TW500754B - Chemically modified fillers and polymeric compositions containing same - Google Patents

Abstract

Described are fillers, e.g., inorganic oxides, chat have been modified to have a carbon content of greater than 1 weight percent, a sulfur content of greater than 0.1 weight percent, a silane conversion index of at least 0.3 and a standard tensile stress @ 300% elongation of 7 or more. Polymeric compositions that contain such modified fillers are also described.

Description

500754 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the Invention (1) Cross References to Related Applications This application claims US Provisional Application No. 60 / 203,427, filed on May 10, 2000, in 1999 The benefit of the serial number 60 / 172,308 filed on December 17, 2015 and the serial number 60 / 149,758 filed on August 19, 1999. DESCRIPTION OF THE INVENTION The present invention relates to chemically modified fillers and the use of such fillers in polymerizable compositions. In more detail, the present invention relates to granular or amorphous fillers' which have a minimum carbon and sulfur content, a minimum sintering index and a minimum standard tensile stress at 300% elongation, And related to polymers containing such fillers such as curable rubber compositions. In most detail, the present invention relates to a functionalized and hydrophobized filler, hereinafter referred to as a "modified filler," which enhances the efficiency of manufacturing polymerizable compositions such as rubber compounding corners, and enhances polymerized or cured products such as Properties of tires. In the manufacture of polymerizable compositions, fillers are usually incorporated to improve the physical properties of the polymer. Surfaces of these fillers are often modified to increase reactivity and the subsequent use of the filler in the polymerizable composition. Two-dimensional and three-dimensional coupling. In the rubber industry, it is customary to incorporate carbon black and other reinforcing fillers in natural and synthetic rubbers to enhance the physical properties of the cured vulcanized rubber. To strengthen these polymerizable compositions Fillers, including natural and natural fillers. (Please read the notes on the back before filling out this page) · Packing -------- Order --------- ^ Awi. Used in the rubber industry One of the main non-blackbody fillers is an amorphous precipitated silica. This silica filler is used to give vulcanizates a boost.

500754 5 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 Invention Description (2) The tensile strength, tear resistance and abrasion resistance. Silica filler is also used in combination with carbon black to obtain the maximum mileage of tires for passenger vehicles and off-road tires, such as those used in mining and logging operations and for road construction equipment. These applications have been well developed. When a silica filler is used as the sole reinforcing filler, the oxidized petrolatum filler that does not disperse and / or couple well in the rubber does not provide the overall improved properties obtained when carbon black is used alone. This is most commonly observed in vulcanized rubber used in tires such as tire treads. When fillers are incorporated into polymerizable compositions such as rubber, various coupling agents such as titanate, zirconate, and silane have been proposed to be used in combination with these fillers to improve the performance of vulcanized rubber. Among the various organosilicon coupling agents proposed for these applications are bis (alkoxysilylalkyl) polysulfides, such as 3,3'_bis (triethoxymethethionylpropane) Base) tetrasulfide. It has been reported that appropriate amounts of these coupling agents are used in synthetic rubber reinforced with shiyu fillers, especially 3,3 '· bis (triethoxymethyryl propyl) tetrasulfide. Major physical properties such as 300% modulus, tensile strength and abrasion resistance provide properties at least comparable to carbon black reinforced synthetic rubber. The high cost of bis (alkoxysilylalkyl) polysulfide, and the time and energy required to mix it into a polymerizable composition, prevent stone fillers from being widely used as a major enhancement in large-scale volume applications Uses of fillers. U.S. Patent No. 4,43,847 describes the addition of a dream-fired coupling agent such as bis (unisyloxymethoxamine) by combining a mono-oxygen dream-fire with a stone-xiyuan to form a coupling composition Based) Efficiency of polysulfide coupling agent. In a specific specific example described in Patent No. 4,436,847, the Chinese National Standard (CNS) A4 specification (210 X 297 public love) is applied with a suitable non-reactive paper size --------- — — — — ^ I — — — — — — ^ illln 11 ^ (Please read the notes on the back before filling this page) 500754

The Silane Filler Formula in the Printed Liquid of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs manufactures the silane coupling composition to prepare a rubber compounding additive, that is, a silicon oxide-silane concentrate, wherein the liquid is for the coupling The composition is chemically inert with the silica filler. U.S. Patent No. 5,116,886 describes a two-step method in which the surface of a natural or synthetic oxide or silicate filler is modified by using a specific organosilicon compound. In the first step, the organosilicon compound is thoroughly mixed with the filler at a temperature below 60 ° C. In the second step, from 60 to 160. . The homogeneous mixture is processed at a temperature to complete the modification of the filler surface. U.S. Patent No. 5,908,660 also describes a one-step process for preparing hydrophobic silica. In the first step, an aqueous suspension of precipitated silica is contacted with an organosilicon compound in the presence of a catalytic amount of an acid to achieve the hydrophobicization of the precipitated silica. In the second step, an aqueous suspension of hydrophobic precipitated silica is contacted with a non-water-miscible organic solvent at a weight ratio of a solvent to silica of greater than 5: 1 to separate the hydrophobic from the aqueous phase. Precipitated silica. At present, it has been found that a modified filler, such as a particulate or amorphous inorganic oxide, can be prepared, which is characterized by a carbon content greater than 丨 wt%, a sulfur content greater than 0.1 wt%, and a silane conversion index (explained later) of at least 0. .3 and the standard tensile stress at 300% elongation (also described later) is 7 or more. The method described in U.S. Patent No. 5,908,660 can be improved, and by using a specific composition of a functionalizing agent and a hydrophobing agent in an aqueous suspension of an inorganic oxide having a pH value of 2.5 or less, and The acid neutralizer treats the acidic aqueous suspension of the modified filler to raise the pH value of the suspension. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 6 -------- -—Ϊ́ιϋι outfit -------- Order --------- (Please read the precautions on the back before filling this page} A7 A7

1. Description of the invention (4) to the range of 3.0 to 10 to manufacture the modified filler of the present invention. As used herein, a functionalizing agent is a reactive chemical that promotes the use of an inorganic oxide as a polymerizable composition. A hydrophobizing agent is a chemical substance that, to the extent that it is combined with an inorganic and / or inorganic compound, can reduce the affinity of the inorganic oxide for water, while increasing the inorganic oxide used in the organic polymerizable composition for the composition. Affinity. The aforementioned standard tensile stress (STS @ 300%) at 300% elongation of at least 7 means the enhanced strengthening effect of the rubber composition. Enhanced strengthening refers to improvements in the mechanical durability of the product, as evidenced by the increase in tear strength, hardness and abrasion resistance. In addition to the improved properties, the 'modified filler' has the advantage of requiring less time and energy to incorporate the polymerizable composition. Detailed description of the invention Except for operating examples or other explanations, it should be understood that all numerical values used herein to indicate quantities, proportions, ranges, etc. are modified in all cases by the word "about". The modified filler of the present invention can be prepared by any method of producing the filler. 'The filler is an inorganic oxide whose carbon content is greater than j% by weight, preferably at least 1.5% by weight, more preferably at least 2.0% by weight; its sulfur content is greater than 0.1% by weight. / 〇, preferably at least 0.3 weight ❶ /. And more preferably at least 6% by weight; its silane conversion index is at least 0.3, preferably at least 0.4 ', and at least 0.5; and the standard tensile stress at 300% tensile action is at least 7.0, preferably At least 7.5, and more preferably at least 8.0. The modified paper size of the present invention is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) I -------! 1 Pack — II Order ·! -Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

The shell filler is also characterized by an enhanced Bruno Emmet-Teller (please read the notes on the back before filling this page) (BrUnaue Enimettjeller, BET) value, that is, a single point surface area of 20 to 350 square Meters / gram, preferably 40 to 300 square meters / gram, most preferably 100 to 200 square meters / gram; pH value is from 5 to 10, preferably from $ 5 to 95, more preferably from 6.0 to 9.0, and optimally from 6.0 to 7.5, or the pH of the product may be between a combination of these values, including the quoted values; and Soxhlet may be The percentage of extractable carbon is less than 30%, preferably less than 25%, more preferably less than 20%, such as 15%. The method for measuring the aforementioned characteristics of the modified inorganic oxide is described in the ninth 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 adsorbed or covalently bonded) or hydroxyl (bonded or free) on its exposed surface Any of inorganic particulate or amorphous solid matter. In addition, the inorganic oxide is a substance suitable for a variety of die casting, compounding, or coating processes, which include injection molding, lamination, transfer molding, compression molding, rubber compounding, and coating. (Such as dip coating, brush coating, knife coating, roll coating, screen coating, printing, spraying, etc.), casting, etc. The inorganic oxide or a mixture of two or more inorganic oxides printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics to make the modified filler of the present invention may be natural or synthetic. The filler includes

First-order inorganic chemistry by Albert Cotton et al., Published by John Wiley & Sons in 1980: A detailed discussion of the flute 4 knees in the middle of the day, called f3, 4, 5, and 6 expired ib, lib, Ilia, nib, IVa , IVb (except carbon), Va, Via, Vila and oxides of Group VIII metals. Among natural silicates, the kaolin or clay system is particularly suitable. However, diatomaceous earth can also be used. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 500754 A7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (6) Alumina, aluminum hydroxide or aluminum trihydrate, and titanium dioxide, which can be obtained from natural sediments, are examples of fillers. Particularly suitable synthetic fillers are aluminosilicates, silicates, fumed silicas, colloidal silicas, and precipitated silicas. The term '' aluminosilicate 'refers to a natural or synthetic substance in which some silicon atoms in silicon dioxide are replaced naturally or artificially with aluminum atoms. For example, 5 to 900 / in silicon dioxide can be replaced naturally or artificially with aluminum atoms. Or, optionally, 10 to 80% of silicon atoms are used to prepare aluminosilicate. Methods suitable for this preparation, such as co-precipitation by adjusting the pH of an alkaline solution or mixture of silicate and aluminate, and, for example, by silanol and silanol on the surface of silica Chemical reaction between sodium alumina. For example, in this co-sedimentation method, 5 to 95% of the surface of the 'synthesized co-precipitated onosate salt is composed of a silicon oxide part, and correspondingly, 95 to 5% of the surface is composed of an aluminum part. Made up of. Examples of natural saucerites include muscovite, beryl, cordierite, sepiolite, and kaolin. Examples of synthetic aluminosilicates include zeolites and those represented by chemical formulas such as [(Al2〇3:) x (Si〇2 ¥ H2⑺z], [(Al203) x (Si〇2) yY 〇] Where γ is magnesium or calcium.

The inorganic oxide used to make the modified filler of the present invention is preferably an aluminosilicate, colloidal silica, precipitated silica, or a mixture thereof, and most preferably a type of precipitated silica commonly used in rubber compounding. Consideration may be given to silica available for various commodities used in the present invention, including from ppG

The silicon oxide obtained by Industries under the Hi-Sil trademark under model 21, 243, and other products, from Rhone-Poulenc, for example, model zll65Mp and this paper size 剌 Chinese National Standard (CNS) A4 specification (210 X 297) — — — — — — — — — — — — — I1111111111 Such as OI- · 11111111 (Please read the notes on the back before filling out this page) 9 Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 500754 Α7 Β7 Five (7) Silicon oxide obtained from Z165GR; and silicon oxide obtained from Degussa AG, for example, models VN2 and VN3. The precipitated silica used to make the modified filler of the present invention can be prepared by, for example, acid precipitation from a solution of a silicate such as sodium silicate. The method for preparing Shendian-type silicon oxide is not limited by the present invention, but will depend on the desired properties of the stone, such as the surface area and particle size required for a particular application. The BET surface area of the precipitated silica used to make the modified silica of the present invention generally ranges from 50 m 2 / g to 1,000 m 2 / g, preferably 100 m 2 / g. A range of grams to 500 square meters per gram. Precipitated silica used to form modified silica can be in the form of an aqueous suspension from one of the manufacturing stages before the drying step, such as a slurry formed during the action of Shen Dian It may be a re-liquefied filter cake. Suspensions can also be formed by redispersing the dried silica in an aqueous and / or organic solvent. The concentration of the hydrophobic Shendian-type oxidant in the aqueous and / or organic suspension is not critical, and it can be in the range of about 1 to 90% by weight. The concentration of the hydrophobic precipitated silica is preferably in the range of 1 to 50% by weight, and more preferably in the range of 1 to 20% by weight. The silane conversion index is defined by the equation T3 / (T! + T2 + τ3). The values of T !, T2, and T3 are measured by solid-state 29 silicon NMR, and are representative of the reaction of the Shixiu unit. The silane conversion index provides an indicator of the degree of reaction, or cross-linking, of stones, sinter, and adjacent silicon atoms. The higher the index value 'represents the amount of cross-linking between silane, silicon oxide surface and adjacent silanes. This standard applies to China National Standard (CNS) A4 specifications ⑽χ 297 public love. 10 (Please read the notes on the back before filling in this Page) -------- I--n ^ __ wi. A7

4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The larger the invention description (8). τ represents a silane unit that is chemically bonded to the surface of the silicon oxide or another silane at one site. T2 represents a silane unit, which is chemically bonded at two sites to a silicon atom on the surface of silicon oxide and an adjacent silane, bond,, ° to an adjacent silane, or bonded to two adjacent surface silicon. Atoms, that is, partially cross-linked structures. τ3 represents a silane unit, which is chemically bonded at three sites to a silicon atom on the surface of silicon oxide and two adjacent silanes, to two silicon atoms and one silane, or to three silane units. It is believed that these skilled coupler artisans can develop organometallic reactant conversions that are comparable to silane conversions, indices, and to provide information on zirconium halide salts and / or titanates (alone or with silanes) (Combination) An indicator of the degree of reaction or cross-linking with inorganic oxides or each other. The standard tensile stress at 300% elongation is measured using a standard composite procedure. The standard compounding procedure described here does not include the addition of free or unbound coupling agents to batch rubbers. This is an important difference, as others have reported 300% modulus values above 7.0. See U.S. Patent No. 5,705,137. In this patent, silane x 50-S, a silica / rubber coupling agent, is added during rubber compounding. Typically, if the coupling agent is added to a batch of rubber, the compounding machine requires a long mixing time. The polymerizable composition such as plastic and / or resin to which a modified filler can be added includes substantially any kind of plastic and / or resin. Rubber compounds are covered by this definition. These polymers are described in Kirk Othmer's Encyclopedia of Flowers and Technology, 4th Edition, Volume 19, pages 881-904, published in 1996. The contents of this description are incorporated herein by reference for reference. Modified filler and polymer or polymerizable component can be pre-blended, and the paper size of the polymer or polymerizable component is applicable to China National Standard (CNS) A4 (210 X 297 mm) 11 — — — — — — — — — — — — — IIIIIII (Please read the note on the back before filling this page) 500754

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) The physical form is any liquid or composite form such as solution, suspension, latex, dispersion, etc. The polymerizable composition containing the modified filler can be ground, mixed, die-cast, and aged by any method known in the art to form 10 to 150 parts of the modified filler dispersed per 100 parts of the polymer. One polymer piece. Examples of suitable polymers include thermoplastic and thermosetting resins, rubber compounds, and other polymers having elastomeric properties. The polymer can be alkyd resin, oil-modified alkyd resin, unsaturated polyester, natural oil (linseed oil, tung oil, soybean oil), epoxide, nylon, thermoplastic polyester (such as polyethylene terephthalate Diesters, polybutylene terephthalates), thermoplastic and thermosetting polycarbonates, polyethylene, polybutylene, polystyrene, polypropylene, ethylene-propylene copolymers and terpolymers, acrylics (acrylic acid Homopolymers and copolymers, acrylates, methacrylates, acrylamides, their salts and hydrogen compounds, etc.), hope resins, polyoxymethylene (homopolymers and copolymers), polyurea Alkane, polyfluorene, polysulfide rubber, nitrocellulose, ethylene butyrate, ethylene resin (containing ethylene gaseous and / or vinyl acetate lipid polymer), ethyl cellulose, cellulose acetate and Butyric acid vinegar, viscose silk, shellac, waxes, ethylene copolymers (such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethyl methacrylate copolymer), organic rubber, silicon Ketone esters, silicone resins and silicone rubbers. The amount of the modified filler in the polymerizable composition may be 5 to 70% by weight / 0 'based on the total weight of the plastic composition. For example, the typical amount of the modified filler in the abs (acrylonitrile-butadiene-styrene) copolymer is 30 to 60% by weight, and it is 5 to 60 in the propylene residual-stilbene-acrylate copolymer. 2〇 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 12 丨 丨 — " ~ ι " Ί ·! Ί Order (Please read the precautions on the back before filling this page) A7

500754 V. Description of the invention (10) Weight 0 / 〇, 15 to 30% by weight in aliphatic polyketones, 30 to 60% by weight in alkyd resins, and 10 to 3 in thermoplastic olefins 〇 重量 〇 / 〇, 5 to 20% by weight in epoxy resin, up to 60% by weight in ethylene vinyl acetate copolymer, up to 80% by weight in ethylene ethyl acetate copolymer It is 30 to 70% by weight in a liquid crystalline polymer (1cp), 30 to 60% by weight in a phenolic resin, and the amount in polyethylene is usually more than 40% by weight. In more detail, organic rubber and silicone rubber are preferred. Examples of these rubbers include natural rubber; those formed from the same polymerization of butadiene and its homologs and derivatives, such as cis ", 4 · polyisoprene, 3,4-polyisoprene Ene, cis-i, 4-polydibutene, trans !, 'polydibutene, 1,2 polydibutylene; and the like from butadiene and its homologs and derivatives, and Producers of copolymerization of two or more polymerizable monomers containing ethylene unsaturation, such as stilbene and its derivatives, ethynyl-pyridine and its derivatives, acrylidine, isobutylene, and alkyl-substituted Acrylates such as methacrylate. Examples include styrene-butadiene copolymer rubbers (hereinafter referred to as 'SBR') composed of different percentages of styrene and butadiene and using various butadiene isomers as needed "); Terpolymers of styrene, isoprene, and butadiene polymers, and various isomers thereof; and isobutylene-based rubber compositions; or mixtures thereof, as described, for example, in US Patent No. 4 No. 53〇, 959, No. 4,616,065, No. 4,748,199, No. 4,866,131, No. 4, Gang, 4 20, 4,925,894, 5,082,901 and 5,162,409. Other suitable organic polymers are ethylene and other advanced ^ olefin papers ^ i Applicable to China National Standard (C4S) A4 size ⑽ x 297 cm) Packing ---- II --------- line (please first Read the notes on the back and fill out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 13 500754 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (11) Such as propylene, butene-1 and pentaene Olefin "and a copolymer of a diene monomer. The organic polymer can be a block, random, or sequential polymer, and can be prepared by polymerization of an emulsion (such as e_SBR) or a solution (such as S-SBR). Other useful polymers include those that are partially or fully functionalized, including coupled or star-branched polymers. Other specific examples of functionalized organic rubbers include polybutadiene, gasbutyl, and bromobutyl. Base rubber, and brominated isobutylene-co-p-methylstyrene rubber. Preferred organic rubbers are polybutadiene, s-SBR, and mixtures thereof. Examples of the silicone rubber include an organic polysiloxane composition, Wherein the organic polysiloxane is linear Branches, and in addition to hydrocarbon groups, may optionally contain some reactive groups such as hydroxyl groups, hydrolyzable groups, alkenyl groups such as vinyl, hydrogen, fluoro, and phenyl groups. Further examples are shown in U.S. Patent No. No. 5,009,874 from Block 5 to Block 27 to Block 6 to Block 23, the disclosure is hereby incorporated into this case for reference. The polymerizable composition is preferably a curable rubber., Curable rubber The term "is intended to include natural rubber and its various raw materials and recycled forms, as well as various synthetic rubbers. For example, the curable rubber may include a combination of sbr and butadiene rubber (BR), SBR, BR and natural rubber, and any other combination of substances previously disclosed as organic rubber. In the description of the present invention, the terms "rubber" ,,, elastomer, and, rubber-like elastomer, etc. are used interchangeably unless otherwise stated. The terms "composite rubber" and "rubber compound" are used interchangeably, and refer to rubbers that are blended or mixed with different ingredients and substances. These renounced systems are made of network-cure rubber. Or well-known by the composite artist. ----------- “— 馨 装 i — — — — — — ^ illm I (Please read the notes on the back before filling this page)

4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (l2) The modified filler of the present invention can be disclosed in U.S. Patent No. 5,908,660 and Step A in No. 5,919,298 was prepared by itself or by both step a and step b. The disclosures of these patent cases are hereby incorporated into this case for reference, and the disclosures thereof are incorporated herein into this case for reference. And make the following changes. The amount of acid is such that the pH of the aqueous suspension is below 25, the pH is preferably below 2.0, the pH is more preferably below 10, and the value is most preferably below 0.5; the modified chemical substance used is A composition of bis (alkoxysilylalkyl) polysulfide and a sulfur-free organometallic compound (hereinafter referred to as a non-sulfur organometallic compound), and bis (alkoxysilylalkyl) polysulfide The weight ratio of the substance to the non-sulfur organometallic compound is at least 0.05: 1, preferably from 0.05: 1 to 10:!, And more preferably from 0 ": summer solstice 5: j, and most preferably from 0.2 · 1 to 2: 1, for example, from 0.5: 1 to 1: 丨, or the weight ratio may be between any combination of these values, including the quoted values; and after the chemical treatment is completed, the Acidity (generated in situ by addition or by hydrolysis of halogenated organometallic compounds). After the chemical treatment is completed, the pH of the resulting aqueous suspension typically rises to the range of 3 to 10. The neutralizing agent may be any type typically used to raise the pH of an acidic solution, as long as it does not impair the properties of the modified filler. Suitable neutralizing agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide and sodium bicarbonate. Neutralization of modified fillers can also be achieved during the spray-drying process by aerating ammonia in the aqueous solution. The acid used in step (A) can be a variety of organic and / or inorganic types. The preferred acid catalysts are inorganic. Examples of suitable acid catalysts include hydrogen paper size applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 public love) M -------- ^ --------- ^ (please first Read the notes on the back and fill out this page) 15 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 500754 A7 _______ V. Description of the invention (13) Gas acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid and benzenesulfonic acid acid. An acid catalyst or a mixture of two or more acid catalysts may be used as necessary. When the organometallic reactant is, for example, a vaporized silane, a catalytic amount of acid can be generated in situ by hydrolysis of the vaporized silane or by direct reaction of a chlorosilane with the hydroxyl group of an inorganic oxide. The temperature at which step (A) is performed is not critical, although a slightly lower or higher temperature can be used when needed, and it is usually in the range of 20 ° C to 250 ° C. The reaction temperature will depend on the reactants used, such as organometallic compounds, acids, and co-solvents if used. Step (A) is preferably performed at a temperature ranging from 30 ° C to 150 ° C, although step (A) may be performed at the reflux temperature of the slurry used in step (A) when necessary. In the foregoing reaction, the modified chemical substance or the coupling agent may be a composition in which a bis (alkoxysilylalkyl) polysulfide is replaced with a functionalizing agent and a non-sulfur organometallic compound is replaced with a hydrophobicizing agent. The weight ratio of the composition of the functionalizing agent and the hydrophobicizing agent can be the same as defined for the composition of the bis (alkoxysilylalkyl) polysulfide and the non-sulfur organometallic compound. The functional groups may contain reactive groups including, but not limited to, ethyl, epoxy, glycidyloxy, and (meth) propyloxy. Sulfides, polysulfides, and sulfo groups may also be reactive groups of the functionalizing agent, provided that they are not combined with the reactants represented by the chemical formulae I and VII covered by this. Chemical substances as the hydrophobizing agent substance include, but are not limited to, such as natural or synthetic lipids and oils, and non-sulfur organic metal compounds represented by Chemical Formulae II, III, IV, and V, and mixtures of these hydrophobizing agents. Combine the acidic aqueous suspension of inorganic oxide with bis (alkoxymethamone). The paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 16 (Please read the precautions on the back before filling this page ) Binding --------- 500754 Α7

V. Description of the Invention (Η) In the initial gamma step of contacting a composition of polysulfide and a non-sulfur organometallic compound with the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the non-sulfur organometallic compound is preferred. As a non-sulfur organosilicon compound, it may further include adding a water-miscible solvent in an amount sufficient to promote their reaction with the inorganic oxide. The solvent acts as a phase transfer agent to accelerate the interaction between the composition of hydrophobic sulfur and non-sulfur organometallic compounds and 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 15 to 50% by weight of the aqueous suspension, and most preferably 20 to 30% by weight, or The weight percentage may be between any combination of these values, including the recited values. Suitable water-miscible solvents include, for example, alcohols such as ethanol, isopropanol, and tetrahydrofuran. Preferably, isopropyl alcohol is used as the water-miscible organic solvent. Surfactants can also be used in the initial step in combination with or in place of water-miscible organic solvents in an amount sufficient to promote the use of bis (alkoxysilylalkyl) polysulfides Chemical modification of inorganic oxides by non-sulfur organometallic compounds. The surfactant may be nonionic, anionic, cationic, amphoteric or a mixture of such surfactants, provided that it does not impair the performance of the chemically modified inorganic oxide produced for its intended use. Typically, when a surfactant is used, its amount is from 0 to 05 to 10% by weight, more preferably from 0.1 to 5% by weight and most preferably from 0 to 3% by weight, or the weight percentage of the aqueous suspension. It can be between any combination of these values, including the recited value. Representative examples of suitable surfactants include alkylphenol polyethylene, paper size applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) M -------- 1 ----- ---- ^ (Please read the notes on the back before filling out this page) 17 500754 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Α7 Β7 5. Description of the invention (15) Alcohol ethers, such as p-octylphenol polyethylene glycol (20 units) ether, p-nonylphenol polyethylene glycol (20 units) ether; alkyl polyethylene glycol Alcohol ethers, such as dodecyl polyethylene glycol (20 units) ether; polyethylene glycols, such as polyethylene glycol 2000; alkyl trimethyl ammonium salts, such as cetyl trimethyl ammonium Gases (or bromides); dimethyl ammonium salts such as dilauryl dimethyl ammonium; alkyl benzyl trimethyl ammonium salts; alkyl benzene sulfonates such as p- Dodecylbenzenesulfonate, sodium p-nonylbenzenesulfonate; alkyl hydrogen sulfate, such as lauryl hydrogen sulfate; and alkyl sulfate, such as lauryl sulfate. The surfactant may also be, for example, a polysiloxane polymer or copolymer having an allyl-terminated polyethylene oxide. The bis (alkoxysilylalkyl) polysulfides used to make the modified fillers of the present invention are described in US Patent Nos. 3,873,489 and 5,580,919 and are represented by the following chemical formula I. These patent cases Incorporated here for reference:

Z-alk-Sn '-alk-Z I 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; η Is an integer from 2 to 12, preferably from 2 to 6 and more preferably from 3 to 4; and Z is: R · R · R1 where R is an alkane having 1 to 4 carbon atoms Or R 'is an alkoxy group having 1 to 8, preferably 1 to 4, more preferably 1 to 2 carbon atoms, or an alkoxy group having 5 to 8 carbon atoms The cycloalkoxy size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 18 — — — — — III — — — — — — — II «— — — — — — I — t Read the notes on the back and fill in this page) Lake 754 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 5. Invention Description (16) 'Or a linear or branched alkane with 1 to 8 carbon atoms base. R and R groups may be the same or different. The divalent alk group may be a straight or branched chain saturated or unsaturated aliphatic hydrocarbon group or a monocyclic hydrocarbon group. The high-purity organosilane 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 (sulphonyl vermiculite group) polysulfide include: bis (2-dialkoxysilylethyl) polysulfide, wherein the trialkoxy system is dimethoxy, Triethoxy, tri (methylethoxy), tripropoxy, tributoxy, etc. up to trioctyloxy, polysulfides are disulfides, trisulfides, tetrasulfides, pentasulfides And hexasulfides. Can also use the corresponding bis (3-dioxomethythyl propyl), bis (3-trioxomethythyl isobutyl), bis (4-trialkoxysilyl) Butyl) and other polysulfides up to bistrialkoxysilylylhexyl). Preferred ones are organosilanes with simpler structures, including bis (3-trimethoxy-, -triethoxy-, and tri-propoxy-fluorenylsilylpropyl) polysulfides; that is, disulfides, Examples of trisulphide and tetrasulfide 0 bis (sulphonylmethylsulfanyl) polysulfides include: bis (2-trisyloxystilbylethyl) polysulfide, where the tris Alkoxy groups are dimethoxy, diethoxy, bis (methylethoxy), tripropoxy, tributoxy, etc. up to trioctyloxy 'polysulfides are disulfides, tris Sulfide, tetrasulfide, pentasulfide and hexasulfide. Corresponding bis (3-trialkylsilylpropyl), bis (3-trialkoxysilylisobutyl), bis (4-trialkoxysilylbutyl) Wait until the bis (6-trialkoxysilylhexyl) polysulfide. The better one is the organic paper with simpler structure, which is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 19 — — — — — — — — — — — — — — — — — — — — — · · 1111111 1 · βτ · 11111111 (Please read the precautions on the back before filling out this page) 500754 A7 B7 V. Description of the invention (17) Silane 'includes bis (3-trimethoxy-, -triethoxy ... -Tripropoxy-methyl crushed propyl) polysulfide, that is, disulfide, trisulfide and tetrasulfide. Specific examples of the bis (alkoxysilylalkyl) polysulfide are described in the aforementioned U.S. Patent No. 3,873,489, No. 6 and Line 5.55, and U.S. Patent No. 5,580,919, Column No. 11, Line 11-41. Representative examples of these compounds are: 3,3 '· bis (trimethoxysilylpropyl) disulfide; 3,3'bis (triethoxysilylpropyl) tetrasulfide; 3 , 3'bis (trimethoxy 曱 silylpropyl) tetrasulfide; 2,2'bis (triethoxy 曱 silylethyl) tetrasulfide; 3,3'bis (trimethoxysilyl) Propyl) trisulfide; 3,3 'bis (triethoxysilylpropyl) trisulfide; 3,3, bis (tributoxysilylpropyl) disulfide; 3,3 '· Bis (trimethoxysilylpropyl) hexasulfide; and 3,3'-bis (trioctyloxysilylpropyl) tetrasulfide and mixtures thereof. The most preferred compound is 3,3 'bis (triethoxyfluorsilylpropyl) tetrasulfide (TESPT). TESPT is available from Degussa under the trade name Si-69. It is reported to be 3,3'bis (triethoxysilylpropyl) monosulfide, 3,3, bis (triethoxysilylpropyl) disulfide, 3,3'bis A mixture of (triethoxysilylpropyl) trisulfide, 3,3 'bis (triethoxysilylpropyl) tetrasulfide and higher sulfide homologues with an average sulfide of 3.5 . This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) tr --------- Φ Employees ’Intellectual Property Bureau, Ministry of Economic Affairs, Consumption Printed by a cooperative 20 Printed by a consumer cooperative of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs 500754 A7 _____B7__ 5. Description of the Invention (is) The non-sulfur organometallic compound that can be used to make the modified filler of the present invention may be at least one non-sulfur organometallic compound It is a mixture of non-sulfur organometallic compounds. These non-sulfur organometallic compounds are selected from the group consisting of organometallic compounds represented by Chemical Formula II. MX (4.a) Π Organometals represented by Chemical Formula III Compound: R22c + 2 Si c ° (cl) ΠΙ Organometallic compound represented by Chemical Formula IV:

R32d Si dod IV Organometallic compound represented by Chemical Formula V:

(R23 Si) k NR4 (3-k) V wherein each M is independently silicon, titanium or hafnium; each r1 is independently a hydrocarbon group having 1 to 18 carbon atoms or R1 may be 1 to 12 An organic functional hydrocarbon group of 1 carbon atom, wherein the functionality is, for example, an amine group, a carboxylic acid, a methanol ester, or a sulfonylamino group; each X is independently selected from the group consisting of: Alkoxy groups of 1 carbon atom and fluorenyl groups having 1 to 12 carbon atoms, a is an integer, 2, or 3; each R2 is independently a dentyl group, a hydroxyl group, or one having 18 to 18 A hydrocarbon group of carbon atoms, provided that at least 50 mole% of the H2 substituent is a hydrocarbon group containing 1 to 18 carbon atoms, and c is an integer from 2 to 10,000; each R3 is independently of each other Is a functional group, a hydroxyl group, or a hydrocarbon group having 1 to 18 carbon atoms, and d is one of + from 3 × Τ0 > throughout the summer; each R4 is independently of each other is hydrogen or is an i 18 antistone And nicotinyl, and k is 1 or 2; and the halogen or halo group is selected from the group consisting of an oxo group, a bromo group, an iodo group or a fluoro group. In the chemical formulas π, ΠΙ, ------------- loaded --------order-! -Line (Please read the notes on the back before filling this page)

754 0754 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of Invention (19) In the definitions of the substituents shown in IV and V, the same symbols have the same meanings' unless otherwise stated. In Chemical Formula II, each R1 may be a saturated or unsaturated monovalent hydrocarbon group 'or a substituted or unsubstituted monovalent hydrocarbon group. For example, R1 can be an alkyl group such as methyl, ethyl, propyl, isopropyl, isobutyl, t-butyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl And undecyl groups, alkenyl groups such as vinyl, allyl, and hexenyl groups; substituted alkyl groups such as methyl, 3,3,3 · trifluoropropyl, and 6 · ethylhexyl; cycloalkyl Such as cyclohexyl and cyclooctyl; aryl such as phenyl and naphthyl; and substituted aryl such as benzyl, tolyl, and ethylphenyl. When X is a monodentin in Chemical Formula II, the halogen is preferably an oxo group. When X is a monoalkoxy group, X may be, for example, a methoxy group, an ethoxy group, and a propoxy group. When X is monomethoxy, X may be, for example, ethoxy. Each X is preferably selected from the group consisting of an oxo group and a methoxy group. The viscosity of the aforementioned organometallic compound is not limited, and it may range from the viscosity of a fluid to a gel. In general, the higher molecular weight organometallic compounds should be cut through the acidic conditions of the chemical modification step so that they can react with hydrophilic inorganic oxides. In Chemical Formulas III, IV, and V, each of R2, R3, and R4 is the same as the hydrocarbon group described for R1. For the purpose of the present invention, when the organometallic reactant is an organosilicon reactant, silicon is regarded as a metal. The non-sulfur organometallic compound is preferably represented by chemical formulae II, III, IV and v or a mixture of these organometallic compounds, where each M is silicon. The non-sulfur organometallic compound is more preferably represented by Chemical Formula II. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 22 (Please read the precautions on the back before filling this page). Order! ί · * 5ίιρ · A7 B7 V. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Description of the invention (2G, where R1 is c, c6 alkyl, hydrazone is fluoro group, and ... (Please read the notes on the back before filling this page) Applicable organic; ^ Examples of compounds include but are not limited to optional From compounds of the following groups and mixtures of these compounds: diethyldiaspore, allylmethyldiasilasane, methylbenzyldiasilasane, phenylethyldiethoxysane, 3,3,3-tri-Ipropylmethyldichlorite, trimethylbutoxysilane, mesityl-tetramethyldisiloxane, trivinyltrimethylcyclotrisiloxane , Octamethylcyclotetrasiloxane, hexaethyldisiloxane, pentylmethyldisiloxane, divinyldipropoxysilane, vinyldimethylsiloxane, vinylmethyldisiloxane , Vinyl dimethylmethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, methyltrifluorosilane, methyltrimethoxysilane, methyltriethyl Oxysilane, hexamethyldisilazane, hexylmethyldiazine, hexyldimethylsilazane, dimethylchlorosilane, dimethyldisilane, Dimethyldimethoxysilane, dimethyldiethoxysilane, hexamethyldisilazane, trivinyltrimethylcyclodisilazane, with 3 to about 20 dimethylsiloxy groups The polydimethylsiloxane of the unit and the poly (dimethylsiloxane) polymer blocked with trimethylsiloxy or hydroxydimethylsiloxy end groups, the viscosity of which is shown at 25γ In the range of 1 to 1,000 mPa · s. Examples of suitable organic titanium compounds include, but are not limited to, tetrakis (c "Cl8) oxyoxytitanate, methyltriethoxytitanium (iv), methyl ethyl (Iv) Triisopropoxide, methyl titanium (W) tributoxide, methyl titanium (iv) tri-tert-butoxide tributoxide, butyl titanium (iv) triethoxide, butyl Titanium (iv) dibutoxide, benkin (iv) triisopropoxide, phenyl aqin (ίν) tributoxide, phenyl titanium (iv) triisobutoxide, [Ti (CH2Ph) 3 23 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 500754 A7

V. Description of the invention (2l) (NC5H1 ())] and [Ti (CH2SiMe3) 2 (Net2) 2]. Examples of suitable organic zirconium compounds include, but are not limited to, tetra (c "C1S) oxyzirconium zirconate, phenylphosphonium (iV) trigas, methylphosphonium trigas, ethylphosphonium (iv) trichloride , Propyl zirconium (iv) trigas, methyl tris (w) tribromide, ethyl zirconium (iv) tribromide, propyl zirconium (iv) tribromide, vaporized triphenyl chloride (iv) It is also expected to include junction compounds similar to the above-mentioned organic titanium compounds, and vice versa. Amounts of bis (carbooxymethylsulfanyl) sulfide and non-sulfur organometallic compounds in the aforementioned chemical modification method Is sufficient to produce an amount of a modified filler, which is characterized by a carbon content of greater than 1 weight 0/0, a sulfur content of greater than 0.1% by weight, a silane conversion index of at least 0 3 and a tensile strength of 300% The standard tensile stress for elongation is at least 70. This amount is referred to herein as a coupling amount, that is, an amount sufficient to bind the filler and promote the adhesion of the modified filler to the polymerizable composition. Di (alkoxy The weight ratio of the silylalkyl) polysulfide to the organometallic compound is at least 0.05: 1, preferably from 0.05: 1 to 10: 1, more preferably from 0.1: 1 to 5: 1, and most preferably from 0.2: 1 to 2: 1, such as from 0.5: 1 to 1: 1, or the weight ratio may be between any combination of these values, including the quoted values. Each organometallic reactant may be added together, or sequentially in any order. The amount of organometallic reactant added The provided organometallic unit is preferably an excess relative to the hydroxyl groups available for reaction on the inorganic oxide particles. The upper limit of the amount of the organometallic reactant added to the method is not critical. The excess of bis (alkoxy) Polysilyl alkyl) Polysulfide and organometallic compounds, can be filtered or distilled. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first) (Please fill in this page again.) Packing -------- Order -------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 24 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i 、 Invention Note (22), remove with solvent washing or other known separation techniques. In another specific example, the bis (alkoxysilylalkyl) polysulfide can be replaced with a combination of a bis (alkoxysilylalkyl) polysulfide and a different sulfur-containing organometallic compound. Weight ratio of bis (alkoxysilylalkyl) polysulfide to sulfur-containing organometallic compound is at least greater than 1: 1, such as 1 · 〇1:!. The weight ratio can be from 1 ·· 1 to 100: 1, preferably from 5: 1 to 50: 1, more preferably from 10: 1 to 30: 1, or the weight ratio may be between any combination of these values, including the quoted values .Any sulfur-containing organometallic compound (except for the bis (alkoxysilylalkyl) polysulfide represented by the chemical formula) that acts as a coupling agent in the vulcanization of a rubber containing a filler, all of which are Be applicable. Suitable sulfur-containing organometallic compounds include mercaptoorganometallic reactants, which can be represented by the following structural formula VII: (L) n

HS-R6-μ / VII \ Q (3-n) where M is silicon, L is halogen or -OR7, q is hydrogen, CrCi2 alkyl or halogen-substituted 2CrC12 alkyl, R% crC12 alkylene, R7 is a CVC12 alkyl group or an alkoxyalkyl group containing 2 to 12 carbon atoms, the functional group or halo group is an oxo group, a bromo group, an iodo group or a fluoro group, and η is 1, 2 or 3. R6 is preferably Γγ0: 3 alkylene, such as methylene, ethylene and propylene, R7 is preferably alkyl, more preferably methyl and ethyl, L is preferably _〇R6, and n is preferably 3. A thiophosphatoorganometallic reactant having two mercapto groups can also be used. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 25 1 — —! Chapter 1111111 11111111 β11——II (Please read the precautions on the back before filling this page) 500754 A7 B7 V. Description of the invention (23) The Weiji organometallic compound used can also have a blocked mercapto group, that is, the Weiji hydrogen The atom is replaced with another radical. The blocked mercaptoorganometallic compound may have an unsaturated heteroatom or carbon directly bonded to sulfur via a single bond. Examples of specific blocking groups include thiocarboxylic acid esters, dithiocarbamates, thiosulfonates, thiosulfates, thiophosphates, thiophosphonates, thiophosphites, and the like . When the reaction of the mixture is required to couple the filler to the polymer, a deblocking agent may be added to the mixture to unblock the blocked mercaptoorganometallic compound. If water and / or alcohol is present in the mixture, a catalyst such as a tertiary amine, Lewis acid or thiol can be used to initiate or facilitate the removal of the blocking group by hydrolysis or alcoholysis to release the corresponding fluorenyl organic Metal compounds. Methods for the preparation and use of these compounds, such as blocked mercaptosilanes, are disclosed in PCT application wo 99/09036. Other methods for making closed cetyl silanes are disclosed in US Patent Nos. 3,692,812 and 3,922,436, which are incorporated herein by reference. Examples of suitable fluorenyl organometallic compounds include, but are not limited to, fluorenylfluorenyltrimethoxysilane, fluorenylethyltrimethoxysilane, fluorenylpropyltrimethoxysilane, mercaptomethyltriethoxysilane, fluorene Ethyl ethyl tripropoxy cyanide, propyl propyl triethoxy lithium, (fluorenylmethyl) dimethylethoxysilane, (fluorenylmethyl) fluorenyl diethoxysilane, 3 -Fluorenylpropylmethyldimethoxysilane and mixtures thereof. The most preferred compounds are fluorenylpropyltrimethoxylithium, sulfopropyltriethoxy dream house or mixtures thereof. Examples of suitable closed-type fluorene-based organometallic stone burners include, but are not limited to, 2-triethoxysilyl-1-ethylthioacetate, 3-trimethoxy 曱 This paper is sized to Chinese national standards (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page)

· I ϋ 1 I ϋ I -0 0, I a ·· MB MB Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 26 500 754 A7 B7

I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (24) Silyl-1-propylthiocaprylate, bis (% triethoxysilyl · b-propyl) -methyl Dithiophosphonate, 3-triethoxysilyl, propyldimethylthiophosphite, 3-triethoxysilylpropylmethylthiosulfate, 3- Triethoxysilylpropyltoluenethiosulfonate and mixtures thereof. After the completion of the chemical modification, the pH value of the aqueous suspension of the modified inorganic oxide increased from a pH value of 2.5 or less to a pH value between 3.0 and 10 · 0 during the treatment. Typically, the pH of the resulting aqueous suspension is raised to 3 or more, preferably to 4 or more, more preferably to 5 or more, and most preferably to 6 or more, and is usually 10 or less, preferably 9 or less, It is more preferably 8 or less and most preferably 7 or less. The pH of the aqueous suspension may be between any combination of these values, including the recited values. This is achieved by neutralizing the added or generated acidity and producing a final product (after drying) with a pH value from 50 to 10.0. By filtration and drying, or the weight ratio of the solvent to the inorganic oxide in the aqueous suspension of the modified inorganic oxide and the non-aqueous miscible organic solvent in an amount greater than 1 ·· 1 and preferably greater than 5 · 1 Contact while recovering the modified inorganic oxide. Modified inorganic oxides recovered from the solvent phase can be used without further processing or drying. A specific example planned by the present invention is a composition comprising a slurry of the modified filler in a non-water-miscible organic solvent. The concentration of the modified filler in the slurry is between ^ and based on the total weight of the slurry. Examples of suitable non-aqueous miscible organic solvents include low-molecular-weight sintered oxygen fired types such as hexamethyl * a dream fired, octamethylcyclotetradoxy fired, diphenyl paper. Applicable Chinese National Standards (CNS) A4 specifications (210 X 297 mm) 27 ---- I ------ install i I (please read the precautions on the back before filling this page) --line · period 754 A7 B7 V. Description of the invention ( 25) Employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed polytetramethyldisiloxane and polydimethyllithium oxide blocked with trimethylsilyl end groups. , Which acts as both the cymbal sheet j and the reactant of the inorganic oxide. In addition, suitable non-aqueous miscible organic solvents include halogenated hydrocarbons, such as toluene and n · gengyuan, and other halogenated hydrocarbons; cyclopentadiene, such as cyclohexane; Lai, such as diethylzine and dibutyl scale; , Such as digas formamidine, gas imitation, vaporized ethylene and gas benzene; and _, such as methyl isobutyl ketone. The non-aqueous miscible organic solvent used to contact the aqueous suspension of the hydrophobic particulate inorganic oxide may or may not contain one or more substances dissolved therein, as desired. Examples of such substances include but are secreted by one or more rubbers, oils, coupling agents, antioxidants and accelerators. The modified fillers (in the form of powder, granules, pellets, slurries, aqueous suspensions or solvent suspensions) of the present invention can be combined with a matrix material, which is used in the product to be manufactured to form—called the master A mixture of materials. In the master batch, the modified filler can be present at a higher concentration than in the final product. In a mixing operation, the mixture is typically added in portions until it reaches a production scale to assist in uniformly dispersing these very small amounts of additives in polymerizable compositions, such as plastic, rubber, and coating compositions. Modified fillers can be combined with emulsions and / or solution polymers such as organic rubbers containing solution styrene / butadiene rubber (SBR), polybutadiene rubber, or mixtures thereof to form a masterbatch. A specific example planned by the present invention is a master batch, which includes a composition of organic rubber, a non-aqueous miscible solvent, a modified filler, and a selective processing oil. This product can be supplied by rubber manufacturers to tire manufacturers. For tire manufacturers, the use of a masterbatch (please read the precautions on the back before filling out this page). • 装 β§ mm§ a— —Order ---------

A7 V. Description of the invention (26 points are dispersed uniformly in the rubber in the filler material, which reduces the cost of manufacturing composite rubber.-Between. In the masterbatch, each rubber part can contain ⑺ to 150 Part_Modified filler, preferably from 20 to U0, more preferably from 30 to 100, and most preferably from 50 to 80. In another preferred embodiment of the present invention, a polymerization is planned. Sexual objects: 1 () to 15G part of the modified filler is dispersed in every 10 Gap parts of polymer. 'Better than 20 to U0 parts, more preferably 30 to 100 parts per part of polymer. Parts, and the best 5G are called partially modified fillers. The amount of optionally modified fillers can be between any of these values, including the quoted values. As explained herein, the polymer is optional From the following groups: thermoplastic resins' thermosetting resins, organic rubbers, and Koreans. The polymer is preferably a curable organic rubber. The main curable rubbers planned for use with the modified fillers of the present invention are skilled rubber chemistry Those skilled in the art, and may include vulcanizable threads and sulfur-curable rubbers. The planners are those typically used for mechanical rubber articles. The modified fillers of the present invention can be mixed with an uncured rubber elastomer to 'by conventional components such as a Banbury mixer or rubber mill. The vulcanizable rubber composition is prepared at a temperature between about 100 ° F to 3004 (38 ° C (-150 ° C). The vulcanizable rubber composition is contained in every 100 parts of the vulcanizable rubber polymer. It can include 10 to 150 parts of modified filler, preferably 20 to 130 | parts, more preferably 30 to i00 parts, and most preferably 50 to 80 parts. Other conventional rubber additives are It is a conventional sulfur or peroxide curing system. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm A7 B7 _ V. Description of the invention (27) The sulfur curing system can include 0.5 to 3 Part of sulfur, 2 to 5 parts of zinc oxide and 0.5 to 2 parts of accelerator. The peroxide curing system can include from 4 to 4 parts of peroxides, such as dicumyl peroxide. Other conventional methods can also be used. Rubber additives. The additives include other fillers such as carbon black; oils; plasticizers, accelerators; Chemical stabilizers; thermal stabilizers; light stabilizers; regional stabilizers; organic acids such as stearic acid, benzoic acid or salicylic acid; other activators; extenders and pigments. The specific compounding formula will depend on the specific preparation The vulcanizates vary, but the formulation is well known to those skilled in rubber compounding techniques. The vulcanizable rubber composition is vulcanized or cured into a vulcanized rubber according to conventional methods known in the rubber industry. The present invention can be used Examples of industrial vulcanized rubber (objects) made of modified fillers include wire and cable sleeves; rubber tubes; tight gaskets and seals; industrial and automotive transmission belts: engine mounts; V-belts; conveyor belts ; Roller protective film; Tires and tire components, such as automotive tire treads, secondary treads, tire carcasses, tire tyres, tire belt frame shapes, tire bead fillers, tire wire skimming surface layers; track shoe materials Packing rings; shock-absorbing elements and many others. In the following discussion of standard compound procedures, examples and comparative examples, the present invention will be explained in more detail. These examples and comparative examples are for illustration purposes only, as the skilled artisan will understand a variety of improvements and changes. Standard Composite Procedure The standard composite procedure was used to prepare test specimens of the S2 * square rubber composition containing silicon oxide in Examples and Comparative Examples (CE). The following ingredients in Part A are based on 100 parts by weight of rubber. The paper dimensions are applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). (Please read the precautions on the back before filling this page. ) III · ι · ϋ · An am— mmmm§ i · — made by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the employee consumer cooperative 30 500 754 A7 B7 V. The description of the invention (28 (phr) is added to an upright in the stated order Put in a 500 liter plastic cup in a polyethylene bag: # Physical weight (phr) Processing oil (1) 30.0 Silicon oxide (2) 2.5 Ozone inhibitor (3) 2.0 Stearic acid (4) 1.0 Silicon oxide sample 12.5 (1) From the refining and marketing department of Sun Corporation, 81111 (16 乂 @ 8125aromatic hydrocarbon processing oil.) (2) Kadox® surface-treated zinc oxide obtained from Zinc Corporation of America as a commercial product. 3) Wingstay® 100 antiozonant obtained from Goodyear Tire and Rubber Company as a commercial product, which is a mixture of diaryl p-phenylene diamine. (4) Rubber obtained from CP · Hall Company as a commercial product. Grade stearic acid ------------- install -------- order --------- line (Please read the precautions on the back before filling this page} Printed by Part B of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Part B uses a 1.89 liter (L) Farrei Banbury current coupler (model "BR" ") To mix various ingredients. Add batch ingredients CV-6O-grade natural rubber into the mixer and pass through the mixer to remove any residue from previous operations and raise the temperature to about 93 ° C (200 ° F). After removing the rubber and adding ingredients to make

500754 A7 B7 V. Description of the invention (29) Before the rubber test sample, cool the mixer to about 65 ° (: (15 () ° 10). Use the test silicon oxide, the other listed ingredients below, and the method described later , To prepare a rubber composition. Ingredient amount (t) h ^ Add the substance to the mixer in minutes (or remove it from the first speed SBR rubber (5) 70.0 mixer of the mixing speed) 0 Opm, 116 BR rubber (6) 30.0 0 116 Test silicon oxide 57.5 0.5 116 All samples from Part A 3.0 116 Dump the contents of the second process All products from the first process ((5.0)) 0 77 Antiozonant (7) 2.0 0 77 Paraffin (8) 1.5 0 77 RM Sulfur (9) 1.4 0.5 77 TBBS (10) 1.7 0.5 77 DPG (H) 2.0 0.5 77 Dump the contents ((4.0)) (5) Goodyear tires 801〇 @ 1216 solution styrene-butadiene rubber (8811) obtained with a rubber company as a commodity. (6) Budene 1207 butadiene rubber (Goody) obtained from Goodyear Tire and Rubber Company as a commodity ( BR) (7) Acquired from Goodyear Tire & Rubber Company as a commodity

Santoflex® 13 antiozonant, described as N_ (l, 3-dimethylbutyl) -N'-phenyl-p-phenylene diamine. (8) Okerin® 7240 microcrystalline wax / paraffin blend commercially available from Astor. This paper size applies the Chinese National Standard (CNS) A4 Regulations (210 X 297 mm) (Please read the precautions on the back before filling this page). ---------- Order -------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 32 500 754 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (30) (9) Rubber Maker sulfur obtained from Taber Company as a commodity, 100% active . (10) Tet-butyl-2-benzothiazylamine obtained as a commodity from Monsanto. (11) Diphenyl vein obtained as a commodity from Monsanto. The first process was started by adding rubber, namely SBr and br rubber, to the mixer and mixing at 116 rpm for 0.5 minutes. Maintain the speed at 116 rpm and add 57.5 phr of treated silica sample. After another 1.5 minutes, lift the plunger and clean the chute, that is, lift the cover of the inlet chute and sweep any material found in the chute back into the mixer. After another 丨 minutes, the sample from Part A is added. After another 1 minute, lift the plug and clean the chute. Mix the contents of the mixer for another minute to reach the upper limit temperature in the range of 145 to 150 ° C (293 to 302 ° F). Depending on the type of sample, the mixer speed can be increased or decreased after another 4 minutes to reach a temperature within the aforementioned range during a specific mixing period. After the first process is completed, the temperature of the substance is measured with a thermocouple to confirm that it does not exceed the upper limit temperature of 150 ° C. The removed material was weighed and rolled into a thin plate in a 12-inch Fairel 12-inch double-roll rubber mill set at 2.027 mm soil 0.127 mm (0.080 inch soil 0.05 inch). . The produced milled material was cut into strips to prepare a second pass in the mixer. Between the completion of the first process in the mixer and the start of the second process, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 33 i_i -ϋ ϋ team ί 1 «ϋ I ϋ 1 ϋ II · ϋ mmm (Please read the precautions on the back before filling this page) Order:-line · Printed by the Consumer Cooperative of Employees of Intellectual Property Bureau, Ministry of Economic Affairs, A7, B7 5. The invention description (31) must be at least 1 hour in order to Allows milled material to cut and cool. If necessary, complete the aforementioned cleaning and heating procedure using CV-60 grade natural rubber before the second process begins. Adjust the temperature of the mixer to about 49. (: (120 ° F). Under the flow of cooling water, the second process is by adding a strip of material from the first process in a mixer operating at 77 rpm and a pre-weighed Santoflex® 13 antiozonant Started with Okerin® 7240 microcrystalline wax / paraffin blend. After 0.5 minutes, add the second addition of the RM sulfur, TBBS and DPG composition. After another 1.5 minutes, lift the plunger and clean the chute. The second process was completed by mixing the materials for a further 2.0 minutes while maintaining the temperature below 125 ° C (257 ° F). Part C heated the Farrel 12-inch double roller rubber mill To about 60 ° C (140 F). Add the material from the second process of Part B to the mill in operation and the gap between the rollers is set to 2.032 mm soil 0.127 mm (0.080 inch soil 0.005 inch). The resulting sheet is placed on a flat surface until the temperature of the sheet is reduced to room temperature. Typically, the sheet is cooled in about 30 minutes. After that, the obstructed sheet is fed into a rubber mill and pressed. The light gap is set at 3_81 mm to 0.51 mm (0.15 inch soil 0.02 inch). If needed, the roll slope can be adjusted to maintain a uniform thickness. The material produced is processed by 16 side cuts and 8 end passes. The roll gap of the rubber mill is adjusted to produce a thickness of 2.032 mm soil. One millimeter (0. 080 inch soil 0. 05 inch). The sheet material produced from the rubber mill is placed on a flat and clean surface. A template is used to cut from the sheet material 203 mm x 152.4 mm (8 inches x 6 inches) rectangular sample. Condition the sample to the original size 剌 + Guanshen Standard (CNS) A4 specification (210 X 297 mm) ----- ---: --- -------------- Order --- (Please read the notes on the back before filling out this page) 34 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 500754 A7 ---- _B7 ^ V. Description of the invention (32) 'That is, at 23 ° ± 2 ° C and relative humidity of 50% to 5%, the sample is stored in a clean polyethylene sheet for 15 to 18 hours. During conditioning After the action, the sample was placed on a 203 square meter with a polished surface X 152.4 mm X 2.286 mm (8 inch X 6 inch X X 0.9 inch)- Frame mechanical steel stamper. The sample is a pressure of 13.79 million Pa (2000 pounds per square inch) at a pressure of 61 cm x 61 cm (24 inches by 24 m) and 890 kilonewtons ( 100 tons) The time to cure τ90 in a four-column electric hot stamping press, that is, the time required for 90% curing according to ASTM D-2084, plus 5 minutes at 150 C (302 F). The maturation is typically completed in about minutes. The resulting cured rubber sheet was removed from the mold and maintained at a temperature of 23 ° soil 2 ° C (73.4 ° soil 3.6 ° F) and a relative humidity of 50% ± 5% 15 to 18 before testing in Section D. hour. Part D testing is performed in accordance with ASTM D-412-98a-Test Method A. Using a mold C, a dumbbell-shaped test specimen was prepared. An Instron tensile strength tester model 4204 with an automated contact tensile tester was used to determine the tensile effect. The truncated speed was found to be equivalent to 508 mm / min. All calculations are performed using the IX series of automated substance testing software provided by the manufacturer. The tensile stress (in MPa) of 300% tensile action of the specimens prepared by this standard composite procedure is reported as the standard tensile stress (STS @ 300%) of 300% tensile action. table. The Dajue-type Qihua Γ silicon is produced by acidifying a sodium oxalate solution with sulfuric acid to produce a Shendian-type silicon oxide. Most precipitates are formed when the pH is higher than 8.5. By holding the paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied. 35 — — — — — — — — — — — 1111111 · 11111111 (Please read the precautions on the back before filling (This page) 500754 A7

V. Description of the invention (33) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Continue to add acid until the pH value of the solution reaches about 3.5 to further produce the precipitate. A precipitated silica sample for surface area analysis as described in Example 9 was prepared by filtering and washing a part of the silica until the washing water showed a conductivity of about 300 to 800 µmohm. The resulting cake was reliquefied using a high shear mixer to form a solid in a liquid suspension. The suspension was dried in a Niro spray dryer (inlet temperature of approximately 3600 ° C and outlet temperature of approximately 110 ° C). The surface areas of the precipitated silicas used to prepare the modified silicas in the examples and comparative examples are shown in Table 1. Example 1-2 In a 30-gallon glass container with a bottom outlet, about 40 kg of a precipitated silica suspension containing about 5.2 kg of silica and about 11.7 kg of isopropanol were added. The container is also equipped with a temperature recorder, a mechanical stirrer, heating elements and a condenser. When stirring and heating the contents of the container, the silicon-69 enhancer, referred to herein as TESPT, is added over a period of time (typically about 10 minutes), which will produce approximately the weight ratio of TESPT listed in Table 3 The amounts are based on the dry weight of silica of the examples listed in the table. After the addition of TESPT is completed, dimethyldichlorosilane (DMDCS) is added in the same manner to obtain an approximate amount of the DMDCS weight ratio listed in Table 3, which is based on the oxidation of the examples listed in the table Based on silicon dry weight. The weight ratio of TESPT / DMDCS is also listed in Table 3. The pH of the resulting solution was approximately 0.8. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 36 --------.-- installation -------- order ---------% (Please read the precautions on the back before filling this page) A7 B7 V. Description of the invention (34 ------------- installation. — I (Please read the precautions on the back before filling out this page ) After the addition of DMDCS is completed, the mixture is heated to about 68 C 'and maintained at that temperature for about 10 minutes. When cooling, add a sufficient amount of toluene to the stirred mixture (typically about 15 kg) In order to achieve the effect of separating the hydrophobic precipitated silica from the aqueous phase without forming an emulsion. The aqueous phase is discharged from the container. Then in the first example, about 30 kg of sodium bicarbonate containing about 400 g Water and about 40 kg of water containing about 500 g of sodium bicarbonate in the second example, the container containing the hydrophobic precipitated silica mixed with the scrambled mixture was washed twice. The water phase was eliminated. After the washing was completed, After the action, a sufficient amount of toluene was again added to the stirred mixture (about 13.9 kg in the first case and about 23.7 kg in the second case) to make a solid. A flowable suspension in a liquid that can be easily discharged from the container. In a rotary cone dryer, dry at a minimum temperature of 14 ° C and vacuum (minimum 23 inches of mercury) The resulting suspension, thread, and float. The drying effect was continued until the weight percent loss when the sample was exposed at 16 ° C for 10 minutes was less than 4.5 weight percent. Examples 3-8 had a bottom outlet in one In a 40-gallon glass container, about 19 kg of precipitated silica suspended in silicon dioxide containing about 1.5 kg of silicon oxide was added. The printing liquid of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was also equipped with a temperature recorder, a mechanical stirrer, and a heating member. And the condenser. When mixing the contents of this container, add about 1 weight 0 // 0 of dry weight of oxidized stone to increase the strength of the province-surface. It is said that the addition of the surface agent at t After the action, the resulting mixture was stirred for 5 minutes. TESPT was added over a period of 5 minutes, based on the dry weight of silicon oxide, about 10 weight 0 / 〇37 This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 public love) 500754

V. Description of Invention (35) TESPT printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The pH of the resulting solution was about 30. After the addition of TEspT was completed, difluorenyl digasilane (DMDCS) was added in the same manner to obtain about 15% by weight of DMDCS based on the dry weight of silicon oxide. The pH value of the resulting solution is between about 0.9 and 6. The mixture is heated to about 61 to 68 ° C and maintained at this temperature typically for about 20 minutes. The suspensions of the fifth and eighth cases were heated for about 40 and 16 minutes, respectively. When cooling, a sufficient amount of 50% by weight sodium hydroxide is added to the mixture for a period of time (typically 10-15 minutes) to adjust the pH to about 70. Twenty liters of the stirred mixture containing hydrophobic precipitated silica was discharged from the container, vacuum-filtered using a Buchner funnel, and then washed three times each with about 8 kg of water. After the cleaning is completed, a sufficient amount of deionized water and high-shear stirring are applied to the filter cake to form a flowable suspension that is solid in liquid. The resulting suspension was spray-dried in a pair of Niro spray dryers (with an inlet temperature of about 4,000 ° C and an outlet temperature of about 150 ° C) to form treated oxidations of cases 3-8. Silicon sample. Examples 1-3: In a container equipped with a mechanical stirrer, π liters of untreated precipitated silica containing 820 g of silica was added. The pH of the slurry before treatment was about 6.5. When the suspension was mixed with a stirrer, a sufficient amount of TESPT was added to obtain an approximate amount of the TESPT weight ratio listed in Table 3, which was based on the dry weight of silica of Comparative Example 1.3. The resulting treated suspension was sprayed in a Niro spray dryer (inlet temperature is about 360 ° C and outlet temperature is about 11.0). The paper size is applicable to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 38 -------- install i _ I (Please read the precautions on the back before filling in this page) I a— ϋ Order --------- 500754 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (36 fog drying. The 9th example uses a dynamic single-point surface area technique, ASTM D-3037-93 method C (revised). Horiba 6200 series instruments measure the treated and untreated silica test samples of 1-8th and Comparative Examples 1-3 (CE). This method is simulated at P / P0 = 0.294 using 30 The Brunauer-Emmett-Teller (BET) method using nitrogen in helium as the adsorbed gas. The ASTM method is modified as follows: a gas mixture using nitrogen in 30% helium; Maintain a flow rate of about 40 ml / min; the sample is dried in an analysis chamber under nitrogen flow at 180 ° C 5 ° C for 1 hour; by removing the liquid A vacuum bottle to desorb the nitrogen adsorbed on the sample, and allow the sample to return to room temperature without an external heat source. The results of the untreated silicon oxide test sample are shown in Table 1, The results of the treated oxidized zone test samples are listed in Table 4. The carbon percentage was determined by CHN analysis using a Carlo Erba Model 1106 elemental analyzer. 1040 in an oxygen-rich environment ° C Burn a 1-2 g sample sealed in a tin capsule with a helium carrier and burn quantitatively on chromium trioxide. The combustion gas then passes through copper at 650 ° C to remove excess oxygen and remove Nitrogen oxides are reduced to nitrogen. The gas is then passed through a chromatography column to be separated and eluted into nitrogen, carbon dioxide, and water. The eluted gas is measured with a thermal conductivity detector. The instrument is calibrated by burning standard compounds The lit fruits are listed in Table 4. The sulfur% was measured by X-ray fluorescence spectrometry (XRF) using a Rigaku RIX 2000 spectral dispersion spectrometer. It is applicable to China on a paper scale of 1: 1 National Standard (CNS) A4 Specification (210 X 297 39) 39 ----------- install — 1 — order ---- — II · line (please read the precautions on the back before filling out this page) 500754 A7 B7 Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative V. Description of the invention (37 volume ratio after mixing the sample with SpectroBlend® adhesive (Chemplex Industries, Tuckahoe, NY), at 344.75 million Pa (25 tons / square foot) The sample was pressed into an aluminum support cup by pressure to form a block. Use the NIST- and NBS-traceable secondary standards (silicon oxide or equivalent for PPG production) for experimental XRF calibration. The detection effect is through a gas flow proportional counter tube using a germanium crystal monochromatic light mirror. The results are listed in Table 4. The silane conversion index reported in Table 4 by SCI is measured by solid-state 29 silicon NMR. The data was obtained at ambient temperature on a Bruker AM-300 NMR with a narrow ID magnet and a 7 mm Doty standard speed MAS probe. The sample was packed in a zirconia drum with an outer diameter of 7 mm and sealed with a short Kel-F cap. The drum rotates in Magic Angle at a speed of approximately 5.0 kHz. Cross-polarization (CP / MAS) data was obtained with 90 ° 4 pulses, 5600-8400 scans per spectrum, 5 ms contact time, high-energy proton decoupling during data measurement, and 3 seconds of relaxation delay. . Using a kaolin sample (J · R〇ch # j KHn〇wski in J. Magn. Reson, Issue 90, p. 567 (1 " year) B) to reach Hartmann Hahn_tmann.Hahn )condition. All μ positions are externally referenced with tetramethylsilane (TMS). All the spectra were analyzed on an Aspect 3000 computer using a non- 飧 #, and sexual music green line A-line (LINESIM) to determine T1. " Relative area of heart 1 (· 49 ppm), T2 (-57 ppm) T3 lean (-65 ppm) peak area 0 /! s GT, area of τ2 and τ3%, will fit from -30 ppm to -80 ppm Area of -1, a curve measurement. The following methods are used to measure the examples and comparative examples of ", heart-treated silicon oxide ------------. 0 ^ -------- tr · I— I · $ (Please read the precautions on the back before filling out this page) 40-V. Printed by A7, Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, A7 Invention Description (38) The value is 15 of a magnetic stick. Add 50 oxidized stone powder (in powder form) to a ml beaker; add 50 liters of isopropanol and M ml of deionized water; stir vigorously without extinguishing until the oxidized stone powder is suspended.- The calibrated pH electrode was placed in a vigorously agitated solution, and the pH value was recorded after 1 knife (5 seconds of soil). The results are listed in Table 4. By adding 5.44 grams of substance to 43 mm x 123 mm ( Inner diameter X Outer diameter) cellulose extraction sleeve, and then place the sleeve into a suitable and sized Soxhlet extraction tube equipped with a condenser, and measure The first example is the percentage of Soxhlet extractable carbon of treated silica. The Soxhlet extractor and condenser system was connected to a round bottom flask containing 700 ml of toluene. The flask was heated to the reflux temperature of toluene. After refluxing for 25 hours, the used toluene was replaced with unused toluene, and the reflux was continued for 22.5 hours. The extracted and treated silica was recovered, and It is dried until the weight loss when the sample is exposed to 10 ° C for 10 minutes is less than ι0% by weight. The carbon of the extracted sample is determined using the method described here. Soxhlet) The percentage of extractable carbon is determined by the following equation: (carbon% before extraction)-(carbon% after extraction) " carbon% before extraction) X 100 carbon% before extraction is 3.50, and The carbon percentage after extraction is 3.02. Therefore, the percentage of Soxhlet extractable carbon in the first treated silicon oxide is 13.7. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — — — — — — — — — — — — — — — — — — — I— ^ 0 — — — — — — (Please read the notes on the back before filling out this page) 41 500754 A7 B7 V. Description of the invention (39) In the example in Table 1 Surface area used: Untreated oxidized stone square meters per gram Example 1-2 and Comparative Examples 1-3 198 Example 3-8 Example 180 Table 2 Example No. Surfactant Example 3 MAFO® CAB (12 4) MASIL® SF 19 (13) 5th AVANEL® N-1525 / 90 (14) 6th MACOL® 48 (15) 7th ... BRIJ® 35 (16) 8th ETHOMEEN® 18 / 60 (17) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (12) An amphoteric surfactant available from BASF, reportedly based mainly on carbamide aminopropyl betaine. (13) A nonionic surfactant available from BASF, reportedly based on ethoxylated silicones. (14) A nonionic surfactant available from BASF, reportedly based on an ethylene oxide terminated with an alkyl chloride at the end. (15) A nonionic surfactant available from BASF. It is reported to be mainly ethylene glycol ether. --------, -M -------- Order --------- (Please read the precautions on the back before filling this page) This paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 public love) 42 500754 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (40) (16) A non-ionic surfactant available from Aldrich Chemical Company, It is reported to be mainly polyoxyethylene lauryl ether. (17) A nonionic / cationic surfactant available from AKZO Chemical Co., reportedly based on ethoxylated (50) stearylamine. Example #% TESPT / Silicon dioxide Table 3% DMDCS / Silicon dioxide TESPT / DMDCS ratio 1 10.0 15.0 0.67: 1 2 10.0 15.0 0.67: 1 3 10.0 15.0 0.67: 1 4 10.0 15.0 0.67: 1 5 10.0 15.0 0.67: 1 6 10.0 15.0 0.67: 1 7 10.0 15.0 0.67: 1 8 10.0 15.0 0.67: 1 1st comparative example 5.0 0.0 5: 0 2nd comparative example 7.5 0.0 7.5: 0 3rd comparative example 10.0 0.0 10: 0 4 Table Carbon Sulfur STS @ (wt%) (wt%) — ^ 00% *** 1 126 7.2 3.5 1.78 ND * 9.4 2 124 7.4 3.4 1.50 0.53 9.9 3 114 9.1 3.7 1.12 ND * 8.0 4 112 8.3 3.6 1.09 ND * 7.7 5 115 9.4 3.5 1.32 ND * 7.8: 6 124 8.4 2.3 0.83 ND * 8.0 7 111 9.5 3.8 1.12 ND * 7.1 / 8 104 8.4 3.8 1.36 ND * 8.1 / 1st comparative example 167 6.7 0.7 0.77 ND * — 6.9 ______j 2 1.25 ND * /6.^ Comparative Example 3 148 6.9 1.7 1.60 0.06 \ 6.2 / ND * means the test was not performed.乂, SCI ** stands for Silane Conversion Index. STS @ 300% *** represents the standard tensile stress at 300% elongation. • I MV I • I I MV I I

The results shown in Table 1 and Table 1 show that the unoxidized oxidation used in the manufacturing method of the modified oxide stone used in the examples and comparative examples is between square meters / gram. / 、 The surface area is between 18. The results to Table 4 show that the standard tensile stress of the treated oxygen-cut sample of the present invention in the difficult tensile action is at least 7.0, its carbon weight% is greater than L0, and its sulfur weight% is greater than Q1 and its ㈣ The conversion index is greater than 0.3. The carbon weight% of the first comparative example is lower than the required amount, and its standard tensile stress at 300% tensile action is 3.6. The carbon and sulfur contents of Comparative Examples 2 and 3 were both within the required ranges, but their standard tensile stresses at 300% elongation were less than 7.0. The SCI value of the third comparative example is also lower than the required value Λ Although the present invention is described with reference to specific details and some specific examples, these details are not intended to be considered as a limitation of the scope of the present invention unless they are included in In the scope of patent application.

Equipment • ϋ 1 ϋ ---- Order --------- Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

A chemically modified filler comprising an amorphous or particulate inorganic oxide is characterized by: '(a) a carbon content greater than 1% by weight; (b) a sulfur content greater than 0.1% by weight; (c) at least Silane conversion index of 0.3; and (d) the standard tensile stress at 300% tensile is at least 7. For example, the chemically modified filler of the scope of application for a patent, wherein the carbon content is at least 1.5% by weight; the sulfur content is at least 0.3% by weight; the stone yaki conversion index is at least 0.4; And the standard tensile stress at 300% elongation is at least 7.5. For example, the chemically modified filler of the second scope of the patent application, wherein the inorganic oxide is a Shenyang type silicon oxide, the carbon content is at least 2% by weight; the sulfur content is at least 0.6% by weight; the silane conversion index is At least 0.5; and the standard tensile stress at 300% elongation is at least the chemically modified filler of item 1 of the patent application range, wherein the filler is further characterized by a range from 20 to 350 square meters per gram. —Improved surface area of BE. The chemically modified filler as defined in the scope of the patent application No. 3, wherein the surface area of the modified BE butt is from 100 to 200 square meters per gram. For example, the chemically modified filler of item 1 of the patent application range, wherein the filler is further characterized by one from 5 to 10? 11 value. For example, the chemically modified fillers in the scope of application for patent No. 5 have an impulse value from 6.0 to 7.5. C8 ---- ^-, patent application range 8. If the chemically modified filler of item i of the patent application range, the filler is further characterized by the percentage of Soxhlet extractable carbon (Please read the notes on the back before filling out this page} The ratio is less than 30%. 9. If the chemically modified filler of item 7 of the patent application scope, the percentage of Soxhlet extractable carbon It is less than 20%. 10. The chemically modified filler according to item 1 of the patent application range, wherein the inorganic oxide is selected from the group consisting of kaolin, clay, diatomaceous earth, alumina, aluminum hydroxide, aluminum dihydrate, Titanium dioxide, aluminosilicate, silicate, fumed silica, colloidal silica, precipitated silica, or a mixture of these inorganic oxides. 11. If the chemically modified filler of item 10 of the patent application scope, wherein The inorganic oxide is aluminosilicate, colloidal silica, precipitated silica, or a mixture thereof. 12. The chemically modified filler according to item u of the patent application scope, wherein the inorganic oxide is a Shenyang type silica. 13 -Species include non-aqueous miscible An organic solvent with a mass of 1 to 90% by weight of an inorganic oxide printed or granular inorganic oxide printed by a consumer cooperative of employees of the Intellectual Property Bureau of the Ministry of Amorphous Economy, characterized by: (a) more than 1% by weight of carbon Content; (b) Sulfur content greater than 0 · wt%; (c) Silane conversion index of at least 0.3; and less than tv-14 · If the polymer of item 13 of the scope of patent application, The non-water-miscible solvent is selected from the following groups: aliphatic hydrocarbons, aromatic hydrocarbons, naphthenes, and halogens. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 46 A8-~- --- ~ --_ VI. Application scope of patents for hydrocarbon solvents and _ (Please read the precautions on the back before filling out this page) If you apply for the patent of the month | The oxide system is Shenyang oxygen cut, and its characteristics further include improved BET surface area from 2G to 350 square A ft / g, pH value from 5 to 1 and Soxhlet extractable carbon. The percentage is less than 30%. 16 · —including organic rubber, non-aqueous miscible solvents and Part of the organic rubber has a master batch of a composition of 10 to 15G partially amorphous or particulate inorganic oxides, characterized by: (a) a carbon content of more than 1% by weight; (b) more than 0.1% by weight. / ❶ Sulfur content; (c) a silane conversion index of at least 0.3; and (d) a standard tensile stress at 300% elongation of at least 7. 17. If the master batch of item 16 of the patent application, The organic rubber includes a solution styrene / butadiene rubber, a polybutadiene rubber, or a mixture thereof. 18. A type having 10 to 150 parts of an amorphous or particulate inorganic oxide per 100 parts of the polymer dispersed therein. A polymer part characterized by: (a) carbon content greater than 1% by weight; printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; (b) sulfur content greater than 0.1% by weight; (c) at least 0.3 The silane conversion index; and (d) the standard tensile stress at 300% elongation is at least 7. 19. The polymer part of claim 18, wherein the polymer is selected from the group consisting of a thermoplastic resin, a thermosetting resin, an organic rubber, and a silicone rubber. 20. If the polymer part of item 19 in the scope of patent application is applied, the size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 47 500 754 A8 B8 C8 Sixth, the scope of patent application is a kind of organic rubber which can be cured. 21 · The polymer piece according to item 18 of the patent application range, wherein the inorganic oxide system is a sintered oxide type, and is further characterized by an improved BET surface area from one to 350 square meters per gram, from 5 to 1 〇One of the pH value and the percentage of Soxhlet extractable carbon is less than 30/0022. For example, the polymer part of the scope of patent application No. 21, wherein the polymer is a kind of organic Rubber, including solution-stabilized ethylene / butadiene rubber, polybutadiene rubber, or mixtures thereof. 23. The polymer piece of claim 22, wherein the article is a tire. ------------- Μ -------- (Please read the precautions on the back before filling out this page) i-line · 48 copies printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Paper size applies to China National Standard (CNS) A4 (210 X 297 mm)