TWI292415B - - Google Patents

Description

1292415 A7 B7 ml .- Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. V. Description of the Invention (Interactive References for the Application) This application claims the US Provisional Application No. 60/203,428, filed on May 10, 2000. The benefit of the application Serial No. 60/172,309, filed on Dec. 17, 1999, and the priority of the application, which is filed on Aug. 19, 1999. The disclosure of the present invention relates to chemically treated fillers and such fillers. In the case of a polymerizable composition, in more detail, the fourth or fourth (4) granular or amorphous filler has a minimum carbon and sulfhydryl content, a minimum decane conversion index, a minimum standard strengthening index, and The invention relates to a polymer containing such a filler, such as a ripe-transformable composition. In most detail, the present invention relates to a functionalized and hydrophobized filler, hereinafter referred to as a "modified filler", which enhances the manufacture of a polymerizable composition. Such as the efficiency of rubber compounding, and the performance of polymerization or curing products such as tires. In the manufacture of polymerizable compositions, fillers are usually included to increase Into the physical properties of the polymer. The surface of the filler is usually modified to increase the reactivity and the two-dimensional and three-dimensional coupling of the filler in the polymerizable composition. In the rubber industry, Carbon black and other reinforcing fillers are included in natural and synthetic rubber to enhance the physical properties of the cured vulcanized rubber. Fillers for reinforcing the polymerizable compositions, including natural and synthetic fillers. The black body filler is an amorphous precipitated oxidation _. The 7-type filler is used for the tensile strength, tear resistance and abrasion resistance of the vulcanized rubber. The oxygen cutting filler is also applicable to the Chinese national standard. (CNS) A4 Specifications>--__ (Please read the phonetic on the back? Please fill out this page again) I------^----Book---------Line---

Φ Φ Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed 1292415 V. Invention Description (2) Combined use to obtain tires and non-road tires for passenger vehicles such as mining and logging operations and tires for road construction equipment The maximum mileage. 4 applications have developed well. When cerium oxide filler is used as the sole reinforcing filler, the oxidized oxide filler which is not well dispersed and/or coupled in the rubber cannot provide the overall improved performance as obtained when carbon black is used alone. This is most commonly observed in vulcanized rubber used in tires such as tire treads. When a filler is incorporated into a polymerizable composition such as rubber, various coupling agents such as titanate, silicate and decane have been proposed to be used in combination with the fillers to enhance the properties of the vulcanized rubber. Among the various organodecane coupling agents proposed for such use are mercaptoalkyltrialkoxydecanes such as mercaptopropyltrimethoxydecane. It has been reported that a suitable amount of such coupling agents, in particular mercaptopropyltrimethoxydecane, is used in synthetic rubber reinforced with enamel fillers in several major physical properties such as 300% modulus, tensile strength, abrasion resistance In terms of force and heat accumulation, it provides at least comparable performance to carbon black-reinforced synthetic rubber. The high cost of ML-based sinter-based oxy-ceramics, the irritating odor of the pure substance and the time and energy required to mix it into the rubber composition, hindering the enamel filler from being more widely used as a large-scale The use of primary reinforcing fillers in volumetric rubber applications. U.S. Patent No. 4,436,847 teaches the use of alkoxy decane in combination with monooxane to form a coupling composition which increases the efficiency of the sulphur coupling agent, particularly the weiji smelting coupling agent. In a specific embodiment of the patent application No. 4,436,847, the decane coupling group is prepared in an appropriate non-reactive liquid enamel filler formulation (please read the back side of the 咅? ) 1292415 A7

众1有 0 ^Λψ Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed, Co., Ltd., additive, Shi Xiyuan Concentrate, where the liquid is chemically inert to the oxidized stone. And the method of the present invention is described in U.S. Patent No. 5,116,886, the disclosure of which is incorporated herein by reference. Change natural or caution, in the first step of the process, in the step of mixing the organic compound with the filler at a temperature lower than C, the temperature is treated at a temperature of 60 to 160 〇C to complete the modification of the surface of the filler. Sexual effect. x =,, this compound, #US Patent No. 5, No. 660, also describes a method for preparing a hydrophobic emulsified stone. In the first step, the precipitated oxygen-cut aqueous suspension is contacted with the _organic stone compound in the presence of a catalytic amount of an acid to effect hydrophobicization of the smectite type oxidized stone. In the second step, the aqueous suspension of the aqueous precipitated oxygen cut is contacted with a non-water miscible organic solvent at a weight ratio of the solvent greater than 5: oxime to the oxygen cut to separate the hydrophobic phase from the aqueous phase. Sexual precipitated cerium oxide. It has been found that it is possible to prepare an improved modified filler, such as a particulate or amorphous inorganic oxide, characterized in that its carbon content is greater than i% by weight, the sulfhydryl content is greater than 〇15% by weight, and the decane conversion index (description) Afterwards) is at least 0.3 and the standard strengthening index (also indicated later) is 4 or more. The method of U.S. Patent No. 5,908,660 can be modified, and a specific composition of one of the functionalized hydrazine and hydrophobizing agent used in an aqueous suspension of an inorganic oxide having a pH of less than 2.5, and Treat the acidic aqueous suspension of the modified filler with an acid neutralizer to raise the pH of the suspension to 3.0 to 1 〇. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 6 I- ---I ΙΓ-----------^----------- (Please read the note on the back? Please fill out this page again) 1292415

, invention description (4) 干 The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed the dry circumference, and the modified filler of the present invention. As used herein, a functionalizing agent is a reactive chemical which promotes covalent bonding of the inorganic oxide used in the polymerizable composition to the composition. a hydrophobizing agent-chemical substance which adheres to and/or binds to an inorganic oxide to reduce the affinity of the inorganic oxide for water while increasing the inorganic oxide used in the organic polymerizable composition for The affinity of the composition. A standard strengthening index of at least 4 or more refers to the interaction between the components of the filler-polymer composition and the modification of the bonding. In more detail, the interaction between the filler and the polymer and/or between the polymer and the polymer is stronger than the amount of interaction between the filler and the filler. In other words, the interaction between the 5' filler and the filler is weaker than the amount of interaction between the filler and the polymer and/or between the polymer and the polymer. It has been reported that these interactions are suitably modified in a rubber composition, such as a longer wear life of the tire tread, a lower rolling resistance, and a lower grip. In addition to enhancing the properties, it takes less time and energy to change the filler to have a nano-polymeric composition. BRIEF DESCRIPTION OF THE DRAWINGS In addition to the examples of operation or the other description, it should be understood that all the numerical values used to represent the quantity, the ratio, the range, and the like are modified in each case by the word "about". By any kind of production of the filler ------1*· - I hi — i 卜 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Please fill out this page again)

1292415 5♦ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7, invention description (5) prepared, the filler is an inorganic oxide, the carbon content is more than 1% by weight, preferably at least 1_5% by weight, more Preferably, it is at least 2.0% by weight; its sulfhydryl content is more than 0.15% by weight, preferably at least 3% by weight, more preferably at least 0.5% by weight, and its decane conversion index is at least 〇3, preferably at least 〇.4. , preferably at least 0.5; and a standard reinforcement index of at least 4.0, preferably at least 4.5, and more preferably at least 5.0. The modified filler of the present invention is also characterized in that the tensile stress at 300% stretching is at least 6.2, preferably at least 7. ’' is more preferably at least 7.5, and most preferably at least 8.0. The modified filler of the present invention is further characterized by a modified Brunauer-Emmett-Teller (BET) single point surface area of 20 to 35 square meters per gram, preferably 40 to 300 square meters / gram, preferably 1 to 2 square meters / gram; pH from 5 to 10, preferably from 5.5 to 9.5, more preferably from 6 to 9.0, and best from 6.5 To 7.5, or the pH of the product may be between the combinations of the values, including the recited values; and the percentage of extractable carbon of s〇xhiet is less than 3%, preferably Less than 25%, more preferably less than 20%, such as 15%. The method for determining the aforementioned characteristics of the modified inorganic oxide is described in the fifteenth example. The filler used to prepare the modified filler of the present invention is an inorganic oxide which is defined herein as having oxygen (chemically or covalently bonded) or hydroxyl (bonded or free) on its exposed surface. Any of the inorganic particulate or amorphous solid materials. In addition, the inorganic oxide is one suitable for use in a variety of molding, compounding or coating processes, including injection molding, lamination, transfer molding, compression molding, rubber compounding, coating ( Such as dip coating, brush coating, blade coating, roll coating, screen coating, printing, this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) — I — III *1 -i- ·丨丨丨1 丨丨丨—丨丨丨—I 丨-丨JL III (Please read the notes on the back and fill out this page) 1292415

5. Description of the invention (6 η spraying, etc.), casting, etc. • An inorganic oxide or a mixture of two or more inorganic oxides used to make the modified filler of the present invention may be either natural or synthetic. The filler includes (10) WUey & 8 company published in 198, such as c 〇 等 等 等 : : : : : : : : : : : : : : : : : : : : 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素 元素nIa, mb, m, IVb (except carbon), % Via Vila and oxides of Group VIII metals. Among the natural oxalates, kaolin or clay is particularly suitable. However, thin soil can also be used. Oxygen, hydrating or trihydrate in natural sediments, and oxidation! Too can be four columns of the fillers exemplified. Particularly suitable synthetic fillers are Mingshixi I salt, serotonate 'pyrolysis oxidized oxide shi, colloidal oxidation ♦ and precipitated yttrium oxide. 4

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. The term "aluminum silicate" refers to a natural or synthetic substance in which a part of the ruthenium atoms in cerium oxide is naturally or artificially substituted with aluminum atoms. For example, 5 to 9 % by weight or optionally 10 to 80 % of ruthenium atoms in the ruthenium dioxide may be naturally or artificially substituted with an aluminum atom to produce an aluminosilicate. Suitable for the preparation, for example by adjusting the coprecipitation of the pH of the alkaline solution or mixture of citrate and aluminate, and for example by cerium oxide or cericol on the surface of the dioxide Chemical reaction with sodium disodium hydride. For example, in the method of 4 total slabs, 5 to 95% of the surface of the synthesized coprecipitated Mingshi compound is composed of yttrium oxide, and correspondingly 95 to 5% of the surface is composed of aluminum. Composed of. Examples of natural aluminosilicates include muscovite, beryl, cordierite, sepiolite and kaolin. Examples of synthetic aluminosilicates, including the boiling paper scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public) 9 -------l·.-------- -----Order---------Line--- (Please read the phonetic on the back? Please fill in this page again) 1292415 A7

Φ---Φ------- , Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed stone and β Hai, etc. Φ chemical formula such as [(4) 2 from (8) 〇 seven (talking) z], [(Al2〇3) x(Si〇2)y is represented by ¥0], where γ is magnesium or calcium. The inorganic oxide used for the preparation of the modified filler of the present invention, preferably I lyxate, colloidal oxidized stone, sedative oxidized stone or a mixture thereof, and is preferably a precipitate type commonly used in rubber compounding. Oxide type. The cerium oxide obtainable for various commodities of the present invention can be considered, including oxidized granules obtained by PPG Ind Heres under the Hi Yun trademark under the model 2iq, (4), etc.; from Rh〇ne_PGulen (^5l to, for example, ζιΐ65Μρ Oxygen cleavage obtained with Z165GR; and cerium oxide obtained by, for example, Models VN2 and VN3 from Ag. The precipitated oxidized oxide used to make the modified filler of the present invention may be, for example, a solution of sodium salt such as sodium salt. The method of preparing the precipitated oxidized stone is not limited by the present invention, and the desired oxygen permeability, such as the surface area and particle size required for the mosquito application, is used. The modified oxidized oxidized stone of the present invention has a surface area of from about 50 square meters per gram to the square of caliph per gram, preferably from about 100 square meters per gram to 500 square meters. / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / According to the pie. The dried re-dispersed in a silicon oxide containing '^ ^ and / or an organic solvent in the water 3, percent. Transportable and oxygen / organic suspension in the aqueous or hydrophobic sink

This paper scales the Chinese national standard (CWSM4 rules (10) 297 297 public shame) _ -------Γ — ------I— ---------—Bu (please read first) Note on the back page again) 1292415

5. Description of the invention (long spoon/length is not critical, it may range from about 1 to 90% by weight. The concentration of 'f / yttrium-type yttrium oxide is preferably in the range of 1 to 50% by weight. The system is in the range of 1 to 20% by weight. Φ Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs (please read the notes on the back and fill out this page) 2 The Shih-Shu conversion index is based on the equation TVa1 + τ2 + τ3 ) to define. The values of T1 stone and strontium are determined by solid-state 29 NMR, and the representative unit = sulphur conversion index provides an indication of the degree of reaction or cross-linking of decane on the adjacent lithium atom and their mutual interaction. . Index value | The door represents the amount of cross-linking between Shi Xizhen, the surface of the oxidized stone and the adjacent Shixiyuan. < Large τ represents a decane unit, which is chemically bonded to the oxidized surface at one site or another. Τ2 represents a sinter unit which is localized to a ruthenium atom bonded to the surface of the ruthenium oxide and an adjacent decane, bonded to two adjacent decanes or bonded to two adjacent surfaces. Atom, also awkward. Know the structure of the father. Τ3 represents a sinter unit, which is localized to a ruthenium atom bonded to the surface of the ruthenium oxide and two adjacent decane, a bond, σ to a shi atom and a stone yoke or bonded to Three seconds burning unit. According to k, such skilled couplers can develop an organometallic reactant conversion index comparable to the number of decane conversions, and can be used to provide acid salts and/or titanates (alone or in combination with decane). An indicator of the degree of reaction or crosslinking with inorganic oxides or their mutual. The standard reinforcement index is determined by a standard compound procedure. The cohesive compounding procedure described herein does not include the addition of free or unbonded coupling agents to the batch of rubber. This is an important difference, as others have reported reinforcement indices, such as 300% modulus/100% modulus ratio, above 4〇. See U.S. Patent Nos. 5,846,311, and 5,876,494. The two patents are all in rubber

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V. Description of invention (9 Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Cooperative, printing compound during the compounding period, x 5G_S, type of oxygen cutting/rubber coupling agent. Blood type 'If the coupling agent is added to the batch of rubber, the compound machine Longer mixing time is required. The polymerizable composition of the modified filler, such as plastic and/or resin, includes any plastic and/or resin, and the rubber compound is covered by the definition. These polymers are described in the coffee published in i996 (10) (10), Encyclopedia of Technology, 4th Edition, Vol. 19, pp. 881, which explains that Neigu is incorporated into this case for reference. The modified filler is a polymer or a polymerizable component thereof, and the physical form of the polymer or its polymerizable component is any liquid or compoundable form such as a solution, a suspension, a latex, a dispersion, etc. The polymerizable composition of each modified filler may be ground, mixed, molded, and aged by any means known in the art to form a polymer having 1 to 15 parts per 1 part of the polymer. Part of the modified filler dispersed - Polymer parts. Examples of suitable polymers include thermoplastic and thermosetting resins, rubber compounds and other polymers having elastomeric properties. σ Hydrazine can be an alkyd resin, an oil-modified alkyd resin, an unsaturated polymer Ester, natural oils (linseed oil, tung oil, soybean oil), epoxide, nylon, thermoplastic polyester (such as polyethylene terephthalate, polybutylene terephthalate), thermoplastic and thermosetting polycarbonate Ester, polyethylene, polybutene, polystyrene, polypropylene, ethylene propylene copolymer and terpolymer, acrylic (acrylic acid homopolymer and copolymer, acrylate, methacrylate, acrylamide, its Such as salt and hydrohalide, etc.), phenolic resin, polyoxygenate (homopolymer and copolymer), polyurethane, polyfluorene, polysulfide rubber, nitrification fiber paper scale applicable to China National Standard (CNS) A4 size (210 X 297 mm) 12 -------.—^-book--------- (please read the phonetic on the back? Please fill out this page again) 1292415 A7 B7 Φ- ----- Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives (10) Vitamins, vinyl butyrate, vinyl (containing ethylene gasification and / or vinyl acetate polymer), ethyl cellulose, cellulose acetate and butyric acid, viscose , shellac, wax, ethylene copolymer (such as ethylene-vinyl acetate co-I, ethylene-propionic acid copolymer, acetoacetic acid vinegar copolymer), organic silicone, ketone ester, oxime Resin, silicone rubber, etc. The amount of the modified filler in the polymerizable composition may be 5 to 70% by weight based on the total weight of the plastic composition. For example, the modified filler is in ABS (acrylonitrile-butadiene). Typical amounts in the -styrene) copolymer are from 30 to 60% by weight, from 5 to 5% by weight in the acrylonitrile styrene-acrylate copolymer, and from 15 to 30 weight in the aliphatic polyketone. %, from 30 to 60% by weight in the alkyd resin, from 1 to 3 % by weight in the thermoplastic olefin, and from 5 to 20% by weight in the epoxy resin, in the ethylene vinyl acetate copolymer Up to 60% by weight, up to 80% by weight in the ethyl acetate ethyl acetate copolymer, in liquid crystal Compound (Lcp) to children is based in Sichuan wt% as 30 to 60% by weight in a phenol resin, and the amount in the polyethylene is generally greater than 40 wt%. In more detail, organic rubber and silicone rubber are preferred. Examples of such rubbers include natural rubber; these are formed by the homopolymerization of butadiene and its homologues and derivatives, such as cis-indene, polyisoprene, 3,4-polyisoprene. Diene, cis-polydibutene, trans-hydrazine, 'polydibutyl, 1,2-polydibutyl; and such self-butyl disaccharides and their homologs 16 and derivatives and one or more A copolymerization of a polymerizable monomer containing ethylenic unsaturation, such as styrene and its derivatives, an ethylene group, a bite and a derivative thereof, a propylene, an isobutylene, and a pyrenyl-substituted acrylic acid. Vinegar such as A-------Γ,--ϋ--------Book---------Line--I (Please read the back note first and then fill out this page )

1292415 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Description of invention (11) acrylate. Examples include styrene-butadiene copolymer rubber (hereinafter referred to as "SBR,") composed of different styrene and butadiene percentages and various butadiene isomers as desired; styrene, isoprene a dimer of a diene and a butadiene polymer and various isomers thereof; and a rubber group or a composition mainly composed of isobutylene; or a mixture thereof, as described in, for example, U.S. Patent No. 4,53,959 , 4, 616, 065, 4, 748, 199, 4, 866, 131, 4, 894, 420, 4, 925, 894, 5, 082, 901 and 5, 162, 409. Other suitable organic polymers are ethylene and other advanced alpha-glycols Copolymers such as propylene, butene-1 and pentene-1 and a diene monomer. The organic polymer can be a block, random or sequential polymer, and can be used by an emulsion (eg e-SBR) Or a solution (such as S-SBR) polymerization process. Other useful polymers include those partially or fully functionalized, including coupling or star-branched polymers. Other specific examples of functionalized organic rubber include Polybutadiene, chlorobutyl and bromobutyl Rubber, and brominated isobutylene-co-p-methylstyrene rubber. Preferred organic rubbers are polybutadiene, s_SBR and mixtures thereof. Examples of the silicone rubber include organic polyoxane compositions, wherein the organic ♦ The milk-fired system is a direct bond or a brancher, and optionally may contain some reactive groups such as a hydroxyl group, a hydrolyzable group, an alkene group such as a vinyl group, a hydrogen group, a fluoro group and a phenyl group in addition to a ketone group. Further examples are shown in U.S. Patent No. 5,009,874, the entire disclosure of which is incorporated herein by reference. Curing rubber.,, maturability This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 14 -------Γ.--------ί--- -Book---------Line-- (Please read the notes on the back and fill out this page) Α7

Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

1292415 V. INSTRUCTIONS INSTRUCTIONS (丨2) "" Rubber" - the term is intended to include natural rubber and its various raw materials and recycled shapes, and various mouths of "rubber. For example, the curable rubber may include a combination with butyl rubber. , coffee, br and natural rubber, as well as any other combination of the previously disclosed as an organic rubber. In the month of the month of the month, the rubber |, "elastomer,, and, rubber-like elastomer, , etc. are used interchangeably unless otherwise stated. , rubber composition,, "composite rubber" and, rubber compound, and other words can be used interchangeably, and refers to blending or different combinations of ingredients and substances of rubber, the vocabulary is mature rubber Mixed or well known to those skilled in the art. The modified filler of the present invention can be disclosed by the step A itself of the U.S. Patent Nos. 5,9,8,66, and 5,919,298, each of which is incorporated herein by reference. It is to be understood that the disclosure of the present invention is incorporated herein by reference. The amount of the acid is such that the pH of the aqueous suspension is less than 2·5, the pH is preferably 2.0 or less, the enthalpy value is preferably 1.0 or less, and the ρΗ value is preferably 0_5 or less; the modified chemical substance used is a composition of a mercapto organometallic reactant and a sulfur-free organometallic compound (hereinafter referred to as a non-sulfur organometallic compound), the weight ratio of the mercapto organometallic reactant to the non-sulfur organometallic compound being at least 〇.〇5 : 1, preferably from 〇. 〇 5 : 1 to 10 : 1, better from 0.1 : 1 to 5 : 1, best from 0 · 2 : 1 to 2 · · 1 'for example from 0.5 · · 1 to 1 : 1, or the weight ratio may be between any combination of the values, including the recited values; and after the chemical treatment is completed, the acidity is applied (by adding or depending on the paper size of the halogenated organometallic compound) China National Standard (CNS) A4 Specification (210 X 297 mm) 15 --------r 11 ----h---Order--- (Please read the notes on the back and fill out this page. ) 1292415

5. The invention description (I3 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed hydrolyzed and produced in situ) is neutralized. After the chemical treatment is completed, the cation value of the aqueous suspension produced by the household is also raised to the mine circumference and the training can be any type that is typically used to raise the pH of an acidic solution as long as it does not wait. It is sufficient to damage the properties of the modified filler. Suitable neutralization d includes sodium hydroxide, potassium hydroxide, ammonium hydroxide and sodium bicarbonate. The neutralization of the modified filler can also be achieved by adding gaseous state 4 to the aqueous solution during spray drying. The acid used in step (A) may be of various organic and/or inorganic types. The more ruthenium catalysts are inorganic. Examples of the preferred acid catalyst include hydrogen acid, hydrogen, odor acid, hydromolybdic acid, sulfuric acid, nitric acid, pot acid, and benzoic acid. A mixture of two or more acid catalysts may be used depending on the desired acid. When the organometallic reactant is, for example, a chlorine cut, a catalytic amount of acid can be generated in situ by hydrolysis of gasified naphthenes or by direct reaction of vaporized decane with a hydroxyl group of the inorganic oxide. The temperature at which step (A) is carried out is not critical, although a slightly lower or higher temperature may be used when needed, which is usually between 2 Torr. (: to 25 〇 (the range of ^. The reaction temperature will depend on the reactants used such as organometallic compounds, acids and cosolvents if used. Step (A) is preferably between 3〇% and 15〇 The temperature in the range of C is carried out, although step (a) may be carried out at the reflux temperature of the slurry used in the step (A) when necessary. In the foregoing reaction, the modifying chemical or coupling agent may be The functionalizing agent replaces the mercapto organometallic compound and the hydrophobizing agent replaces one of the non-sulfur organometallic compounds. The weight ratio of the functionalizing agent to the hydrophobizing agent can be related to the mercapto organometallic compound and non-sulfur Γ. ί I l·----订·--------line (please read the notes on the back and fill out this page)

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Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumption Cooperatives. 5. Description of the invention (I4 metal compound composition is the same as defined.) The functional group may contain reactive groups including, but not limited to, acetamyl, epoxy, glycidol Oxyl and (meth)acrylic 1-yl. Sulfides, polysulfides and sulfhydryl groups may also be reactive groups of functionalizing agents, provided that they do not conform to the chemical formulas and hydrazines encompassed herein. Chemicals as hydrophobizing agents include, but are not limited to, natural or synthetic lipids and oils, and non-sulfur organometallic compounds represented by chemical formulas III, IV, V, and such hydrophobization. a mixture of an acidic aqueous suspension of an inorganic oxide in contact with a composition of a cerium-based organometallic sulfonate and a non-sulfur organometallic compound, wherein the non-sulfur organometallic compound is preferably a non-sulfur The organic cerium compound may further comprise a water-miscible solvent added in one of a reaction sufficient to promote the reaction with the inorganic oxide. The solvent acts as a phase transfer agent, plus The composition of the fast hydrophobic sulfur and the non-sulfur organometallic compound interacts with the parent of the hydrophilic inorganic oxide. When used, the amount of the water-miscible organic solvent will typically constitute at least 5% by weight of the aqueous suspension, more preferably It is 15 to 50 parts by weight of 含水/〇 and preferably 2 to 3 parts by weight of the aqueous suspension, or the weight percentage may be between any combination of the values, including the recited values. The water-miscible solvent includes, for example, alcohols such as ethanol, isopropanol, and tetrahydrofuran. Preferably, isopropyl alcohol is used as the water-miscible organic solvent. It may also be used in combination with water-miscible organic solvents in the initial step. A method of using a surfactant in an amount sufficient to promote chemical modification of an inorganic oxide which is introduced by a mercapto organometallic compound and a non-sulfur organometallic compound. For non-------Γ--h------------------- l (Please read the notes on the back and fill out this page)

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If the invention (I5) is an anionic, cationic, amphoteric or a mixture of such surfactants, the premise is that it does not impair the properties of the resulting chemically modified inorganic oxide for its intended use. Typically, when the surfactant is used, it is 〇〇5 to 1% by weight, more preferably 〇1 to 5, 里/〇, and most preferably 0. 丨 to 3 by weight of the aqueous suspension. %, or the weight percentage may be between any combination of the values, including the recited values. Representative examples of suitable surfactants include alkylphenol polyglycol ethers such as p-octylphenol polyethylene glycol (2〇 unit) ether, p-nonylphenol polyethylene glycol (20 units) Ether; alkyl polyglycol ethers, such as lauryl polyethylene glycol (20 units) ether; polyethylene glycols, such as polyethylene glycol 2 oxime; alkyl trimethyl ammonium salts , such as cetyltrimethylammonium vapor (or bromide); dialkyl monomethyl ammonium salts, such as dilauryl dimethyl ammonium chloride; alkyl benzyl monomethyl ammonium salts; An alkylbenzene sulfonate such as sodium p-dodecylbenzenesulfonate of p-dodecylbenzenesulfonate; an alkyl hydrogen sulfate such as lauryl hydrogen sulfate; and an alkyl sulfate such as sulfuric acid Lauryl ester. The surfactant is also, for example, a polyoxo-fired polymer or copolymer having a dipropyl end-blocked polyethylene oxide. The fluorenyl organometallic compound ' used to make the modified filler of the present invention is represented by the following structural formula I: (L)n HS_R6_μ/ ι • \ρ(3-η) wherein Μ is 矽, L is !i Or -OR7, q is hydrogen, CrCi2 alkyl or Cl-Cl2 alkyl substituted by 13⁄4, R6 is Ci_Ci2 alkylene, R^Ci_c i loaded -------- ------ r (Please read the note on the back and fill out this page), Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1292415 Α7 Β7 Ψ Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Inventions ( I6 alkyl or an alkoxyalkyl group having 2 to 12 carbon atoms, which is a chloro, bromo, iodo or fluoro group, n is 1, 2 or 3 R6 is preferably c^-c:3 alkylene, such as ruthenium, ethylene and propylene, R7 is preferably Ci_C4 alkyl group, more preferably methyl and ethyl, L is preferably -〇R6, and n is more Preferably, a ruthenium-based organometallic reactant having two mercapto groups may also be used. It is also possible to use a mercapto-based organometallic compound in which the mercapto group is a blocked type, that is, the mercapto hydrogen atom is substituted with another group. The closed type The organometallic compound may have an unsaturated hetero atom or carbon bonded directly to the sulfur via a single bond. Examples of specific blocking groups include thiocarboxylates, dithiocarbamates, thiosulfides Acid esters, thiosulfates, phosphorothioates, thiophosphonates, thiophosphites, etc. When a reaction of the mixture is required to couple the filler to the polymer, a deblocking agent can be added to the mixture. To unblock the blocked sulfhydryl organometallic compound. If water and/or alcohol is present in the mixture, a catalyst such as a tertiary amine, a Lewis acid or a thiol may be used to initiate or promote removal by hydrolysis or alcoholysis. The blocking group is used to release the corresponding sulfhydryl organometallic compound. The method for preparing and using the compound such as blocked decyl decane is disclosed in PCT towel request WQ 99/_6 for preparing a closed (tetra) decane. The methods are disclosed in U.S. Patent Nos. 3,692,812 and 3,922,436, the disclosures of each of which are incorporated herein by reference. Methoxylate, mercaptoethyltrimethoxy (tetra), propylpropyltrimethoxydecane, mercaptomethyltriethoxydecane, mercaptoethyltripropoxylate, and propylpropyltriethoxylate Oxane, (sequential methyl) dimethyl ethoxy-------- Γ--装-----^----订---------. (Please first Read the phonetic on the back? Please fill out this page again)

1292415 A7 B7 Φ-ΦΊ Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Inventions (η), decane, (decylmethyl) decyl diethoxy decane, 3-M propyl dimethyl oxane Base decane and mixtures thereof. The most preferred compound is mercaptopropyltrimethoxydecane, mercaptopropyltriethoxydecane or a mixture thereof. Examples of suitable blocked mercapto organometallic decanes include, but are not limited to, 2-triethoxymethane-1-ylthioacetate, 3-trimethoxydecyl-1-propylthio Octanoate, bis-(3-triethoxycarbamid-l-propyl)-methyldithiophosphonate, 3-triethoxymethane-1-yldimethylsulfide Hypophosphite, 3-triethoxycarbamido-1-propylmethylthiosulfate, 3-triethoxymethylidene-1-propyltoluene thiothreate and mixtures thereof . The non-sulfur organometallic compound 'which can be used to make the modified filler of the present invention' can be at least one non-sulfur organometallic compound or a mixture of non-sulfur organometallic compounds selected from the group consisting of Organometallic compound represented by Chemical Formula II: MX(4-a) 有机 Organometallic compound represented by Chemical Formula III:

R22c+2 Si c°(c-l) HI Organometallic compound represented by chemical formula IV:

R32d Si d°d IV Organometallic compound represented by chemical formula V:

(R23 Si )k NR4(3.k) V wherein each M is independently of each other, ruthenium, titanium or ruthenium; each of the Ri is independently a hydrocarbon group having 1 to 18 carbon atoms or R1 may have 丨 to 12 An organofunctional hydrocarbon group of a stone anti-atom, wherein the functionality is, for example, an amine group, a carbure paper scale applicable to the Chinese National Standard (CNS) A4 specification (21G x 297 public)-----II- _ — — I —卜—卜———— I · — — — — — — 1 — 卜· I* (Please read the notes on the back and fill out this page) 1292415 Α7 Β7 ♦ Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed 5, Invention Description (is), methanol or guanamine; each x is independently of one another selected from the group consisting of halogen, amine, alkoxy having from 1 to 12 carbon atoms and oxime having from 12 to 12 carbon atoms Alkoxy, a is an integer 丨, 2 or 3; each R2 is independently a halo group, a hydroxy group or a hydrocarbyl group having from 丨 to 18 carbon atoms, provided that it is 50 mol% of the r2 substituent. Is a hydrocarbon group containing from 1 to 18 carbon atoms, c is an integer from 2 to 1 〇, and each R3 is independent of each other The ground is a halo group, a hydroxyl group or a hydrocarbon group having from 8 to 8 carbon atoms, and d is an integer from 3 to 20, each R4 being independently hydrogen or one having from 1 to 18 carbon atoms a hydrocarbon group, and k is 1 or 2; and the _ or _ group is selected from a chaotic group, a bromo group, an iodo group or a fluoro group. In the definitions of the substituents of the chemical formulas π, ιπ, ιν and V, the same symbols have the same meaning ' unless otherwise stated. In Formula II, each R1 may be a saturated or unsaturated monovalent hydrocarbon group or a substituted or unsubstituted monovalent hydrocarbon group. For example, ... may be an alkyl group such as methyl, ethyl, propyl, isopropyl, isobutyl I, tert-butyl, n-butyl, pentyl, hexyl, heptyl, octyl, decyl, fluorene And a decyl group; an alkene group such as a vinyl group, an allyl group and a hexenyl group; a substituted alkyl group 4 such as a chloromethyl group, a 3,3,3-trifluoropropyl group and a 6-ahexyl group; a cycloalkane; The group is, for example, a hexyl group and a cyclooctyl group; an aryl group such as a phenyl group and a hexa group, and a substituted aryl group such as a benzyl group, a tolyl group and an ethylphenyl group. When X in the formula II is mono-halogen, the halogen is preferably a chloro group, and the oxime may be, for example, a methoxy group, an ethoxy group or a propyloxy group. When hydrazine is a hydrazino group, X may be, for example, an ethoxy group. Preferably, each X is selected from the group consisting of chloro and methoxy. -------Γ---Γ -----«----订--------- I l· (Please read the notes on the back and fill out this page)

1292415

Description of the invention (I9 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). The viscosity of the above organometallic compound is not limited, and it may range from the viscosity of the L body to a gel. In general, the organometallic compound having a relatively high molecular weight should be cleaved by the acidic conditions of the chemical modification step to cause it to react with the hydrophilic inorganic oxide. In Chemical Formulas III, IV, and V, each of R2, R3, and R4 is the same as the one shown for R1. For the purposes of the present invention, when the organometallic reactant is an organoquinone reactant, it is deliberately treated as a metal. The non-sulfur organometallic compound is preferably a compound represented by the formula Π, m, ^ and ¥ or a mixture of the organometallic compounds, wherein each lanthanum is Shi Xi. More preferably, the non-sulfur organometallic compound is represented by the formula II wherein R1 is a Ci-C6 alkyl group, X is a chloro group, and a is 2. Examples of suitable organogermanium compounds include, but are not limited to, mixtures of compounds selected from the group consisting of diethyldichlorodecane, propylpropylmethyldichlorodecane, nonylphenyldichlorodecane, benzene Benzyl diethoxy oxalate, 3,3,3-trifluoropropylmethyldioxane, trimethylbutoxylate, homo-diphenyltetramethyldioxane, triethylene Trimethylcyclotricarbazone, octamethylcyclotetraoxane, hexaethyldioxane, pentylmethyldichlorite, divinyldipropoxydecane, vinyl Base gas decane, vinyl methyl dioxane, vinyl dimethyl methoxy decane, trimethyl chlorite, trimethyl methoxy decane, trimethyl ethoxy decane, methyl trigas Brothel, methyltrimethoxydecane, methyltriethoxydecane, hexamethyldioxane, hexylmethyldichlorodecane, hexyldimethylchlorodecane, dimethylchlorodecane, dimethyldi Chlorodecane, dimethyldimethoxydecane, dimethyldiethoxydecane, hexamethyldioxane, trivinyltrimethylcyclo 22 -------- *1--装---h — — ----------^9--^---- (Please read the note on the back? Please fill out this page again) 1292415 A7 B7 ♦ Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Invention Description (2〇) Trioxane, polydimethyl methoxy alkane having 3 to about 20 dimethyl methoxy units, and trimethyl A poly(methyl methoxy oxane) polymer blocked by a decyloxy group or a hydroxy dimethyl methoxy end group having a viscosity at 25 〇c ranging from 1 to 1,000 mPa·s. Examples of suitable organotitanium compounds include, but are not limited to, Ci(cls) alkoxy titanate, methyltriethoxytitanium (iv), methyltitanium (iv) triisopropoxide, methyltitanium (iv) tributyl oxide, methyl titanium (iv) tri-tert-butoxide, isopropyl titanium (iv) tributyl oxide, butyl titanium (iv) triethoxylate, butyl titanium (iv Tributyl oxide, phenyl titanium (iv) triisopropoxide, phenyl titanium (~) dibutyl oxide, phenyl titanium (iv) triisobutyl oxide, [Ti(CH2Ph)3(NC5H1( ))] and [Ti(CH2SiMe3) 2(Net2) 2]. Examples of suitable organic compounds include, but are not limited to, Ci(cu) alkoxy phthalate, phenyl hydrazine (iv) trichloride, methyl hydrazine (iv) trichloride, ethyl oxa (iv) three Chloride, propyl hydrazine (iv) tri-vapor, methyl ^ (iv) dibromide, ethyl hammer (iv) tribromide, propyl hammer (iv) tribromide, vaporized diphenyl hydrazine ( Lv). It is also contemplated to include anthraquinone compounds similar to the above organotitanium compounds, and vice versa. The amount of the mercapto organometallic compound and the non-sulfur organometallic compound in the foregoing chemical modification method is sufficient to produce an amount of a modified filler characterized by a carbon content of more than 1% by weight and a mercapto group content of more than 0.15. The % by weight, the decane conversion index is at least 〇3 and the standard strengthening index is at least 4.0. This amount is referred to herein as a coupling amount, i.e., sufficient to bond the filler and to cause the modified filler to adhere to the polymeric composition. Mercapto-based organometallic compounds relative to non-sulfur organometallic compounds -------Γ.---Γ ----L------I--I —^^wi 1 l· (please Read the notes on the back and fill out this page)

1292415

Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Cooperatives

V. INSTRUCTIONS (21) The weight ratio is at least 0.05: i, preferably from 0 05 : : i, better from 0.1 : 1 to 5 : !, and the best from 2: summer solstice]: i, For example, from 5:] to 1: 1, or the weight ratio may be between any combination of the values, including the recited values. Each organometallic reactant can be added together or sequentially in either order. The organometallic unit to be added in an amount of the organometallic reactant is preferably present in an excess amount relative to the hydroxyl group available for reaction on the inorganic oxide particles. The upper limit of the amount of organometallic reactant added to the process is not critical. Excess sulfhydryl organometallic compounds and non-sulfur organometallic compounds can be removed by filtration, distillation, solvent cleaning or other known separation techniques. In another embodiment, the mercapto organometallic reactant can be substituted with a composition of a mercapto organometallic reactant and a different sulfur-containing organometallic compound, the weight of the mercapto organometallic reactant relative to the sulfur-containing organometallic compound. The ratio is at least greater than 1: 1, such as 丨〇i: 1. The weight ratio may be from 1·〇1 : 1 to 100 : 1, preferably from 5 : 1 to 50 : 1, more preferably from 1 〇 · 1 to 3 0 : 1, or the weight ratio may be between the values Between any combination, the recited values are included. Any of the sulfur-containing organometallic compounds (other than the mercapto organometallic compound represented by the chemical formula I) acting as a coupling agent in the vulcanization of a filler-containing rubber, and examples of suitable sulfur-containing organometallic compounds to be applied include The bis(alkoxycarbendane 3 alkyl) polysulfide of U.S. Patent No. 3,873,489 and U.S. Patent No. 5,580,919, the disclosure of which is incorporated herein by reference. : This paper is from the Chinese National Standard (CNS) A4 specification (21G X 297 mm) 24 — — — — — — !| I ki III l· III > — — — — — — 1 — I h IIL ( Please read the note on the back? Please fill out this page again. 1292415 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 --~-----2Z____ V. Description of Invention (22)

Z-alk_Sn'_alk_Z VII ^ wherein alk is a divalent hydrocarbon radical having from 1 to 18, preferably from 1 to 6, and more preferably from 2 to 3 carbon atoms; n, from 2 An integer of up to 12, preferably from 2 to 6 and more preferably from 3 to 4; and 2 are:

R r I —10, R, or —siZR· R, R * , R1 wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group; and R is one having 1 to 8 Preferably, it is preferably 4, more preferably an alkoxy group having 2 carbon atoms, or a cycloalkoxy group having 5 to 8 carbon atoms, or a linear chain having 丨 to 8 carbon atoms. Or a branched alkane group. The ruler and the R' base may be the same or different. The divalent alk group may be a straight or branched saturated or unsaturated aliphatic hydrocarbon group or a cyclic hydrocarbon group. The high purity organodecane disulfide disclosed in U.S. Patent No. 5,580,919, requires 80% of η in Chemical Formula I to be 2. Examples of the bis(alkoxycarboalkylalkyl) polysulfide include: bis(2-disalkoxycarboxyalkylethyl) polysulfide, wherein the trialkoxy group is dimethoxy, triethyl Oxyl, tris(methylethoxy), tripropoxy, tributoxy, etc. up to trioctyloxy, polysulfide is disulfide, trisulfide, tetrasulfide, pentasulfide and Sulfide. The corresponding bis(3_trialkoxycarbenylpropyl), bis(3-trialkoxycarbenylisobutyl), bis(4-trialkoxycarbenylbutyl), etc. may also be used. Up to the polysulfide of bis(6-trialkoxycarbenylhexyl). Preferably, it is a relatively simple structure of organic stone sinter, including bis(3-trimethoxy-, triethoxy- and 1,3-tripropoxy-methyl sulfonylpropyl) polysulfide; Disulfide, trisulfide and tetrasulfide paper scales are applicable to China National Standard (CNS) A4 specification (210 X 297 mm) f IL · I I-- ί----^-------- - (Please read the note on the back? Please fill out this page again) 1292415 A7 B7 V. Description of invention (23). (Please read the note on the back and then fill out this page.) A specific example of the bis(alkoxycarboxyalkyl) polysulfide is described in the aforementioned U.S. Patent No. 3,873,489, No. 6-55, and the United States. Patent No. 5, 580, 919, column 11, lines 11-41. Representative examples of such compounds are: 3,3'-bis(trimethoxycarbamidopropyl) disulfide; > 3,3,bis(triethoxydecylpropyl)tetrasulfide 3,3' bis(trimethoxymethyl methacrylate) tetrasulfide; 2,2' bis(triethoxymethyl sulfonylethyl) tetrasulfide; 3,3' bis (trimethoxy矽alkylpropyl)trisulfide; 3,3' bis(triethoxycarbamidopropyl)trisulfide; 3,3'.bis(tributylmethoxymethylalkylpropyl) disulfide; 3,3'-bis(trimethoxymethylglycolylpropyl)hexasulfide; and 3,3'-bis(trioctyloxymethylsulfanylpropyl) tetrasulfide and mixtures thereof. The most preferred compound is 3,3, bis(triethoxycarbamidopropyl) tetrasulfide ►(TESPT). Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives TESPT is available from Degussa under the trade name Si-69. It is reported to be 3,3' bis(triethoxycarbamidopropyl) monosulfide, 3,3, bis(triethoxymethylidenepropyl) disulfide, 3,3, double (triethoxymethyl sulfanylpropyl) trisulfide, 3,3' bis(triethoxy phthalocyanine) tetrasulfide and the higher sulphide with an average sulphide of 3.5 a mixture of one of the things. After the chemical modification is completed, the pH of the aqueous suspension of the modified inorganic oxide is raised from the pH of the treatment to 2.5 or less to 26. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210). X 297 mm) 1292415 A7 B7 ♦ Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed V. Description of the invention (24 pH between 3.0 and 1 〇·〇. Typically, the resulting aqueous suspension The pH value is increased to 3 or more, preferably 4 or more, more preferably 5 or more, and most preferably 6 or more, and usually 1 or less, preferably 9 or less, more preferably 8 or less, and most preferably 7 or less. The value of the 11% aqueous suspension may be between any combination of the values, including the recited values, which is achieved by neutralizing the acidity added or produced, and producing one with The final product (after drying) from pH 5 to 10.0. By filtration and drying, or the aqueous suspension of the modified inorganic oxide and the non-water miscible organic solvent are greater than i: 1 and 軚a solvent greater than 5 · 1 relative to the weight of the inorganic oxide The amount of the contact is in contact with the recovered inorganic oxide. The modified inorganic oxide recovered from the solvent phase can be used without further treatment or drying. One specific example of the present invention is a composition. The slurry comprises a slurry of a modified filler in a non-water-miscible organic solvent. The concentration of the modified filler in the slurry is between 1 and 90 weights, based on the total weight of the slurry. Examples of suitable non-water-miscible organic solvents include low molecular weight oxyhydrogenates, such as hexamethyldiazepine, octamethylcyclotetrazepine, diphenyltetradecyldioxane. And a polydimethyloxane fluid blocked by a trimethylphosphonium alkyl end group. When a nonoxyl alkane is used as a solvent, it acts as a solvent and a reactant which acts as the inorganic oxide. Suitable non-water-miscible organic solvents include aromatic hydrocarbons such as toluene and xylene; heptane and other aliphatic hydrocarbon solvents; cycloalkanes such as cyclohexane; ethers such as diethyl ether and dibutyl ether; Hydrocarbon solvent such as dichloromethane, chloroform, gas Ethylene and gas benzene, and ketones, such as methyl isobutyl ketone. ------- '---装---------- order---------^ 9— (Please read the notes on the back and fill out this page)

Φ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1292415 A7 ------------- V. INSTRUCTIONS (25) Non-aqueous solution for contact with aqueous suspensions of hydrophobic particulate inorganic oxides A mixed organic solvent, which may or may not contain one or more substances selected therein. Examples of such materials include, but are not limited to, one or more of rubbers, oils, couplers, antioxidants, and accelerators. The modified filler (in the form of a powder, granule, pellet, slurry, aqueous suspension or solvent suspension) of the present invention may be combined with a matrix material which is used in the product to be produced to form a A substance of a mixture of masterbatches. In the masterbatch, the modified filler can be present in a higher concentration than in the final product. In the mixing operation, the mixture is typically added in portions until the production scale is reached to assist in the uniform dispersion of such very small amounts of additives in the polymeric composition, such as plastics, rubber and coating compositions. The modified filler can be combined with an emulsion and/or a solution polymer such as an organic rubber containing a solution of styrene/butadiene rubber (SBR), polybutadiene rubber or a mixture thereof to form a master batch. One specific embodiment of the present invention is a masterbatch comprising a composition of an organic rubber, a non-water miscible solvent, a modified filler, and a selectively processed oil. This product can be supplied by rubber manufacturers to tire manufacturers. For tire manufacturers, the advantage of using a masterbatch is that the modified filler is uniformly dispersed in the rubber, which reduces the mixing time required to make the composite rubber. In the masterbatch, each part of the rubber may contain 10 to 150 parts (phr) of modified cerium oxide, preferably from 2 to 13 parts, more preferably from 30 to 100 parts, and the best from 5 to 8 parts. In another preferred embodiment of the present invention, a polymeric article is planned in which a 1 to 15 partial modified filler is dispersed in a portion of the mother 100 polymer, preferably dispersed per 100 parts of the polymer. There are 20 to 13 parts, better -------.------------ order·-------^9-^^ (please read the back first) Note on this page)

1292415 印 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives A7 V. Inventive Note (26) to 100 邛 injury, and the best 5 〇 to 8 〇 part of the modified filler. Optionally, the amount of modified filler can be between any combination of such values, including the recited values. As explained herein, the polymer can be selected from the group consisting of thermoplastic resins, thermosetting resins, organic rubbers, and silicones. The polymer is preferably a curable organic rubber. The main curable rubbers used in combination with the modified fillers of the present invention are well known to those skilled in the art of rubber smelting, and may include vulcanizable and sulfur curable rubbers. Special planners are those typically used for mechanical rubber articles. The modified filler of the present invention can be mixed with an unmatured rubber elastomer to be between about 100 °F and 300 by conventional means such as a Banbury mixer or rubber mill. Take 38. A vulcanizable rubber composition was prepared at a temperature of 〇15. The vulcanizable rubber composition may comprise from 10 to 150 parts of modified filler per one part of the partially vulcanizable rubber polymer, preferably from 20 to 130 parts, more preferably from 30 to 10 parts, and most Good 50 to 80 parts. Other conventional rubber additives present are conventional sulfur or peroxide ripening systems. The & ripening system may include 0.5 to 3 parts of sulfur, 2 to 5 parts of zinc oxide and 〇·5 to 2 parts of accelerator. The peroxide curing system can include a hydrazine to a partial peroxide such as dicumyl peroxide. Other conventional rubber additives can also be used. The additive includes other fillers such as carbon black; oils; plasticizer accelerators, antioxidants; thermal stabilizers; light stabilizers; regional stabilizers; organic acids such as stearic acid, benzoic acid or salicylic acid; , Additives and coloring pigments. The specific compound formulation will be based on the specific sulfur prepared. I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

1292415

Description of the invention (π 履 经济 经济 智慧 智慧 员工 员工 员工 员工 员工 员工 = = = = = = = , , , , , , = = , = , = = = = = = = = = = = = = = = = = = = = = = = = The rubber composition vulcanizes or matures the filler f. The examples of the modified rubber (object) which can be used in the present invention include wires and electric winding sleeves; the sealing and sealing members; the sanitary industry and the automobile Belt with belt V; belt; roller film; tire and tread tire tire tread, secondary tread, tire carcass, tire belly, tire belt frame, tire material filler, tire Steel wire slag surface layer; strip material; packing ring; shock absorbing element and many others. In the following discussion of standard compound procedures, examples and comparative examples, the invention is compared with the invention. The examples are for illustrative purposes only, as skilled artisans will appreciate a variety of modifications and variations. Standard-composite procedures use standard compound procedures to prepare examples and comparative examples (CE) of ruthenium oxide-containing formula rubber compositions Sample A. The following components are added in a weight-based portion (Phr) per 100 parts by weight of rubber, in the order described, to a polyethylene bag placed upright in a 5 (9) ml plastic cup. ^ - Amount (phr) Processing oil (1) 30.0 v Oxidation crush (2) 2 5 Antiozonant (3) 2.0 Stearic acid (4) 1 〇 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 30 — — — — — — — Γ — ll· · III l· III ^ II I------ hill (please read the notes on the back and fill out this page) 1292415 A7 B7 Ministry of Economics Property Bureau employee consumption cooperative printing

V. INSTRUCTIONS (28 yttrium oxide sample 12.5 (1) Sundex® 8125 aromatic hydrocarbon processing oil obtained from Sun's refining and marketing department. (2) Kadox® obtained from Zinc Corporation of America Surface treated zinc oxide. (3) Wingstay® 100 antiozonant available from Goodyear Tire & Rubber Co., Ltd., which is a mixture of diaryl p-phenylene diamine. C. P. Hall uses a 1.89 liter (L) Farrel Banbury mixer (model "BR") for the rubber grade stearic acid B portion obtained from the product to mix the ingredients. Prior to adding the batch* ingredients to the mixer, 800 grams of CV-60 grade natural rubber was placed in and through the mixer to remove any residue from previous operations and raise the temperature to approximately 93 °C (200 °). F) Cool the mixer to about 65 ° C (150 ° F) after removing the rubber and before adding the ingredients to make the rubber test sample. Use the test yttrium oxide, the following other listed ingredients and instructions A method of preparing a rubber composition. (phr) Time in minutes of mass of material (rpm, component added to the mixer (or removed from the mixer). First flow SBR rubber (5) 70.0 0 116 BR rubber (6) 30.0 0 116 Test oxidation矽57.5 0.5 116 Samples from Part A all 3.0 116 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 31 -------VI------.. ----^---------- μ (Please read the note on the back? Please fill out this page again) 1292415 A7 _B7 V. Description of invention (29)

Dumping the contents ((5.0)) The second process is the product from the first process. All 0 77 Antiozonants (7) 2.0 0 77 Paraffin (8) 1.5 0 77 RM sulfur (9) 1.4 0.5 77 TBBS (!〇) 1.7 0.5 77 DPG (") 2.0 0.5 77 Dumping contents ((4.0)) (5) Styrene-butadiene rubber (8611) from Solflex® 1216 solution from Goodyear Tire & Rubber. (6) From Goodyear tires and rubber companies to take the goods (please read the notes on the back and fill out this page) Budene 1207 butadiene rubber (BR) printed by the Ministry of Economic Affairs Intellectual Property Office Staff Cooperatives . (7) Santoflex® 13 antiozonant available from Goodyear Tyre & Rubber Company as N-(l,3-dimethylbutyl)- Ν'-phenyl-p-benzene Alkene diamine. (8) Okerin® 7240 microcrystalline wax/Dendrobium blend obtained from Astor. (9) Rubber Maker Sulfur obtained from the product of Taber, 100% active. (10) N-tert-butyl-2-benzoindole hydrazide from the product of Monsanto. (11) Diphenyl hydrazine obtained from Monsanto Corporation. The first procedure was started by adding rubber, SBR and BR rubber, to the mixer and mixing at 116 rpm for 0.5 minutes. The speed was maintained at 116 rpm and 57.5 phr of treated oxidized oxide sample was added. 1.5 minutes further This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 32 1292415

Fives,

Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives (30), lift the plunger and sweep the chute, that is, lift the cover of the inlet chute and sweep any material found in the chute back into the mixer. After a further minute, the sample from Part A was added. After a few minutes, lift the plunger and sweep the chute. The contents of the mixer were mixed for another minute to reach an upper temperature in the range of 145 to 150 C (293 to 302 ° F). Depending on the type of sample, the speed of the mixer can be increased or decreased after 4 minutes to reach a temperature within the aforementioned range during a specific mixing period. 0 After the first process is completed, the thermocouple is used to determine the temperature. The temperature of the substance to confirm that it does not exceed the upper limit of 150 °c. The removed material was weighed and rolled into a sheet in a Farrel 12 inch two-roll rubber mill set at 2.032 mm: L 0.127 mm (0.080 inch ft. 0.005 inch). The milled material produced is cut into strips to prepare a second process in the mixer. There must be at least one hour between the completion of the first process in the mixer and the start of the second process to allow the obstructed material to be cooled. If necessary, the aforementioned cleaning and heating procedures using cv_60 grade natural rubber are completed prior to the start of the second process. Adjust the temperature of the mixer to approximately 49 〇c (120 °F). Under the cooling water flow, the second process is to add the strip of the first process material and pre-weighing by mixing at 77 rpm.

The Santoflex® 13 antiozonant was started with the Okerin® 7240 microcrystalline wax/paraffin blend. After 0.5 minutes, a second additive of rm sulfur, a composition of TBBS and DPG was added. After another 1-5 minutes, lift the plunger and sweep the chute. By mixing the material for another 2.0 minutes, and maintaining the temperature at the same time -------.-------l------------------------- Read the note on the back? Do this again. 1292415

V. Description of invention (31) Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

The second process is completed at 125 ° C (257 〇F). Part C. The Farrel 12 inch two roll rubber mill was heated to approximately 6 〇 C (14 ° F). The material from the second part of Part B was added to the mill in operation, and the gap between the rolls was set at 2.032 mm ± 127 亳 (〇〇 〇 8 〇 0.00 0.005 吋 ). The resulting sheet was placed on a flat surface until the temperature of the sheet was lowered to room temperature. Typically, the sheet is cooled in about 3 minutes. Thereafter, the milled sheet was fed into a rubber mill, and the gap between the rolls was set at 3_81 ± 0. 51 mm (〇 15 吋 ± 〇 吋 2 inches). If necessary, the roll is pressed to maintain a uniform thickness. The produced material was cut by 16 people and cut through 8 times. Adjust the gap between the rubber mill rolls to produce a sheet of 2.032 m2 soil. 127 m (〇_〇8〇英忖土〇.〇〇 5 英 pairs). The sheet material produced from the rubber mill is placed on a flat and clean surface. A rectangular specimen of 2 〇 3 2 耄 X X 152.4 mm (8 inches X 6 inches) was cut from the sheet material using a template. The sample was conditioned, i.e., at 23 ° 2 ° C and a relative humidity of 50% 5%, and the sample was stored between clean polyethylene sheets for 15 to 18 hours. After the conditioning, the sample was placed in a standard steel mechanical stamper with a polished surface of 203.2 mm X 152.4 mm X 2.286 mm (8 inches X 6 inches X 〇. 〇 9 inches). The sample is at a pressure of 丨3·79 MPa (2000 psi) and is 61 cm X 61 cm (24 ying x 24 ft) and 890 kN (1 ton). The time for aging of τ9 中 in a four-column electric compression molding machine, that is, the time required for 90% ripening according to ASTM D-2084, was added at 150 ° C (302 ° F) for 5 minutes. Typically, the ripening effect is about 1 minute. This paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇X 297 mm). 34 -------.-------hi Order-- -------^^-丨卜(Please read the notes on the back and fill out this page) 1292415 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (completed within 32. The resulting cured rubber sheet was removed and maintained at 23 ° soil 2 ° C (73.4 ° soil 3.6 ° F) and 50% ± 5% relative humidity for 15 to 18 hours before the D test. Part of the test was carried out in accordance with ASTM D-412-98a - Test Method A. A bell-shaped test specimen was prepared using a face mold C. An Instron tensile strength tester Model 4204 with an automated contact tensile tester was used. In order to determine the tensile action, it was found that the truncating speed was equivalent to 5〇8亳m/min. All the calculations were carried out by the manufacturer's IX series automated substance testing software. The strengthening index is equivalent to 300% tensile resistance. Tensile stress (in MPa) divided by tensile stress of 100% tensile force (in MPa). When prepared by a standard compounding procedure, the results are reported by the standard strengthening index. The formation of a precipitated type of oxidized stone by the acidification of sodium citrate solution by sulfuric acid. When the value of the system is higher than 8.5, the precipitate is further produced by adding acid to the solution until the value of the solution 11 reaches about 3 to 4 Torr. The cerium oxide is prepared until the cleaning water shows a conductivity of 300 to 8001⁄4 ohms of the scoop, and a precipitated oxygen-cut sample for surface area analysis as described in the above example is prepared. The filter cake is again liquefied to form a solid in a liquid, suspension. The suspension is dried in a Nero (broken) spray dryer (population temperature of about 360 ° C and outlet temperature of about 110 ° C). Used to make -------, -------- „----订-----------b (please read the phonetic on the back? )

1292415

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. V. Description of the Invention (33) The surface area of the modified oxidized stone in the comparative example in the comparative example is shown in Table 1. Example 1_6 In a 30 gallon glass crucible vessel having a bottom discharge port, a precipitated oxidized cerium suspension containing about 5.25 kg of cerium oxide and about 11.7 kg of isopropanol was added. The container is also equipped with a temperature logger, a mechanical scrambler, a heating element and a condenser. When the agitation and heating of the contents of the vessel is initiated, 3-mercaptopropyltrimethoxydecane (MPtms) is added over a period of time (typically about 10 minutes) which will result in a weight ratio of MPTMS listed in Table 1. The approximate amount is based on the dry weight of cerium oxide in the examples listed in the table. After the addition of MpTMS is completed, dimethyl dioxane (DMDCS) is added in the same manner to obtain the approximate amount of the weight ratio of 1)]^11) of Table 1 The examples listed in the table are based on the dry weight of the oxidized stone. The weight ratio of MpTMS/DMDCS is also listed in Table i. The value of the resulting solution is between about 1.5 and 2.2. The addition of DMDCS is completed. After the action, a quantity of concentrated hydrochloric acid, i.e., about 37% by weight, was added to reduce the solution to about 〇 3. The mixture was heated to about 68 ° C and maintained at this temperature for about 3 minutes. When the cold part is added, a sufficient amount of 5% by weight of sodium hydroxide is added for a period of time to adjust the pH to about 3.5. After the addition of sodium hydroxide is completed, the foot is added to the stirred mixture. The amount of toluene (typically 6 75 to 7 75 kg) is used to achieve the action of separating the hydrophobic precipitated cerium oxide from the aqueous phase without forming an emulsion. The aqueous phase is discharged from the vessel. ·---Order--------- (Please read the notes on the back and fill out this page)

1292415 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description () Then clean the container with about 30 kg of water. The stirred mixture containing hydrophobic precipitated cerium oxide. A sufficient amount of toluene (typically 6.5 to 8 _0 kg) is added to the stirred mixture to effect the separation of the hydrophobic precipitated cerium oxide from the aqueous phase without forming an emulsion. Drain the water phase. Then, the stirred mixture containing the hydrophobic precipitated cerium oxide was washed twice with about 30 kg of water each. The aqueous phase is drained from the vessel after each wash and before the addition of the subsequent wash liquor. > After completion of the cleaning action, a sufficient amount of toluene (typically from 12.5 to 15.3 kg) is added to the stirred mixture to form a liquid, liquid suspension in the liquid, which is readily available from the container. discharge. The resulting suspension was dried in a rotary cone dryer at a temperature of at least 14 〇 〇c and a vacuum (at a minimum of 23 inches of mercury). The drying was continued until the weight loss of the sample was less than 4% by weight when exposed to 160 ° C for 1 minute. Example 7. Follow the method described in Examples 1-6, except for the following: Add 8 grams of hydrazinyl trimethoxy decane (MPTMS) in about 1 minute; in about 1 minute. Add 487 g of dimethyl dichlorocyanide; without using isopropanol and toluene, combine three batches of slurry, filter and wash with water π until the washing water shows about 3 to 8 μm The conductivity of Europe is up to now. The treated cerium oxide sample was dried until the weight loss of the sample was less than 2% by weight when exposed to 16 cc for 10 minutes. The modified cerium oxide sample of the seventh example is about 5% by weight of MPTMS and DMDCS based on the dry weight of cerium oxide, and Μρτ mdcs is applicable to China National Fresh (CNS) A4 specification (210 x 297 mm). -""~~- -------*----r -----^----Book----------- Bu (please read the back Note: Please fill out this page again) 1292415

Weight ratio, series in the second table. · _ brother 8 cases •-f Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed in accordance with the method described in the W example, except for the following: the use of 4 〇 kg of reliquefied solids in liquids Liquid (3.3 kg of oxidized stone eve) and 122 kg of isopropanol; add 171 g of 3 cis propyl trimethoxy sec-second (mptms) in about 7 minutes; add 5 以 in about 2 minutes 6 g of _methyldioxane (DMDCS); adding concentrated hydrogen acid in a time of about 24 minutes to produce a solution having a positive value of about 〇·4; after heating the solution for about 3 minutes at about 68 C, adding the foot The amount of 5% by weight of sodium hydroxide was adjusted to adjust the pH to about 7.0; a sufficient amount of toluene (about 71 kg) was added to achieve the separation of hydrophobic cerium oxide from the aqueous phase without forming an emulsion. The recovered product was not washed with water, and after discharging the aqueous phase, about 2.2 kg of toluene was added to the product to form a solid liquid suspension in the liquid. The treated cerium oxide sample was dried until the weight loss of the sample when exposed to 160 ° C for 1 Torr was less than 丨 5% by weight. The modified cerium oxide sample of the eighth example is based on the dry weight of cerium oxide.

The approximate weight % of MPTMS and DMDCS, and the weight ratio of MPTMS/DMDCS, are listed in Table 2. The ninth example was followed by the method of the eighth example except that 86. 5 g of 3? mercaptopropyltrimethoxy oxime (MPTMS) was used. The modified cerium oxide sample of the ninth example is based on the dry weight of cerium oxide and the approximate weight % of MPTMS and DMDCS and the weight ratio of MPTMS/DMDCS, which are listed in Table 2. The 10th to 13th paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public meals) 38 ----------Book---- (Please read the back note first and then fill out this page ) s'.

Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

This paper size applies to the Chinese National Standard (CNS) A4 specification (210 297 297 mm) 1292415 Before adding to a container, the two kinds of decane (^1?丁)^18 and 1:)]^1:) (: ; ^ and acid (the amount is sufficient to produce about 〇 · 32ρ Η value) and the temperature of about 65 to 85. The newly prepared cerium oxide slurry is mixed. The acid used in other examples other than the 13th example is concentrated sulfuric acid , that is, about 96% by weight, and the 13th case uses concentrated hydrochloric acid. The resulting mixture is allowed to stand for at least 15 minutes. Water is added and mixed, and the value of ρ is 50% by weight of aqueous sodium hydroxide. Adjust to about 3·5. Filter the resulting aqueous suspension of hydrophobic cerium oxide and wash with water until the washing water shows a conductivity of about 3 〇〇 to 8 〇〇 micromohm. Dry hydrophobic cerium oxide, Until the weight loss of the sample is less than 2.5% by weight when exposed to 16 〇 γ for 1 minute. The approximate amount of decane added to the slurry is reported by the dry yttrium based weight 〇 / ❶ Table 2, MPTMS/DMDCS weight ratio is also shown in the table. The 14th case follows the method of the 10th 13th Except that no acid is added, only the acid present is produced by the hydrolysis of DMDCS. A sufficient amount of hydrazinyl propyl trimethoxy decane (MPTMS) and dimethyl dioxane (dmdcs) are added to produce The approximate weight % of each decane listed in Table 2 is based on the dry weight of cerium oxide. The pH of the resulting solution is 1.6. The first to third comparative examples follow the method described in the first to sixth examples. The approximate amount of decane to the slurry, based on the dry weight of cerium oxide, is reported in Table 2. The MPTMS/DMDCS weight ratio is also shown in the table. The fourth comparative example except that only the propyl propyl group is added. In addition to Oxygen, it is the 39th

----------t---- (Please read the notes on the back and fill out this page) ^1 ^1 ϋ ϋ I

1292415 V. INSTRUCTIONS (37) The method of the method 'is based on the approximate weight % of MPTMS in Table 2, based on the dry weight of the oxidized stone, and adding a sufficient amount of concentrated sulfuric acid to produce about 0.0 A pH value. The cover 1 comparative example, except that only dimethyldichloromethane was added, followed the method of the fourth comparative example to obtain about 5% by weight of the DMDCS of the second table, which was based on the dry weight of the oxidized stone. And adding a sufficient amount of concentrated sulfuric acid to produce a pH of about 0.4. The 15th case was measured by a dynamic single-point surface area technique, ASTM D-3037-93 Method C (corrected), and a holly 6200 series instrument was used to measure the first and fourth 1-5 comparative examples. (CE) treated and untreated cerium oxide test specimens. The method is simulated by Ρ/Ρ〇 = 〇·294 using 3〇% of nitrogen in helium as the adsorption gas of Bruno Emmett_Tele ^1^1^1^b £111111 to 1_

Teller ’ BET) method. The ASTM method is modified as follows: a gas mixture of nitrogen in a helium gas of 3% by weight; a flow rate of about 4 〇ml/min is maintained; the sample is dried in a chamber at a temperature of 9 Torr for 5 hours under a nitrogen stream. The nitrogen adsorbed on the sample is desorbed by removing the vacuum enthalpy of liquid nitrogen and allowing the sample to warm to room temperature without an external heat source. The results of the untreated cerium oxide test specimens are shown in Table ,, and the results of the treated cerium oxide test specimens are listed in Table 3. Carbon % was determined by CHN analysis using an elemental analyzer of Carlo Erba Model 11〇6. Burning 1-2 g sample sealed in a tin capsule with a carrier in an oxygen-rich environment at 1〇4〇〇c, in the bismuth-------"--- r ----------Book----- (Please read the notes on the back and fill out this page) s'. Printed by the Intellectual Property Office of the Ministry of Economic Affairs

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 shy) 1292415

A7 B7 V. INSTRUCTIONS (38) The road is burned in a quantitative manner, and the combustion gas is then passed through copper at 650 °C to remove excess oxygen and reduce nitrogen oxides to nitrogen. The gas is then passed through a chromatography column, separated and eluted into nitrogen, carbon dioxide and water. The eluted gas is measured by a thermal conductivity detector. The instrument is calibrated by burning a standard compound. The results are listed in Table 3. The percentage of sulfhydryl groups (SH) listed in Table 3 is determined by accurately weighing 2-3 grams of treated cerium oxide to 0.001 grams and placing it in an Edenmeyer flask with 75 ml of isopropanol. Rinse with nitrogen, seal with a wet stopper and magnetically stir for 3 minutes. The stirred solution was rapidly titrated to a pale yellow final point with a standard 0.01 N iodine solution available from LabChem. In addition to the addition of treated cerium oxide, blank titration was carried out in the same manner. If the modification of the filler is carried out with mercaptodecane, the blocked mercaptodecane needs to be deblocked prior to titration. Use the following equation to get the final value.

Separation base % = (V1 - V2) x N x 3.3 / W where vi is the volume of the iodine solution used for the sample; V2 is the volume of the iodine solution used for the blank titration · 'N is the equivalent concentration of the iodine solution; w is The weight of ruthenium in grams is the unit. The decane conversion index reported by SCI in Table 3 is determined by solid state 矽 NMR. The data was obtained at ambient temperature on a Bruker (fine (four) explosion 300 NMR with a narrow inner diameter magnet and a 7 mm degree (1) state standard speed MAS probe. The sample was loaded at an outer diameter of 7 The millimeter yttria drum is sealed with a short squeegee. The drum is in ..----^---------k (please read the notes on the back and fill out this page) Intellectual Property Bureau employee consumption cooperative printing

1292415 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (39)

Angle rotates at a speed of approximately 5.0 kHz. Cross-polarization (CP/MAS) data was obtained with a 90° pulse wave, a 5600-8400 scan per spectrum, a 5 millisecond contact time, a high energy proton decoupling during the data measurement period, and a 3 second relaxation delay. A kaolin sample (J. R〇cha and J. Klinowski, J. Magn. Reson. 90, p. 567 (1990)) was used to achieve the Hartmann-Hahn condition. All chemical shifts are > tetradecyldecane (TMS) as an external reference. All spectra were analyzed on a Aspect 3000 computer using a non-linear curve fitting program (LINESIM) to determine the relative area % of 1^(-49 ppm), Τ2 (·57 ppm) and T3 (-65 ppm) peaks. The area % of τ1, Τ2, and Τ3 will be determined by fitting a curve from the -30 ppm to -80 ppm region. The pH values of the treated oxidized oxides of the examples and comparative examples were determined by adding 5. gram of cerium oxide (in powder form) in a 15 liter beaker containing a magnetic stirring bar; adding 50 liters of isopropyl Alcohol and 50 ml of deionized water; stir vigorously without spilling until the cerium oxide is suspended. A calibrated pH electrode was placed in the vigorously stirred solution and the pH reading was recorded after 1 minute (5 seconds). The results are listed in Table 3. The standard strengthening index reported in Table 3 is measured by dividing the tensile stress of the tensile force of 3〇〇〇/0 by the tensile stress of 100% tensile action. The tensile stress at 300% and 1% tensile is covered in Table 4. By adding about 5 grams of each material to a 43 mm X 123 mm (inner diameter X outer diameter) cellulose extraction cannula, the cannula was placed in a suitable size Soxhlet equipped with a condenser ( Soxhlet) in the extraction tube, and the Soxhlet extractable of the first, second and seventh treated cerium oxide is applicable to the Chinese National Standard (CNS) A4 specification (21〗 X 297 public) 42 -------,——-------Set-------- (Please read the notes on the back and fill out this page) 1292415 A7 V. Invention Description (4〇百百Knife ratio. The Soxhiet extractor is connected to the condenser system, the first system and the round bottom flask containing 700 ml of toluene. The flask is heated to the reflux temperature of toluene. Typically, after 5% to 5%, the used toluene is replaced with unused toluene, and the reflux is continued for 19 hours (typically 19 to 24 hours). The recovered and treated are recovered. The cerium oxide is dried and until the weight loss of the sample is less than 1.2% by weight when exposed to 160 〇C for 10 minutes. The carbon of each of the extracted samples was measured using the method described herein. / (> The percentage of Soxhlet extractable carbon was determined by the following equation: (% by carbon before extraction) - (% by carbon after extraction) " X 100 (% of carbon before extraction) The results are listed in the example of Table 1 of Table 5. _^ Processed Nitrogen. Dendrobium------->------- -----Order--------- (Please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed surface area 1 square meter / gram _ 1-7 Examples and 1 - 3 Comparative Examples 191 8 and 9 Cases 193 10th Cases 172 11th Cases 187 12th Cases 182 13th Cases 214 14th Cases 188 4th and 5th Comparative Cases 199 This paper scale applies to Chinese national standards ( CNS) A4 size (210 X 297 mm) 43 1292415 Α7 Β7 Five Λ invention description (41 <1 Table 2 Example # %MPTMS/ %DMDCS/ MPTMS/ 二 gasification 矽2 gasification 矽DMDCS ratio / 1 2.5 15.0 0.17 : 1 2 2.5 27.1 0.09 : 1 3 1.0 22.0 0.05 : 1 4 5.0 15.0 0.33 : 1 5 2.5 15.0 0.17 : 1 6 4.0 22.2 0·18:1 7 2.5 15.0 0.17 : 1 8 5.2 15.3 0.34 : 1 9 2.6 15.3 0.17 : 1 10 4.0 22.2 0.18 : 1 11 4.0 10.0 0.40 : 1 12 6.0 15.0 0.40 : 1 13 4.0 22.2 0.18 : 1 14 4.0 20.0 0.20 : 1 1st comparative example 1 15.0 0:15 2nd comparative example 1.0 12.0 0.08 : 1 3rd Comparative Example 0.5 15.0 0.03 : 1 Fourth Comparative Example 4.0 0.0 4:0 Fifth Comparative Example 0 22.0 0 : 22 Ciptane® 1 (12) 3.0 0.0 3:0 (12) A phlegm that can be obtained from PPG Industries, It was reported to be covered with 3% by weight of decylpropyltriazine. Synthetic precipitated oxymethoxy decane pre-coated --------^----r -----r---book------- C Please read the precautions on the back Fill in this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed on this paper scale Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) 44 1292415 A7 B7 V. Invention Description (42) 41

Table 3 Example # Surface area (m^/g) Carbon sulfhydryl (% by weight) (% by weight) 1 132 2.2 0.32 2 112 3.1 0.30 3 119 2.5 0.16 4 128 2.3 ND* 5 128 2.0 0.30 6 113 3.0 0.65 7 126 2.2 0.43 8 103 2.8 0.63 9 108 2.7 ND* 10 118 3.3 0.38 11 146 2.0 0.53 12 123 3.0 0.58 13 115 3.9 0.41 14 139 1.5 0.24 First comparative example 137 1.5 < 0.001 Second comparative example 149 1.4 0.12 Third comparison Example 139 1.6 0.1 Fourth Comparative Example 194 0.6 0.34 Fifth Comparative Example 134 2.6 < 0.001 Ciptane® 1 132 0.5 0.4 ND* means that the test was not carried out. CI S 56261* 2* * * * * * 5* * * **7 .5.5.6.5.5D.5DDDDDD.4DDDDD.2 0.0.0.0.0.N0.NNNNNN0.NNNNNO

RI

Value PH 855963311633017 6 5 9 6 444445455444442 3 3 2 2 6667667810666666 6 5 6 6 7 ___ — — — — — III l· III ^ III (Please read the note on the back and fill out this page) SCI** represents decane conversion index. SRI*** represents the standard strengthening index. Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs. This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 45 1292415

V. Description of the invention (β) Example 仞仞仞仞 More than 45-1011121314 Bibibi ratio 1 2 3 4 5 No. 1

Ciptane® 1 4th Example at 300% Modulus; Tensile Stress 8.9 8.2 7.0 10.8 8.7 12.0 7.8 11.1 9.9 9.3 8.0 10.2 6.2 7.4 2.8 6.1 5.5 5.5 3.8 4.8 Tensile Stress at 100% Modulus 1.8 2 2 2 2 Economy Ministry of Intellectual Property Bureau employee consumption cooperative printing

Table 1 5 Cover 11{i_ % Carbon I after extracting % Carbon I before extraction 8 1- ο 112 2 3 2 14 6 8 5 1 12 2 Extraction 16.97 18.33 1.82 The results of Table 1 are shown for example and The untreated cerium oxide in the manufacturing method of the comparative example had a surface area of between 172 and 214 square meters per gram. The MPTMS/DMDCS ratios listed in Tables 1-14 of Table 2 are based on the Chinese National Standard (CNS) A4 specification (21〇297 mm). 46 — — — — — — — III L ---- Order-!---IIIL, (Please read the notes on the back and fill out this page)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1292415 A7 ___B7___ V. Invention description (44) at 0.05 ·· 1 to 0_40 : 1. For the second and third comparative examples containing the two decanes, the MPTMS/DMDCS ratios were 〇·〇8··1 and 0.03:1, respectively. Although the MPTMS/DMDCS ratio of the second comparative example is within the desired range of 〇·〇5:1 to 10:1, the weight of the thiol (811) of the second comparative example (CE 2) listed in Table 3 The result of % is less than the amount required to be greater than 〇15 weight 0/〇. The results of Table 3 show that the treated cerium oxide samples of the present invention, i.e., Examples 1-14, have a standard strengthening number of at least 4.0, a carbon weight greater than ι·〇, and a thiol weight greater than 0.15. % and its decane conversion index, ie ΤΜτ1 + T2 + Τ3), are at least 0.3. The carbon weight % and/or the sulfhydryl weight % of the comparative example are lower than those of the first to fourth examples, and the standard strengthening number is less than 4 〇, such as 3.6. The results of the fourth table show that the modified cerium oxide of the present invention, i.e., the first yttrium-type tensile stress of 300% tensile action is 6.2 or more. In the comparative example, the tensile stress at 3% by stretching was 6.1 or less. The results in Table 5 show that the percentage of isochhiet extractable carbon can be as low as one of the 1.82% of the seventh case to a high of 18.33% of the second case. The present invention has been described with reference to the specific details and specific examples thereof. The details are not intended to be construed as limiting. -------t---h -----ί----订---------线--k---1 (Please read the notes on the back and fill in This page)

Claims (1)

1292415 Patent application scope β 丨 .. A chemically treated filler comprising an amorphous or particulate inorganic oxide, characterized in that: (a) a carbon content greater than 1% by weight, and (b) greater than 0.15% by weight酼 base content; (c) a decane conversion index of at least 〇.3; and (d) a standard strengthening index of at least 4. 2. The chemically treated filler according to claim 1, wherein the carbon content is at least 5% by weight; the thiol content is at least 〇.3; the decane conversion index is at least 〇· 4; and the standard reinforcement index is at least 4.5. 3. The chemically treated filler according to claim 2, wherein the inorganic oxide is a precipitated cerium oxide having a carbon content of at least 2% by weight; and the thiol content is at least 5% by weight. The decane conversion index is at least 0.5; and the standard strengthening index is at least 5. 4. The chemically treated filler of claim 1, wherein the filler is further characterized by a modified BET surface area from 2 to 35 square meters per gram. 5. The chemically treated filler of claim 3, wherein the modified BE butyl surface area is from 100 to 2 square meters per gram. 6. The chemically treated filler of claim 1 wherein the filler is further characterized by a pH of from 5 to 1 Torr. 7. The chemically treated filler of claim 5, wherein the pH is from 6.0 to 7.5. 8. If the chemically treated filler of the scope of the patent application is applied, the -------------------- order--------- line (Please read the phonetic transcription on the back? Please fill out this page again) Printed by the Intellectual Property Office of the Ministry of Economic Affairs 48 A8B8C8D8 1292415 VI. Scope of Application The characteristic of the filler is that the percentage of extractable carbon in Soxite (s〇xMet) is less than 30%. 9. The chemically treated filler of claim 7, wherein the percentage of the Soxhlet extractable carbon is less than 2%. 10. The chemically treated filler of claim i, wherein the inorganic oxide is selected from the group consisting of kaolin ±, clay, diatomaceous earth, alumina, 1 A alumina, aluminum trihydrate, titanium dioxide, aluminum lanthanum An acid salt, ceric acid salt, pyrolytic cerium oxide, colloidal cerium oxide, precipitated cerium oxide or a mixture of these two organic oxides. 11. A chemically treated filler according to the scope of claim 1G, wherein the inorganic oxide is an aluminosilicate, a colloidal cerium oxide, a precipitated cerium oxide or a mixture thereof. 12. The chemically treated filler of claim U, wherein the inorganic oxide is precipitated cerium oxide. 13. A slurry comprising a composition of a non-water-miscible organic solvent and from a cerium to a weight percent amorphous or particulate inorganic oxide, characterized by: (a) greater than 1 weight. (b) a sulfhydryl group content of greater than 0.15% by weight (c) a decane conversion index of at least 0.3; and (d) a standard strengthening index of at least 4. A slurry according to claim 13 wherein the non-water-miscible solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, cycloalkanes, halogenated hydrocarbon solvents and ketones. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) --------tr---------^# (Please read the notes on the back and fill in the form) Page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 49 Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing 1292415 VI. Patent Application No. 15. The poly-form of claim 13 wherein the inorganic compound is a precipitated cerium oxide and further characterized by a modified BET from 20 to 350 square meters per gram. The surface area, the pH from one of 5 to 1 Torr, and the percentage of Soxhlet's ductile carbon are less than 3%. 16. A masterbatch comprising an organic rubber, a non-water-miscible solvent and a composition of 10 to 150 parts of amorphous or particulate inorganic oxide per 00 part of the organic rubber, characterized in that: (a) is greater than (b) a thiol content of greater than 0.15% by weight; (c) a decane conversion index of at least 〇3; and (d) a standard strengthening index of at least 4. 17. The masterbatch of claim 16 wherein the organic rubber comprises a solution of styrene/butadiene rubber, polybutadiene rubber or a mixture thereof. 18. A polymeric member having a 1% to ι 5 〇 partially amorphous or particulate inorganic oxide dispersed therebetween, wherein: (a) a carbon content greater than 1% by weight; (b) a thiol content greater than 1515.5% by weight; (c) a decane conversion index of at least 〇3; and (d) a standard strengthening index of at least 4. 19. The polymeric member of claim 18, wherein the polymer is selected from the group consisting of thermoplastic resins, thermosetting resins, organic rubbers, and silicones. 20. The polymeric member of claim 19, wherein the polymer is a curable organic rubber. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -------------------- Order--------- Line (Please read the note on the back? Please fill out this page again) 50 1292415 6. Patent application scope 21. The polymer component of claim 18, wherein the inorganic oxide is a precipitated cerium oxide, and the characteristic is further improved from BET to 250,000 square meters per gram. The surface area, the pH value from one of 5 to 1 Torr, and the percentage of Soxhlet extractable carbon are less than 3 〇 0 / 〇〇 22. The polymer part of claim 21, wherein the polymer It is a curable organic rubber comprising a solution of styrene/butadiene rubber, polybutadiene rubber or a mixture thereof. 23. The polymeric member of claim 22, wherein the article is a tire. Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) _______— -------- order---------line # (please read the notes on the back first) Fill in this page) _ 51