TW500755B - Process for producing hydrophobic particulate inorgainc oxides - Google Patents

Abstract

Described is an improved process for producing hydrophobic particulate inorganic oxides useful for reinforcing polymeric compositions, e.g., rubber, by using a certain amount of hydrophobizing agents in an aqueous suspension of inorganic oxide having a pH of 2.5 or less and increasing the pH of the suspension after hydrophobizing the filler.

Description

500755 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (Cross Reference to Related Applications This application is based on US Provisional Application No. 60 / 203,442 filed on May 10, 2000 , Rights of 60 / 156,861 filed on September 30, 1999 and 60/149 755 of filed on August 19, 1999. Particulate inorganic oxides such as deposited silicon oxide It has gradually been found to be useful as a reinforcing filler in cured rubber compositions, especially treads. Reinforcement of the rubber composition is necessary in order to provide acceptable mechanical properties of the cured rubber composition. The problem with the use of particulate inorganic oxides in rubber compositions is that the dispersion of the particulate inorganic oxides in the vulcanizate is relatively low, as can be seen from a considerable percentage of white areas under the field of light microscope. Before the inorganic oxide is ground or powdered to form the vulcanized rubber composition, its dispersing power may be better, and it is under the field of light microscope There are also fewer white areas, but once significant improvement is achieved, 'continuing or even prolonged grinding or powdering for a period of time will not produce further improvement in its dispersing power. US Patent No. 5,908,660 discloses hydrophobicity Amorphous deposited silica can be used as a reinforcing and ductile filler in natural rubber and silicone. The '660 patent describes: (1) by a method of "extraction," from a hydrophilic amorphous deposit Silicon oxide produces hydrophobic granular amorphous silicon oxide, in which a hydrophilic amorphous silicon oxide aqueous suspension is contacted with a catalytic amount of an acid and an organic silicon compound to form a hydrophobic amorphous silicon oxide. Aqueous suspension of silicon, and hydrophobic amorphous deposited oxygen. The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 4 — I ί 1 · ― I · III l · III t ·! 1!-^^ _ (Please read the notes on the back before filling out this page) 500755

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) The aqueous suspension of siliconized silicon is in contact with an organic solvent that is not miscible with water in order to remove the hydrophobic granular amorphous deposited silicon oxide from the liquid. The aqueous phase is shifted to the liquid organic phase; (2) The amount of organic silicon compound added to the liquid phase must be sufficient to produce a hydrophobic particulate amorphous silicon oxide to achieve its intended use; (3) usually The amount of the organic silicon compound added is a unit of at least 0.004 organic silicon per unit of Si02 in the deposited oxidized stone; and (4) the upper limit of the amount of the organic silicon compound added is not important, Because more than the amount of silica used to completely hydrophobize the deposited silica will act as a solvent. U.S. Patent No. 5,908,660 discloses a very wide range of hydrophobization from a small degree of hydrophobicity to a complete hydrophobization. The published European patent application Ep 0 849 32 0 A1 discloses an amorphous deposited silicon oxide that includes an array of chelating agents chemically bonded to a surface. The coupler also optionally has a functional group that has the ability to react with a rubbery thermoplastic polymer during curing or mixing, so that the coupler can be chemically bonded to the polymer. U.S. Patent Nos. 5,739,197 and 5,888,467 disclose a particulate amorphous deposited silicon oxide which has a characteristic of 0.42% of a standard white area as defined herein. U.S. Patent No. 5,852,099 discloses particulate IS oxygen as a reinforcing filler in organic rubber. European Patent Application Nos. 721, 971A1 and Japanese Provisional Publication No. 8.176462 respectively describe an inflatable tread, which is made of a rubber containing caustic silicic acid which contains It is made of H, and the degree of hydrophobization of the partially hydrophobized silicic acid is 70-180mmol / kg measured by di-n-butylamine. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------------: --- II I--III (Please read first Note on the back, please fill out this page) 500755

V. Description of the invention (3) Hydrophobic particulate inorganic oxides have now been found to exhibit an unexpectedly high degree of dispersibility in the vulcanized rubber printed composition of the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Such an unexpectedly high degree of dispersion is not disclosed in the previously described copywriting. The present invention proposes a solution to the above-mentioned dispersion problem and an improved method for this technology. The high degree of dispersibility of the hydrophobic particulate inorganic oxide of the present invention can be measured from the Ml standard white area, and the Ml standard white area will be described in detail later. The hydrophobic particulate inorganic oxides used in the composition of the present invention include (1) hydrophilic inorganic oxides selected from the group consisting of granular or amorphous deposited silica, colloidal silica, and mixtures thereof Group, and (2) at least one organometallic reactant is selected from the group consisting of a first organometallic compound represented by the formula: R ^ MX ^ a a second organometallic compound represented by the following formula: R 2n + 2Sin〇nl The third organometallic compound, which is represented by the following formula: (R33Si) kNR53.k The fourth organometallic compound, which is represented by the following formula: In the group consisting of R42mSimOm and mixtures thereof, where: ( a) each M series is individually silicon, titanium or hammer; (b) each R1 series is individually not olefinically unsaturated (such as unsaturated aliphatic, cycloaliphatic or aromatic unsaturated hydrocarbon groups) and contains is a hydrocarbon group of 18 carbon atoms; (c) each X series is a functional group, an amine group, an alkoxy group containing 1 to 12 carbon atoms or a fluorenyl group containing 1 to 12 carbon atoms; Applicable to China National Standard (CNS) A4 (210 X 297 mm) 6 1 «ϋ n n (Please read the precautions on the back before filling in this page) ▼ Installation ----- II Order---- ▲ 500755

V. Description of the invention (4) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(d) a is 1, 2 or 3; (e) each R2 is individually a halogen group, a hydroxyl group, or an ethylenic unsaturation (as described for R1) and contains 1 to 18 carbon atoms Hydrocarbon group, but at least 50 mole percent of the R2 substituent is the hydrocarbon group; (f) n 疋 from 2 to 10,000; (g) each system is individually a halogen group, a mesogen or a A hydrocarbon group having no ethylenic unsaturation (as described for R1) and containing 1 to 18 carbon atoms, but at least 50 moles of the R3 substituent is the hydrocarbon group, (h) each R5 is individually Is hydrogen or a hydrocarbon group that is not unsaturated (as described for R1) and contains 1 to 18 carbon atoms; (i) kSi or 2; (j) each R4 is individually olefin free Hydrocarbon groups of 1 to 18 carbon atoms that are unsaturated (as described for) and (k) m is 3 to 20; wherein the hydrophobic particulate inorganic oxide is characterized by having a low In 0.4% Ml standard white area. The hydrophobic particulate inorganic oxide of the present invention is also characterized by having a methanol wettability of 15 to 45%, preferably from 20 to 40 percent, more preferably from 25 to 35 or The range of the methanol wettability may be a combination of these values, including the listed values. The hydrophobic particulate inorganic oxide of the present invention is also characterized by having a pH value of 3 to 10, preferably from 4 to 8, more preferably from 5 to 7.5, and most preferably from 6 to 7. , Or a combination of values between these listed ranges, such as from 3 to 7.5. With regard to the organometallic compounds described previously, the halide group includes fluorine, gas, bromine, and iodine, and is preferably gas. "No unsaturation" means that there is substantially no unrefined olefin "-IMr has a source of post-Qin true north compound or the preparation method may cause a small amount of unsaturated ethylene to appear in the hydrocarbon group. For the purpose of the present invention, when the organometallic reactant is an organosilicon 7 (please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 500755 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (5) Reactant, the silicon is considered a metal. Hydrophilic particulate deposited silica that can be used to make the hydrophobically deposited silica of the present invention is well known and commercially available. The manufacturing method of hydrophilic particulate amorphous silicon oxide and the characteristics of the product are described in detail in U.S. Patent Nos. 2,657,149; 2,940,830; 4,132,806; 4,495,167; 4,681, 750 and 5,094,829. Hydrophilic granular or amorphous deposited silica is usually commercially manufactured, combining a water-soluble solution of a soluble metallic silica, usually an alkali metal silicate such as sodium silicate, with an acid, This is so that colloidal particles are formed in a weak alkaline solution and are coagulated by the alkali metal ions of the soluble alkali metal salt formed. Different acids can be used, including inorganic acids such as sulfuric acid and hydrochloric acid. Carbonic acid, such as carbon dioxide, which is filled in a water-soluble solution of the soluble metal silica can also be used. In the absence of coagulant, silica will not deposit at any pH. The coagulant used to affect the deposition may be a soluble alkali metal salt generated during the formation of the colloidal silica particles, an added electrolytic substance, such as a soluble inorganic salt or organic monitor, or A combination of added monitors and monitors formed in situ during the deposition process. Amorphous deposited silicon oxide can be described as colloidal amorphous oxide. The basic aggregates of particles are deposited in the form of gel visible to the naked eye during the manufacturing process.

Regarding the organometallic compound, each of R1 and R4 is individually ethylenically unsaturated and contains 1 to 18 carbon atoms (such as one Cl-C I 18). The paper size applies to Chinese National Standard (CNS) A4 specifications. (210 X 297 mm) ---- 11 # equipment · —order ---- I ---- line · (Please read the precautions on the back before filling in this page) A7 B7 Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed five, the base of the invention description (burning base). Usually each R1 and each R4 individually contain 1 to I] carbon atoms, more commonly 1 to 10 carbon atoms, especially 丨 to 8 carbons Atoms, more particularly 1 to 6 carbon atoms. In many examples, each R1 and each R4 system individually contains 1 to 4 carbon atoms. It is preferred that each Ri and each R4 system are individually fluorenyl or ethyl Each R1 and each R4 are individually saturated or aromatic unsaturated monovalent hydrocarbon groups containing 1 to 18 carbon atoms. Each r1 and each R4 may be individually substituted or unsubstituted without ethylenic unsaturation. Monovalent hydrocarbon group. Examples of suitable hydrocarbon groups having no ethylenic unsaturation include, for example, methyl, ethyl, propyl , Isopropyl, butyl, isobutyl, second butyl, third butyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl and octadecyl; substituted; Alkyl groups, such as alkyl groups such as gas methyl, 3,3,3-trifluoropropyl and 6-hexahexyl; cycloalkyl groups, including groups such as cyclohexyl and cyclooctyl Benzoyl and naphthyl; and alkynyl aryl, such as C1-C4 aryl, and aralkyl such as aryl (c ^ -aoalkyl, including such as viatolyl, ethylbenzyl, benzyl and alkane -Substituted naphthyl, for example, naphthyl substituted with 0 ^ -0: 4 alkyl group, etc. Each X system is individually selected from the group consisting of alkoxy group, amine group, and alkoxy group having 1 to 12 carbon atoms The formed group is preferably an alkoxy group having 1 to 4 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. When X is a halogen group, it is preferably a gas. When X is an alkoxy group When X is, for example, methoxy, ethoxy, or propoxy, it is each X X Xie San, or methyl L-Longyl. When X is fluorenyl, it is usually ethoxy. Each R2 Are individually selected from the group consisting of This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) IIII · · III l · III ^ · 1111111 (Please read the precautions on the back before filling this page) 500755 A7 _____ B7 V. Invention Note (7) In the group of unsaturated hydrocarbon groups containing 1 to 18 carbon atoms, at least 50% of the moles of R2 substituents are hydrocarbon groups without ethylenic unsaturation. R2 can be the same as above The R1 and / or R4 are the same. The viscosity of the organosiloxanes is not limited, and the viscosity ranges from liquid to colloidal viscosity. In general, higher molecular weight organosiloxanes are cut off from the acidic conditions when producing hydrophobic particulate amorphous silicon oxide, thus allowing them to interact with the hydrophilic inorganic oxide. Each R3 is individually selected from the group consisting of a halogen group, a hydroxyl group, and a hydrocarbon group having 1 to 18 carbon atoms without ethylenic unsaturation, but at least 50 moles of R3 substituents Is this hydrocarbon group. When R3 is a hydrocarbon group, it may be the same as or different from the hydrocarbon group described for R1. Preferred R3 is methyl or ethyl. Each R5 system is individually selected from the group consisting of hydrogen and a hydrocarbon group which does not have ethylenic unsaturation and contains 1 to 18, preferably 1 to 8, and more preferably 1 to 4 carbon atoms. . Preferred R5 is argon, methyl or ethyl. The value of m is from 3 to 20. Usually the value of m is from 3 to 8, especially from 3 to 7, and preferably 3 or 4. Examples of useful organosilicon compounds that can be used as organometallic compounds include, but are not limited to, methyltrisilanes, dimethyldiastilane, trimethylsilanes, diethyldiasilanes, methyl Phenyldichlorosilane, phenethyldiethoxysilane, 3,3,3 trifluoropropylmethyldichlorosilane, trimethylbutoxysilane, pentylmethyldiazine, hexamethyldisiloxane Siloxane, hexaethyldisilaxane, mesitylene tetramethyldisilaxane, octamethyltrisiloxane This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) ( (Please read the notes on the back before filling out this page) 1 J · I · III l · III · 1111111 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10

Jw / 55 A7 ~ _B7 _ V. Description of the invention (8) (Please read the precautions on the back before filling out this page), hexamethylcyclotrisiloxane, hexamethyldisilazane, including 3 to 20 Siloxanes in methylsiloxy units and tris-methylsiloxy groups or hydroxydimethylsiloxy-terminated poly (difluorene) blocks with significant viscosity at 25 ° C in the range of 1 to 100 mPa.s Siloxane) polymer. The best organosilicon compounds are trimethylsilyl, dimethyldigasilane and hexamethyldisilane. Examples of organic titanium compounds that can be used include, but are not limited to, > tetrakis (C ^ C! 8) alkoxy acid monitors, fluorenyl triethoxy titanium (iv), methyl titanium (iv) triiso Propoxide, methyl titanium (iv) tributoxide, methyl titanium (iv) tri-butoxide, isopropyl titanium (iv) tributoxide, butyl titanium (iv) triethoxide Butyl titanium (iv) tributoxide, phenyl titanium (iv) triisopropoxide, phenyl titanium (iv) tributoxide, titanium (iv) triisobutoxide, [Ti (CH2Ph) 3 (NC5H10)] and [Ti (CH2SiMe3) 2 (Net2) 2]. Examples of useful organic rhenium compounds that can be used include, but are not limited to, tetra (Ci-Cu) alkoxyphosphonium acid monitors, phenylhydrazone (iv) trigas, methyl hammer (IV) trigas, Ethyl hafnium (iv) gas, propyl zirconium (iv) trigas, methyl hammer (iv) tribromide, ethyl zirconium (iv) tribromide, propyl hafnium (iv) dibromide, gas Triamyl (iv). Miscellaneous compounds printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs similar to the aforementioned organic titanium compounds and titanium compounds similar to the aforementioned organic compound are also included. The hydrophobic particulate inorganic oxide of the present invention has less than 0.4 /. In order to show the characteristics of the quasi-white area, for example, less than 0.35%. Often the mi standard oxygen in the white zone is rounded to the genus ^ ^ 0-25 0/0. The μ 1 standard white area is usually less than 0.2%, preferably less than 01. / (^ The relatively low M1 standard white area obtained by the hydrophobic particulate inorganic oxide of the present invention represents sulfur at 11 This paper size applies Chinese National Standard (CNS) A4 specifications (210x297 public love) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative 500755 A7 _ B7 V. Description of the invention (9) The material in the rubber composition has an unexpectedly high dispersibility. The Ml 'quasi-white area uses standard procedures and standard cured organic rubber forms It will be described in detail below. Because the procedures and forms are standardized, the standard white area is suitable as a feature of the hydrophobic particulate inorganic oxide. According to the present invention, the standard procedure for determining the standard white area is different. Based on the standard procedures determined in US No. 5,739,197 and US No. 5,888,467. The difference of this principle is that the standard cured rubber compound is made from a mixture of two polymer precursors. One of the standard polymers, which is immiscible with water, the hydrophobic inorganic oxide, and the aromatic processing oil. (2) The mixing cycle has been reduced to two, each time being a shorter period; and (3) The mixer used is cwBrabender Prep Mixer instead of Kobelco Stewart Bolling Model "00" Internal mixer 〇 According to this, a further specific embodiment of the present invention is a hydrophobic particulate inorganic oxide, which is selected from the group consisting of granular or amorphous deposited silica, colloidal silica, and mixtures thereof. A reaction product of a hydrophilic inorganic halide, and a further specific embodiment of the present invention is at least one organometallic reactant selected from the aforementioned first organometallic compound, second organometallic compound, third organometallic compound, A group consisting of a fourth organometallic compound and a mixture thereof, wherein the hydrophobic particulate inorganic oxide is characterized by: (a) substantially no functional group capable of chemically reacting with rubber; (b) hydrogen-based amount The range is 2 to 15 OH / nm2; and (c) the Ml standard white area is less than 0.4 percent. The paper size of this specific embodiment of the present invention is applicable National Standard (CNS) A4 Specification (210 X 297 mm) 12 Ϊ ---? L · I --------- Order --------- Line (Please read the first Note: Please fill in this page again.) A7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ~: 1 ~ -------- V. Description of the invention (10) The amount of water-based particulate inorganic oxides is usually between 3 and 3. It is preferably in the range of 14.0 H / nm2; preferably in the range of 4 to 12 OH / nm2. The hydrophobic particulate inorganic oxide of the present invention also has the characteristics of methanol wettability of at least 5%, preferably It is 20%, and more preferably 25%. The methanol wettability is usually less than 45%, preferably less than 40. / ❶ and more preferably less than 35%. The range of methanol wettability may be within the range of any combination of the above values, including the stated range. The methanol wettability value is the methanol concentration (wt%) required to wet 50% of the hydrophobic inorganic oxide, that is, to produce 50% wet (50% suspended and 50% sediment) Amount of alcohol. The methanol wettability value was measured by first measuring the amount of the hydrophobic inorganic oxide wetted with 50% methanol. To do this, add 2.0 g of a sample to a 50 ml conical centrifuge tube containing a 15 ml mixture of 50% methanol (HPLC grade) and deionized water. The centrifuge tubes used are 0.5 ml graduated tubes with a maximum capacity of 10 ml and 1.0 ml graduated tubes with a capacity of 10 to 50 ml. The contents of the tube were shaken for 15 seconds and centrifuged in a bucket-type centrifuge at about 4000 rpm for 15 minutes at room temperature (23-25 ° C). After that, the centrifuge tube was removed, taking care to prevent the sediment from resuspending. The recorded amount of wetted hydrophobic inorganic oxide, ie the deposit, was close to 0.5 ml. Afterwards, a series of at least 3 different concentrations of methanol / water mixtures was tested. This was to determine the wetness of 50 Up to 100% of the hydrophobic inorganic oxide, the ill of the knee. The best choice is to include at least one of the above concentrations and at least one concentration below the concentration required to wet 50% of the hydrophobic inorganic oxide. The selected concentration range is 5 to 95% methanol, in 5% increments. This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm). 13 — — — — — 1 — — — — — — — · 111 l · 111 ^ · 11111111 (Please read the precautions on the back before filling out this page) V. Description of the invention (u) A7 B7 ------—_, end-view is wet with methanol in 50% aqueous solution Depending on the amount. For example, if all hydrophobic inorganic oxides Is wetted with 50% methanol, the tested methanol concentration range is from 5% to 45%. The percentage of hydrophobic inorganic oxides wetted with different concentrations of methanol is calculated as the hydrophobic inorganics that are partially wetted Divide the volume of oxide by the volume of fully wetted hydrophobic inorganic oxide and multiply by 〇〇β. The value obtained is expressed as a graph of the percentage of wetting versus the concentration of methanol. 50% of the hydrophobic inorganic oxide is wetted The concentration of methanol in wet can be calculated from the linear equation. As used in the description of the present invention and the scope of the patent application, the amount of silanol of the hydrophobic particles or amorphous deposited silica is based on the following two methods When the organosilane used as a hydrophobization treatment has a known carbon-to-silicon molar ratio and no silanols are produced from the organosilicone, A. Tuel et al , Langmuir, v.l. 6, page S 770-775 (1990). This method combines the 29Si-nmr of the hydrophobic amorphous deposited silicon oxide sample with the data of the disk volume obtained from the elemental analysis of the sample. Calculate unreacted When the amount of carbon to silicon mole ratio of the organosilane that is used as a hydrophobization treatment is unknown or insufficiently defined, a deuterium exchange method such as G. Foti et al, Langmuir, vol.5, pages 232-239 (1989). These two methods are known to provide very similar values for the alcohol content of Shixiyuan, which provides samples suitable for both methods. The hydrophobicity of this specific embodiment of the present invention The carbon content of the particulate inorganic oxide ranges from 0.1 to 6% by weight, such as from 0.2 to 5% by weight. The amount of carbon preferably ranges from 0.3 to 3 or 4% by weight. If the Chinese paper standard (CNS) A4 specification (210 X 297 mm) is applied in this paper size, please read the notes on the back first (Fill in this page again) Printed by the Employees 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 14 500755 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (12) Used in patent specifications and patent applications The carbon content of the particulate inorganic oxide is determined by a technique modified according to the typical Pregal & Duma method. The sample (1 to 201§) was sealed in a lightweight tin lid iHL and introduced into a vertical quartz tube, maintained at 1040 ° C, and a quantitative amount of helium passed through the sample. After the sample was introduced, the flow of helium was strengthened with oxygen, and instantaneous oxidation occurred, which was caused by the small tin lid. The gas mixture was passed through chromium oxide to achieve a quantitative oxidation. The oxidizing gas was then passed through copper at 650 ° C to remove excess oxygen and reduce nitrogen oxides to nitrogen. The gas was then passed through a porpak QS chromatography tube at 100 ° C. The individual components were separated and eluted into nitrogen, carbon dioxide and water. The instrument is calibrated with the oxidation of standard compounds. The carbon content of the hydrophobic inorganic oxide of the present invention is substantially non-extractable. For example, after the extraction step, the inorganic oxide has at least 80%, preferably at least 85%, and preferably at least 90%. And more preferably at least 93% of the carbon remains. The extractability of the carbon content of the hydrophobic inorganic oxide can be measured by the following method. The method described herein was used to determine the carbon percentage of the hydrophobic particulate inorganic oxide before extraction. 5 to 15 grams of the hydrophobic particulate inorganic oxide was added to a 43 mmxl23 mm (inner diameter x outer tube length) cellulose extraction sleeve, which was placed in a Soxhelt extraction tube of a suitable size and equipped with a condenser. This Soxheh extractor and condenser system was attached to a round bottom flask containing 700 mL of toluene. After the flask was heated to a temperature of the toluene countercurrent for at least 15 hours, the used toluene was replaced with 700 ml of unused toluene, and the countercurrent was maintained for at least 15 hours. The paper size of the extracted paper recovered is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 15 --------- IIII · I I--: --- I ^ «— — — — — 1 — (Please read the precautions on the back before filling out this page) 500755 A7 B7 V. Inventory of (13) Inorganic oxide and dried until the sample is exposed to 160 ° C 丨 0 minutes, display Out loss is about 1.0% by weight or less. The percentage of carbon in the extracted sample was determined. The percentage of Soxhelt extractable carbon is determined by the following formula: (Percent of carbon before extraction) · (Percent of carbon extracted) 100 (Percent of carbon before extraction) The hydrophobicity of various embodiments of the present invention It is preferable that the particulate inorganic oxide has substantially no functional group capable of chemically reacting with the rubber, at least before the hydrophobic particulate inorganic oxide comes into contact with the rubber, either when the rubber compound composition is mixed or at A solution containing one or more rubbers does not react with the rubber in a solvent that is not miscible with water. Functional amounts of functional groups that can chemically react with the rubber but have no substantial effect may be present, but such It is better that none of the groups exist. The BET region of the hydrophobic particulate inorganic oxide printed by various consumer embodiments of the Intellectual Property Bureau of the Ministry of Economic Affairs for the specific embodiments of the present invention is usually, but not necessarily, between 40 and 350 m2. The range of / g is preferably in the range of 60 to 200 m2 / g, and more preferably in the range of 80 to 160 m2 / g. As in the scope of this patent specification and patent application The BET surface area of the hydrophobic particulate inorganic oxide used is a surface area determined by the Brunauer, Emmett, Teller (BET) method, which uses nitrogen as an adsorbent according to ASTM D1993-91, but the The system was modified by exhausting the system and the sample for one hour at room temperature. The BET surface area of the hydrophilic particulate inorganic oxide before being processed into a hydrophobic inorganic oxide was by Brunauer, Emmett, Teller (BET) The surface area is determined by the method according to ASTM 16 (please read the precautions on the back before filling in this page) This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) A7 Description of the invention (14 ) D1993-91 It uses nitrogen as the% Dong Feng and appendages, but the system has been modified to exhaust the system and samples for one hour under 165t. It is used in the method of the present invention (please read the precautions on the back first) (Fill in this page) The BET surface area of the hydrophilic particulate inorganic oxide need not be very precise, usually in the range of 50mVg to greater than gamma2 / g. However, the- Inorganic oxides, especially when the inorganic oxide is used as a reinforcing filler in an organic rubber composition, its value is in the range of 100 to 250 m2 / g, such as 100 to 2000 m2 / g. The pH value of the hydrophobic particulate inorganic oxide in the various embodiments of the present invention is generally, but not necessarily, in the range of 3 to 10. As used in this patent specification and the scope of the patent application, # hydrophobic The pH value of the particulate inorganic oxide is measured by the following steps: 50 grams of the particulate inorganic oxide (in the form of a powder), 50 ml of isopropanol and 50 ml of deionized water are added to a solution containing 150ml beaker with magnetic stir bar. Stir the contents of the beaker vigorously (do not spill) until the inorganic oxide is suspended. A calibrated pH electrode was placed in the vigorously stirred suspension and the pH was read after one minute. (± 5 seconds). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In fact, in the specific embodiment of the present invention, the hydrophobic particulate inorganic oxide and the coupling agent are not covalently bonded to the inorganic oxide. Appears in a rubber (elastomer) composition or in a solution containing rubber (or a mixture of rubbers) in a water-immiscible solvent before recovering and drying a rubber precursor mixture. Therefore, the present invention can be used as a carrier of a coupling agent that is not covalently bonded to the inorganic oxide. A coupling agent covalently bonded to the hydrophobic particulate inorganic oxide may appear in the final sulfurization. 17 · The paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 public love). 500755 Intellectual Property Bureau, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. Description of invention (! 5) in rubber. Coupling agents prior to covalent bonding with inorganic oxides such as silicon oxide are many and well known. Examples of such coupling agents include, but are not limited to, thiopropyltrimethoxysilane, thiopropyltriethoxysilane, bis (3- (trimethoxysilyl) propyl) Tetrasulfide, bis (3- (triethoxy 曱 silyl) propyl) tetrasulfide, bis (3- (trimethoxy 曱 silyl) propyl) disulfide, bis (3- (triethyl Oxysilyl) propyl) disulfide, 3-trialkoxysilylpropylthiocyanate, and trialkoxyvinylsilicon. Hydrophobic particulate inorganic oxidation of any of the embodiments of the present invention The material may be substantially dry or may be dispersed in a slurry. The muddy liquid may be an aqueous solution, which may be pure in the form of an aqueous solution or contain one or more water-soluble organic liquids. The liquid of the mud may be optionally organic, and in the organic form may be a single organic liquid that is soluble or immiscible with water, or it may be a mixture of organic liquids. Dissolved solids may or may not appear depending on need. The overall particles of the hydrophobic particulate inorganic oxide according to any of the embodiments of the present invention may be in various forms, for example, fine particles, beads, tablets, cylinders, flakes, or powders. In powder form, the size of the intermediate particles is usually in the range of 5 to 70 # m. Usually the intermediate particle size of the powder is in the range of 15 to 50 // m, for example, from 25 to 40 // m. In the form of beads, this intermediate particle size is usually in the range of 80 to 350. In a further specific embodiment, the size of the bead-shaped intermediate particles is in the range of 150 to 350 / zm, for example, in the range of 25 to 325 # m. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 18 — — — —. III l · II — ^^ · 1111111 * A— ^ (Please read the notes on the back before filling this page) 500755

5. Description of the invention (16) The measurement of powder, bead or other particles with similar size and shape is performed by laser diffraction technology. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm). When it is a fine particle, tablet, cylinder, flake, or other similar shape, the measurement of its size is implemented by screening and reporting the size term It is named after the standard filter of the American standard filter series according to ASTM E11-87. In most cases, the size of the particles is in the range of 至 to ^ claws. Usually the particles have a size in the range of 1 to 10111111, for example, from 2 to 7mm. The best particles are substantially dust-free, for example, at least 99% (weight percent) obtained by screening with a 200 mesh (U.S. sieve series). The overall particles of the hydrophobic particulate inorganic oxide according to any of the embodiments of the present invention are preferably fine-grained, such as those produced by processing in U.S. Patent No. 4,807,819. When the substantially dry particles are mixed with an unvulcanized rubber composition, the overall size is usually substantially reduced compared to the particles before mixing. The hydrophobic particulate inorganic oxide of any of the embodiments of the present invention can be used as a slurry in an aqueous solution and / or an organic liquid vessel, as described above. If a powder is used to produce the slurry, the size of the intermediate particles is as described for the powder. The slurry may be wet-milled to further reduce the particle size of the inorganic oxide. The average particle size of a hydrophobic particulate inorganic oxide can be reduced to less than 5 by wet milling. The average particle size of a wet-milled hydrophobic particulate inorganic oxide is preferably less than 24 ^ m. The hydrophobic particulate inorganic oxide of the present invention can pass through any of them which will result in a hydrophobic particulate inorganic oxide with a substantial lack of ability to communicate with 19 ^ --------- ^ ------ --- ^ (Please read the precautions on the back before filling out this page) 755 5. Description of the invention (17) The functional group and hydroxyl content of the chemical reaction of rubber from 2 to 15 OH / nm2, the carbon content from 0.1% Produced by methods such as methanol wettability of 6%, 15% to 45%, and Ml standard white area of less than 0.4%. The hydrophobic inorganic oxide of the present invention may also be characterized by a substantially non-extracted carbon content; a BET surface region having a pH value of 3 to 10 and 40 to 350 m / g. The hydrophobic particulate inorganic oxide of the present invention can use step A or both steps A and B to produce hydrophobic oxidation dreams and evaporated oxidation debris, which are disclosed in US Patent Nos. 5,908,660 and 5,919,298, respectively Incorporated into this case for reference. The method has the following changes. The amount of acid used causes the pH of the aqueous suspension to be 2.5 or lower, the preferred pH is 2.0 or lower, and the preferred pH is ΐ · 0 or lower, and the better pH is 0.5 or lower; the amount of organometallic compound used to hydrophobize the inorganic oxide, which results in a hydrophobic inorganic oxide having a hydroxyl group of 2 to 150 H / nm2, having a hydroxyl group of 0.1 to 6% Carbon content and 15% to 45% methanol wettability; and after the hydrophobic reaction is completed, the acidity (added in situ or generated in situ by hydrolysis of the halogenated organometallic compound) is neutralized To produce a hydrophobic inorganic oxide with a pH of 3 to 10, a substantially non-extracted carbon content, and a M1 standard white area of less than 0.4 / 0. Generally, when the hydrophobic inorganic oxide is recovered after step A, the pH value of the obtained aqueous suspension is increased to 3 or higher, preferably 4 or two, more preferably 疋 5 or two, and It is more preferably 6 or higher, usually 10 or less, more preferably 9 or less, more preferably 8 or less and even more preferably 7 or less. The pH of the aqueous suspension may range between any combination of these layers, including the listed layers. The paper size of this neutralization reagent is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) I · III l · III ^ · 111111!. Ministry of Economy Wisdom Printed by the Property Bureau Staff Consumer Cooperatives -20

V. Description of the invention (is) -------------- ^ — (Please read the precautions on the back before filling this page) to any of the commonly used to increase the pH value of an acidic solution Kind, as long as the nature of the modified filler is not adversely affected. Suitable neutralizing agents I include sodium hydroxide, hydroxide, chain hydroxide and sodium bicarbonate. The neutralization of the modified filler can be achieved by adding gaseous ammonia to the water-soluble solution during spray-drying. ^ When using a step to recover a hydrophobic inorganic oxide in a solvent that is not miscible with water By washing the neutralized reagent of the diluted aqueous solution until the pH value of the washed water is 30 or higher, the pH value of the hydrophobic inorganic oxide will increase to a pH value of 3.0 or higher. -Special processing printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs includes: (A) Aqueous suspensions of hydrophilic particulate inorganic oxides and an amount of acid that will cause a pH value of 2.5 or less than 2.5 And at least one organometallic reactant selected from the group consisting of the first organometallic compound, the second organometallic compound, the third organometallic compound, the fourth organometallic compound, and a mixture thereof; (B) making hydrophobic An aqueous suspension of the particulate particulate inorganic oxide is contacted with a water-soluble organic solvent to move the suspended hydrophobic particulate inorganic oxide from the liquid aqueous phase to the liquid organic solution phase. The water-insoluble organic solvent for contacting the aqueous suspension of the hydrophobic particulate inorganic oxide contains or does not contain one or more substances soluble in it, as necessary. Examples of such materials include, but are not limited to, one or more rubbers, oils, coupling agents, antioxidants, and catalysts. In step A, the concentration of the particulate inorganic oxide of the particulate inorganic oxide is an aqueous solution suspension of an aqueous solution. The concentration of the particulate inorganic oxide is not very strict, and is usually in the range of 1% to 90%, although it is sometimes used. Higher or lower concentration. Granular inorganic in the aqueous solution

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 500755 A7 ---- B7 V. Description of the invention (19) The concentration of the substance is usually in the range of 10% to 10%, preferably between 10 / ❶ to 30 %. The aqueous suspension may be ground before the acid and organometallic reactants are processed, for example, wet grinding, to further enhance the dispersibility (suspensibility) of the inorganic oxide in the aqueous medium and / or reduce the inorganic oxide particles. The size of the particles in the suspension. In step A of the method, the aqueous suspension of the particulate inorganic oxide is mixed with one or more of the above-mentioned aqueous solutions at a pH value of 2.5 or less to produce an acidic amount of the suspension of the aqueous solution. Organometallic reactants. The use of acid catalysis in step (A) can take many forms, organic and / or inorganic. The best acid catalysts are inorganic. Examples of suitable acidic catalysts include hydrogenated hydrogen acid, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, phosphoric acid, and benzenesulfonic acid. One acid catalyst or a mixture of two or more acid catalysts can be used, as described above. When the organometallic reactant is, for example, aerosilane, the necessary amount of the acid can be generated in situ by hydrolysis of the aerosilane or by direct reaction of the aerosilane with the hydroxyl group of the inorganic oxide. In step (A), the acid must be present in an amount capable of reducing the pH to 2.5 or less and sufficient to affect the reaction of the organometallic reactant with the particulate inorganic oxide. In step (A), it is preferable to use a sufficient amount of an acid catalyst to provide a pH value of the aqueous suspension of 2.0 or less, preferably a pH value of 1.0 or less, and a better pH value. It is 0.5 or less. The temperature in step (A) is not critical and is usually in the range of 2 ° C to 250 ° (:, although the temperature is sometimes lower or sometimes higher, as needed. The temperature of the reaction depends on the use Depending on the reactants, for example, organometallic compounds, acids and if a co-solvent is used. Although it is necessary, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 22 ----- ----· III I--Order -----— I — (Please read the notes on the back before filling this page) 500755

V. Description of the Invention (20) The printing step (A) of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be processed at the countercurrent temperature of the mud used in step (A), but preferably, step (A) is at the temperature Process from 30t to 150 ° C. In the processing step (A), the presence of a surface agent and / or a water-soluble auxiliary / cereal agent may be required to enhance the reaction between the organometallic reactant and the particulate inorganic oxide. Suitable surfactants include, for example, anionic surfactants such as dodecylsulfonic acid, non-ionic surfactants such as polyethoxyene (23) dodecyl ether and ((CH3) 3SiO) 2CH3Si (CH2) 3 (〇CH2CH2 ) 70 CH3, and a cationic agent such as N. alkyl dimethyl gasification press. One surfactant or a mixture of two or more surfaces may be used. Suitable water-soluble organic co-solvents include tetrahydrofuran and alkanols containing 1 to 4 carbon atoms; i.e. methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol and third Butanol. If desired, one water-soluble organic co-solvent or a mixture of two or more water-soluble organic co-solvents can be used. The amount of organometallic reactant used in step (A) is sufficient to produce the hydrophobic inorganic oxide described herein and provide the desired benefit. The hydrophobic inorganic oxide must maintain a stable fraction in the rubber cement, and after the solvent is removed, it is still dispersed in the wet rubber matrix rubber particles. If the amount of the organometallic reactant is insufficient, the organic oxide will be separated from the rubber and dissolved into the aqueous phase when the solvent is removed. Hydrophobicity is related to the hydrocarbon content of the hydrophobic particulate inorganic oxide and the ratio of argon to carbon in the hydrocarbon. Generally, it is sufficient to provide 3 to 40 / mole of carbon atoms per square meter of organic metal reactant, however, it is good to provide 6 to 20 # moles per square meter. At least some of the organometallic reactants react with the hydroxyl groups on the surface of the inorganic oxide to produce hydrophobic particulate inorganic paper. This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm). 23 — — — — — — — — — —-I II l · III β !! (Please read the notes on the back before filling out this page) 500755 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (21) Oxides. After step (A), the mixture of the aqueous solution may be ground, such as wet grinding, to reduce the size of the hydrophobic inorganic oxide particles before recovery or before step B. In step B, the water-immiscible organic solvent is present at a solvent-to-inorganic oxide weight ratio greater than 5: 1 in order to affect the separation of the hydrophobic particulate inorganic oxide from the aqueous suspension. Alternatively, the hydrophobic inorganic oxide can be recovered by filtration, centrifugation, spray drying, or by other separation methods known in the art. In a preferred method, steps (A) and (B) are performed next. However, if the metal organic reactant cannot be efficiently moved to the organic solvent and cannot react with the inorganic oxide, it can be added before, at the same time as, or immediately after the organic metal reactant used in step (A) is added. Water-insoluble organic solvents. In the first two environments, the conversion of the hydrophilic particulate inorganic oxide into a hydrophobic particulate inorganic oxide is accomplished by phase separation. In the phase separation, the hydrophobic particulate inorganic oxide is separated into the organic phase. For the purpose of the present invention, any water-soluble organic solvent can be used in step (B). Suitable water-insoluble organic solvents include low molecular weight siloxanes such as hexamethyldisilazane, octamethylcyclotetraxane, diphenyltetramethyldisilazane, and trimethylsiloxane. A polydifluorene-based stone with a closed base is oxy-fired liquid. When oxidized by a stone is used as a solvent, it can be used as a solvent and a reactant with a particulate inorganic oxide. Other—Suitable organic solvents that are miscible with water include, but are not limited to, aromatic fumes such as toluene and monobenzene; aliphatic hydrocarbons such as hexane and heptane; cyclocarbons such as cyclohexane; ethers such as diethyl ether And dibutyl ether; tetrahydrofuran; letter paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 24 --------- —r I ----- „--- -I ----- 1 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 500755 V. Description of the invention (22) Hydrocarbons such as sulfenyl chloride, gas Imitation, gasification of ethylene and chlorobenzene; and ketones such as fluorenyl isobutyl ketone. The water-immiscible organic solvent is used to make the weight ratio of the water-immiscible organic solvent to the inorganic oxide greater than 5 : 1. When the weight ratio of the organic solvent that is not miscible with water to the inorganic oxide is less than about 5: 1, the hydrophobic particulate inorganic oxide is usually easy to aggregate in the organic solvent that is not miscible with water and Does not form a true deposit. Larger weight ratio of organic solvents to inorganic oxides that are not miscible with water At 5: 1, the hydrophobic particulate inorganic oxide will be deposited in the organic solvent phase that is not miscible with water, thus affecting the separation of the hydrophobic particulate inorganic oxide from the aqueous suspension. It will not be miscible with water. The upper limit of the amount of solvent added to the method is limited only by economic considerations, such as the cost of the solvent, the cost of solvent recovery or cleaning, and the gluten of the device. The weight of inorganic oxides that are not miscible with organic solvents The ratio is greater than 6: 1. The weight ratio of a good water-immiscible organic solvent to the inorganic oxide is in the range of 6: 1 to 10: 1. A good water-immiscible organic solvent The boiling point is below about 2500c to facilitate its removal from the hydrophobic particulate inorganic oxide. However, the point of the water-immiscible organic solvent is not very strict, because the solvent can be borrowed It is removed from the hydrophobic particulate inorganic oxide by filtration, centrifugation or other suitable liquid-solid separation methods. In step (B), the water-immiscible organic solvent affects the hydrophobic particles without Spread oxide from aqueous solution The suspension is separated into an insoluble organic solvent. The hydrophobic product can be washed and / or neutralized to reduce pollution and produce a product with a pH value of 3 or greater. The resulting hydrophobic inorganic paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) 25 III — — — — — — — — — — III h III a — — — — — — — — (Please read the precautions on the back before (Fill in this page) A7

The organic slurry of oxides printed by employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs may be ground, such as wet ground, to reduce the particle size of the particles before separation or before use in the form of an organic slurry. The hydrophobic particulate inorganic oxide can be recovered from an organic solvent that is not miscible with water, can be dried, and can be further processed by a method such as heating. In a more specific embodiment of the present invention, it is expected that the vulcanized rubber composition includes 10 to 150 parts of a hydrophobic inorganic oxide per 100 parts of rubber, wherein the composition has a characteristic that the Ml white area is less than 04. %, Such as the gradation of the M1 white area described before. The term "rubber" as used herein includes organic rubber and stone rubber. In addition, the hydrophobic particulate inorganic oxide of the present invention can be dispersed in polymer materials such as plastics and resins. In a more specific embodiment, the M1 white area is characteristic of the polymer composition, that is, the hydrophobic inorganic oxide and the polymer itself. As a result, it was determined that the Ml white area was measured according to the method of measuring the Ml standard white area 'except for the polymer mixing test, which does not need to be a standard formula; in other words, the measurement started with the method named "microscopy technique step," Subtitle. The vulcanized rubber composition of the present invention has high strength, which can be seen from a high 3000/0 coefficient. The vulcanized rubber composition may include 10 to 150 parts of hydrophobic particulate inorganic oxide per 100 parts of rubber. In particular, it is # 20 矣 130 ^ per 100 parts of rubber bag, preferably 30 to 100 parts of hydrophobic particulate inorganic oxides. The particulate inorganic oxides with low Ml standard white area characteristics may be higher than this paper size and applicable to China National Standard (CNS) A4 Specification (210 X 297 Public Love) 26 ----- ---- i I-- ·! Ιι! — · (Please read the precautions on the back before filling this page) 500755 A7 _ B7 V. Description of the invention (24) Degree is scattered in many vulcanized organic rubber composition. The rubber may be an organic rubber (natural or synthetic), or it may be a silicone rubber. Many organic rubbers and mixtures are suitable for use. In this Mingzhi vulcanized organic rubber composition. Examples of such organic rubber include, but are not limited to, natural rubber 'cis-1,4-polyisoprene; cis-1,4-polybutadiene; trans- i, 4-polybutadiene; 1,2-polybutadiene; styrene-butadiene copolymer rubber, which consists of various proportions of styrene and butadiene, and various isomers of butadiene required Composition (hereinafter referred to as `` SBR), styrene-isoprene-butadiene terpolymer rubber is composed of various proportions of styrene, isoprene and butadiene and the required butadiene Composition of various isomers (hereinafter referred to as "SIBR"); acrylonitrile-based rubber composition; isobutylene-based rubber composition; and ethoxylated-acrylic-coated-dilute binary copolymer, or as described In, for example, U.S. Patent Nos. 4,530,959; 4,616065; 4,748,199; 4,866,131; 4,894,420; 4,925,894; 5,082,901, and 5,162,409. Other suitable organic polymers are ethylene and other high (2-paraffin such as propylene Copolymer of butene-1, pentene-1 and monodiene monomers. The organic polymer The compound can be block, random, or sequential and can be prepared by an emulsion (such as e-SBR) or a solution polymerization method (such as s-SBR). Additional polymers that can be used include those or Fully functionalized polymers include coupled or star-branched polymers. Examples of functionalized organic rubbers include polychloride, chlorobutyl and bromobutyl rubber, and brominated isobutylene-co-paramethylstyrene rubber. The best organic rubbers are polybutadiene, s-SBR and mixtures thereof. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -------------- Loading --- (Please read the precautions on the back before filling this page) Order: Printed by the Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 27 500 755 A7 B7 V. Description of the invention (25) (Please read the precautions on the back before filling this page) Organic rubber in the cured organic rubber composition The range of the amount is wide. In most examples, organic rubber accounts for 20 to 83.3% by weight of the vulcanized organic rubber composition. More specifically, organic rubber accounts for 20% to 80%, for example from 30% to 75%, preferably 35% to 70%. The proportion of the organic rubber used to prepare the uncured organic rubber composition is substantially the same as that in the cured organic rubber composition. There are many other materials which are usually and / or optionally present in the vulcanized organic rubber composition of the present invention. These include, but are not limited to, such materials as rubber hardeners (usually sulfur, but not required), catalysts, coupling agents, lubricants, waxes, processing oils, antioxidants, reinforced carbon black, semi-reinforced carbon Black, unreinforced carbon black, other pigments, stearic acid and / or zinc oxide. These substance lists are not exhaustive. As long as these materials are not severe enough to interfere with the effect of a good cured organic rubber formulation, these and other elements can be used in their usual amounts for their original purpose. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The constituent elements of this vulcanizable organic rubber can be formed into its composition by any method known in the art. Mixing and grinding are the most commonly used. The vulcanizable organic rubber composition can be shaped and cured using any conventional methods and techniques to form a vulcanized organic rubber article. For example, a tire can be built and shaped in any common method and technique. The organic polymerizable composition ', such as plastics and / or resins, to which the hydrophobic inorganic oxide of the present invention can be added, includes basically any organic plastic or resin. The hydrophobic inorganic oxide of the present invention may be doped with the plastic knee or resin, and the physical form of the plastic or resin is any liquid or miscible form, such as a solution, suspension, emulsion, dispersion, and the like 28 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). It is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 500755 A7-B7 V. Description of invention (26). Suitable plastics and resins include, for example, thermoplastic and thermosetting resins and plastics with rubber-like properties. The plastics and resins can be acid-alcohol resins, oil-modified acid-alcohol resins, unsaturated polyesters, natural oils (such as linseed, tung oil, soybeans), epoxides, nylon, thermoplastic polyesters (such as polyethylene Terephthalic acid monitor, polybutene terephthalate), thermoplastic polycarbonate monitor, thermosetting polycarbonate monitor, polyethylene, polybutene, polystyrene, polyisopropylene, ethylene-propylene copolymer and ternary copolymerization Compounds, acrylic acid (homologous polymers and copolymers of acrylic acid, acrylic blue, methacrylic acid, acrylic acid, acrylic acid, hydrogen halides, etc.), phenol resins, polyalkylene oxides such as polyoxymethylene (same as Source polymers and copolymers), polyurethanes, poly (ureaurethanes), polyfluorenes, polysulfide rubbers, nitrocellulose, vinyl butyrate, ethylene (gas ethylene, Vinyl gas and / or polymer-containing vinyl acetate), ethyl cellulose, cellulose acetate and butyrate, viscose, shellac, paraffin, ethylene copolymers (eg, ethylene-ethylene acetate) Copolymer, ethylene acrylic acid copolymer, Allyl acrylate copolymer) and the like. The amount of the hydrophobic inorganic oxide that can be used in the polymerized composition ranges from more than 5% to 70% by weight, based on the total weight of the polymer composition. For example, the amount of hydrophobic inorganic oxides typically used in ABS (acrylic acid-butadiene-styrene copolymers is from 30% to 60%, and the amount used in acrylonitrile-styrene-acrylate copolymers is from 5% to 20%, the amount of polypropylene scapulae used from 15% to 30%-the amount used in Jun alcohol resin (for pigments and inks) from 30 to 60%, the amount used in thermoplastic paraffin from 10 % To 30%, the amount of epoxy resin used from 5% to 20%, the size of this paper applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 29 ---------- -II ----- ί--II — — — — — — — (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 500755 A7 B7_ V. Description of Invention (27 ) Used in ethylene-ethylene acetate copolymers up to 60%, used in ethylene ethyl acetate copolymers up to 80%, used in liquid crystalline polymers (LCP) 30% to 70%, The amount used in the phenol resin is 30% to 60% and the amount in the polyethylene is usually more than 40%. Another specific embodiment of the present invention is a composition including (a) -The solution includes a solvent that is immiscible with water and an organic rubber that is immiscible with water; and sand) a particulate inorganic oxide is dispersed in the solution; wherein the particulate inorganic oxide is dispersed before the solution is Any of the hydrophobic particulate inorganic oxides described herein. The organic rubber dissolved in the water-immiscible solvent may be any of a variety of organic rubbers and mixtures thereof which are suitable for use in the female vulcanized organic rubber composition of the present invention, as previously discussed and exemplified. Preferred organic rubbers include solution styrene-butadiene rubber, polybutadiene rubber, or a mixture. The standard procedure for measuring the white standard area of Ml according to the present invention is as follows: The standard procedure for measuring the white standard area of Ml is as follows. The preparation of the precursor mixture is carried out in a suitable container equipped with a stirrer under nitrogen. Irganox 1520D Antioxidant (Ciba Specialty Chemicals Corp., Tarrytown, New York) Cyclohexane has a minimum of 120 grams of Solflex 1216 solution styrene butadiene rubber (The Goodyear Tire & Rubber Co., Akron, Ohio) And it was stirred overnight at 60 ° C to completely dissolve the rubber and form a 14% styrene-butadiene paper. The size of the paper was in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 30 — — — — ΊΊΙ — iJ »· III l · III · 1111111 · (Please read the notes on the back before filling out this page) 500755 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (28) The second roasted rubber solution was also It is called "s-SBR cement". In a similar form, in cyclohexane containing 0.365 phr of Irganox 1520D antioxidant, a minimum of 50 grams of Budene 1207 polybutadiene rubber (The Goodyear Tire & Rubber Co., Akron, Ohio) was combined at 60 ° C. Stir overnight to completely dissolve the rubber completely and form an 11% styrene butadiene rubber solution, also known as "BR cement". Adding a hydrophobic inorganic oxide to the stirred portion of the s-SBR cement forms a mud mass. The amount of the hydrophobic inorganic oxide is expressed in phr, which is 30.95 and the density of the hydrophobic particulate inorganic oxide skeleton ( Product in grams / ml). After thorough mixing to produce uniform consistency, Sundex B125 aromatic processing oil (Sun Company, Inc., Refining and Marketing Division, Philadelphia, Pennsylvania) was added in an amount equivalent to 30 phr. The resulting slurry was pumped to a water pot containing a large amount of hot water and the cyclohexane was stripped to a collection chamber to allow the mother mixture colloid particles to be collected into the water in the water pot. Check the water phase > for residual inorganic oxides. The wet matrix mixture colloidal particles were recovered by filtration. The recovered wet matrix mixture pellets were dried in a laboratory oven at 75 t for 4 hours to produce a dry first matrix mixture pellet. Thermal gravimetric analysis was used to analyze the obtained dry first precursor mixture colloidal particles to determine that the residue is at 800t, which is equivalent to the inorganic oxide. It is a hydrophobic particulate inorganic oxide in rubber, oil, and hydrophobic particulate inorganic oxidation. Within the experimental error of the theoretical value of the percentage in the composition of the product, and it was determined that the inorganic oxide was substantially completely transferred to the first matrix mixture colloidal particle. The thermal gravimetric analysis is based on the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 31 — — — — — — — — — — —till · — — — ^ a — — — — — — — — (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Lake 755 A7 ----------- B7 _ V. Description of Invention (29) This is done by heating a small sample (usually about 10 mg) at a rate of 1 rc / min to 8000 ° C in a flowing nitrogen pressure. 200. (: The loss of weight is considered to be the loss of moisture. The calculation of the weight percentage of the residue is [(weight of the sample at 2000 ° C) · (weight of the sample at 800,000)] / (2〇 The weight of the sample at 0 ° C). The incomplete transfer of hydrophobic particulate inorganic oxides to this precursor mixture made the test of the M1 standard white area fail because the measured white area is the volume of inorganic oxide in the final vulcanized rubber compound A function of the percentage 〇 Adding a hydrophobic inorganic oxide to the stirred part of the br bonding agent forms a slurry. The amount of the hydrophobic inorganic oxide is expressed in phr, which is 30.95 and the hydrophobic particulate inorganic oxidation. The product of the skeletal density of the substance (expressed in grams / ml). After thorough mixing to produce uniform consistency, add

Sundex B125 aromatic processing oil (Sun Company, Inc., Refining and Marketing Division, Philadelphia, Pennsylvania) is equivalent to 30 phr. The resulting slurry was pumped to a water pot containing a large amount of hot water and steam-strip cyclohexane was passed to a recovery chamber to allow the matrix mixture colloidal particles to be collected into the water in the water pot. The water phase was checked for residual inorganic oxides. The wet matrix mixture colloidal particles were recovered by filtration. The recovered wet matrix mixture pellets were dried in a laboratory oven at 75 ° C for 4 hours to produce a dry first matrix mixture pellet. #thermal gravimetric analysis Analyze the obtained dry first precursor mixture colloidal particles to determine that the residue is at 800 ° C, which is equivalent to the inorganic oxide. It is a hydrophobic particulate inorganic oxide in rubber, oil, and hydrophobic particles. Within the experimental error of the theoretical value of the percentage in the composition of the inorganic oxide, and the paper size is determined to comply with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 32 -------- t I — — — ^ -111111 I (Please read the notes on the back before filling this page) Five Φ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 500755 A7 B7, Invention Note (3G) will substantially completely transfer the inorganic oxide To the first matrix mixture colloidal particles. The implementation of the thermal gravimetric analysis is as described above. The incomplete transfer of the hydrophobic particulate inorganic oxide to the one parent mixture completely failed the test of the M1 standard white area because the measured white area was a function of the volume percentage of the inorganic oxide in the final vulcanized rubber compound. Mixing steps Use a 310-ml C.W. Brabender Prep Mixer equipped with a mixing knife in the form of minced meat, variable speed propulsion, and a hot liquid thermostatic circulation unit or its equivalent. Before the start of the first round, the temperature of the mixing chamber was adjusted and corrected using the hot liquid thermostatic cycle unit at an initial temperature of 80 ° C. ^ Adjustable variable-speed propulsion to provide a rotating shaft at a speed of 65 rpm. In the first round, the weight of the above-mentioned first master batch rubber particles was equivalent to 89.9 g (70 phr) of Solflex 1216 solution styrene-butadiene rubber, 27.0 g (21 phr) of Sundex 8125 oil, and hydrophobic particulate inorganic oxidation. The weight of the hydrophobic particulate inorganic oxide is equivalent to the product of 27.86 and the skeleton density of the hydrophobic particulate inorganic oxide (expressed in grams / ml). At the same time, the weight of the dry second masterbatch rubber pellets was also measured in the first round, which is equivalent to 38.5 grams (30phr) of Budene 1207 polybutadiene rubber, 11.6 grams (9phr) of Sundex 8125 oil, and hydrophobic particulate inorganic oxidation. The sum of the physical properties and the weight of the hydrophobic particulate inorganic oxide is equivalent to a product of 11.95 and the density of the hydrophobic particulate inorganic oxide skeleton (expressed in grams / ml). The beginning of the first round is to add the measured paper weight to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 33 ------------- ^-I- -Γ I--I I --- II (Please read the precautions on the back before filling out this page) 500755 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (31) The above-mentioned dry first precursor mixture The colloidal particles and the above-mentioned dry second master mix colloidal particles were mixed into the mixer and mixed at 65 rpm for 5 minutes. Raise the hammer and scan at 0.5 minutes. After another 0.5 minute, 16.7 g (13ph0 of X50S 1: 1 Si-69 Shiyaki coupler and N330-HAFcarbon black (Degussa Cor., Ridgefield, Park, New Jersey; supplier: Struktol Corp. of America, Stow, Ohio). After another 5 minutes, raise the hammer and scan and add 3.2 grams (2.5phr) of Katox 920c surface-treated zinc oxide (Zinc Corporation of America, Monac, Pennsylvania), 2.6 grams (2.0phr) Wingstay 100 is mixed with diaryl p-phenylenediamine (The Goodyear Tire & Rubber Co., Akron, Ohio; supplier RT Vanderbilt Company, Inc., Norwalk, Connecticut) and 1.3 grams (l.Ophr) of Rubber grade stearic acid (CPHall, Chicago, Illinois). Mix the ingredients for an additional 2 minutes to reach a maximum temperature in the temperature range of 150 ° C to 160 ° C, and complete the first round in the mixer. Vision Manufacturing The rate of rotation axis is increased or decreased depending on the physical characteristics of the starting material of the hydrophobic particulate inorganic oxide used to produce the polymer matrix mixture, so as to reach the highest temperature range in the aforementioned temperature range during the 3.5 minute mixing period. Temperature. Pour out the raw material and measure its temperature with a thermocouple and weigh it to confirm that the temperature is within the specified range and that the total weight is within 5% of the theoretical weight. The raw material is taken from a rubber mill with one or two rollers Unroll and cut it into strips for the second round in the mixer. After the first round is completed, complete it in the panner ^ and the interval between the start of the second round is about 1 hour. Before the start of the second round, use The hot liquid constant temperature circulation unit adjusts and corrects the temperature of the mixing chamber at the initial temperature of 60 ° c. The adjustable paper size is adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 34- --1 .--- 1 4 · · I I--Γ — — — — — — — — — (Please read the notes on the back before filling out this page) 500755 A7 B7 Five ΑΨ Intellectual Property Bureau, Ministry of Economic Affairs The propulsive force printed by Employee Consumer Cooperative, Invention Note (32) is 40 rpm to provide a rotary shaft. The start of the second round is to add the raw bar of the first round to the mixer. Then add 2 · 6 grams (2.0phr) Santofle x 13 N- (l, 3-difluorenylbutyl) -N, benzyl-p-phenylenediamine (Monsanto, St. Louis, Missouri), 1.9 g (1.5 phr) 0kerin 7240 microcrystalline wax-paraffin mixture ( Astor Corporation, Norcross, Georgia), 1.8 g (1.4 phr) of rubber manufacturing sulfur (Taber, Inc., Barrington, Rhode Island), 2.2 g (1.7 phr) of Santocure NS N-Third-Butyl-2_benzo Noisy sulfenamide (Monsanto, St. Louis, Missouri), and 2.6 grams (2.0phr) DPG diphenyl vein (Monsanto, St. Louis, Missouri). Raise the hammer and scan after 0.5 minutes. If it is necessary to change the speed of the rotary wheel, mix the ingredients for an additional 1.5 minutes to reach a temperature between 100 ° C and 110 ° C and complete the second round in the mixer. Grinding steps First heat one or two roller rubber mills to 60 ° C. Quickly set to 6.35mm (0.25 inches) and supply the second round of raw materials to the mill while the mill is operating. If the thickness needs to be maintained, adjust the roller layer. Make an eight-sided incision and perform eight final rounds. Adjust the nip setting to produce a sheet with a thickness of 2.032mm ± 0.127mm (0.080 inches ± 0.005 inches). The material was unrolled from the mill and it was flattened on a clean surface. A pair of long JT-shaped specimens 101.6 mm X 76.2 mm (4 inches x 3 inches) were cut from the blank using two molds ^ ', and the specimens were stored on a clean polyethylene surface. The conditions for overnight stay are 23 ° C ± 2 ° C and relative humidity of 50 / 〇 ± 5%. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 35 ------- -II --- · I--l · III Order! --I I-(Please read the precautions on the back before filling this page) "υυ /: > 5 V. Invention Description (33: Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

The vulcanization step places the conditioned sample at 101.6mm X 76.2mmXx 1.524mm (4 inch x 3 inch x 0.06 inch) standard typesetting machine stainless steel casting template compression mold with a layer of Teflon polytetrafluoroethylene (EI duPont de Nemours & Co "Wilmington, Delaware) has a thickness of 0.0254mm to 0.0508mm (0.001 to 0.002 inches) or its equivalent and is cured at a height of 61 cm x 61 cm (24 inches x 24 inches) 890 kg ( 100 ton) electronically heated compression press or its equivalent, cured at 13.79 million Basco (2000 psi) at 150 ° C for 20 minutes. The resulting vulcanized rubber sheet was removed from the mold And left to stand overnight. The microtome section procedure uses an RMC MT-6000-XL microtome slicer (RMC Inc., Tucson, Arizona) equipped with a CR2000 freezing accessory and a MSI LH grade, black, standard A boat-shaped diamond knife (Micro Star Technologies, Huntsville, Texas) or its equivalent is used for micro-slicing. A cut edge of a diamond with a length of 6 to 10 mm from the incision is placed at a 45-degree angle in a low-temperature microtome holder for a microtome. And set this The clearance angle of the microscopic slice is 4 degrees as specified at the bottom of the knife. The temperature of the starting specimen and the diamond knife is also set in the range of -70 ° C to -40 ° C. In order to obtain a moderate cut Cutting conditions, and subsequent adjustment of individual temperatures is necessary. From the cured rubber sheet, cut a rough sample of about 15mmx about 15mmx about 1.5mm πη. Place this rough sample on a non-steel steel product RMC paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 36 ----- Τ5 --— 14 ---- h! -Order 丨 丨 丨 丨 _ (Please read the notes on the back first (Fill in this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs? Clothing A7 Description of Invention (34)

The Trome flat microtome microtome specimen was lost and the sample was firmly pressed down with an Allen spiral plate supplied with the microtome microtome. The specimen correction table, Trome clip, and a razor supplied with the microscope slicer were used to trim the specimen, so the specimen protruded the front of the clamp by about 4 mm and the corners of the specimen were trimmed at 45t. Approximately 8mm long. The clip is placed in the low-temperature unit arm of the improved mechanical structure of the microtome for a microtome, so the table surface is vertical. First cool to the temperature setting of the specimen. Use the sharp edges of the diamond knife to flatten the table so that the table has a flat surface. Move the edge of the diamond knife to a clean sharp edge and smooth out some thin slices on the table. Set the cutting stroke to 0.5mm per second and manually or automatically raise the table to a clean sharp area on the edge of the diamond knife or move to a new area of the same knife to cut a slice with a thickness of about 2 // m. Fix each section because it will first be a pair of sharp scissors with a pre-cooled biological rating of 5 and a light touch that will open or close by itself (A. Dunont & Fils, Switzerland) Structure Probe Inc ”West Chester, Pennsylvania) or its equivalent is broken at the edge of the diamond knife. Hold the corner of each slice as it will begin to fall off, and it will not be damaged, broken or broken during the entire cutting stroke. Gently pull the slice away from the edge of the knife to reduce the JTH that the slice rolls up or excessively presses on the edge of the knife. Cut the slice dry; do not use dimethylarsin or xylene to help cut. Before cutting At the end of the trip, gently pull the complete section with scissors to a low-temperature-cooled Fisherbrand® Superfrost ® Plus. The paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 37 ------ -IIIII 1 · II — l · III — — — — — — (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 500755 A7 B7 V. Inventions (3: >) A glass microscope slide, 25mm X 75mm X lmm (Fisher Scientific Co., Pittsburgh, Pennsylvania) or its equivalent. The glass, which has been cleaned with optical lens paper or its equivalent first After that, it is replayed on a custom U-shaped silicone spacer surrounding one of the sides of the knife boat or one of its back surfaces. Place 8 to 10 thin slices on each glass slide and place it on the optical device. Convenient location. Remove the slide from a low-temperature chamber, place it in a microscope slide box to avoid excessive moisture contamination, and allow it to warm to room temperature. Steps to make the slice The thin slice Partially coated on microscope slides with Cargille Series A η = 1.550 + 0.0002 immersion oil or its equivalent (R, P, Cargille Laboratories, Inc., Cedar Grove, New Jersey). Use forceps and / or sharpened probes. Needle-handle the thin section at a low magnification on a Nikon SMZ-Uzoom 1: 10 stereo microscope equipped with Nikon SMZ-U UW 10Xa / 24 binocular equipment (Nikon Corporationn, Tokyo, Japan) or its equivalent To remove folds, wrinkles and Wrinkle and straighten the sliced part. Care must be taken not to tear the finely sliced part during the operation. The straightened thin part is parallel to other straightened slice parts, 1 to 5 (best It is 4) as a group so that a proper space can be placed under an 18mm diameter circular cover glass. Clean an 18mm diameter, 0.13mm to 0.17mm thick round cover glass (Fisher Scientific Co., Pittsburgh, Pennsylvania) with paper for optical lenses or its equivalent ^ and place it on the arranged slice Partial groups. One slide can hold two or three sections if needed. Fold one Scotties This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 38 (Please read the precautions on the back before filling this page) _ 装 ----- „---- Order- --- 500755 A7 B7 V. Description of the invention (36) two-ply 23.3cm x 18.2cm (9.2 x 7.2) face paper (Scott Paper Company, Philadelphia, Pennsylvania) or its equivalents As absorbent paper. Place the absorbent paper on a cover glass to protect the sliced section on the slide and place a flat plate or slide box on the absorbent paper. Hand operation should be stable, gentle, and consistent and steady on the plate Or slide the box downward for about 15 seconds. Remove the plate or slide box and absorbent paper. Repeat the absorbent step P with a new side of Scotties paper or its equivalent but use less force. Equipment The software and selection steps use the following equipment or its equivalent to select the area: NikonMicrophot FXA research optical microscope equipped with a phase difference target module to install a planned 20X / 0.05 Ph2 phase target, a Ph2 phase condenser lens (Nikon Corporation, T okyo, Japan), 1.25X magnification system and a 1.25X intermediate lens; SonyTrinitron PVM 1343MD color TV screen (Sony ^ Corporation, Tokyo, Japan) and a Sony CCD three-chip DXC-760MD camera (Sony Corporation , Tokyo, Japan); a Macintosh Ilfx computer (Apple Coloration, Cupertino, California) with a color Super Mac 43 cm (17 inch) screen and a data translation architecture memory card (Data Translations, Raleigh, North Carolina). Use the following software or its equivalent to capture images and image analysis: ColfliKit® software (Data Translations, RaLeigh, NC) NIH imaging software (National Institute of Health, Washington, DC) and Microsoft® Excel® software (Microsoft Corporation, Redmond, This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) -------------- Install i I i Please read the precautions on the back before filling this page) Revision:-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 39 500 755 A7 V. Description of Invention (37)

Washington) ° Steps for selecting the field of view (please read the precautions on the back before filling out this page) At a magnification of about 250 times, the field of view scans every _ slice of the microscope with a thickness in the range of about 2 to about 3 " m The thick, sliced section has previously been used for phase-contrast optical microscopy to rule out further consideration of sections containing major irregularities such as wrinkles, waves, cracks, and / or dirty particles. . Scan at least two slice sections with consideration in order to determine the local representation of the entire sample ^ Examine these same areas at approximately 500x magnification and use the closed longitudinal movement of the microscope stage and the closed transverse movement Choose a field of view. Use only a low-relief field of view (the measurement of white areas enhances its accuracy by having only a substantially flat field of view; showing a variable high-relief field of view results in blurring and the image has a low depth of field (this is optical Microscope characteristics) without focusing). Capture an image of the entire 10 field of view from at least two slice sections. At least one image is created in a PICT file using ColorKit® software. Stored as a PICT file to optical magnetic disk, computer-assisted measurement of white area. Image analysis Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The image micrograph files stored as PICT files can be opened directly using NIH image software. Opening a PICT file, an image is displayed at a ratio of 2.00 ± 0.03 linear pixels per micrometer object distance, and the image presented on the screen is a light field of 640 pixels by 480 pixels. The actual value of this ratio can be obtained by horizontally projecting an image of a horizontal clip table of 10 // m each on a screen and measuring a distance of 250 μm or more on the displayed image. To determine 40 paper sizes are applicable to China National Standard (CNS) A4 specifications (210 X 297 public love)

. Enter the actual distance to this frame and let the computer calculate its division, also known as the calibration factor. The unit is linear pixels in m. Analyze each selected field of view image individually. Remove background noise. Manually edit the material to confirm the two white areas that were raised and remove the artifacts. The edited image is converted into a binary image and the binary image is stored as a file. Select the area parameter from the optional menu and set the minimum number of pixels to be displayed to 4. Each binary image is analyzed to generate a list of numbers and stores this list of numbers ' Each number is a single ' white area feature. Use Microsoft® to sum the numbers in the column to generate the sum of the white areas of the field of view. Divide the total white area by the total area of a field of view and multiply by 1000 for the percentage of white areas of the field of view. Take 10 The average value of the white areas of the captured field of view finds the M1 standard white area. All files are stored on the optical magnetic disk. This determines the standard procedure for measuring the M1 standard white area. The Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperative, printed this invention The following examples are described, but these examples are used to illustrate and not to limit the scope of the present invention. Unless otherwise specified, all parts are weight parts and all percentages are weight percentages. Except for the examples of operation or some for labeling, all numbers representing quantities, proportions, ranges, etc. are shown here with the word "approximately". In the examples shown, they are _ can be traveled. _____ In the following examples, the amount of moisture (or volatility) is measured using a COMPUTRAC humidity analyzer model MA-5A. The 41 fossil evening paper scale applicable Chinese National Standard (CNS) A4 size (210 X 297 mm), / 55, / 55 A7

5. Description of the invention (39) The sample is heated to 165 ° C and maintained at this temperature until the weight of the sample does not change. The calculation of the moisture content weight percentage is: [(raw sample weight) _ (heated sample weight)] / (raw sample weight)]. The weight percent of solids is calculated as [100-moisture (or volatile) weight percent]. Example A hydrophilic granular amorphous deposited oxidized stone is produced by acidifying a sodium monosilicate solution with sulfuric acid. Most of the deposits were formed above 1) 11 value of 8 · 5. The acid addition is continued until the pH of the liquid reaches a level of 3.3 to 4.0 complete deposition. The resulting suspension of the first aqueous solution was filtered and the filter cake was washed until the washed water exhibited a conductivity in the range of 300 to 800 microohms. The liquefied part of the filter block was liquefied, and a high-shear agitator was used to form a hydrophilic granular amorphous deposited secondary solution suspension of silicon oxide. The suspension contained 12.6% solids. A centrifugal disc sprayer was used to spray-dry this secondary solution suspension to a humidity of 5.7% to form hydrophilic granular amorphous precipitated oxidized dream powder. The powder had a surface area of 159 m2 / gBET. The other part of the above-mentioned cleaned filter block uses a high-shear agitator to form a hydrophilic granular amorphous precipitated oxide secondary solution suspension. The suspension contains 10% . Add 16 kg of the three-solution suspension to a suitable container and stir. Isopropanol (8 kg) and hexamethyldisilazane (0.368 kg) were continuously added to the stirred suspension. The pH of the obtained reaction mixture was adjusted to 0.5 by adding 95% sulfuric acid. The reaction mixture was heated to 73X: and maintained at this temperature for 2.2 hours. After the reaction mixture was cooled to 60 ° C, cyclohexane (8 kg) was added. Then roughly stir the paper size to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page), and install ----- = ---- order ------- 丨 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 42 500755 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (40) The reaction mixture makes hydrophobic particulate amorphous deposits oxidize. The phase of silicon shifts to the cyclohedral phase without causing the formation of an emulsion. The solution phase was removed. The organic phase containing the hydrophobic deposited silica was washed many times with a dilute solution of sodium hydroxide until the washing water had a pH of 5.11. The slurry of lyophilized granular amorphous oxide oxide in cyclohexane was thinned with additional cyclohexane (34 g) and the slurry was allowed to flow out of the container. The container was washed with a ring (1.75 kg) to remove any remaining mud and the washing liquid was combined with the discharged mud. The slurry was filtered and the solid was washed with cyclohexane. The material to be cleaned was placed in a shallow pan and dried in an oven at 85 ° C until the residual volatiles dropped to about 5%. The obtained product is a hydrophobic granular amorphous deposited oxide stone, which is characterized by a surface area of 128 m2 / g BET, stone alcohol of 11.90 H / nm2, carbon of 1.43% by weight, and a pH value of 3.4. The test method for the wettability of the hydrophobic granular amorphous deposited oxidized alcohol is to add 15 ml of 50% by weight of methanol (HPLC grade) and deionized water to a 50 ml conical shape containing 2.0 g of the material. Centrifuge tube. The scale unit of the centrifuge tube to 10 ml is 0.51111 and the scale unit of 10 to 501111 is 1 ml. The contents of the tube were shaken for 15 seconds and centrifuged at room temperature (23-25 ° C) for 15 minutes in a hanging barrel centrifuge at about 4,000 rpin. Carefully remove the centrifuge tube to prevent the sediment from resuspending. All hydrophobic silicas are wet, i.e. the sediment, whose volume is measured in the foregoing steps using a mixture of three different concentrations of I alcohol / water as listed in Table 1 in the previous steps to measure the hydrophobic oxidation of the wetting example. The amount of methanol required for the volume of silicon. In the test examples, two groups A and B are different. Different paper sizes are applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). 43 ------------- Loading -----! ---- Order -------- • Line (Please read the precautions on the back before filling this page) A7 V. Description of the invention (41) The volume percentage of the hydrophobic inorganic oxide wetted by diol The calculation is based on the traumatic injury; the volume of the UC-based inorganic oxide divided by the volume of the completely Runxi hydrophobic inorganic oxide and then multiplied by the rigidity. The result obtained is expressed as a graph of the percentage of wet volume versus the weight of methanol The methanol concentration when 50% of the hydrophobic inorganic oxides in Examples A and B were wetted was calculated from the linear equation, and the average value was 31%. Table 1 Weight percent methanol 26.2 31.8 35.2 (Please read the back first (Notes to fill in this page again) Sample A percentage Sample B percentage M Wet wet 5 2 53 50 87 93 The percentage of sample carbon of the hydrophobic inorganic oxide of this example was tested 3 times using the steps described herein. The average weight percentage of carbon before extraction is 1.32. Another sample of the example material was extracted using the soxheh extraction procedure described herein. The analysis of the carbon percentage was performed 3 times and the average weight percentage after extraction was 1.41% Be The percentage of carbon taken is minimal and within experimental error. The percentage of extracted carbon is usually calculated using the following formula: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (the percentage of carbon before extraction)-(carbon after extraction) (% Of carbon before extraction) Test the Ml standard white area of hydrophobic particulate amorphous deposited silica. The white area of 10 areas, the Ml standard white area (ie, the middle term) and the standard deviation are shown in Table 2. : Table 2 44 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 500755 A7

Installation --- (Please read the precautions on the back before filling out this page) The raw material for the binding thread is separated from the mill and spread out on a clean surface during the implementation of the M1 standard white area steps. It is used To make specimens for other physical tests. Thin specimens are used for compression deformation tests and thick specimens are used for hardness and rebound tests. Two specimens are made from this unvulcanized rubber material. Thin specimens were cured at 15 ° C for 20 minutes, while thick specimens were cured at 150 ° C. (: 30 minutes for intermediate curing. The difference in curing time is to adjust the difference in mold lag time. The curing behavior and curing characteristics of this composition are shown in Table 3. Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 45 This paper applies to China National Standard (CNS) A4 Specification (210 X 297 mm) 500755 A7 _B7_ V. Description of Invention (43) Table 3 Curing Behavior and Curing Characteristics Ammeter (150 ° C) Maximum Torque, dNm Minimum Torque, dNm 5 Torque D 50, minute compression / deformation tensile strength, MPa elongation at break,% 100% factor, Mpa 300% factor Hardness pillar A, 23 ° C pillar A, 100 ° C rebound 100 ° C,% 30.6 3.3 27.3 5.8 19.6 635 2.5 8.3 70 68 66.0 Force and force characteristics ΠΗζ, 2.0% deformation) G 'at 60 ° C, Mpa 3.73 Tan (5 at 60 ° C 0.127 Tan 5 at 0 ° C 0.202 Ml white area, area% 0.03 (please first (Please read the notes on the back and fill in this page.) | Installation ----- „---- Order ------ The rubber formula used in the implementation of printed clothing for employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs and The standard procedure for measuring the M1 standard white area is described as Similarly, the Ml white area of the cured rubber composition is the same as the Ml standard white area used to produce the hydrophobic amorphous silica deposited in the vulcanized rubber composition. The value of 0.03% M1 white area shows The amorphous silica deposited in the cured rubber composition has a high dispersibility. Although the present invention has proposed specific details for certain specific embodiments, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297) (Centi) · 46-500 755 A7 ___B7_ 5. The description of the invention (44) is not a limitation of the present invention, as long as it is included in the scope of the attached patent application, it belongs to the present invention. -------- ----- Installation—— (Please read the precautions on the back before filling this page) --Line-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 47 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

500755 Λ8 BS CS DS, patent application scope 1. A method for manufacturing hydrophobic particulate inorganic oxide, which is optionally in the presence of a surfactant and / or a solvent miscible with water Next, an acidic aqueous suspension of a particulate inorganic oxide selected from the group consisting of deposited silica, colloidal silica, and a mixture of these 4 inorganic oxides is contacted with an organometallic compound, To form an acidic aqueous suspension of a hydrophobic particulate inorganic oxide and recover the hydrophobic particulate inorganic oxide, an improvement of the method includes using the organometallic compound in an amount sufficient to hydrophobize the inorganic oxide. So that in an inorganic oxide suspension having a pH value of 2.5 or lower, the inorganic oxide has a hydroxyl content of 2 to 15 OH / nm2, and 0 to 6 wt%. Carbon content, and a methanol wettability of 15 to 45%, and the acidic aqueous suspension of the hydrophobic particulate inorganic oxide was treated with an acid neutralizer to produce a product having a content of 3 to 10 Hydrophobic particulate inorganic oxide with a pH value, a substantially unextractable carbon content, and a Ml standard white area below 0.4%. 2. The method according to item 1 of the scope of patent application, wherein the organometallic substance is selected from the group consisting of: The first organometallic compound represented by the following formula: RiaMX "is represented by the following formula The second organometallic compound: R22n + 2SinOn-i The third organometallic compound represented by the following formula: (R33Si) kNR53.k This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297) --------- 9 I Γ · II (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 48 刈 0755 AS BS C8 DS Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the scope of patent application, and the fourth organic metal compound represented by the following formula: R 2mSimOm where: (a) each M is individually Shi Xi, Titanium or wrong; (b) Each R1 is individually a hydrocarbon group having no ethylenic unsaturation and containing 1 to 8 carbon atoms; (c) each X series is individually a halide group, an amine group, and an alkane containing 1 to 12 carbon atoms Oxygen or fluorenyloxy containing 12 to 12 carbon atoms; (d) a is BU 2 Or 3; each R2 is a halogen group, a hydroxyl group, or a hydrocarbon group having 1 to 18 carbon atoms without ethylenic unsaturation, but at least 50 mole percent of the R2 substituent is the hydrocarbon group (F) n is from 2 to 10,000; (g) each R3 is individually a halogen group, a hydroxyl group, or a hydrocarbon group having 1 to 18 carbon atoms without ethylenic unsaturation, However, at least 50 mole percent of the R3 substituent is the hydrocarbon group; each R5 is individually hydrogen or a hydrocarbon group without ethylenic unsaturation and containing 1 to 18 carbon atoms; (i) k is 1 Or 2; ⑴ each R4 is an alkyl group having no ethylenic unsaturation and containing 1 to 18 carbon atoms; and (k) m is 3 to 20. 3. If the method of the first item of the scope of patent application, Wherein the inorganic oxide is a deposited silicon oxide. 4. The method according to item 2 of the scope of patent application, wherein μ is silicon and X is an alkoxy or halogen group having 1 to 4 carbon atoms. 5. If a patent is applied The method of the fourth item, wherein X is a gas or a methoxy group. 6. The patent is requested in item II3 ^ Zuo Qishen i The hydrophobized silicon has a hydroxyl content of 4-12 OH / nm2 One is a carbon content of 0.3 to 3% by weight and one M1 standard white area below 0.25%. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) ---- I ---- ---- i IIIIII β — — — — — — (Please read the precautions on the back before filling out this page) 49 500755 Application for Patent Scope 7 · If the method of applying for the scope of patent No.6, 1 person from ΛΛ A 35 of the organic gold compound used in "i" is a carbon atom that provides 3 to 40 pmole per square meter of oxygen cut. 8. The method according to item 7 of the application, wherein the organometallic compound is hexamethyldisilazane. 9. The method of claim 6 in the scope of patent application, wherein the organometallic compound is selected from the group consisting of: R, Mx4.a, wherein each of the 1s is a non-rare and non-existent sum and contains ⑴ Carbon atom hydrocarbon group, XU prime group or-hydroxy group containing m carbon atom, and a is 1, 2 or 3.如 As the oldest method in the scope of patent application, wherein the hydrophobic particulate oxide-free recovery is completed by the following steps: an organic solvent that is immiscible with water and the hydrophobic particulate inorganic oxide The aqueous suspension liquid phase is mixed, and the weight ratio of the solvent to the inorganic oxide is greater than 5: 1, whereby the hydrophobic inorganic oxide is transferred from the aqueous solution phase of the mixture to the organic solvent phase. 11. The method according to claim 10, wherein the water-immiscible organic solvent is selected from the group consisting of aliphatic hydrocarbons, naphthenes, aromatic hydrocarbons, and ketones. The method of item 1, in which the non-water-miscible non-water-soluble dancers 丨 you move to hexane, heptane, toluene, cyclohexane, and methyl isobutyl class β 13. If the method of the first item of the patent application, Among them, there is X 297 mm that is not miscible with water.) This paper size_Medium @National Standard (CNS) A4 Specification ⑵0 Co-solvent for claiming patent scope machine. κ The method according to item 13 of the patent application range, wherein the organic co-solvent which is miscible with water is selected from tetrahydrofuran and cetanol. 15. The method according to item 1 of the application, wherein the aqueous suspension of the particulate inorganic oxide is wet-milled before being contacted with the organometallic compound. For example, the method of claim No. 10 of the patent scope, wherein the aqueous suspension of the hydrophobic particulate inorganic oxide is wet-milled before being mixed with an organic solvent that is not miscible with water. 17. The method of claim 10, wherein the organic solvent phase containing the hydrophobic particulate inorganic oxide is wet-milled. Packing -------- Order · Please read the precautions on the back before filling out this page) i-line. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 51 This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm)