to obtain a low-molecular-weight organic siloxane having a silanol group. Use at this time For the same reason as for the above-mentioned reason, the alkoxysiloxane is preferably the one having a chlorine component of 100 ppm or less, especially 10 ppm or less. In addition, as the water used for the hydrolysis is an organic siloxane having a cyclic siloxane, and the chain length is extended, ion-exchanged water such as N a, C a, Mg or the like is generally used with an ion exchange resin or the like. Distilled water containing this plasma. If the ionic substance is contained in the hydrolyzed water as described above, it will undergo ion exchange with an ion exchange resin used as a hydrolysis catalyst, such as H + of a sulfonic acid group, to make the hydrolyzed water acidic. For this reason, the short-chain silanols generated after hydrolysis cannot be stably present, and sometimes unsuitable cyclic polysiloxanes and organosiloxanes with extended chain lengths are sometimes formed. Therefore, the conductivity of the hydrolyzed water is preferably 101 (MΩ) or more, more preferably 1012MΩ or more, and most preferably 1015MΩ or more. On the other hand, cation exchange resins can keep the hydrolyzed P Η 値 neutral, while causing mild hydrolysis. The cation exchange resin can be used as a hydrolysis catalyst to prevent condensation and other condensation The cation exchange resin can be the same as the cation exchange resin used in the hydrolysis of the dialkoxysilicone. The amount of water used in the above hydrolysis is equal to or more than 1 mole of the alkoxy group in the alkoxysiloxane, and it is preferable that the amount of water is more than 1 mole of the stoichiometry. CNS) Λ4 specification (21〇 × 29ΐmm) _- (Please read the notes on the back before filling in this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 2 Π 6 85 'k Α7 Β7 V. Description of the invention (12) It is an excess, and it is preferably 10 times the mole or less, especially 5 times the mole or less. When the amount of water added is too small, the alkoxy group in the alkoxysiloxane molecule cannot be hydrolyzed, and a problem of a small amount of hydroxyl groups occurs. Although the amount of residual alkoxy groups can be reduced when the amount is more than 10 times the mole, the reaction It is not economical to remove a large amount of water from the mixture afterwards. 01〜1 重量。 The cation exchange resin is added in an amount of 1 0 0 parts by weight of the total amount of alkoxysiloxane and water, preferably 0. 0 0 0 1 ~ 3 0 parts by weight, more preferably 0. 01 ~ 1 weight Serving. When the amount of the ion exchange resin is too large, the silanol group formed will be further condensed, and short-chain ones cannot be obtained, and when it is too small, sufficient activity required for hydrolysis cannot be obtained. The reaction time varies depending on the alkoxysiloxane used, the amount of catalyst, etc. Although it can be set arbitrarily, the siloxane formed by hydrolysis when the time is too long will cut its siloxane bond or cause silane. The condensation reaction of alcohol groups produces unsuitable cyclic materials and organosiloxanes with extended chain lengths. Therefore, to obtain short-chain silanols, the reaction time is preferably within 50 hours. In addition, the reaction temperature can be arbitrary, but the same reaction will occur at too high a temperature, so the reaction temperature is preferably below 80 ° C, especially below 50 ° C. In addition, for the same reason as described in the explanation of the hydrolysis of dialkoxysilane, the hydrolysis reaction must be performed with sufficient stirring and mixing, and the reaction may not proceed uniformly when the stirring and mixing are insufficient. In addition, when the dialkoxysilane of the formula (2) obtained by hydrolyzing the dialkoxysilane of the formula (3) is hydrolyzed to obtain an organosiloxane containing a silanol, the formula (2) Although the hydrolysis of alkoxysiloxane can be interpreted in the paper standard (CNS &gt; Λ4 now (2ΐυχ;! 97mm)) _ _ (Please read the precautions on the back before filling this page)

1T 420685 A7 B7 V. Description of the invention (13) It is not necessary to specifically separate and refine the alkoxysilane of the formula (2) after the hydrolysis of the formula &lt; 3) dialkoxysilane, and the mixture of the compound and the parabiotic is also hydrolyzed. Siloxane having a hydroxyl group at the end of a chain length η of 2 to 5 can be obtained, but a dihydroxysilicone having a chain length corresponding to a desired chain length can be separated from the hydrolysis mixture in the first stage by means such as distillation. After the dialkoxysiloxane of hydroxane is hydrolyzed with an excess of water, a target compound represented by ΗΟ-&lt; S i RSO) with excellent purity can be obtained. . For example, by distilling from a dialkoxysilane mixture containing 50% 1, 3-dimethoxytetramethyldisilazane, which is hydrolyzed using dimethoxydimethylsilane as a raw material, as described above, the mixture is separated. 1,3-Dimethoxytetramethyldisilaxane, and then hydrolyzed to obtain 1,3-dihydroxytetramethyldisilaxane with high purity. In addition, the organosiloxane-based dimer diol of η == 2 and the trimer diol of η == 3 obtained in the present invention are most useful. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) After the above reaction, remove the cation exchange resin. The cation exchange resin of the hydrolysis catalyst can be easily filtered by other methods. Removed from the reaction mixture. Removing the cation exchange resin from the system can stop the hydrolysis and condensation reaction of silanol, so it is not necessary to add a neutralizing agent such as a base. That is, one embodiment of the present invention uses sulfonium based on diethylene The benzene ring formed by the base copolymer is used as a cation exchange resin. Since the benzene ring is chemically bonded with a sulfofluorene group, these sulfofluorene groups will not dissolve in the reaction solution, and the reaction solution can remain neutral. The hydrolysis reaction can be stopped when the ion exchange resin is removed by filtration. Therefore, the reaction mixture after filtration does not include acidic substances. In addition, the cation exchange resin separated from the reaction mixture does not need special treatment, such as regeneration. Can be re-used after waiting for operation. The paper size is applicable to China National Standard (CNS) Λ4 specification (2U) xm. _ μ ^ Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 420685 A7 B7 V. Description of the invention (14) Dissolve the catalyst. Second, the reaction mixture is stripped to remove alcohols and the remaining volatile components such as halo and water. At this time, it is better that the desired silanol is not stripped. Although the stripping pressure can be arbitrarily determined, the stability of the silanol is considered at the temperature, which is preferably 80 ° C or lower. According to the present invention In the manufacturing method, a low molecular weight silanol terminal group can be obtained in an excellent yield, especially a linear organic siloxane containing dimer diol and trimer diol. This organic silicon The siloxane is effectively used as a dispersant when manufacturing the silicone rubber material. The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples. Hydrolysis of Gas-Based Dimethyl Silane (First Stage Hydrolysis) In a 20mi Omi flask equipped with a thermometer and stirring blades and replaced with N 2, 200 g of dimethoxydimethylsilane (chlorine content) 5ppm) was added to 17.8g (p-alkoxy 0.30 Moore) ion-exchanged water having a conductivity of 10 15MΩ to form a two-phase system. 1.0 g (0.46% by weight) of a cation exchange resin (CT — 1 7 5) was added here. 1% ，， Peuroiite company), stirred at 20 ° C for 40 minutes, the solution phase became homogeneous. After another 4 hours of hot stirring. By gas chromatography analysis, the reaction mixture was found to contain 11. 1% Unreacted dimethoxydimethylsilane, 5 0. 0% This paper is suitable for China's National Standard (C'NS) Λ4 size (210X 297 mm) ~~~ —17-(Please read first Note on the back, please fill in this page again) Order A7 B7 420685 V. Description of the invention (15) 1, 3-dimethoxytetramethyldisilazane, 25-1% 1, 5-dimethoxyhexamethyl Trisiloxane, 6.1% 1, 7-dimethoxyoctamethyltetrasiloxane, 1.7% 1, 9-dimethoxydecylpentaoxamine. (Hydrolysis in the second stage) Then, 1.25 g (6.94 Moore) of ion-exchange water having a conductivity of 1015MΩ was added to the above reaction mixture, and stirred for 50 minutes. The ion-exchange resin was filtered to remove solids. Then, the byproduct methanol, water and the like were removed under the condition of 5mm ifg '50 eC, and 1 D 9 g of colorless and transparent liquid was obtained. According to the results of gas chromatography analysis, it was found that it contained 3.1% dimethylol dimethylsilane, 45.1% i, 3-dihydroxytetramethyldisilazane, 20.5% 1, 5 -Dihydroxyhexamethyltrisiloxane, 5.5% 1, 7-Dihydroxyoctamethyltetrasiloxane, 1. 7% 1, 9-Dihydroxydecamethylpentasiloxane. Example 2 Hydrolysis of Dimethoxymethyl Vinyl Silane (First Stage Hydrolysis) In a 20 Omj? Flask equipped with a thermometer and a stirring blade of WN2 substitution, 20 g of dimethoxymethyl Ionic exchange water having a conductivity of 10 was added to vinyl silane (containing 5 ppm of chlorine) at an amount of 1.6 2 g (0.3 mol for alkoxy group) to form a two-phase system. Add 0.10 g (0.46% by weight) of this paper to the Chinese standard (CNS) M specification (2) 0X 297 gong) 10 10 order (discussion of the back reading first) (Fill in this page again)

Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives 4 2 06 85 1 A7 B7 V. Description of the invention (16) Ion exchange resin (CT 1 75, manufactured by Peurolite), mixed for 4 G minutes at 20 ° C As a result, the solution phase becomes homogeneous. Stir for another 4 hours. Analysis by gas chromatography revealed that the reaction mixture contained 8.1% unreacted dimethoxymethylethenyl oxalate, 45.9% 1, 3-dimethoxy-1, 3 —Diethoxy-1,3-dimethyldisilaxane, 28.8% 1, 5-dimethoxy-1; [, 3, 5-trivinyl-1,3,5-trimethyl Trisiloxane, 7.9% 1,7-dimethoxy-1,3,5,7-tetraethanyl-1, 3,5,7-tetramethyltetrasiloxane, 2. 9% 1_, 9._dimethoxy-1,3,5,7,9-pentamethyl_1,3,5,7,9-pentamethylpentasiloxane. (Hydrolysis in the second stage) Then, 12.0 g (0.667 Moore) of ion-exchanged water having a conductivity of 1015 ^ 10 was added to the above reaction mixture, and stirred for 40 minutes. After removing the solid ion exchange resin by filtration, the byproduct methanol, water, etc. were removed under the conditions of 5 mmHg, 5 Q ° C. (Please read the precautions on the back before filling this page) -a Central Standard of the Ministry of Economy It is printed by the bureau's consumer cooperation,--&lt; radical 9 I 1 alkene, alkene, alkane 1 alkane 1 1, hydroxytetradecane siloxane 1%, silicon I 3 7 5 5 radicals, layer I, methyl 5 2 phase, ethyl 3 1 tris, gas radical, I 3 alkane from methyl 1% 5, oxygen. Boryl i 8, 1 sand. Hydroxyl 3 | tetrasodium dihydroxy 5, base liquid 2 2 1% of hydroxymethyl _, _ tetramethamine 3 3 Yuanji | one through., Oxygen is 7 7 color 2 one —_ more than B, no two Three 1 5 g containing% I, 3 of 3 A 5% 3 Its. 2 1 Know 1 I 1SI4 3

♦. Wolang &lt; Dushizhou National Standard (CNS) Λ4 Specification (210X297 mm) _ 19-Central Standards Bureau of the Ministry of Economic Affairs β: Industrial and consumer cooperatives 4 ^ 06 85, A7 B7 —___ V. Description of the invention (17) A dihydroxy-1,3,5,7,9 pentamethyl-1,3,5,7,9 pentamethylpentasiloxane. Example 3 The first-stage hydrolysis was carried out according to the method of Example 1. After completion of the hydrolysis, the 1,3-dimethoxytetramethyldisilazol was separated from the reaction mixture, and the second-stage hydrolysis was performed as follows. . (Second-stage hydrolysis) In 10.0 g of 1,3-dimethoxytetramethyldisilazane, 2.0 g of ion-exchanged water having a conductivity of 10 15MΩ was added, and 0. 0 3 0 g of a cation exchange resin (CT-17 5) manufactured by Peurolite, was stirred at 20 ° C. for 80 minutes. 7g 白晶。 After removing the solid ion exchange resin by filtration, the byproduct methanol, water, etc. were removed under the conditions of 5mniHg, 50 ° C, and 7.7 g of white crystals were obtained. As a result of gas chromatography analysis, it was found that it contained 8 8% 1, 3-dihydroxytetramethyldisilazane. Example 4 The first-stage hydrolysis was carried out according to the method of Example 1, and after the completion of the distillation, 1,5-dimethoxypentamethyltrisiloxane was separated from the reaction mixture, and the second-stage hydrolysis was performed as follows. (Second stage of hydrolysis) (Please read the notes on the back before filling in this card)

ltT This paper size is applicable to China National Standard (CM) Λ4 specification (2 丨 0: &lt; 2 blade mm) 20 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 42U685 A7 _B7____ 5. Description of the invention (18) at 10. 0g 1,5-Dimethoxypentamethyltrisiloxane was added with 2.0 g (0.11 Moore) of ion exchange water having a conductivity of 1015MΩ, and (3.00 g cation exchange resin was added thereto. (CT-175) manufactured by Peurolite), and stirred at 20 ° C for 150 minutes. After removing the solid ion exchange resin by filtration, the byproduct methanol, water, etc. were removed under the conditions of 5mmHg, 50 ° C, and the result was 8.0 colorless transparent liquid. As a result of gas chromatography analysis, it was found to contain 90.5% 1,5-dihydroxypentamethyltrisiloxane. Example 5 The ion exchange resin separated by filtration in Example 1 was directly used again as a hydrolysis catalyst, and hydrolysis was performed in the same manner as in Example 1. After repeating this method 10 times, the obtained hydrolysate was analyzed by gas chromatography. As a result, it was found that it contained 2.5% dimethylol dimethyl silane, 44.0% 1, 3-dihydroxytetramethyl dimethyl siloxane. , 2 0.1% 1, 5-dihydroxypentamethyltrisiloxane, 4.4% 1, 7-dihydroxyoctamethyltetrasiloxane, '1.3% 1, 9 one dihydroxydeca Methylpentasiloxane. From the results of the examples, it can be seen that the cation exchange resin used in the present invention can be recovered and used without being subjected to a special treatment such as regeneration. Comparative Example 1 In a 5 OmJ? Flask equipped with a thermometer, a stirrer, and substituted with N 2, 20.0 g (0.166 mol) of dimethoxydimethylsilane was added and adjusted to Η値 4.2 2 6. 8 8 g (This paper size applies to Chinese National Standard (CNS) A4 specifications (2 丨 0X297 male ulcers) _ 2 丄-(Please read the precautions on the back before filling out this page). Order 42ub85. 'A7 B7__ 5. Description of the invention (19) 〇. 3 6 6 Moore) hydrochloric acid water, that is to reach a maximum temperature of 40 eC, to become a uniform solution. After stirring for 5 minutes, 0.2s (4.96X1 0_3 mole) of magnesium oxide and 15g (0 12 5 mole) of magnesium sulfate were added and stirred for 3 hours. This oil was filtered and stripped at 20 ° C and 5 mm H g. When the oil was analyzed by gas chromatography, it was found to contain 15.7% 1,3-dihydroxytetramethyldisilazane, 24.5% 1,5,5-dihydroxypentamethyltrisiloxane, 15 · 1% 1,7-dihydroxyoctamethyltetrasiloxane, 9.3% of 1.9-dihydroxydecamethylpentasiloxane. In the method of this comparative example, condensation of silanol groups is caused. Compared with the above examples, the amount of 1,3-dihydroxytetramethyldisilanes produced by short-chain silanols is obviously lower. Moreover, in this method, Although a mixture of hydroxy compounds can be obtained, it is difficult to isolate a hydroxy compound of a desired chain length from this mixture. Comparative Example 2 Consumption Cooperation by Employees of the Central Bureau of Standards, Ministry of Economic Affairs, J-11 ^^ — ^ 1 1, ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 (Please Read the precautions on the back before filling in this page) In a 5 Omj? Flask equipped with a thermometer, stirrer, and N 2, at 10. Og (〇. 514 mol) 1 '3 -dimethoxy tetra Methyldisilazane was added to adjust pH 2.0 to 2.0 g (0. G 1 11 Moore) of hydrochloric acid water to reach a maximum temperature of 40 ° C, and became a uniform solution. After stirring for 8 minutes, 0.1 g (2.48 × 10-3 mole) of magnesium oxide and 3 g (0.025 mole) of magnesium sulfate were added and stirred for 1 hour. This oil was filtered and stripped under a pressure of 20,5 mm H g. When the oil was analyzed by gas chromatography, it was found that it contained 16.3% 1,3,2-dihydroxytetramethyldisilazane, 25.5. This paper is in accordance with China National Standard (CNS) A4 (2IOX 297). Mm) _ 2-420685 · ν Λ7 B7 V. Description of the invention (20)% 1,5-Dihydroxypentamethyltrisiloxane, 23.8% 1,7-Dihydroxyoctamethyltetrasiloxane , 8.6% of 1.9_dihydroxydecamethylpentasiloxane. In the method of this comparative example, the condensation of silanol groups is caused. Compared with the above examples, the formation of 1,3-dihydroxytetramethyldisilanes of short-bonded silanols is obviously lower. Moreover, in this method, Although a mixture of hydroxy compounds can be obtained, it is difficult to isolate a hydroxy compound of a desired chain length from this mixture. Example 6 Hydrolysis of Dimethan, Dimethan and Silane (First Stage Hydrolysis) In a 20 Omj? Flask equipped with a thermometer and stirring blades replaced with &gt; 12, in a 2.0 Og dimethoxydi To methylsilane (5 ppm chlorine content), 1.19 g (0.2 mole for alkoxy group) of ion-exchanged water having a conductivity of 1015 MΩ was added to form a two-phase system. Add 0.10g (0.46% by weight) of cation exchange resin (printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling in this I) CT1 1 1 5 ， Peurolite Company System), and stir at 20 ° C for 40 minutes. As a result, the solution phase became homogeneous. Continue stirring for another 4 hours. Analysis by gas chromatography revealed that the reaction mixture contained 33.2% unreacted dimethoxydimethylsilane, 45.4% 1, 3, -dimethoxytetramethyldisilazane. 1%, 2.8% 1, 5-dimethoxyhexamethyltrisiloxane, 2.5% 1,7-dimethyl: oxyoctamethyltetrasiloxane, 0.6% 1 ， 9 ~ dimethoxydecylpentasiloxane. This paper size is applicable to CNS A4 specifications (210X297 mm) _ 42 0685 A7 B7 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) (Second stage hydrolysis) To the above reaction mixture was added 12.5 g of ion-exchanged water having a conductivity of 1 015 MΩ, and stirred for 40 minutes. After removing the solid ion exchange resin by filtration, the byproduct methanol, water, etc. were removed under the conditions of 5mmHg, 50 ° C, and the result was 11. 0 &amp; colorless and transparent liquid. From the results of gas chromatography analysis, it was found that it contained 25.7% dimethyl dimethyl silane, 4 3. 0% 1, 3-dihydroxytetramethyl dimethyl siloxane, 1 3. 5% 1 , 5-Dihydroxytetramethyltrisiloxane, 2.4% 1,7-Dihydroxyoctamethyltetrasiloxane, 0.6 ·% 1, 9,9-dihydroxydecamethylpentasiloxane. Example 7 Except that the amount of ion-exchanged water used in the first-stage hydrolysis in Example 6 was changed to 3.0 Og (0.5 times mole for alkoxy group), the same hydrolysis was performed. Results The reaction mixture contained 2.1% dimethoxydimethylsilane, 48.9% 1, 3,3-dimethoxydimethyldisilazane, 2 * 9.1% 1, 5-two Methoxyhexamethyltrisiloxane, 8.8% 1, 7-dimethoxyoctamethyltetrasiloxane ', 2.2% 1, 9-dimethoxydecamethylpentasiloxane. Secondly, the hydrolysis in the second stage was performed in the same manner as in Example 6. As a result, 11.6% was obtained as a colorless and transparent liquid, which contained 0.9% of dimethyldimethylsilane, 46.3% of 1,3-dihydroxytetrazine. Methyldioxane '28. 0% 1,5-Dihydroxyhexamethyltrisoxacin' 9-1% 1,7-Dihydroxytetramethyltetrasiloxane, 3.0% 1,9 — Yixiang τ-Come 1-IT {Please read the precautions on the back before filling this page) This paper is fully applicable to China National Standard Soap (CNS) 8 4 old grid (210X297 mm) _ 24-420685 A7 B7 Ministry of Economic Affairs Printed by the Consumers' Cooperatives of the Central Bureau of Quasi-Bureaus 5. Description of Invention (π) Decamethylpentasiloxane. Comparative Example 3 Except that the amount of ion-exchanged water used in the first-stage hydrolysis in Example 6 was changed to 8.9% (1.5 times mole for alkoxy group), the rest were hydrolyzed in the same manner. Contains 70. 1% Dihydroxydimethyl Silane, 8. 5% 1, 3-Dihydroxytetramethyldisilazane, 3.2% 1, 5-Dihydroxyhexamethyltrisiloxane, 12. 5% Hydroxylmethoxydimethylsilane, 3.0% 1_hydroxyl-3._methoxytetramethyldisilazane. As described above, when the alkoxy group of p-alkoxysilane is used in a stoichiometric excess of water during the first-stage hydrolysis, dialkoxysiloxane is scarcely formed, but a hydroxy compound is formed. At this time, the yield of 1,3-dihydroxytetramethyldisilazane is small, and it is difficult to separate the siloxane of a desired chain length from the above-mentioned hydroxyl compound mixture. Example 8 In a 50m flask equipped with a thermometer and stirring blades replaced with &amp; N2, at 10.0g (0.0458 times mole) 1,5 -dimethoxy-1,5-divinyldimethylformate 8 g (0.10 mol) of ion-exchanged water having a conductivity of 1015 MΩ was added to the disiloxane. 0.30 g of cation exchange resin (CT-17.5, manufactured by Peurolil: e) was added here, and it was carried at 20 ° C for 80 minutes. After removing the solid ion exchange resin by filtration, the paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) at 5mmHg.-(Read the precautions on the back before filling this page) Order A7 B7 420685 V. Description of the invention (23) Remove methanol, water, etc., which are byproducts at 50 ° C, and obtain 7.6 g of white crystals. Based on the results of the gas phase layer analysis, it was found that it contained 80.3 (please read the precautions on the back before filling in this page)% 1,5-dihydroxy-1,5-divinyldimethyldisiloxane 〇 Ο Example 9 In a 5 Om flask equipped with a thermometer, stirring blade of ΗΝ2 replacement, in 10. 0g (0. 514 Moore) 1,1-dimethoxytetramethylsilane was added 2. Ion-exchanged water with a conductivity of 0 g (0.111 Moore.) Of 1015 MΩ. 0.030 g of a cation exchange resin (CT-17.5, manufactured by Peurolite) was added thereto, and the mixture was stirred at 20 ° C. for 80 minutes. After removing the solid ion-exchange resin by filtration, the byproduct methanol, 7K, etc. were removed under the conditions of 5 m m H g * 50 ° C, and 7.4 g of white crystals were obtained. Based on the results of gas-phase layer analysis, it was found that it contained 82.0% 1, 1_dihydroxytetramethyldisilaxane, printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Example 1 0 In a 5 OmJ? Flask replaced by WN2, 1.10 g (0. 62 Moore) was added to 10. 0 g (0.0561 times mole) of 1-methoxypentamethyldisilazane. It is 10 15 MΩ of ion-exchanged water. 0. 0 300 g of cation exchange resin (CT-1 75, manufactured by Peurolite) was added here, and it stirred at 20 ° C for 80 minutes. Ion-exchange tree paper sheets with solids removed by filtration are again applicable to Chinese national standards ((each (210X297 mm)-420685 A7 _ B7) V. Description of the invention (after 24 · fat, at 5 mm H g, 50 ° C) After removing byproduct methanol, 7_R, etc., 7.6 g of colorless transparent oil was obtained. From the results of gas phase layer analysis, it was found that it contained 8 1.3% 1-hydroxypentamethyldisilazane. Example 1 1 In a 5 Omi? Flask equipped with a thermometer and stirring blades replaced with N 2, 10. 7 g (0.0396 Moore) 3-methoxyheptamethyltrisiloxane was added 0.7 8 4 g ( 0. 〇. 436 Moore) ion-exchange water having a conductivity of 1015 MΩ. 30 g of a cation exchange resin (CT-175, manufactured by Peurolite) was added thereto, and the mixture was stirred at 20 ° C for 80 minutes. After removing the solid ion exchange resin by filtration, the byproduct methanol, water, etc. were removed under the conditions of 5mmHg, 50 ° C, and 8.0 g of white crystals were obtained. From the results of gas phase layer analysis, it was found to contain 9%. 3% 1, 3-Hydroxyheptamethyltrisiloxane. Implementation Example 1 2 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ ipi I-^^^^ 1 tti ^ i ^^^^ 1 ^^^^ 1 1— I 1 d «(Please read the notes on the back before filling this page) With a thermometer, stir the leaves In a 50 m flask replaced with N2®, 20 g of 9.8% dimethoxydimethylsilane 51.0% 1,3-dimethoxytetramethyldisiloxane 26.0% 1,5-Dimethoxyhexamethyltrisiloxane 7 3% 1, 7-Dimethoxyoctamethyltetroxaline 2 4% 1,9 Dimethoxydecamethylpentasiloxane paper i Good-standard general-purpose national standard (CNS) A4 specification (2IOX2 mm) -27-Printed by a member of the Central Standards Bureau, Ministry of Economic Affairs and Consumer Cooperative, 420685 A7 __B7 ________ V. Description of the invention (25) Add 5.0 g of ion-exchanged water with a conductivity of 10 15MΩ to the oxane mixture and stir for 50 minutes. After removing the solid ion-exchange resin by filtration, remove the byproduct methanol at 5mmHg, 50 ° C, Water, etc., as a result, 15.lg was obtained as a colorless and transparent liquid. According to the results of gas chromatography analysis, it was found that it contained 2.7% dihydroxydimethylsilane 4 7. 8% 1, 3-dihydroxytetramethyl. Disiloxane 2 2.3% 1, 5-Dihydroxy Hexamethyltrisiloxane, 5.9% 1, 7-dihydroxyoctamethyltetrasiloxane, 2.4% 1, 9-dihydroxydecamethylpentasiloxane Example 1 3 With a thermometer, In a 5 OmJ? Flask with agitating leaves replaced by N2, 20 g of 7.5% dimethoxymethylethylene silane 46.8% 1, 3-dimethoxy-1, divinyl-1 , '3-Dimethyldisilazane 27.1% 1, 5-Dimethoxy-1, 3, 5-trivinyl-i, 3, 5-trimethyltrisiloxane 6. 1% 1,7-dimethoxy-1,3,5,7-tetravinyl-1,3,5,7-tetramethyltetrasiloxane 2.9% 1,9-dimethoxy -1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylpentasilane This paper size applies to Chinese national standards (cns specification (2 丨 0x297 mm) _ 28 _ _--- I!-^^^ 1 —1-1 · ^ -I 1: -II &gt; ^ 1 n (Please read the precautions on the back before filling this page) A7 420685 __B7_ V. Description of the invention (26) Add 4.5 g of ion-exchanged water with a conductivity of 1,015MΩ to the resulting alkoxysilane mixture, and stir for 40 minutes. After removing the solid ion exchange resin by filtration, the byproduct methanol 'water, etc.' was removed under the conditions of 5 mmHg and 50 ° C to obtain 16.7 g of a colorless and transparent liquid. From the results of gas phase layer analysis, it was found that it contained 2.0% dihydroxymethyl vinyl silane 4 2.4% 1, 3-dihydroxy-1, 3- divinyl-1, 3-dimethyldisiloxane Siloxane 2 4. 5% 1,5_ dihydroxy-1,3,5-triethylamine. 1 — 3,5-trimethyltrisiloxane 7.5% 1, 7-dihydroxy-1 1 '3, 5, 7 —tetravinyl-1,3,5,7 —tetramethyltetrasiloxane 2. 9% 1,9_dihydroxy —1,3,5,7,9 —pentavinyl One 1,3,5,7,9 One pentamethylpentasiloxane (please read the precautions on the back before filling in the unpaged page) Order the Central Government Procurement Bureau's Consumer Cooperation of the Ministry of Economic Affairs' Common printed paper ft standard universal China National Standard (CNS) A4 specification (2 丨 OX2W male stitch)

Claims (1)

89 · 8, 1 year /) Supplement 420685 Hh Cb DH This VI. Application for Patent Scope 'Patent Application No. 84104067 Patent Application Amendment for Chinese Patent Application (Please read the notes on the back before filling this page) Republic of China 8 9 years 8 Month correction 1. A method for producing a low-molecular-weight organosiloxane having a silanol group, which is characterized by the presence of a coarse porous cation exchange resin having a pore volume of 0 lmi / g or more when measured by a mercury injection method. In the following formula (1) • · 1 ^ CROWiO ^ (1) ~ Z (where RM is an alkyl group having 1 to 4 carbon atoms, alkenyl 'phenyl' R2 group having 2 to 4 carbon atoms is the same or The different carbon numbers are 1 to 4 radicals, a is 0 to 2.2, b is 0.2 to 3, a + b is 2 to 3, but the number of silicon atoms in the molecule is 2 to 5), so Shows that alkoxysiloxane is added to the above-mentioned alkoxysiloxane alkoxy group of 1.0 times mole of water * or more, and is subjected to hydrolysis. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation. 2. If the manufacturing method of the first scope of the patent application is applied, the formula (1) for the alkoxysiloxane is the following formula (2) Ri RO- ^ SiOV -R1 (2) I R1 (where R1 »R2 is defined as shown above, and η is an integer of 2 to 5). This paper size applies the Chinese national standard 0:. \ $) Λ4 (210x 297 male S) 0685 Η8 1) 8 κ, please apply for the patent scope 3 _ If the manufacturing method of the second scope of the patent application, the above formula ( 2) Dioxosiloxane is in the presence of a cation exchange resin in the following formula (3) R \ Si / 〇RJ Note / \ 〇 纪 (3) (where R1 'R 2 is as defined above To the dialkoxysilane shown in (1), water obtained by adding 0-1 mol to 1 mol of alkoxy present in the above dialkoxysilane molecules was hydrolyzed by stirring. 4. The manufacturing method according to item 2 or item 3 of the scope of patent application, wherein the low-molecular-weight organic polysiloxane having a silanol group is represented by formula (4) or (5). R1 HOKSiOkH R1 R1 HCHSiO) rK Rl (4) (5) (R1 is as defined above). 5. The manufacturing method according to item 1 of the scope of patent application, wherein the water used for the hydrolysis is ion-exchanged water having a conductivity of 10 μαΜΩ or more. 6. If the manufacturing method of the scope of patent application is the first one, in which the above-mentioned paper size is applicable _ national national standard profile do X 297g g) ----- — — — — — — — ----- order --- I ----- line (please read the precautions on the back before filling out this page) l; 8 1) 8 VI. Patent Application Scope 3. For the manufacturing method of the second scope of patent application, where the above formula (2) The dialkoxysilane is in the presence of a cation exchange resin, in the following formula (3) Rlv y〇R2 NSi R1 / \ 〇RZ (3) (where R1 and R2 are as defined above) ) Shown in the above dialkoxysilane, adding 0.1 mol to 1 mol of alkoxy present in the above dialkoxysilane molecules, and stirring and hydrolyzing. 4. The manufacturing method according to item 2 or item 3 of the scope of patent application, wherein the low molecular weight organic polysiloxane having a silanol group is one represented by formula (4) or (5), R1 HO-iSiOir- t R1 ¢ 4) (Please read the notes on the back before filling out this page) ------- Order -------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1¾ R1 HCMSiOVH Rl (5 ) (Where R1 is as defined above). 5. The manufacturing method according to item 1 of the scope of patent application, wherein the water used for the hydrolysis is ion-exchange water having a conductivity of 1010 MΩ or more. 6. For the manufacturing method of item 1 in the scope of patent application, in which the above paper size is applicable to the national standard (CNS) A4 specification (210 X 297 meals) ^ ϋ b 85 tif B8 'CH 1) 8 6. Application The residual chlorine content in the dialkoxysilane of the patent range (3) is below 100 p pm. (Please read the precautions on the back before filling in this -nn I— It nnn This paper printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is again applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm). The application period is 84 years Case No. 84104067 on April 25 (Categories above are filled out by the Bureau) Notice A4 C4 4206i5 Patent Specification for Mold (Amendment) Chinese Low-molecular-weight organosilane with silanease group The name of the new invention in English Process for preparing organosiloxane terminated with silanol group Name (1) Igarashi 実 0 Takahashi Masaru Nationality (1) Japanese version {25: Name of the creator, residence of the present invention (name) Nationality ⑴ Japan 囲 Gunma Prefecture 碓 Ice-gun pine Meet the big characters of Wadata — Q Q See the great characters of Matsuda-machi, Ogami-gun, Gunma Prefecture, Japan — 0⑴Betsu Chemical Industry Co., Ltd. Betsu Chemical Industry Co., Ltd. ------ Order I Ai applicant's residence, residence (office) (1) Japan, Japan, Chiyoda, Tokyo, Japan Representative name of Fanyi 一 Jinchuan Chihiro This paper size is applicable to Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) 89 · 8, 1 year /) Supplement 420685 Hh Cb DH The sixth, the scope of patent application 'No. 84104066 Patent Application No. Chinese Patent Application Amendment (please read the precautions on the back before filling out this page) Republic of China August 1989 Amendment 1. A method for producing low molecular weight organosiloxanes with silanol groups' its It is characterized by the presence of a coarse porous cation exchange resin with a pore volume of 0 lmi / g or more when measured by the mercury injection method. In the following formula (1) • · 1 ^ CROWiO ^ (1) ~ Z (where RM system is Represents an alkyl group having 1 to 4 carbon atoms, and an alkenyl 'phenyl' group having 2 to 4 carbon atoms. R2 represents the same or different carbon group having 1 to 4 carbon atoms, a is 0 to 2.2, and b is 0. The number of 2 to 3, a + b is 2 to 3, but the number of silicon atoms in the molecule is 2 to 5). The alkoxysiloxane shown above is added with 1 of the alkoxyl of the above alkoxysiloxane. Water with more than 0 times Moore * is stirred and hydrolyzed. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation. 2. If the manufacturing method of the first scope of the patent application is applied, the formula (1) for the alkoxysiloxane is the following formula (2) Ri RO- ^ SiOV -R1 (2) I R1 (where R1 »R2 is defined as shown above, and η is an integer of 2 to 5). This paper size applies Chinese national standard 0:. \ $) Λ4 (210x 297mm S)