TW500753B - Hydrophobic particulate inorganic oxides and polymeric compositions containing same - Google Patents

Abstract

Described are hydrophobia particulate inorganic oxides useful for reinforcing polymeric composition, e.g., rubber. The materials are characterized by: (a) the substantial absence of functional groups capable of chemical reaction with rubber; (b) a BET surface area of in the range of from 40 to 350 m<SP>2</SP>/g; (c) a hydroxyl content in the range of 2 to 15 OH/nm<SP>2</SP>; (d) a carbon content in the range of from 0.1 to 6 percent by weight that is substantially non-extractable; (e) a pH in the range of from 3 to 10; (f) an M1 standard white area less than 0.4 percent and (g) a methanol wettability of from 15 to 45 percent. Compositions such as polymers, cured organic rubber articles, master batches and slurries containing the hydrophobic fillers are also described.

Description

Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of Invention (1) Cross-participants in the relevant application This application claims the rights of the following cases: US Provisional Application No. 60/203, No. 442, please request Date: May 10, 2000; No. 60/1 56,861, application date: September 30, 1999; and No. 60 / 149,755, application date: August 19, 1999. Particulate inorganic oxides such as precipitated silica are increasingly used as reinforcing fillers for hardened rubber compositions, particularly tire treads. The rubber composition needs to be reinforced to provide acceptable mechanical properties to the hardened rubber composition. The problem with the use of particulate inorganic oxides in the hardened rubber composition is that the resolving power of the hardened rubber is relatively low 'because the percentage of the white area in the field of the optical microscope is quite large. It is better to disperse or grind the inorganic oxide before forming the hardened rubber composition to obtain better dispersion, so there are fewer white areas in the field of view of the optical microscope, but once it has been substantially improved, continue to roll or grind, and it will not be able to obtain dispersion even for a long time. The degree of further improvement. U.S. Patent No. 5,908,660 discloses hydrophobic amorphous precipitated silica as a reinforcing and incremental filler for natural rubber and polysilicone rubber. The description of the patent case No. (1) The hydrophobic granular amorphous silica is prepared from the hydrophilic amorphous precipitated silica by the "explosion" method, in which the aqueous suspension of the hydrophilic granular amorphous precipitated silica is exposed to the catalytic amount. Acid and organic silicon compound to form a hydrophobic granular amorphous precipitated silica suspension, and then the hydrophobic granular amorphous precipitated silica suspension is contacted with a water-immiscible organic solvent to remove the hydrophobic granular amorphous precipitated silica from the liquid state. The aqueous phase is transferred to the liquid organic phase; (2) the amount of the organic silicon compound added to the aqueous phase is sufficient to produce a hydrophobic granular amorphous silicon oxide suitable for its intended use; (3) the organic silicon compound is usually added to this paper on a paper scale Chinese National Standard (CNS) A4 Specification (21G χ 297 Meals) --- "· 4 · __--- -------- 1 -------- r --- ^- ----------% »--- (Please read the notes on the back before filling this page) juvj / 33 A7

Please read the precautions on the back of S before filling in this page k 500753 A7 I _ — B7 _ V. Description of the invention (3) '' — 'Hydrophilic granular aluminum oxide and its mixture of aluminum oxide and its mixture -An organometallic reactant is selected from the _ organometallized character represented by the following formula: 〇 The second organometallic compound represented by the following formula: R22n + 2Sinon_i The third organometallic compound represented by the following formula: (R33Si) kNR \ k A fourth organometallic compound represented by the formula: a group consisting of R42mSim〇m and mixtures thereof, where (a) each is silicon, titanium, hafnium, or hafnium; (b) each R1 contains 1 to 18 carbons Atoms without olefinic unsaturation (such as saturated aliphatic, cycloaliphatic, or aromatic unsaturated hydrocarbon groups); (C) each X is a _ atom, an amine group, an alkane containing from 12 to 12 carbon atoms Oxy or fluorenyloxy containing 1 to 12 carbon atoms; (d) a is 丨, 2 or 3; (e) each R2 is a halogen atom, hydroxyl or non-olefinic containing 1 to 18 carbon atoms Unsaturated (as described for R1) hydrocarbyl, but at least 50% mole ratio ... The substituent is free of rare unsaturated (F) n is 2 to 〇〇〇〇〇〇; (g) each R3 is a halogen atom, a hydroxyl group or a hydrocarbon group containing 1 to 18 carbon atoms without olefinic unsaturation (such as for R1 (Mentioned), but at least 50% of the molar ratio r3 substituents are hydrocarbon groups without olefinic unsaturation; (h) each R5 is hydrogen or contains i to 18 carbon atoms without olefinic unsaturation (I) k is 1 or 2; (j) each R4 is a hydrocarbon group containing 1 to 18 carbon atoms without olefinic unsaturation (as described for R1) And (k) m is a number from 3 to 20; This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) • Order --- ------ Line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 500 753 A7 B7 White area less than 0.4% Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the invention (4) The hydrophobic granular inorganic oxide is characterized by the standard. The hydrophobic granular inorganic oxide of the present invention is also characterized by methanol thirstability of 15 to 45%, which is better than ㈣ to 4G% and better 25 to 35%: or methanol wettability can be in any combination of these values (including quoted values). The further characteristics of the hydrophobic particulate inorganic oxide of the present invention are 1 to 3 to 10, preferably 4 to 8, more preferably 5 to 7.5, and most preferably 6 to 7, or any combination of the product pH (including the quoted range) such as pH 3 to 7.5. As used herein, for the aforementioned organometallic compounds, halogen The term atom includes fluorine, chlorine, bromine, and iodine, and is preferably chlorine. The term "unsaturated" means that it is substantially free of olefinic unsaturation because some sources of hydrocarbon groups or processes may result in the presence of small amounts of hydrocarbon groups. The amount of ethylenic unsaturation. For the purpose of the present invention, when the organometallic reactant is an organosilicon reactant, silicon is regarded as a metal. The hydrophilic granular precipitated silica that can be used to make the hydrophobic precipitated silica of the present invention is Known and available on the market. Hydrophilic granular amorphous Shen Dianshi Oxygen production method and productive benzyl chloride are described in U.S. Patent Nos. 2,6 5 7,14 9; 2,940,830 '4,132,806, 4,495,167, 4,681,750 and 5,094,829. Hydrophilic granular amorphous precipitated silicon oxygen. Common commercial production methods It is produced by combining soluble metal silicate aqueous solution, usually alkali metal silicates such as sodium silicate and acid 'against the weak alkaline solution to produce colloidal particles and coagulate from alkali metal ions of the obtained soluble test metal salt. Various acids can be used Including inorganic acids such as sulfuric acid and hydrochloric acid. Carbonic acid, such as carbon dioxide, can also be used to inflate the soluble gold paper to the size of China National Standard (CNS) A4 (210 X 297 mm) ------------- Packing ---- l · --- Order · (Please read the precautions on the back before filling in this page) 5. The A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the invention description (is a silicate aqueous solution. Yu Wu Ning ·

Precipitation from solution. It is a combination of salt and cocoa that will not be produced during the formation of any pH particles. "Adding salt and forming an amorphous sinker in situ during the sinking process can be colloidal amorphous. The final particle aggregates: the aggregate does not appear to be a giant at any point in its preparation. ♦ Collective size And the degree of hydration can vary widely. Hydrophilic granular aluminum oxides which can be used to make the hydrophobic granular aluminum oxides of the present invention are also known and commercially available. The method for making them is also known. Hydrophilic granular aluminum oxide can be crystalline It may be substantially amorphous. The particle size and hydration degree may vary widely. Hydrophilic granular oxygen includes, but is not limited to, gibbsite 'Bayerite', Bayomatite (⑹⑽⑷False wave) Buying stone (pseudoboehmhe), diaspore and nordstrandite. Preferred hydrophilic granular alumina is false wave buying stone, which is occasionally called alumina gel. The main thing of false wave buying stone is The components can be obtained, for example, as follows: (1) precipitation from a soluble aluminum salt using ammonia, (2) hydrolysis of a trialkane alumina, or (3) hydrolysis of the trialk alumina followed by adenogenesis to form a sol, and then the sol forms a gel. . Fake wave buy stone has Wave-like stone buying structure. But the X-ray diffraction pattern is composed of extreme diffusion bands or haloes. The wide reflection interval is approximately equivalent to the main line interval of the crystal wave buying stone pattern, but the first reflection often shows perceptually ectopic Values up to 0.66 to 0.67 nanometers, compared to Pomexite 〇〇２〇wire 0n This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

--- (Please read the notes on the back before filling this page) Order --------- line ...

V. Description of the invention (6 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to print nanometers for reflection. It has been suggested that although the fake wave f stone structure is similar to the wave buy stone in some aspects, but its order is only in a very small range and belongs to the molecule or gel. Intragranular properties. Refer to HP Rooksby "Aluminum and Iron Oxides and Hydroxides", Drum Identification and Crystal Formation, edited by G. Brown, Institute of Mineralogy, London (1961), pages 354-661 including figure X "and Figure χ · 2. The manufacturing method of false wave buying stone is described in, for example, U.S. Patent No. 5,88〇, 196; PCT International Application No. WO 97/22476; Be. Yóldas, Rev. Gazette, Vol. 54 No. Third issue (March 1975), pages 289-290; Beta · E. Yoldas, Applied Chemical Biotechnology, Vol. 23 (1973), pages 803-809; Beta · E · Yoldas, Journal of Technical Materials Science No. 10 (1975), pages 1856-1860 and the research work quoted above HP ROOksby. As for the organometallic compounds, each of R1 and R4 contains 1 to 18 carbon atoms and contains no ethylenic unsaturation. Degree hydrocarbon group such as CrCi8 alkyl group. Often each R and each R each contain one to 12 carbon atoms Often 1 to 10 carbon atoms, especially 1 to 8 carbon atoms, and more particularly 1 to 6 carbon atoms. In many cases, each of R1 and R4 contains 1 to 4 carbon atoms, respectively. Preferably, 1 ^ 1 and Each R4 is a methyl group or an ethyl group. Each R and each R is a saturated or aromatic unsaturated monovalent hydrocarbon group containing 1 to 18 carbon atoms. Each R1 and each R4 may be free of ethylenic unsaturation. Degree of substituted or unsubstituted monovalent hydrocarbon group. Hydrocarbon groups suitably free of ethylenic unsaturation include, for example, alkyl groups such as methyl'ethyl'propyl, isopropyl, butyl, isobutyl-yl-y- Tertiary butyl and ethyl, heptyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl; substituted alkyls include _alkyls such as azido, Fluoropropyl and 6-hexahexyl; Cycloalkyls include, for example, ring paper sizes applicable to China National Standard (CNS) A4 (210 X 297 mm) 9 -------------- Install -----: ---- Order --------- line <Please read the notes on the back before filling this page) A7 B7 V. Description of the invention (7) Hexyl and cyclooctyl; Alkyl includes phenyl and naphthyl; and alkylaryl such as c, C4 alkylaryl and Alkyl groups such as aryl (Ci-C4) alkyl groups include, for example, tolyl 'ethylbenzyl' benzyl and alkyl substituted naphthyl groups such as Crc4 alkyl substituted naphthyl. Each X is independently selected from the group consisting of a halogen atom, an amine group, and contains 1 A group consisting of 2 carbon atoms to i, preferably 1 to 4 carbon atoms, and 1 to 4 carbon atoms. The group consisting of fluorene groups containing 1 to 12 carbon atoms is preferred. When X is a _ atom, it is preferably gas. When X is In the case of alkoxy, X is preferably, for example, methoxy, ethoxy or propoxy. Preferably, each x is chlorine or fluorenyloxy, respectively. When X is fluorenyloxy it is often ethynyloxy. Each R2 is selected from the group consisting of a halogen atom, a hydroxyl group, and a hydrocarbon group containing i to 18 carbon atoms without olefinic unsaturation, and is specified to be at least 5000 /. Morbihan 2 substituents are hydrocarbon groups that do not contain ethylenic unsaturation. R2 can be the same as ... and Han 4. The viscosity of such organosiloxanes is not particularly limited and can range from fluid viscosity to gum viscosity. Generally, higher molecular weight organosiloxanes can be cleaved by acidic conditions, and hydrophobic granular amorphous precipitated silicas are prepared under the acidic conditions, so that they can eventually react with hydrophilic inorganic oxides. Each R3 is selected from the group consisting of chlorine, a hydrocarbon group containing from 1 to 18 carbon atoms, and no unsaturation, but at least 50% of the molar ratio r3 substituent is a hydrocarbon group. When R3 is a hydrocarbon group, it may be the same as or different from the hydrocarbon group described in Para. Preferably R3 is methyl or ethyl. Each R5 is selected from the group consisting of hydrogen and a hydrocarbon group containing 1 to 18, preferably 1 to 8, more preferably 1 to 4 carbon atoms, and no olefinic unsaturation. Preferred RS is nitrogen, methyl or ethyl. The m value is 3 to 20. Often the value of m is 3 to 8, especially 3 to 7 and better. It is -------- 1 ------- l · --- order --------- line Φ (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10.500753 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Inventory Note (8) 3 or 4 〇 Can be used as Useful organosilicon compounds of organometallic compounds include, but are not limited to, fluorenyltrifluorosilane, dimethyldichlorosilane, trimethylsilane, diethyldisilane, methylphenyldisiloxane, phenyl Ethyl monoethoxylate, 3,3,3 · difluoropropylmethyl dipyridite, trimethylbutyrate, pentylpyroxylate, hexamethyl Ershixoxan, hexaethyldioxane, mesityl-tetramethyldisilazane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, hexamethyldisilazine Alkane, cyclosiloxanes containing 3 to 20 dimethylsiloxy units, and trimethylsiloxy with a nominal viscosity of 25 ° C in the range of 1 to 1,000 mPa · s or Hydroxydifluorenyl siloxy terminal polysaccharide Silicon methyl siloxane) polymer. The preferred organosilicon compounds are trimethylgasparite, dimethyldiagassilane and hexamethyldisilaxane. Useful organotitanium compounds include, for example, but are not limited to tetrakis (Ci_Cy alkoxytitanates, methyltriethoxytitanium (iv), triisopropyloxytitanium oxide (丨 ..., tributylmethyltitanium oxide (iv) , Titanium tert-butyl butoxide (iv), Tributyl titanium isopropoxide (iv), Titanium triethoxylate (0ν), Titanium tributyl oxide (IV), Triisopropyl benzene oxide Titanium (iv), Tributylphenyl oxide, Triisobutylphenyl oxide (iv), [Ti (CH2Ph) 3 (NC5H1G)] and [Ti (CH2SiMe3) 2 (NEt2) 2] Useful organic zirconium compounds Examples include, but are not limited to, tetra (CVCi8) alkoxylates, tri-gasified phenyl (iv), tri-gasified methyl (iv), tri-chloro-charged ethylene-monofluorene (iv), trichloride Propylamidine (iv), methyl bromide and dodecyl bromide ethylammonium (iv), propyl bromide (iv), chlorotripentyl ammonium (iv). It is also expected to contain similar to the above for organic Titanium compound wrong compound, reverse -------------- install --- (Please read the precautions on the back before filling this page) Order: i-line-III · This paper Standards are applicable to the Zhongguanjia Standard (CNS) A4 specification (⑵〇χ 297). 11 500 753 V. Description Ming (9) or vice versa. The hydrophobic particulate inorganic oxide of the present invention is characterized in that the standard white area is less than 0.4%, for example, less than 0.35%. Often the standard white area is smaller than 0. For example, less than 0.25%. Often, M1 standard white area is less than 0.2%, preferably less than. 'The relatively low value obtained for the Mi standard white zone of the hydrophobic particulate inorganic oxide of the present invention indicates that the material has an unexpectedly high dispersion in the hardened rubber composition. The standard white zone is determined using standard protocols and standard hardened organic rubber formulations, which will be described in detail later. Because the scheme and formula are standardized, the M! Standard white area is suitable for the properties of hydrophobic particulate inorganic oxides. The standard measurement scheme of the M1 standard white area according to the present invention is different from the standard measurement scheme of the standard white area according to the disclosure of mg, ⑼ and US 5,888,467. The main differences are (1) the standard hardened rubber compound is prepared from two polymer master batches, each of which is recovered from a water-immiscible solvent containing one of two standard polymers, namely hydrophobic inorganic oxides and aromatic processing Oil; (the magic mixing cycle is shortened to pass twice, each time is shorter; and (3) a mixer is used to prepare a mixer for CW Brabender and a # K〇belc〇Stewan Bolling model "00" internal mixer. Economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau. Another specific embodiment of the present invention is a hydrophobic granular inorganic oxide, which is a reaction product of a hydrophilic inorganic oxide and at least one organometallic reactant. The hydrophilic inorganic oxide is selected A group consisting of hydrophilic granular amorphous precipitated silica, hydrophilic granular aluminum oxide, and mixtures thereof; and an organometallic-reactant system selected from the aforementioned first organometallic compound, second organometallic compound, and second organometallic compound The fourth organometallic compound and its mixture 12 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) V. Invention Explain the group consisting of () compounds, in which the characteristics of hydrophobic granular inorganic oxides are (a) they do not contain functional groups that can react with rubber chemically; (b) the content of the radical is between 2 and 15; The range of square nanometers; and the standard white area of ⑷M1 is less than 0-4%. The fluorene group content of the hydrophobic particulate inorganic oxide of the specific embodiment of the present invention is usually 3 to 14 hydroxyl / square nanometer; preferably 4 to 12 hydroxyl / square nanometer range. The hydrophobic particulate inorganic oxide of the present invention is also characterized by methanol wettability of at least 15%, preferably 20% and more preferably 25%. Generally, methanol wettability is less than 45%, preferably less than 40% and better less than 35%. The methanol wettability can be any combination of the foregoing values (including the quoted range). The methanol wettability is the methanol concentration (percentage of weight) required to wet 50% of the hydrophobic inorganic oxides. 50% of the amount of methanol needed for wetting is suspended and 50% is precipitated). Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives The methanol wettability value is determined by first determining the amount of 50% by weight wet inorganic hydrophobic oxide used. The measurement method is to add a 2.0 g sample to a 50 ml conical centrifuge tube containing 15 ml of a 50% by weight methanol (甲醇 ρχχ grade) mixture with deionized water. Centrifuge tubes are marked with a 0.5-liter day scale to a height of 10 ml, and a 10-ml scale is used for a rise of 10 to 50 ml. Shake the contents for 15 seconds and centrifuge in a bucket centrifuge at room temperature (23-25 ° C) for 15 minutes at about 4,000 revolutions per minute (rpm). Remove the centrifuge tube and handle it carefully to prevent the pellet from resuspending. Record the amount of wetted inorganic oxide, i.e., the sediment that formed the sediment, to the nearest 0.5 ml. Subsequently, a series of at least three different methanol / water mixture concentrations were tested. The 4 ° test method was determined to cause hydrophobic inorganic oxides of 50 and 100. / 〇 Wet 13 This paper size applies the Zhongguanjia Standard (CNS) A4 specification (21G X 297 public love) 500753 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (11) / 闰 Alcohol concentration. The preferred concentration includes at least one concentration higher than and less than ≧ 20 ° C, which is required to cause 50% of the hydrophobic inorganic oxide to be wetted. The concentration for remote use is determined by the wetness of 50% by weight of aqueous methanol, which is in the range of 5 to 95% by weight of methanol, and is increased by 5% by weight. For example, if all hydrophobic inorganic oxides are wetted with 50% by weight of methanol, then a methanol concentration of 5 to 45% is tested. The calculation method of the percentage of hydrophobic inorganic oxides wetted by different methanol / methanol is calculated by dividing the volume of moistened hydrophobic inorganic oxides by the volume of fully wetted hydrophobic inorganic oxides by 100. The results were plotted as a line graph of percent wetness versus methanol concentration and fitted lines. The linear equation determines the methanol concentration at which 50% of the hydrophobic inorganic oxide is wetted. As used in this specification and the scope of patent application, the alcohol content of the hydrophobic granular amorphous Shendian Stone Xixian Shixianyuan is determined according to one of the following two methods. When the carbon-to-stone mullite ratio of organic stone yaki for hydrophobic treatment is known and no stone yoshino alcohol from organic stone yoshino is used, ATuel et al., Lanqmn; r, 6th, 77.775 p.100). This method combines unreacted Shixiyuan alcohol content with the carbon content of the sample and the elemental analysis of the sample of the hydrophobic amorphous immersion oxygen sample. When the carbon-to-stone mullite ratio of the organic stone xiyuan used for hydrophobic treatment is unknown or poorly defined, use gas exchange methods such as G. Fotl et al., No. 5, pp. 232-239 (1989) As described. These two methods are known to provide approximately equal values for the silanol content of samples to which both methods are applicable. The meridian that exists on the surface of Ming oxygen can be operated in transmission mode by using Fourier transform infrared spectroscopy, such as the NieGlet 73G spectrometer. It is a Chinese standard (CNS) A4 specification. x _ ------------ i 丨 —.ί-- 丨 丨 Order ----- 丨 ί · Line (Please read the precautions on the back before filling this page) 14 A7 B7- ----—--- For example, Unbhd, M. and R00t, A · “Atom Controlled Preparation of Silicon Oxygen to Aluminum Oxide”, Surface Science and Catalysis Research, “Preparation of Catalysts vn, 7th International Heterogeneity Proceedings of the Symposium on the Basics of Catalyst Preparation, Louvain-la-Neuve, Belgium, September 1-4, 1998 ", edited by Delmon B et al., No. 118: Elsevier Science Press, 1998, Amsterdam. The carbon content of the hydrophobic particulate inorganic oxide in this embodiment of the present invention is in the range of 0.1 to 6% by weight, for example, 0.2 to 5% by weight. A carbon content of 0.3 to 3 or 4% by weight is preferred. For the purposes of this specification and patent applications, the carbon content of hydrophobic particulate inorganic oxides is determined by modified techniques based on traditional pregal and Dumas methods. The sample (丨 to 2 mg) was sealed in a light-weight tin bladder. It was placed in a quartz tube and maintained at 1040. The quartz tube passed a steady flow of helium. After the introduction of the sample, the helium stream was enriched with oxygen and allowed to flash, and was primed with a tin oxide capsule. The gas mixture is burned quantitatively by chromium oxide (Cl &gt; 203). The combustion gas then removes excess oxygen through copper at 650 ° C, reducing the button oxide to become a button. The gas was then passed through a 100 ° C 2 Porpak QS chromatography column. The components are then separated and dissolved into nitrogen, carbon dioxide and water. The instrument is calibrated by burning standard compounds. The carbon content of the hydrophobic inorganic oxide of the present invention is substantially unextractable, that is, at least 80 ° / ◦ after the extraction process, preferably at least 85%, more than 90%, and at least 93% of the carbon on the inorganic oxide remains in the inorganic Oxide. The extraction capacity of the carbon content of the hydrophobic inorganic oxide was measured by the following method. The percentage of carbon in partially hydrophobic particulate inorganic oxides was determined using the procedure described herein prior to extraction. The extraction method is to add 5 to 15 grams of succinate. 5. Description of the invention (丨 2)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-------------- Installation—— Please read the precautions on the reverse side before filling out this page) Η ^ τ_ The size of thread paper is applicable to China National Standard (CNS) A4 (210 X 297) 15 MJ0753 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13) Water granular inorganic oxide to 4 3 mm X 12 3 mm (inner diameter x outer length) cellulose extraction sleeve, The cannula was placed in a roughly sized Soxhlet extractor and fitted with a condenser. This Soxley extractor and condenser system was attached to a round bottom flask containing 700 ml of toluene. The beaker was heated to the reflux temperature of toluene. After refluxing for at least 15 hours, the used toluene was replaced with 700 ml of unused toluene, and refluxing was continued for at least another 15 hours. The resulting extracted inorganic oxide was recovered and dried until the sample was exposed to 1 and it showed a loss of about 1.0% by weight or less after 10 minutes. Determine the carbon percentage of the sample after extraction. The percentage of Soxley extractable carbon is determined using the following formula: [(% carbon before extraction) _ (% carbon after extraction)] / (.// carbon before extraction) x 100 The particulate inorganic oxide is preferably substantially free of functional groups that can chemically react with the rubber, at least during the mixing of the hydrophobic particulate inorganic oxide in the rubber compound composition or in a solution of one or more rubbers in a water-immiscible solvent. This is the case before the rubber in contact. There may be a trace amount of a functional group that can chemically react with rubber but it does not have a substantial effect ', but it is preferred that such a group does not exist at all.

The bet surface area of the hydrophobic particulate inorganic oxides of the specific embodiments of the present invention is usually, but not necessarily, 40 to 350 square meters per gram, preferably 60 to 20 square meters per square meter and more preferably 80 to 160. M / g range. As used in the scope of this specification and the patent application, the BET surface area of the hydrophobic particulate inorganic oxide is based on the method of Bnmauer, Emmett, Teller (BET) according to ASTM D 1993-91. Nitrogen is used as the adsorbent. The surface area was measured by degassing at ambient room temperature for 1 hour. Before the treatment makes the inorganic oxides hydrophobic, the size of the hydrophilic granular non-paper is subject to the Chinese National Standard (CNS) A4 (21〇x 297 meals) 16 --------: —iMW —l · —Order --------- Line Φ (Please read the notes on the back before filling this page)

500753 V. Description of the Invention (Η) The BET surface area of organic oxides is the surface area measured by the method of ASTM D 1993_91 using nitrogen as the adsorbed substance according to the method of ASTM D 1993_91 (Brunauer, E_ett, bet), but modified to the system and sample at 165 . 〇Outgassing 丨 hours. The bet surface area of the hydrophilic granular inorganic oxides used in this method is particularly limited. It is usually in the range of 50 square meters / gram to more than 1 square meter / gram; this method is more effective than When an oxide is used as an organic rubber composition as a reinforcing filler, the surface area is in the range of 250 m2 / g, preferably 100 to 200 m2 / g.

The pH of the hydrophobic particulate inorganic oxide of the various embodiments of the present invention is usually, but not necessarily, in the range of 3 to 10. For the purposes of this specification and the patent application, the pH of the hydrophobic particulate inorganic oxide is measured by the following procedure: 50 grams of particulate inorganic oxide (in powder form), 50 ml of isopropanol and 50 ml Ionized water was added to a 150 ml beaker containing magnetic tritium. The contents of the beaker are stirred up (not spilled) until the inorganic oxide is suspended. The calibrated anodes are placed in a fiercely suspended suspension! After 5 minutes (± 5 seconds), pΗ readings are recorded. Actually, the hydrophobic particulate inorganic oxide and the coupling agent (not covalently bonded to the inorganic oxide) representing specific embodiments of the present invention may exist in the rubber elastomer composition before hardening, or may exist in the rubber (or rubber) Solution) in a water-immiscible solvent, and the rubber master batch is then recovered and dried. As a result, the granular inorganic oxide of rat water in this month can be used as a coupling agent carrier, which is not covalently bonded with the inorganic oxide. Coupling agents covalently bonded to the hydrophobic particulate inorganic oxide may be present in the final hardened rubber. Examples of non-filament compounds before covalent bonding: There are many types of coupling agents for Shi Xioxi and are well known. Non-limiting examples of these couplers include: --------- Order --------- line (please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperative

This paper size is applicable to γ_Home Standard (CNS) A4_i grid ⑽χ 297 public love 753 A7

Γ t order

A7 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the invention (I6 particle size measurement is achieved by sieving. The particle size is reported by the standard sieve number of the American standard sieve series according to astem en 87. In most cases, the particle size is mainly in the range of] to 15 mm. Often the particle size is in the range of] to 10 millimeters, such as 2 to 7 millimeters. The preferred particles are substantially dust-free, that is, at least .99% by weight can be retained by a sieve (American sieve series). The present invention The coarse particles of the hydrophobic particulate inorganic oxide of any of the specific embodiments are preferably particles, for example, particles manufactured by the method and apparatus of U.S. Patent No. 4,80,719. Δ Through-dry particles are mixed with unhardened rubber In the composition, the coarse size is generally smaller than the size before the particles are mixed. The hydrophobic particulate inorganic oxide according to any embodiment of the present invention can be used in an aqueous and / or organic liquid slurry as described above. If powder For the production of aggregates, the intermediate particle size is as described for powders. The aggregates can be further reduced in size by wet milling. The average particle size of hydrophobic particulate inorganic oxides can be reduced to 5 by wet milling. micro- The average particle size of the hydrophobic particulate inorganic oxide after the wet milling is preferably less than 2 microns. The hydrophobic particulate inorganic oxide of the present invention can be produced by any method, and the method of obtaining the hydrophobic particulate inorganic oxide can be obtained by the method. Features are essentially free of functional groups that can react with rubber, hydroxyl content of 2 to 15 hydroxyl per square nanometer, carbon content of 0 "to 6% by weight, methanol wettability of 15 to 45 /. And Ml standard The white area is less than 0.4%. The hydrophobic inorganic oxide of the present invention is also characterized by a carbon content that is substantially non-extractable; a pH of 3 to 10 and a bet surface area of 40 to 350 m2 / g. The hydrophobic granular inorganic of the present invention The oxide can be used in US Patent Nos. 5,908,660 and 5,919,298 (the disclosures of which are described herein for reference) and the paper size applicable to the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) (please read the note on the back first) Please fill in this page again) 19 500753 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (17) Separate step A or steps A and B for the preparation of hydrophobic silica and smoked silica, but there are The amount of acid causes the pH of the aqueous suspension to be 2.5 or below ', preferably pH 2.0 or below, and more preferably pH 1.0 or below, and optimal pH 0-5 or below; used in organically hydrophobizing inorganic oxides Metal compounds are used to obtain hydrophobic inorganic oxides with a hydroxyl content of 2-15 hydroxyl per square nanometer, a carbon content of 0.1 to 6% by weight and a methanol wettability of 15 to 45%; and after the hydrophobicization is completed, the acidity (Adding acidity or acidity generated in situ by hydrolysis of halogenated organometallic compounds) is neutralized to produce a hydrophobic inorganic oxide with a pH of 3 to 10, a carbon content of substantially non-extractable and a mi standard white area of less than 0.4%. Typically when the hydrophobic inorganic oxide is recovered after step A alone, the pH of the aqueous suspension obtained is increased to 3 or more, preferably 4 or more, more preferably 5 or more and most preferably 6 or more, and usually 1 〇 or less, preferably 9 or less, more preferably 8 or less and most preferably 7 or less. The pH of the aqueous suspension can be any combination of these levels (including the level of quotation). The neutralizing agent may be any type commonly used to raise the pH of an acidic solution, as long as the properties of the modified filler are not adversely affected. Suitable neutralizing agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide and sodium bicarbonate. Neutralization of the modified filler can also be achieved by adding aqueous ammonia to the aqueous solution during spray drying. When using step B to recover the hydrophobic inorganic oxide in a water-immiscible solvent, 1) 1_1 of the hydrophobic inorganic oxide can be raised to pH 3 by washing with a diluted aqueous neutralizing agent until the 13 ^ 1 of the washing water is 30 or more. 0 or higher. More specifically, the method comprises: (A) Aqueous suspension of hydrophilic granular inorganic oxides is contacted with a quantitative acid to obtain a pH of 2.5 or below, and at least one organic paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇x297 Mm) 20 ---------------- ^ ---- Order --------- Line (Please read the precautions on the back before filling this page) Economy Printed by A7, ^ B7 of the Consumer Cooperatives of the Ministry of Intellectual Property Bureau. 5. Description of the Invention (IS) A metal reactant selected from the aforementioned first organometallic compound, second organometallic compound, third organometallic compound, and fourth organometallic compound. And its mixture; (B) then the aqueous suspension of the hydrophobic particulate inorganic oxide, the liquid contacts the water-immiscible organic solvent and the suspended hydrophobic particulate is free. The organic oxide is changed from a liquid aqueous phase to a liquid The organic phase. The water-immiscible organic solvent used for contacting the aqueous suspension of the hydrophobic particulate inorganic oxide may or may not be dissolved in it (with or without one or more materials). Such materials include, but are not limited to, one or more rubbers, oils, coupling agents, antioxidants, and accelerators. The particulate inorganic oxide is present as an aqueous suspension during step (A). The concentration of the particulate inorganic oxide contained in the aqueous suspension of the step (A) is not particularly limited, and is usually in the range of 5 to 90% by weight, but a slightly higher or lower ratio can be used. The concentration of the particulate inorganic oxide in the aqueous suspension is usually in the range of 10 to 50% by weight and preferably in the range of 10 to 30% by weight. Before treatment with acid and organometallic reactants, the aqueous suspension can be ground, such as wet milling, to further improve the dispersibility (suspension) of the inorganic oxide in the aqueous medium, and / or reduce the particulate inorganic oxide in the suspension particles size. In step (A) of the aforementioned method, the aqueous suspension of the particulate inorganic oxide is contacted with the aforementioned one or more organometallic compounds in the presence of a quantitative acid, which can produce a pH of 2.5 or less in the aqueous suspension. The step (A) using an acid catalyst may be of various types, including organic and / or inorganic. The preferred metal catalyst is inorganic. Suitable acid catalysts include, for example, hydrogen acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, and benzenesulfonic acid. Optionally, an acid catalyst or a mixture of two or more acid catalysts may be used. When the organometallic paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 21 ^ ------ III ----- II (Please read the precautions on the back before filling this page) A7 5. The invention description printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (l9) (please read the notes on the back before filling this page) The reactant is chlorosilicic acid, and the required amount of acid can be hydrolyzed in situ by aerosilane Produced, or chlorosilane directly reacts with the hydroxyl group of an inorganic oxide. In step (A) ', it is required that the amount of acid present is sufficiently reduced to 2.5 or less, and that the reaction of the organometallic reactant with the particulate inorganic oxide is performed. In step (A), is it preferable to use a sufficient amount of acid catalyst so as to provide an aqueous suspension? ^ 1 is 20 or less, more preferably pH 1.0 or less and optimal ρΗ0.5 or less. The temperature at which step (A) is performed is not particularly limited, and is usually in the range of 20 ° C to 250 ° C, but a slightly lower or higher temperature may be used if necessary. The reaction temperature depends on the reactants used, such as organometallic compounds, acids and (if used) co-solvents. The preferred step (A) is carried out at a temperature range from 它 to ⑽ ⑽ ′. However, when required, step (A) may be carried out at the reflux temperature of the slurry used in step (A). When performing step (A), the presence of a surfactant and / or a water-miscible co-solvent is required to facilitate the reaction between the organometallic reactant and the particulate inorganic oxide. Suitable surfactants such as anionic surfactants such as dodecylbenzenesulfonic acid, non-ionic surfactants such as polyoxyethyl (23) lauryl_ and ((CH3) 3SiO) 2CH3Si (CH2) 3 (OCH2CH2 7OCH3, and cationic surfactants such as gasified alkyltrimethylammonium. One surfactant or a mixture of two or more surfactants can be used. Suitable water-miscible organic co-solvents include, for example, tetrahydrofuran and alcohols containing 1 to 4 carbon atoms, i.e. methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol And the third butanol. If desired, a water-miscible organic co-solvent or a mixture of two or more water-miscible organic co-solvents may be used. The amount of organometallic reactant in step (A) is enough to produce 22 here. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297). A7 printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs: --- ---- Nine, the description of the invention (20) This type of hydrophobic inorganic oxide can provide a predetermined amount of effect. Such hydrophobic inorganic oxides must be stably dispersed in the rubber adhesive, and remain dispersed in the wet rubber master batch debris after removal of solvent. If the organometallic reactant is insufficient, the inorganic oxide will be separated from the rubber and separated into the aqueous phase during solvent stripping. Hydrophobicity is related to the hydrocarbon content of the hydrophobic particulate inorganic oxide and the hydrocarbon barrier to hydrogen ratio. Organometallic reactants are usually provided per square meter &gt; 3 to 40 micromolar carbon is sufficient, but 6 to 2 () micromolar carbon / square meter is preferred. At least part of the organometallic reactant reacts with hydroxyl groups on the surface of the inorganic oxide to produce a hydrophobic particulate inorganic oxide. After step (A), before recovery or step (B) -7, the aqueous mixture may be subjected to abrasive particles such as wet milling to reduce the particle size of the hydrophobic inorganic oxide. In step (B), the weight ratio of the water-immiscible organic solvent in the solvent to the inorganic oxide is greater than 5: 1 so that the hydrophobic particulate inorganic oxide is separated from the aqueous suspension. In addition, hydrophobic inorganic oxides can be recovered from aqueous suspensions by filtration, centrifugation, spray drying, or by other separation methods known in the industry. Steps (A) and (B) are performed sequentially in a privately preferred method. However, the water-immiscible organic solvent may be added before, at the same time or after the addition of the organometallic reactant used in step (A). It is stipulated that the organometallic reactant does not prefer to transfer to the organic solvent and does not react with the inorganic oxide. In the first two cases, the conversion of hydrophilic particulate inorganic oxides into hydrophobic particulate inorganic oxides is achieved by phase separation, where the hydrophobic particulate inorganic oxides are separated into the solvent phase. For the purpose of the present invention, any water-immiscible organic solvent can be used in step (B). Suitable water-immiscible organic solvents include low-molecular-weight siloxanes such as hexamethyldisilazane, octadecylcyclotetrasiloxane, and this paper is sized for China National Standard (CNS) A4 (210 X 297 mm) ) 23 ------------- Install -----: ---- Order --------- Line (Please read the precautions on the back before filling this page) 500753 A7

V. Description of the invention (22) Oxide is separated into water from aqueous suspension). Hydrophobic

The product may be subjected to washing and / or neutralization to reduce pollutants and produce a product having a PHH or higher. The obtained organic material of the hydrophobic inorganic oxide may be reduced in particle size by grinding, such as wet milling, before being separated or used in the form of an organic slurry. The hydrophobic particulate inorganic oxide can be recovered by water J, organic solvents, dried, and further processed by heating. Another embodiment of the present invention is intended to include a kind of hardened rubber composition, which contains 4 parts by weight of the rubber, which contains a hydrophobic inorganic oxide per 100 parts by weight, wherein the composition is characterized by a white area of less than 0.4%. , Such as the aforementioned Mi white zone degree. As used herein, the term "rubber" includes organic rubber and polystyrene rubber. In addition, the hydrophobic particulate inorganic oxide of the present invention can be dispersed in polymer materials such as plastics and resins. In the example of moon bean shell, the M1 white area is characteristic of the polymer composition, that is, the characteristic of the hydrophobic inorganic oxide and the polymer itself. Results The M1 white area was determined according to the M1 standard white area measurement method, but the polymer composite to be tested need not have a standard formula; in other words, the measurement was started with the subtitle "Slicing scheme, ° the hardened rubber composition of the present invention It has high strength, which can be proved by the high modulus of 300%. The hardened rubber composition contains 10 to 15 parts of hydrophobic particulate inorganic oxides per 100 parts by weight of the rubber. Especially for every 100 parts of rubber, the hardened rubber composition contains one 20 to T30 parts, preferably 30 to 100 parts, hydrophobic granular inorganic oxides. Hydrophobic granular inorganic oxides are characterized by hydrophobic granular inorganic oxides with low M1 standard white zone characteristics and can be highly dispersed in various hardened organic rubber sheets. Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 25 — — — — — — — — — I- IIII l · III ^^ 1111111 (Please read the notes on the back before filling this page) A7 A7

V. Description of the invention (23 "Mouth rubber can be organic rubber (natural or synthetic) or can be polysilicone rubber and its mixtures are suitable for use in the hardened organic rubber of the present invention. Such organic rubbers include, for example, but are not limited to, natural rubber; cis-isoprene; cis · 1,4-polybutadiene; trans-M · polybutadiene, '1,2-polybutadiene; from a variety of styrene Styrene-butadiene copolymer (hereinafter referred to as "SBR") composed of various butadiene isomers, which is composed of various percentages of acetophenone, isoamidine, and butyl Diene and optionally a styrene-isoprene-butadiene terpolymer composed of various butadiene isomers (hereinafter referred to as "SIBR"); a rubber composition mainly composed of acrylonitrile; Isobutylene-based rubber compositions; and ethylene · diluents, or mixtures of this specialty rubber are described, for example, in U.S. Patent Nos. 4,530,959; 4,616, G65; 4,748,199; 4,866,131; 4,894,420; 4,925,894; 4,082,901; and No. 5,162,409. Other suitable organic polymers are ethylene and other high carbon alpha Copolymers of hydrocarbons such as propylene, butene-1 and pentene-1, and a diene monomer. Organic polymers can be block, random, or sequential polymers, and can be via emulsion (such as e_SBR) or solution polymerization ( Such as s-SBR). Other useful polymers include partially or fully functional polymers including coupling or star-branched polymers. Other special examples of functional organic rubbers include polybutadiene, gasbutyl, and Bromobutyl rubber and brominated isobutylene-co-p-methylstyrene rubber. The preferred organic rubber is polybutadiene, s-SBR and mixtures thereof. The amount of organic rubber present in the hardened rubber composition can vary widely. In most cases, organic rubber accounts for 20 to 83.3% by weight of the hardened organic rubber composition. Better organic rubber accounts for the paper size of the hardened organic rubber composition. Applicable to China National Standard (CNS) A4 (210 X 297) Li) --------- ^ --------- (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economy Employees Cooperatives 26 A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 to 80. /. The weight ratio is, for example, 3Q to 75% by weight. The weight ratio is relatively high: the proportion of the organic rubber in the uncured organic rubber composition is substantially the same as that in the cured organic rubber composition. Other materials are used for whitening and / or selectively present in the hardened organic rubber composition of the present invention. Including but not limited to tritium (usually but not necessarily sulfur), accelerators, coupling agents, lubricants, it, processing oils, antioxidants, reinforced carbon black, semi-reinforced carbon black, unreinforced carbon black, other pigments, , Fatty acid and / or zinc oxide. These materials are not exhaustive. These and other ingredients can be used in conventional amounts for conventional uses, as long as they do not severely interfere with the good formula specifications of the hardened organic rubber. The hardenable organic rubber composition can be mixed and ground from its ingredients using any of the materials known in the industry. The hardenable organic rubber composition is then formed and hardened using methods and techniques generally known in the industry to form a hardened organic rubber article. For example, tires can be built, shaped, and hardened using common methods and techniques known in the industry. A wide variety of silicone rubbers and mixtures thereof are suitable for use in the hardened silicone rubber composition of the present invention. Examples of polyoxane rubbers include organic polyoxane compositions, in which the organopolysiloxane is linear or branched, and contains certain reactive groups such as meridian groups, hydrolyzable groups, and dilute groups such as ethyl acetate in addition to the hydrocarbon group. Radicals, hydrogen, fluorine and phenyl. Further examples are listed in U.S. Patent No. 5,009,874, No. 5, No. 27, No. 6, Column No. 6, and No. 23, which is disclosed in its entirety and described herein for reference-', Silicone rubber in hardened polysilicon The amount of oxygen rubber composition present can vary widely. In most cases, silicone rubber accounts for the hardened silicone rubber group.

This paper standard stab towel family standard ㈣S) A4 size (210 X 297 public love equipment ---- Γ --- order --------- line (Please read the precautions on the back before filling this page ) 5U0753

V. Description of Invention (25) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

= Weight ratio of 2G to 8G%. In particular, the polyoxyethylene rubber accounts for 30 to 75% by weight and preferably 35 to 75% by weight of the hardened polylithic latex rubber composition. The amount of silicone rubber used to prepare the uncured silicone rubber composition is substantially equal to the amount of the cured silicone rubber composition present. A variety of other materials are commonly and / or selectively present in the hardened water silicone rubber composition of the present invention. Including cross-linking agents; cross-linking catalysts; conventional filling; buckets such as 'blade quartz' silica bath clay, talc, carbon black and various carbonates such as carbonic acid and carbon; anti-structural agents are also known as plasticizers; heat Stabilizers; thixotropic agents, pigments; and anti-retaining agents. The hardenable silicone rubber composition can be formed from its ingredients in any manner known in the industry. Mixing and grinding are most commonly used. The hardenable polysilicone rubber composition can then be shaped and hardened using any method and technique known in the art to form a hardened silicone rubber composition. The polymer composition to which the hydrophobic inorganic oxide of the present invention can be added, such as plastics and / or resins, contains substantially any plastic or resin. The hydrophobic inorganic oxide of the present invention can be mixed with plastic or resin, and the physical form of the plastic or resin is in any liquid or miscible form, such as a solution, a suspension, a latex knife, or a night. Suitable plastics and resins include, for example, thermoplastic and thermosetting resins and plastics having elastomeric properties. Plastics and resins can be alkyd resins, oil-modified alkyd resins, unsaturated polyesters, natural oils (such as linseed oil, tung oil, soybean oil), epoxides, nylons, thermoplastic polyesters (such as Polyethylene terephthalate, polybutylene terephthalate), thermoplastic polycarbonates, thermosetting polycarbonates, polyethylenes, polybutylenes, polystyrenes, Paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Printed by A7 _______B7, Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (26) Butane-type 'ethylene-propylene copolymers and terpolymers, acrylics (acrylic acid homogeneous substances and copolymers, hyaluronic acid) Type, methacrylic acid, glyme, its salts, hydrohalides, etc.), phenol resins, polyalkylene oxides, such as polyoxymethylene (homopolymers and copolymers) Materials), polyurethanes, poly, (urea urethanes), polyfluorenes, polysulfide rubbers, nitrocellulose 'vinyl butyrate, vinyl (containing vinyl chloride, Polymers of vinylidene and / or vinyl acetate), and cellulose, cellulose acetate and cellulose butyrate, mucocellulose, shellac, wax, ethylene copolymers (such as ethylene-vinyl acetate copolymers) Polymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer) and the like. The amount of the hydrophobic inorganic oxide to be used in the polymer composition is 5 to 70 ❶ / based on the polymer composition. Range of weight ratio. For example, the ABS (acrylonitrile butadiene-styrene) copolymer has a hydrophobic inorganic oxide typically used in an amount of 30 to 60% by weight, and an acrylic nitrile-phenethyl acrylate copolymer is 5 to 2%. % By weight, aliphatic polyketones are 15 to 30% by weight, alkyd resins (for coatings and inks) are 30 to 60% by weight, thermoplastic dilute hydrocarbons are to π% by weight, and epoxy resins are 5 to 20% by weight, up to 60% by weight of ethylene · ethyl acetate copolymer, up to 80% by weight of ethylene · ethyl acetate copolymer, and 30 to 70% by weight of liquid crystalline polymer (LCP) Ratio, the phenol resin is 30 to 60% by weight, and the amount of polyethylene is usually more than 400 /. weight ratio. Another embodiment of the present invention is a composition comprising: (a solution comprising a water-immiscible solvent and an organic rubber dissolved in a water-immiscible solvent; and (b) a granular inorganic oxide dispersed in the solution; The inorganic inorganic oxide is any of the hydrophobic granular inorganics described herein before being dispersed in the solution. The paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — · III l · III ^ · 1111111 (Please read the precautions on the back before filling out this page) 29 500753 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (27) Oxide. Dissolved in water and insoluble The miscible organic rubber may be any of a wide variety of organic rubbers and mixtures thereof suitable for use in the hardened organic rubber composition of the present invention, as discussed and exemplified above. Preferred organic rubbers include solution styrene-butadiene Rubber, polybutadiene rubber, or mixtures thereof. The standard protocol for determining the M1 standard white zone according to the present invention is as follows. The batch was prepared in a suitable container equipped with a stirrer and purged with nitrogen, combining at least 120 grams of sofiflex 1216 solution styrene-butadiene rubber (Goodyear Tire & Rubber Co., Ohio Clone) A solution containing 0.365 phr of Irganox x520D antioxidant (Cibuter Chemicals, Dali, NY) in cyclohexane. Stir overnight at 60 ° C to completely dissolve. The rubber forms a 14% by weight styrene-butadiene rubber solution, also known as an "s-SBR adhesive." In a similar manner, a minimum of 50 grams of Budene 1207 polybutadiene rubber (Gute Yi Tire & Rubber Company, Ekron, Ohio) In cyclohexane containing 0.365 phr of Igano i520D antioxidant, at 60t: stir overnight to completely dissolve the rubber to form an 11% by weight polybutadiene rubber solution. Shou Ran makes "BR adhesive". In the stirred part of s_SBR adhesive, by adding hydrophobic granular inorganic oxide to form a slurry, the inorganic oxide is characterized by quantity, and the quantity is expressed in phr, which is 30.95 With hydrophobic granular inorganic oxides Chain Density (Each (please read the precautions on the back before filling in this page) t order --------- line · This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 meals) 30 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 500753 A7 ________B7 V. Product Description (28) Expressed in gram units (g) Units. After sufficient mixing to produce a consistent consistency, add Sundex 8125 aromatic processing oil (Shenyang Refining and Marketing Branch, Philadelphia, PA) The amount is equal to 30phr. The obtained material was fed into a kettle containing a large amount of hot water by a pump, and the cyclohexane was stripped by water vapor into the recovery chamber. Any mother batch scraps were collected in the kettle water. Check the aqueous phase for residual inorganic oxides. The wet mother batch scrap was recovered by filtration. The wet master batch scraps were dried in a laboratory oven at 75 ° C for 4 hours to produce dry &gt; first master batch scraps. Thermogravimetric analysis of the first dried mother batch scraps confirmed that the 80 ° C residue corresponding to the inorganic oxide was composed of the weight of the hydrophobic particulate inorganic oxide in rubber, oil, and the hydrophobic particulate inorganic oxide. The experimental error of the percentage theoretical value is within the experimental error range, thus confirming that the inorganic oxide is substantially completely transferred to the first mother batch debris. If the gravimetric analysis is carried out under the flow of nitrogen gas to 10. (3 / minute heating of small samples (typically about 10 mg) to 800 ° C. Weight loss below 200 ° C is considered as moisture loss. From [(200 ° C sample weight)-(800 ° C Sample weight)] / (200 ° C sample weight) Calculate the weight percentage of the residue. The hydrophobic granular inorganic oxide is not completely transferred to the first master batch debris, which constitutes the M1 standard white zone test failure, the reason The measured value in the white area is a function of the percent volume ratio of the inorganic oxide of the final hardened rubber compound. A hydrophobic granular inorganic oxide is added to the stirring portion of the BR adhesive to form a slurry. The inorganic oxide is expressed in terms of phr (in phr). ) Is characterized by a phr of 30.95 multiplied by the density of the hydrophobic-granular inorganic oxide backbone chain (expressed in grams per milliliter). After sufficient mixing to produce a consistent consistency, Sanders 8125 aromatic processing oil (refined by Shengyang Company) is added. And marketing branch, Philadelphia, PA) The number is equal to 30. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 31 ------------- Packing --- -l · --- Order --------- Line (Please read the precautions on the back before filling this page) Ministry of Economic Affairs Hui Property Office employees consumer cooperatives printed A7 - B7 _ V. Description (29) invention

Phr. The slurry is fed into the kettle containing a large excess of hot water by the pump, and the base gas stripping ring has been burned into the recovery chamber, and any mother batch debris is collected in the kettle water: check whether the water phase has residual inorganic oxides. By filtering and recovering the wet mother batch scraps, the dried mother batch scraps were recovered for 4 hours in a laboratory oven at 75t by roasting the door A ΛΑ, I Ichiban. Dry-by thermogravimetric analysis. One row of yttrium yttrium crumbs confirms that the residue is at 800 C, which corresponds to the weight percentage theory of the granular inorganic oxides and the weight of the hydrophobic particulate inorganic oxides in the rubber, oil and hydrophobic granular inorganic oxide composition The value is within the experimental error range, thus confirming that the inorganic oxide is substantially completely transferred to the second mother batch debris. Thermogravimetric analysis was performed as previously described. The incomplete transfer of the hydrophobic particulate inorganic oxide to the second mother batch debris constitutes the Ml standard white zone test failure because the measured white zone is a function of the volume percentage of the inorganic oxide of the final hardened rubber product. Mixing square cords are equipped with a 3 丨 〇CW CW Brabender preparatory mixer equipped with a Banbury-type mixing blade, a variable speed drive, and a hot liquid thermostatic circulation unit or equivalent. ingredient. Before starting the first round, use a hot liquid thermostatic circulation unit to adjust the temperature of the equilibrium mixing chamber to a starting temperature of 80 ° C. Adjustable variable speed drive provides a rotor speed of 65 卬 m. For the first round, it was determined that the weight of the dry first master batch scrap was equal to the sum of 89.9 grams (70 phr) of Sofieli 1216 solution styrene-butadiene rubber and 27.0 grams (21 phr) of Sanders 8125 oil; The product of the hydrophobic particulate inorganic oxide weighs 14 to 27 · 86 and the density of the hydrophobic particulate inorganic oxide backbone (expressed in grams per ¾ liter). It is also used in the first round to determine the weight of the scrap of the second master batch equal to 38.5 grams (30 phr). Buting 1207 polybutadiene. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). 32 ---------.------- l · --- order --------- line (please read the precautions on the back before filling this page) A7 A7 5 2. The invention description (3G) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -------------- install --- (Please read the precautions on the back before filling this page) --line The sum of rubber and 11.6 grams (9 phr) of Sanders 8125 oil; the weight of the hydrophobic particulate inorganic oxide is equal to the product of 11.95 and the density of the hydrophobic particulate inorganic oxide backbone (expressed in grams per liter). By adding a measured amount of the aforementioned dry first mother batch scrap and the aforementioned dry second mother batch scrap, the mixer started at 65 Γρπη ^ for 5 minutes, and the first round was started. At 0.5 minutes, the bump was raised and passed. After another 0.5 minutes, add 16.7 grams (13 phr) of X50S 1: 1 Si-69 Shiyaki coupling and N330-HAF carbon black (Degusa Corporation, Ridgefield Park, New Jersey, • Supplier: History Struktol, American company, Ohio Historical Investment). After 0.5 minutes, raise the ram, brush over and add 3.2g (2.5 phr) Kadox 920C surface-treated zinc oxide (US zinc company Monaka, PA) '' 2.6 g (2.0? 111 &gt;) Wayne (\\ ^ 1 ^ 813 &gt; 〇〇〇〇 Diaryl p-phenylene monoamine (Goodyear Tire & Rubber Company, Ekron, Ohio; supplier : RT Vanderbilt, Novak, Connecticut 'and 1.3 grams (1.3 · phr) of rubber-grade stearic acid (p Haii, Chicago, Illinois). The prepared materials are mixed for another 2 minutes to reach the highest temperature i50c> c to 16 ° C, and the first round is completed in the mixer. Based on the raw materials for the preparation of hydrophobic granular inorganic oxides for the production of polymer master batches, granular inorganic oxidation Depending on the physical characteristics of the rotor, the rotor speed must be increased or decreased. The maximum temperature within the mixing time of 3.5 minutes is within the aforementioned range. The thermocouple is used to measure the temperature when the material is poured out, and the weight is verified to be within the specified range. It is within the range of ± 5% of the theoretical weight. Remove the material from the double rubber mill and cut it into long strips for preparation. : The round passes the mixer between the completion of the first round of this mouth machine and the start of the second round. It takes about! Hours. This paper ruler @ 国 ®? ^ Α4 Specifications⑽ 33 500753 A7 B7 V. Description of the invention (31 (Please Read the notes on the back before filling this page.) Before starting the second round, use the hot liquid thermostatic circulation unit to adjust and balance the temperature of the mixing chamber to a starting temperature of 60. Adjust the variable speed drive to obtain the rotor speed of 40. Borrow Add the 1st material strip to the mixer to start the second round. Then add 26 grams (20 SantofleX) 13 N- (1,3-dimethylbutyl) _N, _ Bentyl p-phenylenediamine (Monsanto, St. Louis, Missouri), 19 g (15 phr) Okerin 7240 microcrystalline wax / paraffin admixture (Astor (Eight to 00, Georgia) Knox, TX), 1.8 grams (1.4 phr) of sulfur for rubber manufacturing (Taber, Barrington, Rhode Island), 2.2 grams (1.7 phr) of Sandocure NS N-Third-Butyl-2-Benzothiazole Sulfinamide (Monsanto, Saint Louis, Chasuri) and 2.6 g (2.0 phr) DPG Benji Vein (Monsanto's "St. Louis, Suriname") 〇 5 minutes later, raise the ram and skim. If necessary to change the rotor speed, mix and prepare the material for another 5 hours to reach 100. 00 to 11 () ° C temperature to complete the second round of the mixer. Grinding program The Intellectual Property Bureau of the Ministry of Economic Affairs employee consumer cooperative prints a pre-heated double newspaper rubber mill to about 60 ° C. The pressure section is set to 6.35 mm (0.25 inch), When the mill is running, feed stock from the second round to the mill. If necessary, adjust the rolling row to maintain uniform thickness. Make 8 side cuts and then 8 end rounds. Adjusting the setting of the pressure section results in a sheet thickness of 2.032 mm and 0.127 mm (0.080 inch ± 0.005 inch). Remove the flakes from the mill and lay them flat on a clean surface.

Using a stencil, cut a rectangular sample of 101.6 mm x 76 · 2 mm (4 in. X 3 in.) From the prepared material, and then store the sample in two pieces of dry polyethylene. At 23 ° C ± 2 ° C 34 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 500753 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (32) Temperature and Relative humidity 50% ± 5% conditioning overnight. The hardened formula places the conditioned sample in a 101 · 6 mm x 76 · 2 mm x 1.524 mm (4 inch x 3 inch x 0.06 inch) standard frame machine steel template compression mold, the mold has a layer of 0.0254 mm thick Teflon coating 'polytetrafluoroethylene (DuPont, Wilmington, Delaware) or equivalent' to a thickness of 0.0005 mm (0.011 to 20002 inches) and at 61 Cm × 61 cm (24 inches × 24 忖) 890 kilonewtons (100 tons) 4-column electric compressor or equivalent. Hardened at 150 ° C under pressure of 13.79 million Baska (2000 bar / square inch) for 20 minutes. . The hardened rubber sheet was taken out of the mold and allowed to rest overnight. The slicer uses a RMC MT-6000-XL microtome equipped with a CR2000 low temperature accessory (RMC, Taxon, Alexandra) and McrOStar LH black standard boat diamond knife (MSI Technology, Texas Han) Swell) or equivalent. Set a cutting edge diamond with a length of 6 to 10 mm at an included angle of 45 degrees. Use a private knife to slice the low-temperature knife holder and set the slice clearance angle at the bottom of the knife to 4 degrees. Set the initial sample and diamond knife temperature to _70 ° C to -40 ° C. Subsequently, individual temperature adjustments are required to obtain optimal cutting conditions. An initial sample of about 15 mm x about 15 mm x about 1.5 mm was cut from a hardened rubber sheet. Place this preliminary specimen on the stainless steel RMC Torme flat specimen holder of the microtome and use the square-hole screw head attached to the microtome to firmly tighten the specimen downward with a wrench. Use the sample trimming cube, Torme inflammation tool and blade attached to the slicer to trim the specimen, so about 4 mm of the specimen is raised from the surface of the fixture, and the angle of the specimen is trimmed at 45 degrees. Meter. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 35 ------------- Loading -----! ---- Order ------- I line (Please read the notes on the back before filling this page) 500753 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (33) Fixture placed The low-temperature unit arm of the advance mechanism of the microtome has a vertical direction of the square surface. Cool to sample temperature set earlier. Use a diamond knife blunt edge area to manually plan the block surface to form a smooth flat surface on the block surface. Move the knife edge to the sharp area of the diamond knife edge and plan out a few thin sections from the surface of the block. Set the cutting stroke to 0.5 mm per second and manually or automatically advance the surface of the block to cut a section of about 2 microns thick in the sharp area of the edge of the diamond blade, or move the diamond blade to a new area. When the block breaks at the edge of the diamond, use a recorder or equivalent to securely fix each section. The tweezers are a pair of straight tweezers that are pre-cooled to a biological grade of 5 fine tips and usually open or close by themselves (Α · Dumont &amp; Fils , Switzerland; Structural Probes Corporation, West Drizzt, PA) or equivalent. Clamp the corners when each section starts to leave, gently pull the section from the cutting edge without breaking, breaking or pulling it through the entire cutting stroke, minimize the possibility of the section being rolled up or excessively compressed to hold the cutting edge . Dry cutting section; do not use dimethylarsin or xylenes to assist cutting. At the end of the cutting stroke, use tweezers to take the entire section to a cryo-cooled Fisherbrand ultra-frozen sectioned glass with a size of 25 pens x 75 mm x ΐ mm (卩 Science and Technology Corporation, Pittsburgh, Pennsylvania) or Quite material. The glass slides are wiped clean with optical lens paper or equivalent beforehand, and placed on top of the silicone rubber spacers commonly cut into U-shapes, and the spacers surround the sides and back of the knife boat. 8 to 10 pieces are taken from the sample The thin slices are placed on the glass sheet, and are prepared during the optical installation and placed into a convenient preparation method during the optical installation. Take out the glass sheet from the low greenhouse, put it in the sliced glass sheet box to prevent excessive water pollution and allow it to warm to Room temperature 0 --------, -------- ^ ---- order --------- line (please read the precautions on the back before filling this page) New Zealand Standard _ t country (2f x 297 mm) 500753 A7 B7 V. Description of the invention (34) Preparation of printed sheet for consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs · Coated Cargill with a thin section on a microscope glass sheet ( CargiUe) Series A nD-1.5 50 ± 0.0002 impregnated oil (RP Cargill, Hedgrove, NJ) or equivalent. Yu Yueguang 81 ^ 2_1 ^ 〇〇111 i: 1〇〇 Stereo microscopy. Mirror or equivalent equipment equipped with Yueguang SMZ-U uw 10 / eight / 24 binocular eyepiece assembly (Nikko Corporation Tokyo, Japan) or Use the tweezers and / or pointed probe to comb the thin section to remove the folds, wrinkles, and punches to make the section straight when the accessory table is at low magnification. Be careful not to tear the fine 4 sections during this operation. Straight thin slices are arranged in groups of 5 to 5 (preferably 4 slices) lined up under a circular cover glass with a diameter of 18 mm to obtain the best space configuration. Use optical lens paper or equivalent to clean 18 mm in diameter Thick, 0.13mm to 0.17¾m round microscope cover glass (Fisher Scientific, Philadelphia, PA) or equivalent, placed on a set of aligned slices. If necessary, two or three, and the slice can be Gu Na was placed on a microscope slide. Fold Shu Jie ⑼〇 “ies) 23.3 cm x 18.2 cm (9 対 χ72 ^) tissue paper (Shu Jie Paper Company, Philadelphia, PA) or equivalent to a glass slide. The sheet is approximately the size and used as a suction paper. Place blotting paper on the cover glass protection area on the microscope slide. Place a plate or microscope slide cassette on the blotting paper. Manually apply a gentle and steady downward force to the tablet or slide box, and maintain pressure for ~ 15 seconds. Remove the plate or slide cassette and blotting paper. Repeat the blotting procedure with a clean surface of a cleansing paper or equivalent but with less power. Equipment description Carcass selection Fangtu uses the following equipment or equivalent for field selection: MiCrophot FXA search optical microscope is equipped with a comparative objective lens module with ink solids ^ -----:- --- ^ --------- ^ (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (&amp; S) A4 specification (210 X 297 Gongrong 37

20x0.05 Ph2 phase objective lens, Ph2 phase polycondensation lens (Nikko Corporation, Tokyo, Japan), system magnification 1.25 times, intermediate lens magnification 丨. 25 times; Sony's Trinitro PVM 1343MD color video monitor Tokyo, Japan), and the Sony CCD three-chip DXC-760MD camera (Sony Corporation, Japan's East Hall,); MacIntosh nfx computer with a color Super Micro (SuPerMaC) 43 cm (17 inch) monitor (Apple Corp., Cupertino, California) and Data Translation Frame Memory Cards (Data Translation Corporation, Larleigh, North Carolina). Use the following software or equivalent software to capture images and perform image analysis: ColorKit software (data translation company, Larleigh, North Carolina), NIH imaging software (National Institutes of Health, Washington, DC), and Microsoft Excel software (Microsoft Redmond, Washington). The field of view is selected to scan the slice section visually at about 250x magnification, with individual thicknesses of about 2 to about 3 microns and which have been prepared for comparative optical microscopy and have been removed. Contains major abnormalities such as wrinkles, creases, waves, tears And / or sections contaminated by dirt particles. Scan the remaining at least two sections to determine the representative area of the entire sample. Examine the area at approximately 500x magnification and use a blind longitudinal traverse and a blind lateral traverse of the microscope stage to select the field of view on each segment. Use only a field of view with low slack (only accepting a substantially flat business can improve white-area measurement accuracy; having a variable height slack field will result in blurred unfocused images due to the low depth of field, which is a characteristic of optical microscopy). At least two sections ‘capture ten fields of view using color kit software’ at least 1 image uses color kit software as a PIct format file. Store the PICT file on a disc for computer-aided white area measurement. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) .f Order --------- line. Ministry of Economic Affairs Intellectual Property Printed by the Bureau's Consumer Cooperatives 38 500 753 A7

Image analysis · Save as PICT㈣ video microscope W imaging software and open directly.彳 Using NIH video (please read the precautions on the back before filling this page) When opening the PICT file, the image is X480 pixels on the monitor. The distance per micro ticket is determined by the field of 2_. Called 〇 = The method is to slice each grid from a 10 micron stage = horizontally project on a monitor, and measure a distance of 250 micrometers or more on the display image. The actual distance is marked in the software and the computer calibrates the scale, also called the calibration factor, expressed in linear pixels / micron units. Analyze each selected field of view image. Smooth the image to remove background noise. Manually find the threshold and edit the image to count the self-regions and remove the human error. Convert the edited image into a binary image and save the image as a slot. … From the options menu, select the area parameter and set the minimum pixel value to 4. Analyze each binary image to generate the number details, where each number is the characteristic area of each white area and the details are stored. The total number of white areas in this field of view is obtained using the Microsoft Ike Sui software plus the total number of menus. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Divide the total number of white areas by the total number of areas in a field of view and multiply the quotient by 100 to find the percentage of white fields in a field of view. Take the average value of 10 white areas of the visual field to obtain the M1 standard white area. Save all files on disc. In this way, a standard scheme for measuring the M1 standard white zone is obtained. Ming will further illustrate the following example, which is to be regarded as an example, but not restrictive, in which all parts are 1 parts by weight and all percentages are percentages by weight unless otherwise specified. Except for the operation example or 39 paper size standards (CNS) A4 (210 X 297 public love) 500753

V. Description of the Invention (37) Except as indicated, all the numbers, ratios, ranges and other numbers used herein are modified by the word "about" in each case. (Please read the precautions on the back before filling out this page.) In the following examples, the moisture (or volatile) content is measured using a COMPUTRAC moisture analyzer model MA-5A. The silicon dioxide sample was heated to 165 ° C and maintained at this temperature until the weight of the sample no longer changed. The weight percentage of moisture (or volatile matter) content is calculated as [(the original sample weight after heating the sample weight)] / (the original sample weight). The solid content weight percentage is calculated as [100-weight percentage of moisture (or volatile matter)]. Example The preparation method of the hydrophilic granular amorphous Shendianshixiu is to acidify the sodium soxate with sulfuric acid. Most of the precipitates form at a pH above 8.5. Acid was continuously added until the pH of the liquid reached 3.3 to 4.0 to complete the precipitation. The obtained first aqueous suspension was filtered through a filter cake to wash the strips until the strip-washing water showed a conductivity of 300 to 800 μm. After partially washing, the filter cake was again liquefied using a high-shear agitator to form a hydrophilic amorphous precipitated silica second aqueous suspension. The suspension contained a solid weight ratio of 126 / 〇. A centrifugal disc atomizer is used to spray dry this second aqueous suspension to 5.7% by weight of water to form a hydrophilic amorphous precipitated silica powder. The powder had a BET surface area of 159 m2 / g. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Another copy of the aforementioned filter cake was again liquefied using a high-shear agitator to form a third aqueous suspension of hydrophilic granular amorphous precipitated silica, which contained 10% solids by weight. 16 kg of the third aqueous suspension was added to a suitable container and stirred. Isopropanol (8 kg) and hexamethyldisilazane (0.368 kg) were added sequentially to the stirred suspension. The pH of the obtained reaction mixture was adjusted to 0.5 by adding 96% by weight sulfuric acid. The reaction mixture is heated to 73 ° C and 40 ° C at this temperature. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 500753 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A5. Description of the invention (38) The degree was maintained for 2.2 hours. After cooling the reaction mixture to below 60 ° C, cyclohexane (8 kg) was added. The reaction mixture was then briefly agitated to cause the hydrophobic particulate amorphous precipitated silica phase to be transferred into the cyclohexane phase without forming an emulsion. Remove the water phase. • Wash the organic phase containing hydrophobic Shendian silica with dilute sodium hydroxide solution several times until the pH of the washing water is 5.11. The slurry of hydrophobic granular amorphous precipitated silica in cyclohexane was diluted with additional cyclohexane (3.4 kg), and the slurry was leached from the solution. The solution was washed with cyclohexane (175 kg) to remove the remaining slurry, and the washing liquid was combined with the leached slurry. The slurry was filtered and the solid was washed with cyclohexane. The washed material was placed in a shallow dish and dried in an oven at 85t: until the residual volatilizer concentration dropped to about 5%. The obtained product is a hydrophobic granular amorphous precipitated silicon oxide, which is characterized by a BET surface area of 128 square meters per gram, a silanol content of lh9 hydroxyl groups per square micrometer, a carbon content of 1.43% by weight, and a pH of 3.4. The hydrophobic granular amorphous precipitated silica in this example was added with 5 ml of 50% by weight methanol (HPLC grade) and deionized water mixture to a 50 ml conical centrifuge. 2.0 grams of material was used to test the wettability of methanol. Centrifuge tubes are marked at 0.5 ml scales to a height of 10 ml, and 10 to 50 ml heights are drawn at a scale of 10 ml. The contents of the examiner were shaken for 15 seconds and centrifuged at room temperature (23_25σ (:) in a second basket centrifuge at about 4,000 revolutions per minute (rpm) for 15 minutes. The centrifuge tube was removed and handled carefully to prevent the sediment from resuspending. All hydrophobicity is wet, that is, a precipitate is formed. As a result, the volume of the precipitate is 14 ml. Table 1 lists three methanol / water mixtures with different concentrations, which are used in the foregoing procedure to determine the methanol required to wet 50% of the hydrophobic oxygen in this example. Test. One batch of this example is marked as eight and B. Wet by different concentrations of methanol ------------- pack ----- j ---- order --- ------ Line (Please read the notes on the back before filling this page)

I 500753

V. Explanation of the invention (39) The volume percentage of the wetted hydrophobic silica is calculated by dividing a part of the wet hydrophobic silica capacity by the total wet hydrophobic silica capacity multiplied by i 00. The results were plotted on a line graph of the percentage of wet silicon dioxide volume versus the weight of methanol to match a straight line. Example A and B. The wet methanol concentration of 50% volume ratio hydrophobic silica is calculated from the straight line and the equation, and the average is 3 1 (%. Table 1 Methanol weight test sample A wet sample B wet percentage percentage 26.2 5 2 31.8 53 50 35.2 87 93 The carbon percentage of the sample of hydrophobic inorganic oxide printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was repeated three times using the procedure described here. The average was 1.32% by weight carbon before extraction. Materials for this example Another sample was extracted using the Sosley extraction procedure described here. The carbon percentage analysis was repeated three times, with an average weight of 1.41% after extraction. The percentage of extracted carbon was minimal or non-existent and within the experimental error range. The percentage of extracted carbon It is typically calculated using the following formula: [(% carbon before extraction, H% carbon after extraction)] / (% carbon before extraction) x 100. Hydrophobic granular amorphous precipitated silica test M1 standard white area. White area of ten fields, The Ml standard white area (ie average) and standard deviation are shown in Table 2: This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 42 --------, ----- ------- Order --------- line (please first Note read back surface of the page and then fill) 500753 A7 ____B7 V. invention is described in () Table View 2 + 1 0.02 0.02 0.03 0.02 0.02 0.12 0.02 0.02 0.01 0.04 Μ1 standard white area standard deviation 0.03 0.03%

# Printed by the Consumers ’Cooperative of the Ministry of Economy ’s Intellectual Property Bureau. Part of the material removed by the mill and laid on a clean surface during the Ml standard white zone scheme was used to prepare other samples for physical testing. Thin specimens for stress, strain, and dynamic properties, and thick specimens for hardness and rebound tests were prepared from this uncured rubber stock. Thin specimens were hardened at 150 ° C for 20 minutes and thick specimens were hardened at 150 ° C for 30 minutes. The difference in hardening time matches the difference in mold delay time. The hardening properties of these compositions are shown in Table 3. 43 This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 issued) 500753 B7_ V. Description of invention (41) Table 3 Hardening performance and hardening rheometer printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ( 150 ° C) Maximum torque, dNm 30.6 Minimum torque, dNm 3.3 △ Torque 27.3 T50, min 5.8 Stress / strain tensile strength, MPa 19.6 Elongation at break,% 635 100% modulus, MPa 2.5 300% modulus 8.3 Hardness Shore A, 23 ° C 70 Shore A, 100 ° C 68 Rebound 100 ° C,% 66.0 Dynamic properties (1 Hz, 2.0% strain) G, at 60 ° C, MPa 3.73 Tan △ at 60 ° C 0.127 Tan △ at 0 ° C 0.202 Dispersion M1 white area, area% 0.03 (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 44 500 753 A7 V. Description of the invention (42) Since this example uses the formula of rubber and the formula stipulated in the standard scheme for measuring the M1 standard white area, the M1 standard white area of the hardened rubber composition is the same as the hydrophobic amorphous precipitate used to make the hardened rubber composition. Silicon oxide M1 standard white zone. The Ml standard white zone value of 0.03% indicates amorphous precipitated silica and a high degree of dispersion in a hardened rubber composition. Although the present invention has been described with respect to specific details of certain specific embodiments, it is by no means intended to treat these details as limiting the scope of the present invention. The scope of the present invention is included in the scope of the accompanying patent application. ^ --------- (Please read the notes on the back before filling out this page) -Line-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 Specification (210 X 297 mm) 45

Claims (1)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, patent application scope 1.1 Hydrophobic granular inorganic oxide, selected from amorphous Shen Cai oxygen, A group consisting of a mixture of Lu Ru and this temple's thermomechanical emulsion. The hydrophobic particulate inorganic oxide is characterized by (a) substantially no functional groups that can react chemically with rubber, and (b) hydroxyl content of 2 · 15 hydroxyl per square nanometer, (c) carbon content is from ⑺ to ^% by weight, (d) methanol wettability is from 15 to 45%, and (e) Ml standard white zone is less than 0.4 / 0. 2. The hydrophobic particulate inorganic oxide according to item i of the patent application, wherein the carbon content is substantially unextractable. 3. As the hydrophobic granular inorganic oxide in item i of the patent application scope, in which the inorganic oxide is amorphous precipitated silicon oxide, the hydroxyl content is usually 3 to M hydroxyl per square micron, and the carbon content is 0 to 4% by weight. The ratio is less than 0.3%. 4. The hydrophobic particulate inorganic oxide according to item 1 of the application, wherein the hydroxyl group content is 4-12 hydroxyl / square nanometer, the carbon content is 0.3-3% by weight and the M1 standard white zone is less than 0.2%. 5. The hydrophobic particulate inorganic oxide according to item 1 of the patent application scope, wherein the inorganic oxide has a pH of 3 to 10. 6. The hydrophobic particulate inorganic oxide according to item 4 of the application, wherein the coarse particles are in the form of powder, granules or beads. 7. The hydrophobic particulate inorganic oxide as described in the scope of the patent application No. 6 wherein the particles are: Table paper size 剌 Zhongguanjia Standard (CNS) A4 &amp; Grid (210 X 297mm f 46 A8 B8 C8 Please read the notes on back &amp; then fill in ▲ page k 4 VI. Scope of patent application12. For the hardened rubber object of item u in the scope of patent application, the organic rubber 骖 includes the ethylene styrene butadiene rubber, polybutylene Dilute or its mixture. 13. The hardened rubber object according to item 10 of the application, wherein the rubber is a silicone rubber and the inorganic oxide is an amorphous precipitated silicon oxide. Μ · A hardened organic rubber article in which 10 to 15 parts of hydrophobic granular inorganic oxide is dispersed per -100 parts of rubber, and is selected from the mixture of inorganic oxides such as amorphous Shen Dian Shi Xi Liao, Shao Ru and A The group of the hydrophobic granular inorganic oxide is characterized by (a) being substantially free of functional groups capable of chemically reacting with rubber, (b) having a hydroxyl content of 4-12 hydroxyl / square nanometer, and (0) ¼ containing 1 is 0.3 to 3% by weight, which is substantially non-extractable, (d) the wettability of methanol is 25 to 35%, (e) the standard white zone is less than 0.2%, and (f) the BET surface area is 40 to 350 m2 / g. 15 · If the hardened organic rubber article of item 14 of the patent application, wherein the organic rubber contains stupid ethylene-butadiene rubber 'polybutadiene or a mixture thereof 16. · If the hardened organic rubber article of item 15 of the patent application, The object is a tire. Π. — A seed slurry comprising a hydrophobic particulate inorganic oxide as described in the scope of the patent application in a water-immiscible organic solvent. 18. The slurry according to item 17 of the scope of patent application, wherein the water-immiscible organic solvent is selected from the group consisting of aliphatic tobaccos, environmental compounds, aromatic hydrocarbons and steel 500753 Scope of patent application a As described in the scope of application of the patent No. 18, where the organic solvent is hexafluorobenzene, heptyl toluene, cyclohexane and methyl isobutyl methyl steel; and the hydrophobic particulate inorganic oxide is further characterized by the content of The base / square milliH rabbit content Q 3 to 3% by weight and the M! Standard white area is less than 0.2%. ^ -------- ^ --------- ^ (Please read the notes on the back before filling out this page) Printed on paper scales printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, applicable to Chinese national standards (CNS) A4 size (210 X 297 mm) 49