TW403767B - Synthesis of hydridosiloxane resins - Google Patents

Abstract

Novel processes for preparing hydridosiloxane and organohydridosiloxane resins are disclosed. The processes of the invention broadly provide for the steps of contacting a silane monomer with a phase transfer catalyst in the presence of a reaction mixture that includes a nonpolar, e.g., hydrocarbon, solvent, and a polar solvent, e.g., alcohol and water. The process is conducted under conditions effective to catalytically convert said silane monomer into hydridosiloxanes and organohydridosiloxanes. Recovery of the products is advantageously aided by the ease of separating the solid state catalyst from the reaction mixture. Hydridosiloxanes and organohydridosiloxanes resins produced by the processes of the invention are also provided.

Description

A7 B sells 5. Description of the invention (13) and the product has substituted and unsubstituted aryl groups having about 6 to 20 carbon atoms. For example, when R 1 is an alkyl group, R 1 includes, but is not limited to, methyl, p-methyl and ethyl, linear and branched propyl, 2-chloropropyl v-butylpentyl Base and 'hexyl. When R1 is a ring pit group, R1 includes, but is not limited to, determined by cyclopentyl, cyclohexyl, chlorocyclopentyl, and cycloheptyl; when the rule is aryl, R includes 'but not limited to' benzene Group, fluorenyl, tolyl, and benzyl. It will be understood that 'the specific carbon content of any organohydrosiloxane resin according to the present invention is related to the molar ratio of the organotrihalosilane to the hydrotrioxane starter used. In a more advantageous case, the product produced by the method of the present invention is a polymer having a cage structure whose polymer skeleton surrounds alternating silicon and oxygen atoms. In particular, each skeletal silicon atom is connected to at least one triskeleton oxygen atom to form the aforementioned cage structure. Basically, all the additional silicon is only connected to the hydrogen and oxygen present as defined in formulae 2, 3, 4, 5 and 6. Therefore, the polymer of the present invention is substantially free of a hydroxyl group or an alkoxy group bonded to a backbone silicon atom, and inhibits a crosslinking reaction. In contrast, the organosiloxane resins previously known have a large proportion of alkoxy groups bonded to backbone silicon atoms, and therefore, significant hydrolysis to silanol groups was observed. This hydrolysis allows cured polymer films formed from previously known resins to have a higher dielectric constant, while also shortening the storage life of solutions of these resins. The report states that the effects mentioned later are due to unwanted chain lengthening and cross-linking. Therefore, in the method of the present invention, the provided hydrogen and organic groups are only bonded to the skeleton silicon atom, which is beneficial to avoid the condensation reaction of hydroxyl or silane groups. -16- This paper is applicable to China National Standard (CMS) A4 specifications (2iOX297 mm) _ (Please read the notes on the back before writing this page): Packing. Order the consumer cooperation of the Central Sample Bureau of the Ministry of Economic Affairs · Du printed A7 ___403767_b7___ 5. Description of the invention (1) Scope of the invention Related applications t This patent application claims the advantages of the following U.S. patent applications: xj.S. provisional application serial number 60 / 044,479 filed on April 21, 1997; US nonprovisional application filed on March 20, 1998 Serial number 09 / 044,831 and US nonprovisional. application serial number 09 / 044,798, filed March 20, 1998, are incorporated herein by reference for their disclosure. BACKGROUND OF THE INVENTION The present invention relates to the preparation of substrates for integrated circuits. In particular, the present invention proposes a new and improved method for the preparation of siloxane resins (including hydrosiloxanes and organohydrosiloxanes) without the disadvantages previously associated with the preparation of such materials. More specifically, the present invention relates to a synthesis method that uses solid catalysts to avoid the disadvantages of previously used catalyst systems that require the use of harmful catalysts. The present invention also relates to a synthetic method that does not require additional washing and purification steps and is believed to be necessary for preparing such a resin. Description of previous techniques Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (read the 4 items of the rain first and then fill out this page) This technique has been known that siloxane-based resins can be used in electronic parts and semiconductors. It is used to coat wafers and other similar parts. Such a coating protects the surface of the substrate and forms a dielectric layer between the conductive objects of the integrated circuit. Such coatings can be used as protective coatings, interlayer dielectric layers, complex dielectric layers that form transistor-like devices, pigment-containing silicon-containing adhesives used to make capacitors and capacitor-like devices. System, multi-layer device, 3D device, this paper size is applicable to Chinese National Standard (CNS) Λ4 Regulation (210X297 km) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 〇37β7 Α7 ----- R7 V. Description of the invention (2) ~ ---, the coatings on the superconducting to, the superlattice g are located on the insulation device. These resins include hydrogen osmium and oxygen pits containing a large amount of organic moieties. In this technique #, the production system of oxo-fired resin (such as hydrogen dream sesquioxane) has been well known. For example: U.s. Patent No. 5,486,564 describes the production of polyhydrogen sesquioxane resins used for coating electric parts. However, this method uses hazardous oleum / sulfuric acid as a catalyst to make polyhydric sesquioxins. Although washed several times with water containing a low percentage of sulfuric acid, and all water was removed using a co-steam distillation method, the product was still contaminated with a large amount of tiny metal deposits. To remove these disadvantages, us patem NO 5416 19〇 describes the use of polar and non-polar solvents to fractionate this hydrosilsesquioxane product. Other methods to remove these shortcomings of hydrogen-producing silsesquioxane compounds include the use of superfluid extraction (such as described in U.S. Patent No. 5,063,267) in purification procedures and the use of fumes / concentrated sulfuric acid, but CaCO3 is neutralized (as described in us patem% 5,010,159). It is also known that the dielectric constant of such an insulating film is an important factor for an integrated circuit or 1C that requires low energy consumption, line interference, and low signal delay. This factor is even more important as IC size continues to shrink. As a result, it is highly desirable to develop a siloxane-based resin material having a dielectric constant of less than 3.0 and a method for manufacturing such a material. In addition, it is desirable that a resin based on oxygen sintering and a method for making the resin can provide a film having a low dielectric constant and a high breaking strength. It is also desirable that such a film should be small at a thickness of about 10 micrometers or more. In addition, it is hoped that this siloxane-based resin will provide a film with a low dielectric constant by standard processing techniques. In this way -5- This paper size applies to the Chinese National Standard (〇 奶) 6 4 specifications (210 father 297 male dust) First please 5fr "#Notes on the back before filling this page) Attack-

, 1T A7 V. Description of the invention (3) ~~ 'formula, it is necessary to avoid the atmosphere of ammonia or ammonia derivative type (please refer to, Ballance et al., September 8, 1992, Us Patent No. 5,145,723) 2. Ozone atmosphere (please refer to Haluska et al., US patent N. 5,336,532) curing process or other non-standard semiconductor process. Therefore, it is hoped that the # oxygen-fired coating composition (such as cutting, oxygen-fired, and organic hydrogen-oxygen-fired) can be prepared by an effective method without using a toxic catalyst. 4 Discovered a different place: the reaction of the off-state polymerization catalyst can produce the desired hydrogen stone oxygen and organic hydrogen second oxygen burn, and at the same time can avoid all the aforementioned shortcomings of the previous method. The method of the present invention proposes to replace the resin in a high yield manner by catalyzing the hydrolysis reaction of the monomer precursor j with the general formula R1 siX3 (such as hydrogen second-oxygen burn, hydrogen sulfonium semi-oxygen burn, Organic hydrogen dream sesquioxo and organic hydrosiloxane) method. In this formula, 乂 is a quotient or 〇2, R2 is 1H or fluorenyl or aryl functional group, respectively. R > / iiR2 is not selected from substituted or unsubstituted straight or branched fluorenyl, fluorenyl, and ^ Aryl., Or a combination thereof. Therefore, the aforementioned starting compounds or monomeric precursors are used in the hydrolysis reaction and the condensation reaction—or a plurality of rhenium catalysts to form the desired silicone resin. Therefore, the method of the present invention includes the reaction between Shi Xiuyao monomer and solid catalyst in a non-polar solvent (such as hydrocarbons) and polar solvents (such as alcohol and water). The percentage of steps of the produced oxoxane and hydrogen oxide with contact and recovery are obtained after contact and afterwards. -Exhaustion The method of the present invention is preferably carried out using a two-phase solvent system. In addition, Bu-6-this paper is of suitable size; iif Guan Jia Zhuan (CNS) μ size (2 number 297 males Ί 4 0 3 7 6 7 Α7 _ Β7 V. Description of the invention (4 Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs) The printing method is preferably carried out without contact with atmospheric oxygen, such as: reacting in a container that has been purged of oxygen and maintained an inert gas (such as nitrogen v 2). In particular, in one embodiment, this In the method, one or more of the aforementioned monomers (eg, trichlorosilane and / or one or more organic trichlorosilanes) are added to a mixture including a solid catalyst, a hydrocarbon solvent, and an alcohol and water. Other known silane monomers. Once the reaction is complete, the reaction mixture is filtered, deposited, or centrifuged (for example) to remove any filterable impurities or sediment, and to remove solid catalysts. The water is then separated and the remaining The solution was exploded to leave the product (basically a white solid). After that, the recovered solid was gelatinized in an appropriate hydrocarbon solvent to remove the remaining low molecular weight components, after which the solvent was evaporated to leave Give birth The resulting product can be formulated in a suitable solvent, and the weight average molecular weight (Mw) of the polymer prepared by spin coating polymerization 20 using a method known in the art is from about 1 to about 1 atomic mass unit ( _). In addition, the MW of the towel is from about 10, to about 8 to 1 u, which depends on the reaction condition t. More specifically, in a specific embodiment, the polymer of · To about 75, __. Simply by non-limiting examples, the heart of the material produced by each method of the invention is, for example: about 20, 2, 40,000, and about 60,000 amu, good Coating properties ... Therefore, the present invention proposes the use of an appropriate initial sintered oxygen burn (such as the oxygen fresh organic hydrogen $ _ material = also surprisingly found that the method of the present invention can be touched in a solid state, according to this The catalysts of the invention include, for example, changing from 1 to 4 times, and changing resin, acidity or alkalinity. -7 Paper size Gut Guanjia materials (CNS) Read ▲ Read… Read back ~ Note

I write page 1 D Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 403707 .Α7 V. Description of the invention (5) A giant network resin, clay (including acid clay) and the like. Light examples are detailed. According to the present invention, it is provided with a new compound that is not previously prepared and useful compounds (such as the aforementioned resin). In addition, while describing the present invention with reference to various embodiments, it should be understood that these embodiments are merely examples, and are not intended to limit the present invention. Therefore, those skilled in this art obviously know the various modifications or variations of special materials and methods. All such modifications, variations, or alterations as suggested herein and suggested in the present invention are within the spirit and purpose of the present invention. Precursor-Any precursor that conforms to the aforementioned general formula can be used in the method of the present invention. Therefore, the precursor is usually R ^ SiX, among which is the prime or 〇2, r1 and & 2 are fluorene or alkyl or aryl, respectively, when R1 and / or R2 is not] ^, one of Or both are substituted or unsubstituted, linear or branched alkyl, cycloalkyl, and / or aryl, or a combination thereof. Therefore, in one embodiment, χ is a prime element, preferably chlorine. In a better mood, the three visions are the same, as the book is called. In addition, in a preferred embodiment, Ri is the aforementioned one, x * 〇r2, and the ruler 2 of the towel is a thio group and a aryl or aryl substituent, which are selected to provide a desired reaction product. Discussed simply by way of example, the size of the R2 alkyl substituent is Ci to Cm or more, and may be linear, branched, or cyclic. Aryl substituents can also be., Linear or branched alkyl, aryl, and heterocyclic aryl substituents, preferably in size from h to Cm or greater, and are optionally alkyl and / or Aryl Substituted. In a preferred embodiment, all R2 are the same, in a preferred embodiment, all are C2H5-. In another alternative embodiment, it is 1, χ々χ3

-8-103767 V. Description of the invention (A7 B7 Printed by the Central Consumers Bureau's Consumer Cooperatives of the Ministry of Economic Affairs, each of X, x2, and x3—as defined by the eighth side] Issued from: Sufa and / Or ⑽; examples of alkane precursors include, but, available silicon, ethyldichlorosilane, trichlorosilane, methyltrichlorosilane, trichlorosilane, n-butyltrichloro The valence of chlorhexyl chloride and their mixed premises are only a small part of it. Of course, the skilled worker knows that the technique =: =: species: alkane precursors and / or derivatives can be used as a precursor to the method of the present invention ^ Depending on the desired end product, „single or combined use. Solvents. Appropriate solvent systems can be used in the method of the present invention. Preferably, the present method uses a non-polar solvent and a polar solvent system including a continuous phase. Secondary / combined non-polar solvents The non-polar solvents used in the method of the present invention include, but are not limited to, any common aliphatic or aromatic compound or any or all mixtures of these suitable compounds, referred to herein as & quot Appropriate " includes functional properties as follows: 1) Yes Analytical precursors, such as: monomeric trihalogen sintered silicon compounds, 2) those that can be dissolved during the formation of the polymerization product and can be extracted during the reaction period, knife 3) those that can stabilize the polymerization product in a solvent, and 4) Make undesired reaction products insoluble in non-polar solvents to facilitate removal. = Non-polar solvents " Examples include, but are not limited to, pentane, hexane, heptane, ring Hexane, benzene, toluene, xylene, chemical solvents (such as: carbon tetrachloride 1 / (Please read down the following: translation meanings and then fill out this page} '-·. 袭-,-& rirl: ,.-. -9-This paper scale applies Chinese National Standard (CNS) Λ4 gauge coffin (2 | 〇χ 297mm) 5 403767 A7 B7 'Invention description () and their mixtures. ^ Polar phase of solvent Substantially not compatible with * 41:., Sex> cereals, and include any suitable solvents known in beta β, and hydroalcoholic mixtures. The amount of alcohol present is included but not limited to, water, alcohol * The amount of Λ is sufficient to ensure the solubility of the reactive intermediate. In particular, 'applicable step ν + hit ai ,,,. ^ Χ, used for this Polar phase alcohols and other polar solvents = examples include, but are not limited to, water, methanol, ethanol, isopropanol, and their mixture It is present in an amount that will not dissolve in the alcohol-extracted ionic impurities that hinder the production of the product compounds in the solvent extraction solution alcohol. The polar phase has the possibility of the existence of hydrochloric acid (HC1) condensation products and any metal salts or other ionic contamination. Basically, all ionic compounds are maintained in the agent phase. The hydrosilicone of the present invention has good properties, and the milk product and / or organic lice siloxane products have high purity and are substantially free of ionic cold dyes. Ba has been known to hope that the weight / weight ratio between the raw solvent and the non-polar solvent is between about 5 and 80%, and between about 9% and about 100%. The best method is to avoid exposure of the reaction mixture to atmospheric oxygen. This reaction is to utilize, seal and / or sufficient any non-reactive protective gas flow (ie, H: gas, such as: Helium, argon, and nitrogen) are preferably isolated from the atmosphere. With this method, nitrogen is preferred because it is the most economical. In addition, in a better case, please read the tile container in the reaction procedure first-• Read the precautions on the back 'refill,'. This page is economically bound, printed by the Central Standards Bureau ’s Consumer Cooperatives _ _- 10- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ 03767 V. Description of the Invention (8) ~~~ — 'Clean up the atmospheric dyes (ie, oxygen) with an inert gas stream. More preferably, when the reaction is performed in a container with an open top, an inert gas maintained during the reaction procedure is positioned above the reaction mixture. Invention (During the reaction process, the dream precursor (eg, in some embodiments, trichlorosilane or a combination with one or more different silane precursors) is added to the catalyst, a mixture of non-polar solvents and polar solvents In order to form a reaction mixture, the polymerization reaction is preferably carried out under the condition of mixing. After the polymerization reaction is complete, the reaction mixture is filtered to separate the polar solvent, and the solvent is dried and evaporated to leave a white solid. Then, as appropriate, This solid is dissolved in a hydrocarbon solvent to remove the remaining small molecular weight material, and finally evaporated to leave the desired product. The siloxane produced thereby is suitable for any application known in the art, such as A formulation is formed in the solvent to serve as a spin-coated dielectric film. The reaction of the present invention is performed under acidic conditions as necessary, such as: By adding to the reaction mixture, such as: HC1, as shown in the following example Shown.-The process of the invention & can be carried out at any suitable temperature, examples of temperature ranges. For example, from about 1 (TC to about 4 trc. For example, this reaction can be In a reactor (eg, a water jacketed reactor). The technician understands that the reaction temperature will vary depending on the degree of exothermic energy release (if any) of any particular desired reaction procedure. Therefore, the reactor must Cooling or heating to achieve the optimal reaction temperature range (this range is measured by the length of time 'yield relationship in the routine test of the particular desired procedure). This method is at room temperature (usually about 25 ° C) It ’s better to go.-_-11-This paper size is applicable to Chinese National Standard (CNS) A4 standard orange (210 x ^ 97mm t) (Please chant _ read the notes on the back ^ before filling in this page j,-口A_7 B7 403767 V. Description of the invention (9 Reaction time The execution time of the method of the present invention varies greatly depending on the situation. Basically, when all other parameters are fixed, the longer the reaction mixture is stirred, the more the product of this reaction is produced. The higher the MW. For example, the reaction procedure of the present invention can be carried out from about 1-4 minutes to about 12 hours or more. The catalyst was unexpectedly found that the method of the present invention is catalyzed by a solid catalyst, which is usually It also includes, 'such as Ion exchange resins \ y form, 'but not limited to this. Therefore, the preferred catalysts according to the present invention include, for example: strongly acidic macroreticular resin (such as: Amberlyst-15; bead size from 0.3-1.2 mm), weak Acid macroreticular resin (such as: AmberliteIRP-64 and / or AmberliteCG-50; bead size from 100-200 mesh), strong acid gel resin (such as: Nafion NR50), strong alkaline macroreticular resin (Amberlyst- 27; bead size 0.48 mm), acid clay (eg: Montmorillonite KSF), weakly alkaline ion exchange resin (eg:

Amberlite CG-420, Amberlite 1-6766 and / or Amberjet 4200 (CI) /. (Amberjet bead size is 4200-625 microns), the mentioned are just a few of the available catalysts. This catalyst can be used alone or in combination. For example, two or more different catalysts can be used simultaneously or successively in the reaction procedure. Preferably, a weakly ion-exchange resin is used as the solid catalyst according to the present invention. Among the weaker ion exchange resins, the best is Amberjet 4200 (Rohm and Haas). Therefore, the preferred catalysts according to the present invention include, for example, strongly acidic macroreticular resins (eg, Amberlyst-15, weakly acidic macroreticular resins (eg, Amberlite IRP-64 and / or Amberlite CG-50), strong acid Gel-type resin (such as: 12 · This paper size applies to Chinese National Standards (CNS) A4 Orange (210X297K)) Please note on Ί ii i Printed by 4QS767 A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (10)

Nafion NR5〇), strong macroreticular resin (AmberiySt_27), acid clay (such as: Montmorillonite KSF), weakly basic ion exchange resin (such as:

Amberlite CG-420, Amberlite 1-6766 and / or Amberjet 4200 (CI)) are only a few of the catalysts available. This catalyst can be used singly or in combination. For example, two or more different catalysts can be used simultaneously or successively in the reaction procedure. Preferably, a weakly basic ion exchange resin is used as the solid catalyst according to the invention. The best of the weakly basic ion exchange resins is Amberjet 4200 (Rohm and Haas). The catalyst of the present invention also includes the viscosity of a catalytic substance, such as acid clay, which can retain the reactant and its amount can be used to promote the desired reaction. The solid catalyst of the present invention also has the advantage of being easily and inexpensively removed from the reaction mixture (eg, sedimentation, centrifugation, and / or filtration), thereby avoiding the expense of using sulfuric acid based catalysts Careful cleaning procedures. Therefore, there is no strict limit on the size and shape of Xianxin solid catalyst materials, as long as there is sufficient catalytic activity to assist the reaction process and the size of the particles and / or beads is suitable for physical separation from the reaction mixture. As a simple example, the bead size of an ion exchange catalyst ranges from about 300 to 50,000 microns or more. In particular, the bead size ranges from about 600 to about 4200 microns. The size of the ion-exchange catalyst beads may be from about 0.4 to about 2 millimeters, especially from about 0.3 to about 0.1 millimeters. The size of the ion exchange catalyst beads can also be from about 25 to about 300 mesh or more, and more particularly from about 100 to about 200 mesh. Skilled artisans understand that the aforementioned materials and equivalents can be easily made by methods known in the art, and are readily available on the market—for example, Amberlite, Amberlyst, and Amberjet resins are available from Rohm & Haas (Philadelphia, PA) ), Nafion resin and -13 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm), please read the note before filling out this page, Ministry of Economic Affairs, Central Standards Bureau, Staff Consumer Cooperatives, India, Ministry of Economic Affairs, Central Standards Bureau Printed by Employee Consumer Cooperatives 4 0376 7 A.7 _ _ B7 V. Description of Invention (")

Montmorillonite KSF is available from Aldrich (Milwaukee, Wisconsin). Technicians also know that the applicability of similar catalytic materials in the practice of the present invention can be learned from the results of normal screening and reaction product analysis in the presence of catalysts and starting materials. . The technician knows the amount of catalyst to be used, such as: the specific reaction to be catalyzed, the particle size of the appropriate catalyst used, the particle size range of the desired product, and the yield of the desired product. Generally, simply by way of example, the amount of solid catalyst added in the reaction is from about 0.2 g to about 2.0 g catalyst / ml silane precursor. More specifically, this solid catalyst is added to the reaction in an amount ranging from about 0.30 to about 10 g / ml of silane precursor. Alternatively, the solid catalyst is added to the reaction in an amount ranging from about 50 to about 100 grams per mole of precursor. In a more specific case, the solid catalyst is added to the reaction in an amount of from about 70 to about 90 g / mole silane precursor. Μ # ^ Polymers made by the method of the invention include, simply, but not limited to. Hydrosiloxanes and organohydrosiloxane resins, such as: Hydrosilyl siloxane ^ methyl silicon Oxane, Hydrogen Siloxane, Hydropropyl Siloxane, Hydrobutyl Butane Oxygen Burner, Hydrogen Tertiary Butyl Oxygen Burner, Hydrophenyl Phenyl Oxygen Burner, Gas Methyl Sand = Hexane Ethylsilsesquioxane, hydropropylsilsesquioxane, butylsilsesquioxane, hydrogen tert-butylsilsesquioxane, the above are only a few of them. ^ Beifeng oxygen. The hydrosiloxane resin prepared by the method of invention i can be one of six general formulas: Xing Bu Xi j [Ho.si.oSiO, 5.J 8] p-1 [HSi 〇i 5] n [Si〇2] w ⑤ Zhang scale 3 uses China _

^ 03767 A7 ---:-. B7, description of the invention (12) Formula 3 Formula 4 [H〇-i .〇Si〇! 5, 2 〇] [R1 Si〇! 5] m Formula 5 where P is an integer , From about 8 to about 5000; η and w are integers from about 8 to about 5000; n and melons are integers from about 8 to about 5000; ^ is selected so that the organic substituents are The mole ratio is present from about 1 to about 99 mole% or more. In another embodiment, the melons used are selected such that the molar ratio of the organic substituent is from about 4 to about 40 mole% or more. In another embodiment, m is selected such that the mole ratio of the organic substituent is from about 4 to about 20 mole% or more. Among them, the sum of X, y, and Z is from about 8 to about 500, and y is selected so that the organic substituent is present in a mole ratio from about i to about 99 mole% or more. In another embodiment, y is selected such that the molar ratio of the organic substituent is from about 4 to about 40 mole% or more. In another embodiment, y is selected such that the organic substituent is present in a molar ratio of from about 4 to about 20 mole% or more. Printed by the Consumer Cooperative of the Central Directorate of Bureau of the Ministry of Economic Affairs. In another embodiment, R 1 is selected from substituted or unsubstituted organic groups, including straight-chain and branched-chain alkyl, cycloalkyl, and aryl. And their combinations, the specific mole% of organic or carbon-containing substituents is related to the amount of starting material. In some embodiments of the method of the invention, the product has substituted and unsubstituted, linear and branched chains. Alkyl group with 丨 to 20-carbon atoms; this product has substituted and unsubstituted cycloalkyl groups with about 4 to ○ carbon atoms, -15- This paper is applicable to Chinese national standards ( CNS) Regulations (2 丨 〇 > < 297)

A7 B sells 5. Description of the invention (13) and the product has substituted and unsubstituted aryl groups having about 6 to 20 carbon atoms. For example, when R 1 is an alkyl group, R 1 includes, but is not limited to, methyl, p-methyl and ethyl, linear and branched propyl, 2-chloropropyl v-butylpentyl Base and 'hexyl. When R1 is a ring pit group, R1 includes, but is not limited to, determined by cyclopentyl, cyclohexyl, chlorocyclopentyl, and cycloheptyl; when the rule is aryl, R includes 'but not limited to' benzene Group, fluorenyl, tolyl, and benzyl. It will be understood that 'the specific carbon content of any organohydrosiloxane resin according to the present invention is related to the molar ratio of the organotrihalosilane to the hydrotrioxane starter used. In a more advantageous case, the product produced by the method of the present invention is a polymer having a cage structure whose polymer skeleton surrounds alternating silicon and oxygen atoms. In particular, each skeletal silicon atom is connected to at least one triskeleton oxygen atom to form the aforementioned cage structure. Basically, all the additional silicon is only connected to the hydrogen and oxygen present as defined in formulae 2, 3, 4, 5 and 6. Therefore, the polymer of the present invention is substantially free of a hydroxyl group or an alkoxy group bonded to a backbone silicon atom, and inhibits a crosslinking reaction. In contrast, the organosiloxane resins previously known have a large proportion of alkoxy groups bonded to backbone silicon atoms, and therefore, significant hydrolysis to silanol groups was observed. This hydrolysis allows cured polymer films formed from previously known resins to have a higher dielectric constant, while also shortening the storage life of solutions of these resins. The report states that the effects mentioned later are due to unwanted chain lengthening and cross-linking. Therefore, in the method of the present invention, the provided hydrogen and organic groups are only bonded to the skeleton silicon atoms, which is beneficial to avoid the condensation reaction of hydroxyl or silane groups. A4 specifications (2iOX297 mm) _ (Please read the precautions on the back before writing this page): Packing. Order the consumer cooperation of the Central Sample Bureau of the Ministry of Economic Affairs · Du printed 403767 β] 5. Description of the invention (14) Unwanted chain growth and cross-linking. Therefore, the storage life of the solution of the organohydrosiloxane resin prepared by the method of the present invention is much longer than that of the resin solution prepared by the method previously used, which is another advantage. Yield The polymer component produced by the method of the present invention ranges from about 20% to about 90 mole% of the starting material. In particular, the yield of the product obtained is from about 35 to about 75 mole% of the starting material. Polymer Applications The following characteristics illustrate the properties of the aforementioned organohydrogen-silicon-fired polymer resins obtained by the novel method of the present invention. The measurement methods used are as follows: 1) Film thickness (A): Using a calibrated Nanospec® AFT-Y CTS-102 model 010-180 Film Thickness Measurement System (Nanometrics,

Co.) to measure film thickness. The average 値 measured at five places on the wafer was taken as the film thickness of each sample. Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 2) Molecular weight (MW): The molecular weight is based on polyphenylenesulfonate, using a gel phase chromatography (GPC) system (Waters Corporation, Milford, MA, equipped with Waters 510 pump, Water s 410 differential refractometer and Waters autosampler). The procedures used can be found in S. Rosen, " Fundamental Principles of Polymeric Materials, 53-81 (2nd edition 1993), which is incorporated herein by reference. ... tm. _ The following non-limiting examples illustrate the invention. -17- This paper size applies the Chinese National Standard (CNS) M specification (210X 297 cm) 403767 Μ B7 V. Description of invention (15) Example printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 Catalyzed by Amberlyst-15 118丨 (: 13 to prepare hydrosilane) 50.59 grams of Amberlyst-15 (Chenghe) strongly acidic macroreticular resin, 25 ml of 38% HC1 and 50 ml of denatured ethanol were placed in a 2 liter Morton bottle. This The bottle was purged with N2, and 425 ml of hexane was added. An N2 coating was formed and maintained above the container for the remaining reaction period. While the solution was being stirred, the mixture of 150 ml of hexane / 50 ml of HSiCl3 was peristaltic pumped It was added at a rate of 1.00 ml / minute. After the addition, the reaction mixture was stirred; stirred overnight. The solution was then allowed to settle and the solid and liquid phases were separated by passing through Whatman # 1 filter paper. The two liquid phases were then placed In a separatory funnel and discard the lower layer. Then place the upper layer in a bottle and add 25 g of K2C03 and 25 g of CaCl2 to form a mixture. Stir the mixture; stir overnight and filter through Whatman #J filter paper to remove solids. The remaining solution is in It was evaporated to dryness in a rotary evaporator. 7.3 grams of a white, highly viscous material remained. Its weight average molecular weight (Mw) was 7729 measured by GPC, the number average molecular weight (Μη) was 889, and the Mw / Mn ratio 测 was 8.6943. Example 2 Amberlvst-15 catalyzed (C? JH ^ O; USiH to prepare hydrogen stone oxyhydroxide) 52.65 g of Amberlyst-15 (Chengzhong) strongly acidic macroreticular resin, 25 ml 38% HC1 and 50 ml denatured ethanol Placed in a 2 liter Morton bottle. This bottle was purged with N2, and 425 ml of hexane was added. A N2 coating was formed and maintained above the container for the remaining reaction period. While the solution was stirred, 150 ml of hexane was added. A mixture of alkane / 80 ml (C2H50) 3SiH was added in a peristaltic pump at a rate of 1.00 ml / minute. After the addition, the C reaction mixture was stirred overnight. The solution was then allowed to settle and filtered through Whatman # 1, Paper is solid-18 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297g t) Please read-Try again after exhaustion 1 D 40S767 A7 B7 V. Description of the invention (16) Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs The printed body is separated from the liquid phase. The liquid phase was placed in a separatory funnel and the lower layer was discarded. Then the upper layer was placed in a bottle, and 25 g of K2C03 and 25 g of 〇3〇: 12 were added to form a mixture. The mixture was stirred overnight and filtered through Whatman # 1. Filter paper to remove solids. The remaining solution was evaporated to dryness in a rotary evaporator. 5.86 grams of white dry substance remained. The Gw measured by GPC was 243649, the Mn was 8175, and the Mw / Mn ratio was 28.7031. Example 3 Preparation of Hydrosiloxane with Amberlite IRP-64 / Amberlyst A-26 Catalyzing HSiClq 18.24 g of ba 111 ^ 1 '1 tha 11) -64 weakly acidic macroreticular resin, 20 ml of denatured ethanol and 10 38 ml HC1 was placed in a 500 ml Morton bottle. This bottle was shielded with N2, and 250 ml of Jiyu i was added. A N2 coating was formed and maintained above the container for the remaining reaction period. While the solution was being stirred, 22 ml of HSiCl3 was added at a rate of 0.60 ml / min with a peristaltic pump. After the addition was complete, the reaction mixture was allowed to stir for 4 hours. The stirring was stopped and the reaction mixture was allowed to settle overnight. The solid and liquid phases were separated by vacuum filtration through Whatman # 4 paper. The two liquid phases were then placed in a separatory funnel and the lower layer was discarded. The upper layer was then placed in a bottle and 10.67 g of Amberlyst A-26 ferromagnetic ion exchange resin and 19.34 g of silicone were added. The mixture was stirred for 1.5 hours, and then the solids were removed by vacuum filtration. The solution was evaporated to dryness in a rotary evaporator. Leave 3.1 grams of white material. Mw was 21527 measured by GPC, Mη was 1540, and Mw / Mn ratio 値 was 13.9755. Example 4 Nafion NR50 ~ ^ acid gel-type resin catalyzes HSiC! 3 to prepare Fengmiao Milk Entertainment < 250 ml of hexane, 20 ml of ethanol and 9.7 g of Nafion NR50 strongly acidic -19-This paper size applies to Chinese national standards (CNS) Α4 Regulations (21〇 × 297 mm) Please read first--Notes to read back

I. Order Μ Μ. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (17) The gel-type resin is placed in a 500 ml Morton bottle. This bottle is purged with N2 to form an N2 coating, which is maintained above the container for the remaining reaction period. Add 6.3 ml of deionized water to the bottle. While the solution was being stirred, 18 ml of HSiCl3 was added at a rate of 1.20 ml / min with a screw pump. After the filling was completely completed, the reaction mixture was stirred for 4 minutes. The stirring was stopped and the solid and liquid phases were separated by air filtration through Whatman # 4 paper. The two liquid phases were then placed in a separatory funnel and the lower layer was discarded. The upper layer was then placed in a bottle and 60 grams of 4 A molecular sieves were added. This mixture was allowed to stand for 3 hours with occasional stirring, and then solids were removed by vacuum filtration through Whatman # 1 filter paper. The solution was evaporated to dryness in a rotary evaporator. 3.73 grams of white material remained. Measured by GPC] ^ rating is 7053,] ^ 11 is 2118, and the ratio of Dish \ ¥ / Dish 11 is 3.3296. Example 5 Preparation of Hydrosiloxane with Amberlyst-27 catalyzing HSiCl3 Amberlyst-27 is a strong macroreticular resin made by washing with twice the volume of deionized water and then washing with twice the volume of anhydrous methanol. It was then dried by blowing N2 overnight and evaporated at 30 ° C to completely dry. 250 ml of burned and .18.27 g of Amberlyst-27 were placed in a 500 ml Morton bottle and allowed to stir for 5 minutes. This bottle is purged with N2 to form an N2 coating, which is maintained above the container for the remainder of the reaction period. Add 20 ml of denatured ethanol and 6.3 ml of deionized water to the bottle. While the solution was being stirred, 18 ml of HSiCl3 was added at a rate of 1.20 ml / min with a peristaltic pump. After the addition was complete, the reaction mixture was allowed to stir for 80 minutes. Stop stirring and separate the solid and liquid phases by vacuum filtration through Whatman # 4 filter / paper. The two liquid phases were then placed in a separatory funnel and the lower layer was discarded. Then put the upper layer in the bottle, -20- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 males) —.---; ------- ^ pack-'-(Please (Read the notes of the memorandum before filling out this page)

、 1T A7 B7 40S767 V. Description of the invention (18) Please read — 1A back Φ-Note the matters and then Yan page Add 65 grams of 4 A molecular sieve. This mixture was allowed to stand for 2 hours and stirred occasionally; it was stirred, and then solids were removed by air filtration through # 3 Whatman filter paper. The solution was evaporated to dryness in a rotary evaporator. This left 1.85 grams of a white solid substance. The Gw measured by GPC was 4,670, the Mn was 1310, and the Mw / Mn ratio was 3.5637. Example 6 1T catalyzed HSiCl with Amberlyst-31 to prepare hydrosiloxane. 250 ml of hexane and 18.13 g of Amberlyst-31 strongly acidic gel-type resin were placed in a 500 ml Morton bottle and allowed to stir for 5 minutes. This bottle is purged with N2 to form an N2 coating, which is maintained above the container for the remainder of the reaction period. Add 20 ml of denatured ethanol and 6.3 ml of deionized water to the bottle. While the solution was being stirred, 18 ml of HSiCl3 was added at a rate of 0.85 ml / min with a peristaltic pump. Complete. After the addition, stir the reaction mixture; stir for 60 minutes. Stop stirring and separate the solid and liquid phases by emptying the filter through Whatman # 4 filter paper. The two liquid phases were then placed in a separatory funnel and the lower layer was discarded. The upper layer was then placed in a bottle and 61 grams of 4A molecular sieves were added. This mixture was allowed to stand for 2 hours with occasional stirring, and then solids were removed by air filtration through # 2 Whatman filter paper. The solution was evaporated to dryness in a rotary evaporator. 6.17 grams of white solid matter remained. The Gw measured by GPC was 17062, the Mn was 3666, and the Mw / Mn ratio was 4.6548. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Example 7 Preparation of HSiCl3 with Montmorillonite KSF acid clay for oxyhydrogen sintering 250 ml of hexane and 18.08 g of Montmorillonite KSF acid clay were placed in a 500 ml volume 6¾ Morton bottle and It was stirred for 5 minutes. This bottle is purged with N2 to form an N2 coating, which will remain above the container for the remaining reaction period. 21-This paper size applies the Chinese National Standard (CNS) A4 Regulations (210 × 297 mm) kl B7 V. Description of the invention (19). Add 20 ml of denatured ethanol and 6.3 ml of deionized water to the bottle. While the solution was being stirred, 18 ml of HSiCl3 was added with a peristaltic pump at a rate of 0.85 ml / min. After the addition was complete, the reaction mixture was allowed to stir for 45 minutes. Stop the agitation and separate the solid and liquid phases by air filtration through # 2 Whatman filter paper. The two liquid phases were then placed in a separatory funnel and the lower layer was discarded. The upper layer was then placed in a bottle and 61 g of 4L molecular sieve was added. This mixture was allowed to stand overnight, and then solids were removed by vacuum filtration through # 2 Whatman filter paper. The solution was evaporated to dryness in a rotary evaporator. 3.06 grams of solid white resin remained. Its Mw was 6348, Mη was 1929, and Mw / Mn ratio was 3.2919 as measured by GPC. Example 8 Preparation of a hydrosiloxane 2-liter Morton bottle with Amberlite CG-420 / Ambedyst 15 as a catalyst for 2 liters of Morton via nitrogen overnight . 500 ml of hexane, 40 ml of denatured ethanol, and 20 ml of 38% hydrochloric acid were combined with 36.1 g of Amberlite CG-420 weakly basic Lime exchange resin. While the solution was agitating, 44 ml (0.436 moles) of trichlorosilane was added with a peristaltic pump at a rate of 0.42 ml / minute. After the addition was complete, the reaction mixture was stirred for another 3 hours. The solution was allowed to settle and was filtered by air filtration through Whatman # 4 paper in a Buchner funnel. The filter cake was washed twice with 100 ml of hexane. Place the solution in a separatory funnel 'and discard the lower layer (about 10 ml). The remaining solution was placed in a bottle with 62 g of Amberlyst 15 strong acid ion exchange resin and 60 g of silicone. After the solution was stirred for 1 hour, it was allowed to stand overnight. The solution was gravity filtered through a grooved filter paper, and the Amberlyst / silica mixture was washed twice with 100 ml of hexane. The solution was evaporated to dryness in a Buchi rotary evaporator. Collected 10.3 g of a white solid. Calculate -22- This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) Please read _ matters and fill in this page. Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _ B7_: __ V. Description of the invention (20) The yield obtained was 44.6%. The Mw was 45,278, Mη was 6496, and Mw / Mn ratio was 6.97 as measured by GPC. Example 9 Hydrogenite was burned in a 2 liter Morton bottle with nitrogen gas using Amberlite CG-420 / Amberlyst A26 as the catalyst. Overnight. 5000 ml of hexane, 41 ml of denatured ethanol and 20 ml of 38% hydrochloric acid were combined with 36.2 g of Amberlite CG-420 weakly basic ion exchange resin. While the solution was agitating, 44 ml (0.436 moles) of trichlorosilane was added at a rate of 1.3 ml / min with a peristaltic pump. After the addition was complete, the reaction mixture was stirred for another 3 hours. The solution was allowed to settle and was filtered by emptying through Whatman # 4 filter paper in a Buchner funnel. The filter cake was washed three times with 100 ml of hexane. The solution was placed in a separatory funnel. 'The lower layer was discarded. Approximately one third of the solution was placed in a bottle with 26.22 g of strong acid ion exchange resin and 20.22 g of 8 11 ^ 61 >1; and stirred for 70 minutes. The solution was emptied through an oven through Whatman # 4 filter paper in a Buchner funnel, and Amberlyst was washed twice with 50 ml of hexane. This solution was evaporated to dryness in a Buchi rotary evaporator. Collected 4.6 g of a white solid. The Gw measured by GPC was 75,055, the Mn was 6786, and the Mw / Mn ratio was 11.06. Example 10 Hydrogen siloxane was prepared using Amberlite CG-420 / Amberlyst A26 CaCl24 ^ 4HSiCl], and a 2-liter Morton bottle was purged with nitrogen overnight. 5,000 ml of hexane, 41 ml of denatured ethanol and 20 ml of 38% hydrochloric acid were combined with 36.2 g of 8-11 ^ 61'1 such as 00-420 weak ion exchange resin. Stir in the solution; while mixing, 44 ml (0.436 mol) of trichlorosilane is added at a rate of 1.3 ml / min with a peristaltic pump-23-This paper size applies the Chinese National Standard (CNS) Λ4 standard orange (210X297) 1) μ itsis7 B7 5. Description of the invention (21) Add. After the addition was complete, the reaction mixture was allowed to stir for another 3 hours. The solution was allowed to settle and filtered by air filtration through a Whatman # 4 filter paper in a Buchner funnel. The filter cake was washed three times with 100 ml of keto *. Place the solution in a separatory funnel. 'Discard the lower layer. Approximately a third of the solution was placed in a bottle with 15.03 grams of Amberlyst A-26 strong ion exchange resin and 3.51 grams of chlorinated sodium. The solution was stirred for 60 minutes. The solution was emptied through Whatman # 4 filter paper in a Buchner funnel. The Amberlyst / Chlorinated # 5 mixture was washed twice with 50 ml of hexane, and the solution was evaporated to dryness in a Buchi rotary evaporator. Collected 3.0 grams of a white solid. Its Mw was 51,480, Mη was 6575, and Mw / Mn ratio was 7.83 as measured by GPC. Example 1 1 Amberlite I-6676 / Amberlyst A26 CaCM Cuihua 1181 (313) was used to prepare hydrosilicon oxide. 500 ml capacity The Morton bottle was purged with nitrogen overnight. 250 milliliters of hexane, 20 ml of denatured ethanol and 10 ml of 38% hydrochloric acid were combined in the bottle. 18.2 g of Amberlite 1-6766 weak ion exchange resin was added and stirred. Solution. 2 2 ml (0.218 moles) of trichlorosilane was added at a rate of 0.5 ml / min with a peristaltic pump. After the addition was complete, the reaction mixture was stirred for another 3 hours. The solution was allowed to settle and filtered through the Buchner funnel with empty filtration. Filter through Whatman # 4 filter paper. Wash the filter cake twice with 100 ml. Place the solution in a separatory funnel and discard the lower layer (about 1 ml). The remaining solution is tested with 18.3 g of Amberlyst A-26. An ion exchange resin and 18.4 grams of chlorinated # 5 were placed in a bottle. The solution was mixed for 30 minutes, and then 12.2 grams of "Amberlyst and 12.9 grams of chlorinated chloride were added. Continue mixing for more than 30 minutes. The solution was emptied.遽 Via Buchner Funnel-24-This paper size applies Chinese National Standard (CNS) Λ4 gauge Taiwan (210X297 公 #_)-Please read the note on the back-the matters before filling in this page)

* 1T Printed by the Consumers 'Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Α7 Β7 03767 V. Description of the invention (22) Please read-'-Read the back-notes and filter on the page of Whatman # 4 filter paper, Amberlyst / chlorinated The dance mixture was washed twice with 50 ml of hexane, and the solution was evaporated to dryness in a Buchi rotary evaporator. Collected 6.3 g of a white solid. The calculated yield was 54.5%. The Gw measured by GPC was 33,446, the Mn was 4005, and the Mw / Mn ratio was 8.35. Example 1 2 Amberlite CG-420 / Amberlyst A26 CaCl2 was used to catalyze HSiCli to produce hydrogen siloxane: A 500-ml Morton bottle was printed with a 500-ml Morton bottle and suffured with nitrogen overnight. 250 ml of hexane, 20 ml of denatured ethanol and 6.3 ml of deionized water were combined in a bottle. Add 18.2 grams of Amberlite CG-420 weakly basic ion exchange resin and stir the solution. 2 2 ml (0.218 mol) trichlorosilane is added at a rate of 0.6 ml / min with a peristaltic pump. After the addition was complete, the reaction mixture was stirred for another 3 hours. The solution was allowed to settle and filtered through a Whatman # 4 filter paper in a Buchner funnel by emptying the oven. The filter cake was washed twice with 100 ml of hexane. The solution was placed in a separatory funnel, but no separation was observed. The solution was placed in a bottle with 3 0.1 g of Amberlyst A-26 strong ion-exchange tree, lipid, and 2 8.9 g of calcium carbonate, and stirred for 1 hour. The solution was emptied and filtered through Whatman # 4 filter paper in a Buchner funnel. The Amberlyst / Chlorinated Mai mixture was washed twice with 100 ml of hexane, and the solution was evaporated to dryness in a Buchi rotary evaporator. Collected 7.4 g of a white solid. The calculated yield was 64.0%. The Gw measured by GPC was 36,356, the Mn was 4709, and the Mw / Mn ratio was 7.72. Example 1 3 Preparation of HSiCU with Amberlite C0-50 catalyst—Hydroxysiloxane 500 liters. A Morton bottle was purged with nitrogen overnight. 250ml has been entertained ^, -25- This paper size applies to China's national standard (CNS) Λ4 specification (210X297mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 403767 at B7 V. Description of the invention (23) 20ml denatured Ethanol and 6.3 ml of deionized water were combined in a bottle. Add 18.05 grams of 8-11 ^ 61'1 such as 00-50 weak ion exchange resin and stir the solution. 22 ml (0.218 mol) of trichlorosilane was added at a rate of 0.5 ml / min with a peristaltic pump. After the addition was complete, the reaction mixture was allowed to stir for an additional 45 minutes. The solution was allowed to settle and filtered by vacuum filtration through Whatman # 4 filter paper in a Buchner funnel. The filter cake was washed twice with 100 ml of hexane. Place the solution in a separatory funnel and discard the lower layer. The solution was placed in a bottle with 15.37 grams of silicone and stirred for 30 minutes. The solution was filtered by air filtration through a Whatman # 4 filter paper in a Buchner funnel, and Shi Xijiao was washed twice with 50 ml of hexane. The solution was evaporated to dryness in a Buchi rotary evaporator. Collected 4.6 g of a white solid. The calculated yield is 3 9.8%. The Gw measured by GPC was 11,192, the Mn was 1930, and the Mw / Mn ratio was 5.71. Example 14 Preparation of Hydrosiloxane with HSiCl3M Catalyzed by Amberlite I-6676 / Amberlite 1-6676 A 500 ml Morton bottle was purged with nitrogen overnight. 15.02 g of Amberlite 1-6676 weak ion exchange tree, 250 ml of hexane, 20 ml of denatured ethanol and 6.3 ml of deionized water were combined in a bottle, and the solution was stirred. 22 ml (0.218 mol) of trichlorosilane is added at a rate of 0.6 ml / min with a peristaltic pump. After the addition was complete, the reaction mixture was stirred for another 9 5 minutes. The solution was allowed to settle and was filtered by vacuum filtration through Whatman # 4 filter paper in a Buchner funnel. The oven and cake were cleaned twice with 100 'ml of vegan. Place the solution in a separatory funnel and discard the lower layer. Place the solution with 20.33 grams of Drieritre in a bottle and stir for 10 minutes: add 3.03 grams of Amberfite 1-6676, and continue stirring for 15 minutes. The solution was emptied through the furnace and passed through Whatman # 1 遽 paper in a Buchner funnel. 26- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (read the M " read back-¾. (Fill in this page) _-

A7 408787 _ £ L __ ^ __ 5. The method of invention description (24) is filtered, and the solution is evaporated to dryness in a Buchi rotary evaporator. Collected 6.94 g of a white solid. The calculated yield was 60.1%. The Mw measured by GPC was 28,929, the Mn was 4150, and the Mw / Mn ratio was 6.97. Example 1 5 Film-forming properties of the product of Example 1 0.9949 g of the product from Example 1 was dissolved in 3.0077 g of cumene. This solution was spin-coated on the wafer at 3000 rpm for 20 seconds, and then baked at 150 ° C, 200 ° C, and then 250 ° C for 1 minute each. The material forms a 7100-strand film. Example 1 6 Film-forming properties of the product of Example 5 1.0088 g of the product from Example 5 was dissolved in 0.3357 g of heptane and 0198 g of cumene. This solution was spin-coated on the wafer at 3000 rpm for 20 seconds, and then baked at 150 ° C, 200 ° C, and then 300 ° C for 1 minute. The material forms a 2400A film. '' Example 17, Wafer coating properties of the product of Example 7 Printed by an employee of the Central Standards Bureau of the Ministry of Economic Affairs, printed by a cooperative (please read the precautions for rain before filling this page) _-0.8 to 50 grams from Example 7 The product was dissolved in 0.5903 g of heptane dried with MgS04, 2.2257 g of cumene dried with MgS04 and 0.4038 g of heavy mineral oil. This solution was spin-coated on the wafer at 3000 rpm for 20 seconds, and then baked at 150 ° C, 200 ° C, and then 300 ° C for 1 minute each. The wafer was cured at 400 ° C for 1 hour at 4 L / min N2. The material forms a 5500A film. Example 1 Preparation of 8 and 25 mol% fluorenyl hydrosiloxane. A 250 ml capacity Morton bottle is equipped with a condensing tube and connected to an arrow 1750 motor. -27- This paper size applies to Chinese National Standard (CNS) A4 (210X297).蝥) 403767 at B7 V. Description of the invention (25) The stirrer connected. This bottle was purged with nitrogen. During the reaction, nitrogen was blown into the NaOH scrubber from the top of the condenser tube. 15 g of Amberlite 1-6676 ion exchange resin catalyst, 20 ml of ethanol, 6.3 ml of water and 250 ml of hexane were added to the bottle and stirring was started. 13 ml (0.129 mole) of trichlorosilane and 5 ml (0,043 mole) of fluorenyltrichlorosilane (24.9 mole% methyltrichlorosilane) were combined in HDPE bottles. This silicon-fired mixture was added to a Morton bottle via a screw pump at a rate of 0.6 ml / min. After the addition is complete, continue mixing for 90 minutes. The solution was filtered emptied through Whatman # 4 filter paper in a Buchner funnel. Place the solution in a separatory funnel and discard the underlying aqueous layer. The upper layer was dried with 40 g of 3 A molecular sieve for 2.5 hours. The solution was filtered by air filtration through a Whatman # 1 filter paper in a Buchner funnel, and the solution was evaporated in a Buchi rotary evaporator at 60 ° C. Collected 5.2 g of a white solid. The calculated yield was 53.5%. The Gw measured by GPC was 12,300 AMU and the polydispersity was 4.35. -Example 1 9 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) _ _ 2 Preparation of 20 mol% methyl hydrosiloxane 2 liters. Equipped with a capacity Morton bottle There is a dry ice condenser and a blender connected to the arrow 1750 motor. Place the reactor in a water bath at 25 ° C. This bottle was purged with nitrogen. During the reaction, nitrogen was blown into the NaOH scrubber from the top of the condenser tube. 60.25 g of Amberjet 4200 (CI) ion exchange resin catalyst, 80 ml of ethanol, 25 ml of water, and 1000 ml of hexane were added to the bottle and stirring was started. 5 8 ml (0.575 mol) of trichlorosilane and 17 ml (0.145 mol) of fluorenyltrichlorosilane (20.1 mol% fluorene "tritrisilane") were combined in a FEP bottle. This silane mixture was passed through a peristaltic pump to 1 / 4-inch Teflon tube is added to -28 at a set rate of 8.0 RPM. This paper size applies Chinese National Standard (CNS) A4 orange (210X297 cm) 403767 at B7 V. Description of invention (26) bottle. Calculation The addition rate is 2.5 ml / min. After the addition is complete, continue to stir; mix for 185 minutes. The solution is filtered through the Whatman # 4 filter paper in the Buchner funnel by emptying. Add the solution to the separating funnel and discard the lower part. Aqueous layer. The upper layer was dried with 171 g of 4 Ϊ molecular sieve for 3.5 hours. The solution was filtered by air filtration through Whatman # 2 filter paper in a Buchner funnel, and the solution was evaporated in a Buchi rotary evaporator at 60 ° C. 2 5.2 was collected G of white solid. The calculated yield is 62.7%. Its Mw is 26,014 amu and the polydispersity is 13.68 as measured by GPC. Example 204 Preparation of Molar% methylhydrosiloxane_ 2 liter Morton bottle Equipped with dry ice condenser and with arrow 1 A stirrer connected to a 750 motor. This reactor was placed in a water bath at 25 ° C. This bottle was purged with nitrogen. During the reaction, nitrogen was blown from the top of the condensation tube to the NaOH scrubber. 60.40 grams eight 11 ^ 61 ^ 1 4200 (0: 1) ion exchange resin catalyst, 80 ml of ethanol, 25 'ml of water and 1000 ml of sintered oil were added to the bottle and started to stir; 70 ml (0.6 to 4 moles) of trichlorosilane And 3.5 ml (0.030 mol) methyltrichlorosilane (4.1 mol% methyltrigassilane) in a FEP bottle. This silane mixture was passed through a peristaltic pump in a 1 / 4-inch Teflon tube at 10.0 RPM Add the set removal rate. The calculated addition rate is 2.45 ml / min. After the addition is complete, continue to mix for 60 minutes. The solution is filtered by air filtration through Whatman # 4 filter paper in a Buchner funnel. In the funnel, discard the lower aqueous layer. The upper layer was dried with 171.53 g of 4A molecular sieve for 3 hours. The solution was emptied through Whatman # 1 paper in a Buchner funnel. The solution was passed through a Buchi rotary evaporator at 6 Evaporated at 0 ° C. 2 5.1 grams of white solid were collected. Using the Chinese National Standard (CNS) Λ4 gauge (210X 297 mm) 403767 a7 B7 V. Description of the invention (27) body. The calculated yield is 64.7%. The Mw measured by GPC is 22,094 AMU, polydispersity It is 8.77. Example 2 Preparation of a 20 mol% ethylhydrosiloxane. A jacketed 1-liter reactor was equipped with a dry ice condenser, a stirrer connected to an arrow 850 motor, and a glass immersion tube. This reactor was connected to a circulating water bath set at 25 ° C. This bottle was confirmed with nitrogen. During the reaction, nitrogen was blown into the NaOH scrubber from the top of the condenser tube. 60.6 grams of Amberjet 4200 (CI) ion exchange resin catalyst, 80 ml of ethanol, 25 ml of water, and 1000 ml of hexane were added to the reactor and stirring was started. 58 ml (0.575 mole) of trichlorosilane and 19 ml (0.145 mole) of ethyltrichlorosilane (20.1 mole% ethyltrichlorosilane) were combined in a FEP bottle. This calcined mixture was added to the reactor via a screw pump at a set rate of 11.2 RPM at 1/4 inch to Teflon tube. The calculated addition rate was 2.2 ml / min. After the addition was complete, stirring was continued for 120 minutes. The solution was emptied and passed through Whatman # 4 filter paper in a Buchner funnel. Add the solution to a separatory funnel and discard the lower aqueous layer. The upper layer was dried with 171 g of 4 A molecular sieve for 3 hours. The solution was emptied on a 1 micron pore size Teflon membrane on porous glass. The solution was evaporated in a Buchi rotary evaporator at 60 ° C. Collected 31.0 g of a white solid. The calculated yield was 73.5%. Measured from 〇〇〇 the boundary is 23,987 collapse 1 ;, the degree of polydispersity is 10.27. Example 2 Preparation of 220 mol% propylhydrosilane A sheathed 2 ^ capacity reactor was equipped with a dry ice condenser, a stirrer connected to an arrow 6000 motor, and a glass immersion tube. Make this reactor and set 2 5 -30. This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X297 mm) Please read the precautions on the front-side and then the page I book the staffing cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Print 403767 a ________ Β7 V. Description of the invention (28) ^ ° c Circulating water bath communication. This bottle was purged with nitrogen. During the reaction, nitrogen was blown into the NaOH scrubber from the top of the condenser tube. 59.5 g of Amberjet 42,000 (CI) ion exchange resin catalyst, 80 ml of ethanol, 25 ml of water and 1,000 ml of hexane were added to the reactor and stirring was started. 58 ml (.575 mole) trichlorosilane and 21.5 ml (0.145 mole) of propyltrichlorosilane (20; [mol% propyltrichlorosilane) were combined in a FEP bottle. This silane compound was added to the reactor via a peristaltic pump in a 1/4 inch Teflon tube at a set rate of 11.0 RJPM. The calculated addition rate was 2.3 ml / min. After the addition was complete, stirring was continued for 12 minutes. The solution was filtered through a Whatman # 4 filter paper in a Buchner funnel by air filtration. The solution was added to a separatory funnel, and the lower aqueous layer was discarded. The upper layer was dried with 170,5 g of 4A · molecular sieve for 3.5 hours. The solution was air filtered on a 1 micron pore size Teflon membrane on porous glass. The solution was evaporated in a Buclu rotary evaporator at 60 ° C. Collected 35.8 grams of a white solid. The calculated yield was 81.0. / 〇. 〇 卩 (: Measured) ^ The evaluation is 17,840, and the polydispersity is 7 49. '' Example 2 3 Printed by 20 Molar% of n-butylphosphonium silanol A jacketed 1 liter capacity reactor was equipped with a dry ice condenser, a stirrer connected to the arrow 6000 motor, and a glass immersion tube. This reactor was connected to a circulating water set at 2 5 C. This bottle was purged with nitrogen. During the reaction, nitrogen was blown into the NaOH scrubber from the top of the condenser. 59.9 g of Amberjet 4200 (CI) ion exchange resin catalyst, 80 ml of ethanol, 25 ml of water and 1000 ml of hexane were added to the reactor. Start stirring. 58 ml (0.575 mole) of trichlorosilane and 24 ml (0.14, mole) of n-butyltrichloro-silane (20.2 mole% of n-butyltrigassilane) in a FEP bottle This silane mixture is passed through the screw pump to i / 4 -31-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 male A7 B7 403767) 5. Description of the invention (29) Please read _ S- Fill in this page. Inch Teflon tubes are added to the reactor at a set rate of 7.0 RPM. The calculated addition rate is 2.3 ml / min. After the addition is complete, continue to stir for 120 minutes. The solution is filtered by air filtration through Whatman # 4 filter paper in the Buchner funnel. Add the solution to the separatory funnel and discard. Discard the bottom Aqueous layer. The upper layer was dried with 171.6 g of 4 A molecular sieve for 3 hours. The solution was air-filtered on a 1 micron pore size Teflon membrane on porous glass. The solution was evaporated in a Buchi rotary evaporator at 60 ° C. 38.1 was collected Grams of transparent viscous liquid. The calculated yield was 82.4%. Its Mw was 16,022 amu and the polydispersity was 6.45 as measured by GPC. Example 2 4 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs '20 Molar% Cyclohexyl hydrosiloxane preparation The sheathed 2 liter capacity reactor is equipped with a dry ice condenser. A stirrer and glass dip tube connected to the arrow 6000 motor. This reactor is connected to a circulating water bath set at 2 5 ° C This bottle was purged with nitrogen, and nitrogen was blown into the NaOH scrubber from the top of the condenser during the reaction period. 60.2 g of Amberjet 4200 (CI) ion exchange resin catalyst, 80 ml of ethanol, 25 ml of water and 1000 ml of hexane alkyl Add to the reactor and start stirring. 59 ml (0.585 mole) of trichlorosilane and 26 ml (0.147 mole) of cyclohexyltrichlorosilane (20.1 mole% of cyclohexyltrichlorosilane) are combined in a FEP bottle The silane mixture was added to the reactor via a peristaltic pump at a set rate of 11.0 RPM in a 1/4 inch Teflon tube. The calculated addition rate was 2.7 ml / min. After the addition is complete, continue to stir for 120 minutes. The solution was emptied through a Whatman # 4 filter paper in a Buchner funnel. Add the solution to a separatory funnel and discard the lower aqueous layer. The upper layer was dried with 172.1 g of 4 A molecular sieve for 5 hours. The solution is located on porous glass -32- This paper is in accordance with Chinese National Standards (CNS) A4 regulations (210X297 Gong) A? B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (30) 1 Air filtration on micron pore size Teflon membrane. The solution was evaporated in a Buchi rotary evaporator at 60 ° C. Collected 42.33 grams of a white solid. The calculated yield is 83.3%. The Gw measured by GPC was 12,721 AMU and the polydispersity was 7.18. Example 2 Preparation of 20 mol% phenylhydrogen oxyhydroxide jacketed 1 liter capacity reactor was equipped with a dry ice condenser, a stirrer connected to an arrow 6000 motor, and a glass immersion tube. This reactor was connected to a circulating water bath set at 25 ° C. This bottle was purged with nitrogen. During the reaction, nitrogen was blown into the NaOH scrubber from the top of the condenser tube. 6Ό. 2 grams of Amberjet 4200 (CI) ion exchange resin catalyst, 80 ml of ethanol, 25 ml of water, and 1000 ml of hexane were added to the reactor and stirring was started. 58 ml (0.575 mole) of trichlorosilane and 23 ml (0.144 mole) of phenyltrichlorosilane (20 mole% phenyltrichlorosilane) were combined in a FEP bottle. This silane mixture was added to the reactor via a peristaltic pump in a 1/4 inch Teflon tube at a set rate of 7.0 RPM. The calculated addition rate was 2.03 ml / min. After the addition was complete, stirring was continued for 120 minutes. The solution was filtered by vacuum filtration through Whatman # 4 filter paper in a Buchner funnel. Add the solution to a separatory funnel and discard the lower aqueous layer. The upper layer was dried with 171.3 g of 4 A molecular sieve for 3 hours. The solution was air filtered on a 20 micron pore size Teflon membrane on porous glass. The solution was evaporated in a Buchi rotary evaporator at 60 ° C. Collected 22.2 grams of a white solid. The calculated yield was 45-3%. From 0 卩 (: measured), ^^ is 77,827, and the polydispersity is 37.92. 'Example Γ6 Preparation of 20 mol% third butyl hydrosiloxane -33- This paper size applies to Chinese national standards ( CNS) A4 size (210X297gt) (please read the precautions on the back before filling out this page) Order kl 408767 V. Description of the invention (31) The sheathed 2 liter capacity reactor is equipped with a dry ice condenser tube, and A stirrer and a glass immersion tube connected to a 6000 motor. This reactor was connected to a circulating water bath set at 25 ° C. This bottle was purged with nitrogen, and nitrogen was blown into the NaOH scrubber from the top of the condensation tube during the reaction. 60.77 G of Amberjet 4200 (CI) ion exchange resin catalyst, 80 ml of ethanol, 25 ml of water and 1000 ml of hexane were added to the reactor and stirring was started. 5 8 ml (0.575 mol) of trichlorosilane and 27.84 mg (0.145) Moore) tertiary butyltrichlorosilane (20.2 mol% tertiary butyltrichlorosilane) was combined in a FEP bottle. This silane mixture was passed through a peristaltic pump in a 1/4 inch Teflon tube at a set rate of 12.3 RPM Add to the reactor. After the addition is complete, continue stirring: mix for 120 minutes. The solution was filtered through the air and passed through a furnace through Whatman # 4 filter paper in a Buchner funnel. The solution was added to a separating funnel and the lower aqueous layer was discarded. The upper layer was dried with 172.J grams of 4 molecular sieve for 3 hours. The solution was air filtered on a 1 micron pore size Teflon membrane on porous glass. The solution was evaporated at 60 ° C in a Buchi rotary evaporator. 35.35 grams of a white gel were collected. The calculated yield was 76.5%. 〇 卩 0: The measured value is 11,379 & 1, and the polydispersity is 4.51. (Please 'read the precautions of the world before filling this page) " Clothing-Central Bureau of Standards, Ministry of Economic Affairs Printed by Employee Consumer Cooperatives-34- This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 403 ^ 67 A7 B7 V. Description of the invention (32 Example 27 Results and discussion Table 1 By examples and catalysts Examples of results obtained Mw Mn ... polydispersity% yield catalyst: 1 7729 889 8.6943. 28% Amberlyst-15 2 243649 8175 28.7031 26% Amberlyst-15 3 21527 1540 13.9755 28% Amberlite-IRP64 4 7053 2118 3.3296 39% Nafion NR50 5 4670 1310 3.5637 20% A mberlyst-27 6 17062 3666 4.6548 65% Amberlyst-31 7 6348 1929 3.2919 32% KSF (clay) 8 45,278 6496 6.97 44.6% Amberlite CG-420 9 75,055 6786 11.06 NA Amberlite CG-420 10 51,480 6575 7.83 NA Amberlite CG-420 11 33,446 4005 8.35 54.5%-Amberlite 1-6766 12 36,356 4709 7.72 64.0% Amberlite CG-420 13 ll, 192 1930 5.71 39.8% Amberlite CG-50 14 28,929 4150 6.97 60.1% Amberlite 1-6766 18 12,300 2828 4.35 53.5% Amberjet 4200 (Cl) 19 26,014 1902. 13.68 62.7% Ambenet 4200 (Cl) 20 22,094 2519 8.77 64.7% Amberjet 4200 (Cl) 21 23,987 2336 10.27 73.5% Amberjet 4200 (Cl) 22 17,840 2382 7.49 81.0% Amberjet 4200 (Cl) 23 16,022 2484 6.45 82.4% Amberjet 4200 (Cl) 24 12,721 1772 7.18 83.3% Amberjet 4200 (Cl) 25. 77,827 2054 37.92 45.3% Amberjet 4200 (Cl) 26 11,379 2523 4.51 76.5% Amberjet 4200 (Cl) 'Please read — Read the meaning of the matter again and try to print the NA representative printed by the employee's consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs failed to obtain the data. Mingzhi solid catalyst can make Mw, Mn and polydisperse color range like _ pan. In particular, with weakly basic ion exchange resins (such as Amberjet 4200), the best results can be obtained using a polyether polymer coated with electronic wafers. The data of the foregoing examples confirm that solid and colloidal materials catalyze the polymerization of silane precursors to produce, such as: desired hydrosiloxane and organohydrosiloxane polymers, which are widely used. 35- This paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm)

Claims (1)

B8 C8 Chinese patent application for patent application Fan Yuanzheng Zheng Tainian year 1 P |) Announcement VI. Application for patent scope 1.-A method for manufacturing hydrosiloxane and organohydrosiloxane resin, the steps include (Please read the precautions below before filling in this page) a. Mix the silane monomer with the solid catalyst in a reaction involving hydrocarbon solvents, alcohols, and water. In the presence, it is sufficient to catalyze the silane The monomer is converted into hydroxane and organohydrosiloxane under the conditions of contact; and b. Recovering the hydrosiloxane and the organohydrosiloxane produced, and the general formula R & 3, wherein χ is a dentition or 0, 2, and R2 are alkyl groups selected from Η, substituted or unsubstituted, straight or branched chain, having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms, a substituted or I selected ^, an aryl group having 6 to 20 carbon atoms, and Combination 丨 Among them, the catalyst is selected from the group consisting of strongly acidic macroreticular resin, every 7th climbing macroreticular resin, strongly acidic gel-type resin, and strong alkaline giant Shu-shaped ', with the clay-containing catalyst portion, weakly basic ion exchange resins and mixtures thereof. 2. The method according to item 丨 of the patent application park, wherein the hydrocarbon solvent, alcohol and water form a two-phase solvent system I 3. The method according to item 丨 of the patent application scope, wherein the viscosity is acidic. 4. The method according to item 丨 of the scope of patent application, wherein the step includes separating the reaction mixture and the produced hydrosilane and organic and hydrosilane from the consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Steps of suspension. 5. The method according to item 4 of the scope of patent application, wherein the suspension is separated from the reaction mixture by a method selected from the group consisting of filtration, centrifugation, gravity sedimentation, or a combination thereof. 6. The method according to item} of the patent application park, in which the paper size of the selected silane monomer is applicable to China National Standard (CNS) A4 (210X297 mm) B8 C8 Fan Yuanzheng is too young. 1P |) Announcement VI. Application for patent scope 1.-A method for manufacturing hydrosiloxane and organohydrosiloxane resin, the steps include (please read the precautions of ¾ before filling in (This page) a. Mix the silane monomer with a solid catalyst in a reaction involving a hydrocarbon solvent, an alcohol, and water. In the presence, sufficient to catalytically convert the silane monomer to hydrogenoxane and organohydrogensilane. Contact under the conditions of oxane; and b. Recover the hydrosiloxane and organohydrosiloxane produced, and the general formula R & 3 of cough silane monomer in the basin, where χ is a tooth element or 0 square 2 , ... and R2 are selected from Η, substituted or unsubstituted, straight or branched chain, alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted, and having between Cycloalkyl having 4 to 10 carbon atoms, substituted or I taken ^, having a carbon atom between 6 and 20 The aryl group and its combination 丨 Among them, the catalyst is selected from the group consisting of a strongly acidic macroreticular resin, every 7th type of macroreticular resin, a strongly acidic gel type resin, a strongly alkaline macroreticular 丨 ′, containing a catalyst Part of clay, weakly alkaline ion exchange resins and mixtures thereof. 2. The method according to item 丨 of the patent application park, wherein the hydrocarbon solvent, alcohol and water form a two-phase solvent system I 3. The method according to item 丨 of the patent application scope, wherein the viscosity is acidic. 4. The method according to item 丨 of the scope of patent application, wherein the step includes separating the reaction mixture and the produced hydrosilane and organic and hydrosilane from the consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Steps of suspension. 5. The method according to item 4 of the scope of patent application, wherein the suspension is separated from the reaction mixture by a method selected from the group consisting of filtration, centrifugation, gravity sedimentation, or a combination thereof. 6. The method according to item} of the patent application park, wherein the paper size of the selected silane monomer applies to China National Standard (CNS) A4 (210X297 mm) 4〇3ϋ67 Λ8 δδ C8 D8 'Scope of patent application 7 Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China. Trichlorosilane and triethylsilane. The method according to item 丨 of the patent application park, wherein the expression of the obtained product is selected from the following: [Ho.5-l.oSiOm.8lp [HSi〇! .5] n [Si02] w [册Doing miscellaneous calls [Ho.5-l.oSiO! Sl ^ ntR ^ .Sl.oSiOi.Si.gJm [HfM.QSiOm.aRiSiOdm where: p is an integer from 8 to 5000; the sum of η and w is an integer, From 8 to 5000; the sum of η and m is an integer from 8 to 5000; and m is selected so that the organic substituent is present in a molar ratio from 1 to 99 ear%; and wherein R 1 is selected from substituted or unsubstituted Substituted, straight or branched chain alkyl groups having 20 carbon atoms between i, substituted or unsubstituted cycloalkyl groups having 4 to 10 carbon atoms, substituted or substituted ", Aryl groups having 6 to 20 carbon atoms and combinations thereof", the catalyst is selected from the group consisting of strongly acidic macroreticular resins, acidic nettic resins, strongly acidic gel-type resins, and strong test giants Resin contains catalytic clay, weakly alkaline ion exchange resin, and mixtures of them. · Mo He Ju (Please read the precautions on the back before filling out this page} --δ. -2- Ϊ [} Economy Central Standards Bureau employees Cooperative cooperative seal 403767 b! C8 ______ D8 VI. Patent application range 8 · According to the method in the scope of patent application, the formula of the product is PSiOi.sHR ^ iO ^^ SiO ^: where: X, y The sum of z and z is from 8 to 5000, and y is selected so that the presence of organic substituents is from 1 to 99 mole%; and wherein R is selected from substituted or unsubstituted, straight or branched, Alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted 'cycloalkyl groups having 4 to 10 carbon atoms, substituted 1¾¾ [Substituted, having between 6 and 20 Aryl groups of carbon atoms and combinations thereof wherein the catalyst is selected from the group consisting of strongly acidic macronets, weakly acidic macroreticular resins, strongly acidic gel-type resins, strong bases and network resins, and catalysts Part of clay, weakly ion-exchange resin, and mixtures thereof. 9. The method according to item 7 of the scope of patent application, wherein R1 is selected from the group consisting of methyl, chloromethyl, ethyl, propyl, 2-aminopropyl , Butyl, pentyl, hexyl 'cyclopentyl, cyclohexyl, chlorocyclopentyl, cycloheptyl, phenyl, fluorenyl, toluene 10. The method according to item 7 of the scope of patent application, wherein Ri is selected from the group consisting of methyl, chloromethyl, ethyl, propyl, 2-chloropropyl, butyl, pentyl, and hexyl. , Cyclofluorenyl, cyclohexyl, chlorocyclopentyl, .cycloheptyl, phenyl, phenyl, tolyl, and benzyl, R1 is straight or branched. 1 1. According to the scope of patent application 1 The method of clause, wherein the product is selected from the group consisting of hydrosilsesquioxane, hydrosiloxane, hydromethylsiloxane, hydroethylsiloxane, hydropropyl hardox, hydrobutyl hardox. Burning, hydrogen third butyl stone oxoxolite, hydrogen phenyl sand oxycarbon, gas. Methyl sesquioxane, hydrogen ethyl stone sesquioxane This paper is applicable to the Chinese National Standard (CNS) Α4 standard (210X297) (Mm) (Please read the precautions on the reverse side before filling out this page) ', φ— -Type 403767 S D8 VI. Patent application scope Oxane, propylpropylsilsesquioxane, hydrobutylsilsesquioxane , Hydrogen third butyl silsesquioxane and argon phenyl silsesquioxane and mixtures thereof. 1 2. The method according to item 1 of the scope of patent application, wherein the reaction mixture comprises a polar solvent and a non-polar solvent in a weight ratio between 5% and 80%. 1 3. The method according to item 1 of the scope of patent application, wherein the catalyst is a weakly basic ion exchange resin. (Please read the precautions on the back before filling out this page); Packing --- Order printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives -4- This paper size applies to the Chinese National Standard (CNS) A4 standard (210X29? %) '