TWI260335B - Process for producing chemically modified fillers - Google Patents

Abstract

Described is an improved process for producing chemically modified fillers by using a certain combination of functionalizing and hydrophobizing agents in an aqueous suspension of inorganic oxide having a pH of 2.5 or less and increasing the pH of the suspension after chemically modifying the filler.

Description

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I 1260335 V. INSTRUCTIONS (1 A7 B7 Interacting with the relevant application) This paper claims to apply for the US Provisional Application No. 60/203,427, filed on May 10, 2GGG, and filed on December 17, 1999. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; a method for producing a particulate or amorphous filler having a minimum carbon and sulfur content, a minimum decane conversion index, and a minimum standard tensile stress at 300% tensile action, and A polymer of a filler such as a curable rubber composition. In most detail, the present invention relates to a process for producing a functionalized and hydrophobized filler, after which the filler is referred to as a "modified filler," which enhances manufacturing. The efficiency of polymerizable compositions such as rubber compounding, and the performance of polymerized or cured products such as tires. In the manufacture of polymerizable compositions, fillers are usually incorporated. Into the physical properties of the polymer. The surface of the filler is typically modified to increase reactivity and subsequent two-dimensional and three-dimensional coupling of the filler to the polymerizable composition. In the rubber industry, conventionally Carbon black and other reinforcing fillers are included in natural and synthetic rubber to enhance the physical properties of the cured vulcanized rubber. Fillers for reinforcing the polymerizable compositions, including natural and synthetic fillers. One of the black body fillers is an amorphous precipitated cerium oxide. The enamel filler is used to impart a modified paper grade to the vulcanized rubber. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1260335 A7

1260335 A7 Filling with the decane coupling to make the decane coupling invention (and the enamel in the non-aming liquid to prepare a rubber composite additive, that is, an oxidized stone = Shi Xi burning concentrate) The coupling composition (tetra) filler is chemically inert. '3 US Patent No. 5,116,886 describes a method having two steps in which a natural or oxidized oxide is changed by using a specific organic cerium compound. Or the surface of the silicate filler. In the first step, the organic ruthenium compound is thoroughly mixed with the filler at a temperature lower than 60 C. In the second step, the temperature is treated from 6 (^16 (rC) The mixing of the s of the singularity of the sulphur saponin is also described in the first step, in a first step, in a catalytic amount. In the presence of an acid, the aqueous suspension of the (4) oxygen cut is contacted with the -organic (tetra) compound to achieve the hydrophobization of the precipitated cerium oxide. In the second step, the solvent is greater than 5:1 relative to the oxidation. Shi Xizhi's weight For example, an aqueous suspension of water-based money Weiqi is contacted with a non-water-miscible organic agent to separate a hydrophobic precipitated cerium oxide from the aqueous phase. "At present, it has been found that a modified filler can be prepared. , for example, a particulate or amorphous inorganic oxide characterized by a carbon content of more than 1% by weight, a sulfur content of greater than °, a weight of *%, and a conversion index (described later) of at least Ο·: at 3 The standard tensile stress (also shown later) of 〇〇°/° tensile action is 7 or more. The method described in U.S. Patent No. 5,9,8,66, can be modified and used for a specific composition having a enthalpy value of 2.5 or less - a specific composition of a functionalizing agent and a hydrophobizing agent in an aqueous suspension of an inorganic oxide, and an acid neutralizing agent - a one--- --------Book --------- Line j (Please read the notes on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

This paper scale applies to China National Standard (CNS) A4 specifications (2) 0 X 297 Ministry of Public Affairs Intellectual Property Office Staff Cooperatives Printed 1260335 A7 ____________B7__ V. Description of invention (4) Acidic aqueous suspension of modified filler to suspend suspension The positive value of the invention is increased to a range of 3.0 to 1 Torr to produce the modified filler of the present invention. As used herein, a functionalizing agent is a reactive chemical which promotes covalent bonding of an inorganic oxide to one of the polymerizable compositions to the composition. a hydrophobizing agent-chemical substance which adheres to and/or combines with the -inorganic oxide to reduce the affinity of the inorganic oxide for water while increasing the inorganic oxide used in the organic polymerizable composition The affinity of the composition. The above-mentioned standard tensile stress (STS@300%) having a tensile strength of at least 7 or more of 300% means an enhanced strengthening effect of the rubber composition. Enhanced strengthening refers to an improvement in the mechanical durability of the product as evidenced by an increase in tear strength, hardness and abrasion resistance. In addition to enhancing properties, the modified filler has the advantage of requiring less time and energy to incorporate the polymeric composition. DETAILED DESCRIPTION OF THE INVENTION In addition to the examples of operation or the other description, it should be understood that all values used herein to refer to the quantities, ratios, ranges, etc., in all cases, are modified by the word "about". A method for producing the filler for preparing the modified filler of the present invention, wherein the filler is an inorganic oxide having a carbon content of more than 1% by weight, preferably at least 1.5% by weight, more preferably at least 2.0% by weight; More than 0.1% by weight, preferably at least 〇3 ❶/〇, more preferably at least 〇6% by weight: its decane conversion index is at least 0.3, preferably at least 〇.4, and most preferably at least 〇·5 And the standard tensile stress of 300% tensile action is at least the Chinese National Standard (CNS) A4 specification (210 X 297 mm) for the paper scale. *Ί'1^装-------- --------- Line j (Please read the notes on the back and fill out this page) 1260335

The Ministry of Economic Affairs' Intellectual Property Office employee consumption cooperative prints 7.0, preferably at least 7.5, and even better at least 8 〇. The modified filler of the present invention is also characterized by a modified Brunauer_E_ett- Teller (BET) value, that is, a single point surface area of 2 to 35 square meters per gram. Preferably, it is 40 to 300 square meters per gram, preferably 丨 (10) to 2 square meters per gram; pH is from 5 to 10, preferably from 5.5 to 9.5, more preferably from 6 to 9.0, and most Preferably, the pH of the product may be between the combinations of the values, including the recited values; and Soxhlet (the percentage of extractable carbon in the state of s〇xhl is less than 30) %, preferably less than 25%, more preferably less than 20%, such as 15%. A method for determining the aforementioned properties of the modified inorganic oxide is described in Example 9. For preparing the modified filler of the present invention A filler, which is an inorganic oxide, defined herein as either inorganic particulate or amorphous having either oxygen (chemically or covalently bonded) or hydroxyl (bonded or free) on its exposed surface. Solid matter. In addition, the inorganic oxide is one of various materials suitable for use in a variety of molding, compounding or coating processes, including such injections. Molding, lamination, transfer molding, compression molding, rubber compounding, coating (such as dip coating, brush coating, knife coating, roll coating, screen coating, printing, spraying, etc.), casting, and the like. The inorganic oxide used to make the modified filler of the present invention is preferably a type of precipitated cerium oxide commonly used in rubber compounding. Various commercially available cerium oxides for use in the present invention can be considered, including from ppG Industdes Oxidation enthalpy obtained under the Hi-Sil trademark under the designation 210, 243, etc.; ruthenium oxide obtained by, for example, the model z1165Mj^zi65gi^ from Rh〇ne-pouienc^; and papers such as models VN2 and VN3 from Degenssa AG Ruler with Zhongguanjia Standard (CNS) A4 specification (2) G x 297 gong ^ ----- Production ----1 — Installation -------- Order --------- Line j (Please read the notes on the back and fill out this page) 1260335

Wait for the oxidized stone eve. The immersed oxidized oxide used to make the modified filler of the present invention can be prepared by, for example, the acidity of a solution of a (iv) salt such as sodium (tetra). The method for preparing precipitated cerium oxide is not limited by the present invention; it will depend on the desired oxygen cleavage properties, such as the surface area and particle size of the particular application. ^ Used to make the modified oxygen cut of the present invention, the BET surface area is generally in the range of 50 square meters / gram to 1 〇〇〇 square meters / gram, preferably between 100 square meters / gram To the 5 ft. square meter / gram of the Fan of the Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, printed the precipitated cerium oxide used to form the modified cerium oxide, which may be in the form of an aqueous suspension from one of the manufacturing stages prior to the dry step. , such as a slurry formed during the sinking action or a filter cake that is reliquefied. The suspension may also be formed by redispersing the dried cerium oxide in an aqueous and/or organic solvent. The concentration of the hydrophobic precipitated oxidized oxide in the aqueous and/or organic suspension is not critical&apos; which may range from about 1 to 9 〇 wt%. The concentration of the aqueous precipitated cerium oxide is preferably in the range of from 丨 to 5% by weight, more preferably in the range of from 1 to 20% by weight. The decane conversion index is defined by the equation T3/(Ti + T2 + T3). The values of T2 and T·3 are determined by solid state 29 NMR and represent the reaction. The decane conversion index provides an indication of the degree of reaction or cross-linking between the nearby cesium atoms and their mutual interaction. The higher the index value, the greater the amount of cross-linking between the decane, yttrium oxide surface and the adjacent decane. T1 represents a decane unit, which is chemically bonded to oxidized o-precipitate at an address to sequester T1. __----1·&quot;^^ --Book --------- line (please read the note on the back and fill out this page) This paper scale applies to China National Standard (CNS) A4 specification (21〇x 297 mm) 9 1260335 A7

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Ϊ260335 A7

V. Description of the invention (8) Liquid, latex, dispersion, etc. The polymerizable composition containing the modified filler may be ground, mixed, molded, and aged by any means known in the art to form a dispersion of 10 to 15 Å of modified filler per 100 parts of the polymer. One of the polymer parts in between. Examples of suitable polymers include thermoplastic and thermosetting resins, rubber compounds, and other polymers having elastomeric properties. The polymer may be an alkyd resin, an oil-modified alkyd resin, an unsaturated polyfluorene, a natural oil (linseed oil, tung oil, soybean oil), an epoxide, a nylon 'thermoplastic polyester (such as a polyethylene pair). Benzoate, polybutylene terephthalate), thermoplastic and thermosetting polycarbonate, polyethylene, polybutylene, polystyrene, polypropylene, ethylene propylene copolymers and terpolymers, acrylics Acetic acid homopolymers and copolymers, acrylates, methacrylates, acrylamides, salts thereof and hydrohalides, etc.), phenolic resins, polyoxymethylene (homopolymers and copolymers), poly Uracane, polyfluorene, polysulfide rubber, nitrocellulose, vinyl butyrate, vinyl (containing ethylene chloride and / or vinyl acetate polymer), ethyl cellulose, cellulose acetate and butyric acid Ester, viscose, shellac, wax, ethylene copolymer (such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene acrylate copolymer), organic rubber, and the like. The amount of the modified filler in the polymerizable composition may be 5 to 7 Torr and 0/Torr, based on the total weight of the plastic composition. For example, a typical amount of the modified filler in the ABs (acrylonitrile-butadiene-styrene) copolymer is from 3 to 60% by weight, and in the acrylonitrile-styrene-acrylate copolymer is $ to 2% by weight, in the aliphatic polyketone, 15 to 3% by weight, applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) on the alkyd resin paper size (please read the back note first) Matters fill out this page) ~* — — — — — — — ^ 1111111 - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed 11 1260335 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed A7 V. Invention Description (9) 30 to 60% by weight of the thermoplastic olefin is from 1 to 3 Å by weight, and is from 5 to 20% by weight in the epoxy resin, and up to 60% by weight in the ethylene vinyl acetate copolymer. Up to 80% by weight in the ethyl acetate ethyl acetate copolymer, 3〇 to 7〇% by weight in the liquid crystalline polymer (Lcp), and 30 to 60% by weight in the phenolic resin, and in the polyethylene The amount is usually greater than 40% by weight. In more detail, organic rubber and silicone rubber are preferred. Examples of such rubbers include natural rubbers; those formed by the homopolymerization of butadiene and its homologues and derivatives, such as cis 4,4-polyisoprene, 3,4_polyisoprene Alkene, cis-polybutene, trans-丨, 'polydibutene, anthracene, fluorene-polybutene; and such self-butadiene and its homologues and derivatives, and one or The formation of a copolymerizable monomer of a saturable polymerizable monomer, such as styrene and its derivatives, vinyl pyridine and its derivatives, acrylonitrile, isobutylene, and alkyl-substituted acrylates such as yttrium methacrylate Purpose. Examples include styrene-butadiene copolymer rubbers composed of different styrene and butadiene percentages and various butadiene isomers as appropriate (this = called ''SBR,,); benzene And a mixture of isopentadiene and butyl bismuth polymers and various isomers thereof; and a rubber composition mainly composed of isobutylene; or a mixture thereof, as described in, for example, U.S. Patent No. 4,53,959. Nos. 4,616,065, 4,7485199, 4,866,131, 4,894,420, 4,925,894, 5, 〇82,9()1 and 5162 4〇9. Other suitable organic polymers are copolymers of ethylene with other advanced alpha flue gases such as propylene, dibutyl-1 and pentane, and a dimer monomer. The organic polymer may be a block, a random or a sequential polymer, and may be emulsified by -------I---- - Line (please read the notes on the back and fill out this page)

V. INSTRUCTIONS (10) Liquid (such as e-SBR) or solution (such as s_SBR) polymerization method. Other useful polymers include those which are partially or fully functionalized, including coupled or stellate branched polymers. Other specific examples of functionalized organic rubbers include polychloroprene, chlorobutyl and butyl rubber, and desertified isobutyl-co-p-methyl styrene rubber. Preferred organic rubbers are polybutan, s-S B R and mixtures thereof. The polymerizable composition is preferably a curable rubber. , "curable rubber" - the word system is intended to include natural rubber and its various raw materials and recycled forms, as well as a variety of synthetic rubber. For example, the curable rubber may include a combination of sbr and butyl rubber, SBR, BR and Natural rubber, and any other combination of the previously described organic rubber materials. In the description of the present invention, "rubber,,,, elastomer, and, rubbery elastomer," are used interchangeably. Unless otherwise stated. , "Rubber composition", ", composite rubber," and "rubber compound" and other words can be used interchangeably, and refers to the rubber blending or mixing different ingredients and substances, the vocabulary is mixed with the rubber Or well known to the skilled artisan. The modified filler of the present invention can be disclosed by the step A itself of the U.S. Patent Nos. 5,9,8,66, and 5,919,298, each of which is incorporated herein by reference. Both step a and step B are prepared, and the disclosures of the patents are hereby incorporated by reference in its entirety herein in its entirety in the the the the the the the The amount of the acid is such that the pH of the aqueous suspension is 2.5 or less, the pH is preferably 2. 〇 or less, the pH is preferably 1 〇 or less, and the pH is preferably 〇·5 or less; the upgrading chemistry used is The material is bis(alkoxycarboxyalkylalkyl) polysulfide and sulfur-free organometallic compound. The paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public interest). 13 Ministry of Economic Affairs Intellectual Property Bureau Printed by employee consumption cooperatives

1260335 V. Composition of the invention (11) (hereinafter referred to as a non-sulfur organometallic compound), the weight ratio of the bis(oxyalkylmercaptoalkylalkyl) polysulfide to the non-sulfur organometallic compound is at least 0.05:1, preferably from 〇.〇5:1 to 10:1, better from 〇·1:1 to 5:1' best automatic. 2:1 to 2:1, for example, from .5 :1 to 1: 1, or the weight ratio may be between any combination of the values, including the recited values; and after the chemical treatment is completed, the acidity (via addition or inclusion of organometallic compounds) The hydrolysis is carried out and neutralized in situ. After the completion of the chemical treatment, the enthalpy of the resulting aqueous suspension typically rises to a range of from 3 to 1G. The neutralizing agent can be any type which is typically used to raise the pH of an acidic solution as long as it does not detract from the nature of the modifying filler. Suitable neutralizing agents include sodium chlorate, potassium hydroxide, ammonium hydroxide and sodium bicarbonate. The neutralization of the modified filler can also be achieved by adding gaseous ammonia in the aqueous solution during spray drying. The acid used in step (A) may be of various organic and/or inorganic types. Preferred acid catalysts are inorganic. Examples of suitable acid catalysts include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, and benzenesulfonic acid. An acid catalyst or a mixture of two or more acid catalysts may be used as desired. When the organometallic reactant is, for example, decane chloride, a catalytic amount of acid can be generated in situ by hydrolysis of chlorocyclohexane or by direct reaction of decane with the hydroxyl group of the inorganic oxide. The temperature at which step (A) is carried out is not critical, although a lower or slightly higher temperature may be used when needed, which is usually in the range of 2 〇 0CS25 〇 〇c. The reaction temperature will be in accordance with the Chinese National Standard (CNS) A4 specification (2) Q χ 297 liters according to the reactants used, such as organometallic compounds, acid and paper. 1-- n^^ ^-------- (please Read the notes on the back and fill out this page. Line; 14 1260335 A7

1260335 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Print A7 I---------_ V. Description of Invention (13) or the weight percentage may be between any combination of these values, including the quoted The value. Suitable water-miscible solvents are, for example, such as ethanol, isopropanol and tetrahydrofuran. Preferably, the propanol is used as a water-miscible organic solvent. The surfactant may also be used in the initial step in combination with or in place of the water-miscible organic solvent, in an amount sufficient to promote the polymerization by bis(Aoxocarbazide) Chemical modification of inorganic oxides by sulfides and non-sulfur organometallic compounds. The surfactant may be nonionic, anionic, cationic, amphoteric or a mixture of such surfactants, provided that it does not detract from the properties of the resulting chemically modified inorganic oxide for its intended use. Typically, when a surfactant is used, it is used in an amount of from 5 to 5% by weight of the aqueous suspension, more preferably from 0.1 to 5% by weight and most preferably from 0.1 to 3% by weight, or the weight. Percentages may be between any combination of such values, including the recited values. Representative examples of suitable surfactants include alkylphenol polyglycol ethers such as p-octylphenol polyethylene glycol. (20 units) ether, p-nonylphenol polyethyl alcohol (20 units); calcined polyethylene glycols, such as 12-alkyl polyethylene glycol (20 units) ether; polyethylene glycol, Such as polyethylene glycol 2 〇〇〇; alkyl trimethyl ammonium salt such as hexadecyl trimethyl ammonium chloride (or bromide); dialkyl dimethyl ammonium salt, such as dilauryl Dimethylammonium chloride; alkylbenzyl dimethyl kean salt; alkyl benzoic acid S, such as p-dodecyl benzoic acid, sodium p-nonyl benzoate; Sulfuric acid hydrogenated esters, such as lauryl hydrogen sulfate, and sulfuric acid esters such as lauryl sulfate. The surfactant can also be applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) on the paper scale. 16 "- --- Install i· — — — — —---I--- (Please Read the notes on the back and fill out this page. Line i 1260335 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Β7 Β7 V. Inventive Note (14) For example, a polyglycol end group-blocked polyethylene oxide The bis(alkoxycarboxyalkylalkyl) polysulfide used to make the modified filler of the present invention is described in U.S. Patent Nos. 3,873,489 and 5,580,919 and the following Represented by the chemical formula I, the patents are hereby incorporated into the present invention to determine the tea: Z-alk-Sn, -alk-Z \ where alk is a divalent hydrocarbon radical having from 1 to 8 Preferably, from 1 to 6, and more preferably from 2 to 3 carbon atoms; n, from one to two integers from 2 to 12, preferably from 2 to 6 and more preferably from 3 to 4; Is: /R /R R1 -Si-R -Si-R · _si-R· \ \ \ R· R- R* wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group;R' is an alkoxy group having from 1 to 8, preferably from 1 to 4, more preferably from 1 to 2 carbon atoms, or a cycloalkoxy group having from 5 to 8 carbon atoms' or Is a linear or branched sulphur group having 1 to 8 broken atoms. The r and R' groups may be the same or different. The divalent alk group may be a straight or branched saturated or unsaturated aliphatic hydrocarbon group. Or a high-purity organic decane disulfide as disclosed in U.S. Patent No. 5,580,919, which requires 80% of η in the formula I to be 2. Examples of bis(oxyalkylcarbamalkylalkyl) polysulfide Including bis(2-trisoxyalkylidene alkylethyl) polysulfide, wherein the trialkoxy group is trimethoxy, triethoxy, tri(methylethoxy), tripropoxy , tributoxy, etc. up to trioctyloxy, polysulfide is disulfide, trisulfide. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 DON) 17 ------ ·------^装--------Book---------Line« (Please read the notes on the back and fill out this page) 1260335 Ministry of Economic Affairs Intellectual Property Office staff consumption Cooperative printing A7 B7 5. Inventive Note (15), tetrasulfide, pentasulfide and hexasulfide. The corresponding bis(3_di-burned methoxy-methyl sulfopropyl), bis (3-three-burn) can also be used. A polysulfide of bis(6-trisoxycarbazide hexyl), etc., bis-(4-di- oxy-methoxycarbazide butyl) or the like. Preferred are organodecane having a relatively simple structure, including bis(3-trimethoxy-, -triethoxy- and-tripropoxy-methylidenepropyl) polysulfide; that is, disulfide, Trisulfide and tetrasulfide. Specific examples of the bis(sodium oxomethionate) polysulfide are described in the aforementioned U.S. Patent No. 3,873,489, No. 6-55, and U.S. Patent No. 5,580,919, No. 11-41 Row. Representative examples of such compounds are: 3,3'-bis(trimethoxycarbamidopropyl) disulfide; 3,3' bis(triethoxycarbamidopropyl) tetrasulfide; , 3 bis (dimethoxymethyl propyl propyl) tetrasulfide; 2, 2' bis (triethoxymethyl sulfonyl ethyl) tetrasulfide; 3, 3 ' bis (trimethoxy group)矽alkylpropyl)trisulfide; 3,3' bis(triethoxycarbamidopropyl)trisulfide; 3,3'-bis(tributylmethoxymethylalkylpropyl) disulfide; 3,3'-bis(trimethoxycarbamidopropyl)hexasulfide; and 3,3 bis(trioctyloxymethylalkylpropyl) tetrasulfide and mixtures thereof. The most preferred compound is 3,3' bis(triethoxycarbamidopropyl) four-disc (TESPT). TESPT is available from Degussa under the trade name Si-69. It is reported to be 3,3' bis(triethoxycarbamidopropyl) monosulfide, 3,3, bis (this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) :18 · ~^~ -------------装--------订---------Line one (please read the notes on the back and fill in This page) 1260335 A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (l6 j triethoxymethyl sulfonyl propyl) disulfide, 3,3, bis (triethoxymethyl stone a mixture of sulphonyl propyl)trisulfide, 3,3, bis(triethoxy phthalocyanine) tetradecane and one of the higher sulphide homologues having an average sulphide of 35. The non-sulfur organometallic compound which is used to produce the modified filler of the present invention may be at least one non-sulfur organometallic compound or a plurality of non-sulfur organometallic a species. The non-sulfur organometallic compounds are selected from the group consisting of An organometallic compound represented by the chemical formula 下列 in the following group: Rla MX(4-a) II an organometallic compound represented by the chemical formula III: R 2c+2 Si c° (cl) III represented by the chemical formula IV Metal organic compound: R32d Si d〇d ιν Organometallic compound represented by chemical formula V: (R23 Si )k NR4(3.k) v wherein each M system is independently of each other, Shi Xi, Ti or Bis; Independently a hydrocarbon group having 1 to 18 carbon atoms or R1 may be an organofunctional hydrocarbon group having from 丨 to 12 stone counter atoms, wherein the functionality is, for example, an amine group, a carboxylic acid, a methanol ester or a guanamine group, each X Independently from each other, selected from the group consisting of halogen, an amine group, a silk group having 1 to 12 carbon atoms, and an acid oxygen group having a (2) carbon atom, a being an integer i, 2 or 3; &amp; 2 series are each a halogenated group, a hydroxyl group or a hydrocarbon group having from 8 to 8 carbon atoms, and it is mentioned that at least 50 mol% of the Han 2 substituent is contained in the original paper size. China National Standard (CNS) A4 specification (21〇X 297 public place m (please read the back note first and then fill out this page) ί 111--^ Book·!--II--j 1260335 A7 Five invention description ( a hydrocarbon group of I7, (: is an integer from 2 to 1 〇, 〇〇〇 each; each 113 series is independently a halogen group, a hydroxyl group or a member a hydrocarbon group having up to 18 carbon atoms, and (1 is an integer from 3 to 20; each of the Han 4 systems is independently hydrogen or a hydrocarbon group having from 1 to 18 carbon atoms, and is 丨 or 2 And a halogen or a halogenated group is selected from a chloro, bromo, iodo or fluoro group. In the definitions of the substituents represented by the chemical formulas π, ΙΠ, IV and V, the same symbols have the same Meaning, unless otherwise stated. In Formula II, each R1 may be a saturated or unsaturated monovalent hydrocarbon group, or a substituted or unsubstituted monovalent hydrocarbon group. For example, ... may be an alkyl group such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl-n-butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl and Eleven alkyl, olefinic groups such as ethylene, dipropyl and hexyl; substituted alkyl such as chloromethyl, 3,3,3-trifluoropropyl and 6-hexyl; cycloalkyl For example, cyclohexyl and cyclooctyl; aryl such as phenyl and naphthyl; and substituted aryl such as benzyl, tolyl and ethylphenyl. When the X system in the hydrazine car type II is a halogen, the dentate is preferably a chloro 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 a monooxy group, x may be, for example, an ethoxy group. Preferably, each X is selected from the group consisting of chloro and methoxy. The viscosity of the aforementioned organometallic compound is not limited and may range from the viscosity of a fluid to a gel. In general, the organometallic compound having a relatively high molecular weight is cleaved by the acidic conditions of the chemical upgrading step, and the like can be reacted with the hydrophilic inorganic oxide. In Chemical Formulas III, IV, and V, each of R2, R3, and R4 is for the line of Rl I ---1 — 1 — ---------Please read the notes on the back and fill in the form. Page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

20

The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed 1260335, the same hydrocarbon base. For the purposes of the present invention, when the organometallic reaction is a rich reactant, the tie is considered to be a metal. The non-sulfur organometallic compound is preferably represented by the chemical formulas n, m, n^v or a mixture of the organometallic compounds, wherein each μ is a stone sulphur non-sulfur organometallic compound. Representative of η, wherein R1 is cvc6, K is a chloro group, and (8). 'Examples of suitable organic compounds include, but are not limited to, a mixture of a compound selected from the group consisting of the following compounds··=ethyl diclosan, propyl propyl methyl chlorodecane, methyl phenyl Dichlorodecane, phenylethyldiethoxydecane, 3,3,3-difluoropropylmethyldichlorodecane, trimethylbutoxydecane, homo-diphenyltetramethyldioxane , trivinyltrimethylcyclotrioxane, octamethylcyclo oxy, Acetam, pentylmethyldioxane, divinyldipropoxydecane, vinyl II Methylchlorodecane, vinylmethyldichlorodecane, vinyl dimethyl methoxy decane, trimethylchloro decane, trif-methoxy decane, trimethyl ethoxy decane, methyl trioxane , methyltrimethoxydecane, methyltriethoxydecane, hexamethyldioxane, hexylmethyldichlorodecane, hexyldimethylchlorodecane, dimethyl chloride, dimethyl Chlorodecane, dimethyldimethoxydecane, dimethyldiethoxydecane, hexamethylene diazoxide, trivinyltrimethylcyclotrizepine, Polydimethyl oxime with 3 to about 20 dimercaptooxy units and poly(dimethyl methoxy hydride) blocked with trimethyl methoxy or hydroxy dimethyl oxy end groups a polymer, which is at 25. (The performance viscosity is in the range of 1 to 1,000 mPa · S. Examples of suitable organotitanium compounds include, but are not limited to, titanate IV (Cr) This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)

• II i IIIIII ^ « — — — — I! (Jing Xian read the back of the note and fill out this page) Line i 21 1260335 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (19) C! 8) alkoxy ester, methyltriethoxytitanium 〇ν), methyl titanium (w) triisopropoxide, methyl titanium (W) tributyl oxide, f-based titanium (iv) tri-te _ Butoxide, isopropyl titanium (iv) tributyl oxide, butyl titanium (iv) triethoxylate, butyl titanium (iv) tributyl oxide, phenyl titanium (iv) triisopropoxide Phenyltitanium (iv) dibutoxide, phenyltitanium (iv) triisobutylene oxide, [Ti(CH2Ph)3(NC5H1())], and [Ti(CH2SiMe3)2(Net2)2]. Examples of suitable organic dysfunctional compounds include, but are not limited to, acid quaternary acid (Cr cj alkoxylate, stupid (iv) trichloride, methyl zirconium (iv) trichloride, ethyl zirconium (iv) trigas Compound, propyl hydrazine (iv) trichloride, methyl monobromide, ethyl oxa (iv) tribromide, propyl hydrazine (iv) tribromide, triphenyl zirconium chloride (iv). Also expected Including a compound similar to the above-mentioned organotitanium compound, and vice versa. The amount of the bis(alkoxycarboxyalkylalkyl) polysulfide and the non-sulfur organometallic compound in the aforementioned chemical modification method is sufficient to produce one An amount of a modified filler characterized by a carbon content greater than 丨% by weight, a sulfur content greater than 0.1% by weight, a decane conversion index of at least 〇.3, and a standard tensile stress of at least 300% tensile. This amount is referred to herein as a coupling amount, that is, an amount sufficient to bond the filler and to cause the modified filler to adhere to the polymerizable composition. Bis(alkoxycarbenylalkyl) The weight ratio of polysulfide to organometallic compound is at least 0.05: i Preferably, from 5: i to ι〇: 1, better from 0·1 · 1 to 5: 1, and best from 0·2 : : i, such as from 5:1 to 1: 1, or The weight ratio may be between any combination of the values, including the recited values. Each organometallic reactant may be added together Λ ^ ^ - - 订 ------ -Line· (Please read the notes on the back and fill out this page) 22 1260335

Or add the order in order. The organometallic unit to be added in an amount of the organometallic reactant is preferably in excess of the available base on the inorganic oxide particles. The upper limit of the amount of organometallic reactant added to the process is not critical. Excess bis(alkoxycarboxyalkylalkyl) polysulfides and organometallic compounds can be removed by filtration, distillation, solvent cleaning or other known separation techniques. ΛInvention Description (2G In another embodiment, the acesulfate group can be substituted with a combination of a bis(alkoxycarboalkylalkyl)polysulfide and a different sulfur-containing organometallic compound. The polysulfide, the weight ratio of the bis(oxomethoxymethyl sulfoalkyl) polysulfide to the sulfur-containing organometallic compound is at least greater than 1: 1, such as 101: i. The weight ratio may be from 1〇1 : i to 100 : 1, preferably from 5 : 1 to 50 : i, more preferably from 10 : u3 〇: i, or the weight ratio may be any combination of the values In addition to the numerical values quoted, any sulfur-containing organometallic compound acting as a coupling agent in the vulcanization of a rubber containing a filler (except for the bis(alkoxycarboxyalkylalkyl) polysulfide represented by the formula 丨Suitable for use. Suitable sulfur-containing organometallic compounds include sulfhydryl organometallic reactants, which can be represented by the following structural formula VII: ------------ Pack---- ----Book---------Line (please read the notes on the back and fill in this page) Bureau employee consumption cooperative printing (L)n

HS R6 Μ

VII Q(3-n) wherein Μ is Shi Xi, the element or _0R7, Q is chlorine, c "Ci2 alkyl or CVCu alkyl substituted by halogen, R6 is CrCi2 alkyl, ... is ^ a alkoxyalkyl group having 2 to 12 carbon atoms, the element or letter

C Generation 23 1260335 Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives A7 V. Inventive Note (21) The base is chloro, bromo, iodo or fluoro, η is 1, 2 or 3. R6 is preferably crc:3 alkylene such as methylene, ethylene and propylene, and R7 is preferably Cl. The alkyl group is more preferably a methyl group and an ethyl group, and L is preferably _〇R0, preferably 3. A mercapto organometallic reactant having two mercapto groups can also be used. The mercapto organometallic compound used may also be a group having a blocked fluorenyl group, i.e., the sulfhydryl group is substituted with another group. The blocked fluorenyl organometallic compound may have an unsaturated hetero atom or carbon bonded directly to the sulfur via a single bond. Examples of specific blocking groups include thioresin vinegar, monothiocarbamate, thiosulfonate, thiosulfate, phosphorothioate, thiophosphonate, thiophosphite, and the like. . When a reaction of the mixture is desired to couple the filler to the polymer, a deblocking agent can be added to the mixture to unblock the blocked sulfhydryl organometallic compound. If water and/or alcohol is present in the mixture, a catalyst such as a tertiary amine, Lewisman or thioindole may be used to initiate or promote the removal of the blocked group by hydrolysis or alcoholysis to release the corresponding sulfhydryl organic Metal compound. Methods for the preparation and use of such compounds, such as blocked decyl decane, are disclosed in PCT Application No. WO 99/09036. Other methods for the preparation of the occlusive-type sulphate are disclosed in U.S. Patent Nos. 3,692,812 and 3,922,436, the entireties of each of which are incorporated herein by reference. Examples of suitable sulfhydryl organometallic compounds include, but are not limited to, mercaptomethyltrimethoxycarbazide, sulfoethyltrimethoxycarbazide, propylpropyltrimethoxycarbazone, and transmethyltriethoxylate. Xishou, Wei Ke ethyl tripropoxy decane, decyl propyl diethoxy decane, (decylmethyl) dimethyl ethoxy sulphur, (Wilyl methyl) methyl diethoxy sulphur, base Propyl two paper size is applicable to China National Standard 4 (CNS) A4 specifications (21〇X 297 public) · -------- order --------- line one (please read first) Note on the back side of this page) 24 Ϊ260335 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Description of Invention (22) Methoxy-stone and its mixture. The compound of Yuan Jia is Wei-propyl propyl trimethoxy sulphate, succinylpropyl triethoxy sulphur or a mixture thereof. Examples of suitable blocked Wei-based organometallic stone courts include, but are not limited to, 2-triethoxymethane-1-ethylthioacetate, trimethoxymethyl sulfonyl-1-propyl Thiooctanoate, bis-(3-triethoxycarbamimidyl)-methylpropyl dithiophosphonate, 3-triethoxymethyl sulfonyl hydrazine Thiophosphite, 3-triethoxymethylidene-hydrazine-propylmethylthiosulfate, 3-triethoxycarbamido-1·propyltoluenesulfonate and mixture. After completion of the chemical upgrading, the pH of the aqueous suspension of the modified inorganic oxide is raised from a pH of 2.5 or less to a pH between 3.0 and 1 Torr. Typically, the pH of the resulting aqueous suspension is raised to above 3, preferably to 4 or more, more preferably to 5 or more, and to Yuan 仏 to 6 or more, and usually 1 〇 or less, preferably 9 or less. More preferably, it is 8 or less and the table is preferably 7 or less. The pH of the aqueous suspension may be between any combination of the values, including the recited values. This is achieved by neutralizing the acidity added or produced and producing a final product (after drying) having a pH of from 5 Torr to 10.0. By filtration and drying, or the aqueous suspension of the modified inorganic oxide and the non-water-miscible organic solvent are greater than 丨··丨 and preferably greater than 5·1 of the solvate relative to the inorganic oxide The weight ratio is contacted while the modified inorganic oxide is recovered. Further treatment or drying can be carried out using the modified inorganic oxide recovered from the solvent phase. A specific example system composition planned by the invention, which includes the modified filler in a non-water-miscible property ------*1----«.!!11 --Line fji (please read the notes on the back and fill out this page)

1260335 A7

1 in the solvent of the machine. The concentration of the modified filler in the slurry is between 1 and 90 weights, based on the total weight of the slurry. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives - Examples of suitable non-water-miscible organic solvents include low molecular weight siloxanes such as hexamethyldioxane, octamethylcyclotetraoxane, diphenyl Tetramethyl-alkali-oxygenated and polydimethyl-stone-oxygenated fluid sealed with trimethyl-Oxygen-based end groups. When money is used as a solvent, it acts simultaneously as a solvent and a reactant which acts as the inorganic oxide. Further, suitable non-water-miscible organic solvents include aromatic hydrocarbons such as toluene and dimethyl strepene; heptanes and other aliphatic hydrocarbon solvents; cycloalkanes such as cyclohexane; ethers such as di- and dibutyl halides. Alkyd hydrocarbon solvents such as methylene chloride, chloroform, vaporized ethylene and chlorobenzene; and ketones such as methyl isobutyl ketone. The non-water-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. Examples of such materials include, but are not limited to, one or more of a rubber, an oil, a coupling agent, an antioxidant, and an accelerator. The modified filler of the present invention (in the form of a powder, granule, pellet, slurry, aqueous suspension or solvent suspension) may be combined with a matrix material which is used in the product to be produced to form a A substance of a mixture of masterbatches. In the masterbatch, the upgraded filler can be present at a higher concentration than in the final product. In the mixing operation, the mixture is typically added in portions until it reaches the scale of production to assist in the uniform dispersion of such very small amounts of additives in the polymeric composition, such as plastics, rubber and coating compositions. The modified filler can be applied to the Chinese National Standard (CNS) A4 specification with an emulsion and/or a solution polymer such as an organic paper containing a solution of stupid ethylene/butadiene rubber (SBR), polybutadiene rubber or a mixture thereof. (21〇X 297 shy) 26 I-^-------!-Book i-! ——Line mF (please read the note on the back and fill in this page) 1260335 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative A7 V. Inventions (24) Rubber...a to form a masterbatch. One specific embodiment of the present invention is a masterbatch comprising a combination of an organic rubber, a non-water miscible solvent, a modified filler, and a selectively processed oil. This product is supplied to the tire manufacturer by the rubber manufacturer. For tire manufacturers, the advantage of using a masterbatch is that the modified filler is uniformly dispersed in the rubber, which reduces the mixing time required to make the composite rubber. In the masterbatch, each part of the rubber may contain up to 150 damaged (phr) modified fillers, preferably from 2 to 13 inches, more preferably from (10) to 100 parts, and the best from 5 Please go to the 8th part. In another preferred embodiment of the present invention, a polymerizable article is planned in which (7) to (9) partially modified fillers are dispersed in each of the 1GG partial polymers, preferably dispersed in each of the 1% partial polymers. There are 2 to 13 parts, more preferably 100 to 100 parts, and the best 5G to 8G partial modification filler. Optionally, the amount of modified filler can be between any combination of the values, including the recited values. As described herein, the polymer may be selected from the group consisting of thermoplastic resins, thermosetting resins, and organic rubbers. The polymer is preferably a malleable organic rubber. The main curable rubbers contemplated for use with the modified fillers of the present invention are well known to those skilled in the art of thermal rubber chemistry and may include vulcanizable and sulfur curable rubbers. Special planners are those typically used for mechanical rubber articles. The modified filler of the present invention can be mixed with an unmatured rubber elastomer to be passed from about 10 to 3 (by means of a Banbury mixer or a rubber mill). The temperature is prepared as a vulcanizable rubber composition. The vulcanizable rubber composition is sulphurizable on every 1 ' 'paper scale using the Chinese National Standard (CNS) A4 specification (210 X 297 mm).

Mi I 1♦1 i — — — — — — ^» — — 1 ———————^ (Please read the notes on the back and fill out this page) 27 1260335 A7 B7 Filling in the five, invention description (25 rubber polymerization The material may comprise from 1 to 15 parts of modified filler, preferably from 2 to 1 part, more preferably from 30 to 1 part, and most preferably from 50 to 80. Other existing knowledge The rubber additive is a conventional sulfur or peroxide curing system. The sulfur curing system can include 0.5 to 3 parts of sulfur, 2 to 5 parts of oxidation and 0.5 to 2 parts of accelerator. The peroxide curing system can be Including hydrazine to a portion of a peroxide such as dicumyl peroxide. Other conventional rubber additives may be used. The additive includes other fillers such as carbon black; oils; plasticizers; accelerators; antioxidants; Thermal stabilizer; light stabilizer; regional stabilizer; organic acid such as stearic acid, benzoic acid or salicylic acid; other activators; one agent and color pigment. The specific compound formula will be based on the specific sulfide prepared. However, the formula is well known to those skilled in the art of rubber compounding. The vulcanizable rubber composition is vulcanized or cured into a vulcanized gelatin. The examples of industrial vulcanizates (objects) which can be manufactured using the modified materials of the present invention include wires and cable ferrules. ' Rubber hose; close gasket and seal; industrial and automotive transmission belt; engine base; V-belt; conveyor belt; roller film; tire and tire components': car tire tread, secondary tread , tire carcass, tire belly, tire belt frame, tire bead filler, tire wire slag surface layer; track plate material packing ring; shock absorbing components and many others. Also in the following standard composite procedures, examples In the discussion of the comparative examples, the present invention will be described in more detail, and the examples and comparative examples are for illustrative purposes only, as those skilled in the art will recognize various modifications and changes. __(CNS) A4 specifications (2f -------------------- order --------- line (please read the notes on the back and then fill out this Page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed x 297 mm) 28

Amount (phr) 30.0 2.5 2.0 1.0 12.5 1260335 V. Description of the invention (Test samples using the standard compound procedure to prepare the formulation rubber composition containing cerium oxide in the example and the comparative example (4). Part A The following components are per 100 weight. The amount of part of the weight of the rubber-based part is added to the blister bag placed upright in a liter of plastic cups in the order described: Material processing oil (1) Antimony oxide (2) Antiozonant (3 ) Stearic acid (4) Cerium oxide sample (1) Sundex® 8125 aromatic hydrocarbon processing oil obtained from Sun's refining and marketing department. (2) Obtained from Zinc Corporation of America

Kadox® surface treated zinc oxide. (3) obtained from Goodyear tire and rubber companies

Wingstay® 100 antiozonant, which is a mixture of diaryl p-phenylenediamine. (4) Rubber grade stearic acid obtained from C. P. Hall. Part B Use a 1.89 liter (L) Farrel Banbury mixer (model "BR") to mix the ingredients. Prior to adding the batch ingredients to the mixer, 800 grams of CV_60 grade natural rubber is placed in and passed the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^------- -----Order---------Line j (Please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 29 1260335 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Α7 Β7 V. INSTRUCTIONS (27) Mixer to remove any residue from previous operations and raise the temperature to approximately 93 °C (200 °F). The mixer was cooled to about 65 ° C (150 ° F) after removing the rubber and before adding ingredients to make a rubber test specimen. A rubber composition was prepared using the test cerium oxide, the following other listed components, and the methods described hereinafter. Ingredients First Process (phr) Time in revolutions (rpm) to add substances to the mixer (or removed from the mixer) SBR Rubber (5) 70.0 0 116 BR Rubber (1 2) 30.0 0 116 Test Cerium oxide 57.5 0.5 116 Sample from Part A Dumping contents Second process all 3.0 ((5.0)) 116 Product from the first process All 0 77 Antiozonant (3) 2.0 0 77 Paraffin (4) 1.5 0 77 RM sulfur (5) 1.4 0.5 77 TBBS (6) 1.7 0.5 77 DPG(U) Dumping contents 2.0 0.5 ((4.0)) 77 30 ------^--------- -----Order---------Line (please read the note on the back and fill out this page) 1 From Goodyear tire and rubber company to get 8〇1!^乂@1216 solution styrene-butadiene rubber (8611). 2 Budene 1207 butadiene rubber (BR) obtained from Goodyear Tire & Rubber Company. 3 Self-made Goodyear tire and rubber company obtained 4

Santoflex 813 antiozonant, described as N-(l,3-dimethylbutyl)-oxime-benzene-5-p-phenylenediamine. 6 The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1260335 A7 ____B7___ V. Invention description (28) (8) From Astor company to obtain the product 1 {&lt; π仔之〇kerin® 724 〇 microcrystalline wax / stone soil blend. (Please read the precautions on the back and fill out this page.) (9) Rubber Maker sulfur, ι〇〇% active from Taber. (10) N_tert-butyl-2-benzoic thiazolidine obtained from Monsanto Corporation. (11) Diphenyl hydrazine obtained from Monsanto Corporation. The first * private system was started by adding rubber to the mixer, that is, the ruler and the rubber, and mixing at 116 rpm for 0.5 minutes. The speed was maintained at 116 rpm and 57_5 phr of treated cerium oxide sample was added. After another 15 minutes, the plunger and the cleaning chute are lifted, that is, the cover of the inlet chute is lifted and any material found in the chute is swept back into the mixer. After a further minute, the sample from Part A was added. After 1 minute, lift the plunger and sweep the chute. The contents of the mixer were mixed for another minute to reach an upper temperature in the range of 145 to 150 ° C (293 to 302 T). Depending on the type of sample, 'the speed of the mixer can be increased or decreased after 4 minutes' to reach one of the above ranges within a specific mixing period. 〇 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed in the first After the completion of a process, the temperature of the substance was measured by a thermocouple to confirm that it did not exceed the upper limit temperature of 150 °C. The removed material was weighed and rolled into a sheet of Farrel 12-inch pair of double-fortunate rubber mills set at 2.032 mm + 0.127 mm (0.080 inch + 0.005 inch). The milled material produced is cut into strips to prepare the second process in the mixer. 31 The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1260335 Ministry of Economic Affairs Intellectual Property Office staff consumption Co-operative printing A7 _______B7 _ V. Invention description (29) Between the process of the brother of Yuancheng and the start of the second process, there must be at least one hour to allow the milled material to be cooled. If necessary, complete the aforementioned cleaning and heating procedures using CV-60 grade natural rubber prior to the start of the first process. Adjust the temperature of the mixer to approximately (12 〇卞). Under the cooling water flow, the second process is to add the strip of the first process material and pre-weighing by mixing in a mixer operating at 77 rpm.

The Santoflex® 13 antiozonant was started with the Okerin® 7240 microcrystalline wax/paraffin blend. After 0. 5 minutes, pjy [second additive of sulfur, TBBS and DPG composition was added. After another 1.5 minutes, lift the plunger and sweep the chute. The second process is completed by remixing the material for a further 2 minutes and while maintaining the temperature below 125 C (257 °F). Part C Heat the Farrel 12-inch two-roll rubber mill to approximately 6 〇 〇c (140 F). The material from the second part of Part B was added to the mill in operation, and the gap between the rolls was set at 2.032 mm + 0.127 mm (0.080 inch + 0.005 inch). The resulting sheet was placed on a flat surface until the temperature of the sheet dropped to room temperature. Typically, the sheet is cooled in about 3 minutes. Thereafter, the milled sheet was fed into a rubber mill with a press roll gap set at 3.81 + 0.51 mm (0.15 inch + 0.02 inch). If necessary, the roll can be trimmed to maintain a uniform thickness. The resulting material was processed through 16 side cuts and 8 end passes. Adjust the pressure roller gap of the rubber mill to produce a sheet of thickness 2.032 metre + 0.127 mm (0.080 ft + 0005 ft). The sheet material produced from the rubber mill is placed on a flat and clean surface. Use a template to cut 2〇3 2 from the sheet material. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^--------Book------- --Line - (Please read the notes on the back and fill out this page) 32 1260335

V. Description of the invention (30) A rectangular sample of 152.4 pens (8 inches 6 inches). Conditioning the sample, -------Γ——Ί# (Please read the notes on the back first) Fill in this page) Store the sample between clean polyethylene sheets at 23°+2t: and relative humidity 5G% + 5% for 5 to 8 hours. After the action in ° weeks, The sample was placed in a standard frame mechanical steel stamping die with a polished surface of 2 〇 3 2 亳 ΧΠ 2.4 mm X 2.286 亳 m (8 英 χ 6 χ〇. (10) 忖). The sample was attached to 13.79 Under the pressure of Wanpa Yingshi, under the pressure of 61 cm, 61 cm (24 in χ 24 吋), 890 kN (100 ton) four-column electric molding machine, τ (eight), that is, according to ASTM D-2084 allows 90% of the time required for curing, plus 15 minutes at 15G ° C (3G2 ° F). Typically, the ripening is completed in about 1 minute. The resulting cured rubber sheet was removed from the mold and maintained at 23 before the test of the crucible portion. +2. (: (73.4.+3.6卞) temperature and 50%+5% relative humidity 15 to 18 hours. Part P Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing test system according to ASTM D-412-98a-test method a. A dull test specimen was prepared using a mold C. An Instron tensile strength tester model 42〇4 with an automated contact tensile tester was used to determine the tensile action. 5〇8 mm/min. All calculations were carried out with the manufacturer's 1:2 series of automated substance testing software. The tensile strength of the specimen prepared by this standard compounding procedure was 3 MPa is the standard tensile stress (STS @ 300%) for 300% tensile action reported in Table 3. Precipitated cerium oxide is produced by acidifying a solution of sodium sulphate with sulfuric acid. Sedimentary oxidation

1260335 V. Description of the invention (Shi Xi. Most of the Shen Dian system is formed at a pH higher than 85. By continuously adding acid until the positive value of the solution reaches about 35,沈 Prepare the oxygen for the surface area analysis as described in the ninth example by filtering and washing a portion of the oxidized stone until the cleaning water shows a conductivity of about 3 〇 0 to the micro ohm Cut the sample. Use the high shear to impart the crying and re-liquefy the resulting filter cake to form a solid in the liquid suspension. In a Nir〇 spray dryer (inlet temperature is about 36) The suspension was dried in (TC and outlet temperature was about 1 HTC). The surface area used to prepare the modified oxygen cut of the modified oxygen cut in the examples and the comparative examples is shown in Table 1. Examples 1 - 2 A 30-gallon glass crucible container with a bottom discharge port was added with about 4 kg of precipitated cerium oxide suspension containing about 5.2 kg of cerium oxide and about 11.7 kg of isopropanol. The container was also equipped with a temperature recorder. , mechanical agitator, heating element and condenser. When the contents of the vessel are initially stirred and heated, the 矽-69 enhancer, referred to herein as TESPT, is added over a period of time (typically about 10 minutes) which will result in a weight ratio of butyl ESPT listed in Table 3. The amount is based on the dry weight of cerium oxide listed in the table. After the completion of the h, and addition of TEspT, dimethyl chlorite (DMDCS) is added in the same manner to The approximate amount of the weight ratio of DMDCS listed in Table 3 is based on the dry weight of cerium oxide in the examples listed in the table. The weight ratio of TESPT/DMDCS is also listed in Table 3. New Chinese Money Standard (CNS) A4 Specification (10)X 297 mm) ^ --------Book --------- Line 0— (Please read the notes on the back and fill out this page. ) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 34

The temperature of the suspension clock is 1260335. 5. The pH of the invention (32) is about 〇.8. . &amp; After the addition of DMDCS, the mixture was heated to about 68 broth for about 10 minutes. When cooling, mix in agitation. The addition of the foot 1 of the foot (typically about U kg) is added to achieve the action of the hydrophobic phase of the oxidized rock oxide from the aqueous phase without forming an emulsion. The aqueous phase is drained from the vessel. Then, in the first example, a water containing a water of about 400 g, a spoonful of 30 A pounds, and a water containing a weight of about 2,000 grams of water in the second example, contains a hydrophobic sink; Shi Xi disturbed the mixture twice. Exclude the water phase. ^ After washing, 'additional toluene in the stirred mixture (the first case is about 13.9 kg and the second case is about 23 7 kg), and it is easy to form a pure suspension in liquid. Out of the ground. In a rotary cone dryer, at a minimum of 14 generations, with a limit of 23 inches of mercury, the resulting suspension is dried by two drying processes: until the sample is at 160. 〇 Exposure 10 minutes ^% of the loss is less than 4.6 wt%. Brother 3 - 8 Yes: There is a 40-life drain on the bottom of the outlet.", section - A emulsified stone eve of about 19 kg of Shen "type oxidized stone eve suspension condenser two ^ (four) degree recorder , mechanical transfer device, heating member and cold when mixing the contents of the container 'Oxygen dry weight::: The surfactant listed in Table 2. After the surface activity is completed' Mixture for 5 minutes. Take 5 minutes of this paper ruler.

-------Γίι·_ϋ^------η---------Line_- (Please read the notes on the back and fill out this page) _ · 35 1260335 A7 Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed five, invention description (33 time to add TESPT, to oxygen-cut dry weight based on (four) weight% of TESPT. The positive value of the resulting solution is about 3 (). In the completion of Ding (four) Ding After the addition, 'addition of dimethyldichlorodecane (DMDCS) 'in the same way, about 15% by weight of DMDCS based on oxidized stone dry weight. The positive value of the resulting solution is about ο" The mixture is heated to about 61 to 68 ° C ' and maintained at this temperature for about 20 minutes. The suspensions of the fifth and eighth examples are heated for about 4 and 16 minutes, respectively. A sufficient amount of 50% by weight sodium hydroxide was added to the mixture over a period of time (typically 15 minutes) to adjust the pH to about 7. The 20 liters of the stirred mixture containing the hydrophobic precipitated cerium oxide was discharged from the vessel. Vacuum filtered using a Buchner funnel and then washed three times with approximately 8 kg of water. After the washing is completed, a sufficient amount of deionized water is applied to the filter cake to effect a high shear agitation to form a liquid suspension in a liquid. The resulting suspension is in a Nero (Nh&gt; 〇) The spray dryer (inlet temperature is about 400t: and the outlet temperature is about i5〇ct) is dried in a haze to form a treated cerium oxide sample of the third to eighth examples. In a vessel equipped with a mechanical stirrer, 17 liters of untreated precipitated cerium oxide containing 820 grams of cerium oxide in the second example 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 the cerium oxide of the comparative example of μ3. The resulting treated suspension is sprayed in a Nir(R), mist-dried household (at an inlet temperature of about 360 ° C and an outlet temperature of about 11 ° C) -------^-- --i 丨!!丨定--------Line ▲ (Please read the notes on the back and fill out this page) 36 1260335 Ministry of Economic Affairs Bureau employee consumption cooperative printed A7 B7 V. Invention description (34) Drying. With a singular single-point surface area technology, AS Ding M D-3037-93 Method C (corrected) to a Horiba The 62〇〇 series of instruments were tested for the treated and untreated cerium oxide samples of the first and third 1-3 comparative examples (CE). The method was simulated using 30% helium in P/P 〇 = 0.294. Nitrogen is used as the adsorption method for the Brunauer_Emmett_ Teller 'BET method. The ASTM method is modified as follows: a gas mixture of nitrogen in helium gas is used; a stream of about 4 〇 ml/min is maintained; the sample is dried in an analysis chamber under a nitrogen stream at i 8 〇 + 5 for 1 hour; The nitrogen adsorbed on the sample was desorbed by removing the vacuum bottle of liquid nitrogen and allowing the sample to be warmed to room temperature without an external heat source. The results of the untreated cerium oxide test specimens are listed in Table 1, and the results of the treated cerium oxide test specimens are listed in Table 4. Carbon % was determined by CHN analysis using an elemental analyzer of Carlo Erba Model 1106. In an oxygen-rich environment at 1〇4〇χ: 1-2 grams of sample sealed in a tin capsule with a carrier charge, burned in a quantitative manner on the trioxide system, and the combustion gas then passed through 650°. Copper of C to remove excess oxygen and reduce nitrogen oxides to nitrogen. The gas is then separated and eluted through a column of nitrogen into nitrogen, carbon dioxide and water. The eluted gas was measured by a thermal conductivity detector. The instrument is calibrated by burning a standard compound. The results are listed in Table 4. The sulfur % was determined by X-ray fluorescence spectrometry (XRF) using a Rigaku RIX 2000 spectral dispersion spectrometer. Apply the Chinese National Standard (CNS) A4 specification (210 x 297 mm) on a paper scale of 1:1. 37 -------^-------- Order ------ ---Line' (Please read the note on the back and fill out this page) 1260335 A7 B7 V. INSTRUCTIONS (35) Proportion of sample and SpectroBlend® adhesive (Takaho, NY, USA) After mixing (^11 € 111 ^ 16 \ industry company), the sample was pressed into an aluminum support cup at a pressure of 344.75 MPa (25 ton / square inch) to form a block. The NIST- and NBS-traceability secondary standards (phosphorus or equivalents of PPG production) were used to perform the XRF calibration of the experiment. The detection was performed by using a gas crystal monochromator with a monochromatic crystal. The results are listed in Table 4. The decane conversion index reported by SCI in Table 4 is determined by solid-state 29 NMR. The data is at ambient temperature in a Brooke (Bruke OAM-300 NMR with a narrow inner diameter magnet). Obtained with a 7 mil Doty standard speed MAS probe. The sample was loaded into a zirconia drum with an outer diameter of 7 mm and a short Ke The lF cover is sealed. The drum rotates at approximately 5.0 kHz in Magic Angle. High energy proton decoupling with 90° 4 pulse wave, 5600-8400 scan per spectrum, 5 ms contact time, and data measurement period And a 3 second relaxation delay to obtain cross-polarization (CP/MAS) data. A kaolin sample was used (j. R0Cha and J. Klinowski, J. Magn. Reson. 90, p. 567 (1990) B) to achieve Hartmann-Hahn conditions. All chemical shifts are based on tetramethyl decane (TMS). A nonlinear curve-fitting program is used on the Aspect 3000 computer (LINESIM). Analyze all spectra to determine the relative area % of Ti (-49 ppm), t2 (-57 mouth 111) and 1^ (-65 ppm) peaks. The area % of τι, τ2 and τ3 'will be fitted by - Curve determination of one of the 3 0 ppm to -80 ppm areas. The paper size of the treated yttrium oxides of the examples and comparative examples is determined by the following method in accordance with the Chinese National Standard (CNS) A4 (210 χ 297 gong) -- ---- (Please read the notes on the back and then fill out this page) Order --------- Line 1 Ministry of Economics Property Office employees consumer cooperatives printed 38 1260335 A7 B7

X V. Description of invention (36 positive value) Add 5 〇, gram litter (powder form) to a 15G soar beaker containing TM magnetic stir bar; add 5G ml of isopropanol and 50 ml of deionized water; Stir vigorously without spilling until the oxygen-cut suspension is placed - the calibrated pH electrode is placed in a vigorously stirred solution and the pH reading is recorded after 1 minute (+ 5 seconds). Table 4. By adding 5.44 grams of material to a 43 mm χ123 mm (outer diameter OD) cellulose extraction cannula, # placed the cannula into a suitable size Soxhlet fitted with a condensation σσ ( The Soxhlet was extracted from the tube and the percentage of Soxhlet extractable carbon in the first treated oxide oxide was determined. The Soxhlet extractor and condenser system contained one A 700 liter f-benzene round bottom flask was connected. The flask was heated to the reflux temperature of the benzene and benzene. After refluxing for 25 hours, the used hydrazine was replaced with unused toluene, and refluxing was continued for 22 hours. Recovering the extracted and treated oxygen矽, and dried until the weight/❻ loss of the sample when exposed to 16 ° C for 10 minutes is less than 1.0% by weight. The carbon % of the extracted sample is determined using the method described. Soxlet (Soxhl State The percentage of extractable carbon is determined by the following equation: (% by carbon before extraction) - (% by carbon after extraction) (% by weight of carbon before extraction) The carbon % before extraction is 3.50, and the carbon after extraction. The value is 3〇2. Therefore, the percentage of soxhlet extractable carbon in the first treated cerium oxide is 13.7. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297). i) ------! Order --------- Line I (please read the note on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 39 !260335 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (37 surface area used in the first complex example _ untreated cerium oxide _ m ^ 2 / g _ 1-2 cases and the first _3 comparative example 198 3-8 Case 180 Table 2 Example No. Surfactant 3rd Example MAFO® CAB (12) 4th Case MASIL® SF 19 (13) 5 cases AVANEL®N-1525/90 (14) 6th case MACOL® 48 〇5) 7th case BRIJ® 35 (16) 8th case ETHOMEEN® 18/60 (17) (12) available from BASF An amphoteric surfactant, reportedly based on cocamamine propylamino betaines. (13) A nonionic surfactant available from BASF's reported to be ethoxylated. 3 is the main. (14) A nonionic surfactant available from BASF, Inc., which is reported to be a type of ethyloxide oxide blocked by an alkyl chloride end group (15). A nonionic property available from BASF. Surfactants, reportedly based on ethylene glycol ether. -------^----,ρ----------Book---------Line ‘ (Please read the notes on the back and fill out this page)

1260335 A7 B7 V. INSTRUCTIONS (38) (16) A nonionic surfactant available from Aldrich Chemical Company has been reported to be based on polyoxyethylene lauryl ether. (17) A nonionic/cationic surfactant available from AKZO Chemical Co., Ltd., reportedly based on ethoxylated (5 〇) stearylamine. The third table --------------------- order --------- line - (clear the first business of the back of the business and then write a table Page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example # %TESPT / cerium oxide %DMDCS / cerium oxide 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 41 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1260335 A7

Please read the backnote item and then fill out this page. 4 δΤ ν 1260335 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Print A7 B7_ V. Invention Description (4Q) 本 Although the present invention is described with reference to specific details and specific examples, The details are not intended to be limiting as to the scope of the invention, unless they are included in the scope of the claims. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 43 (Please read the notes on the back and fill out this page)

Claims (1)

1260335 A3 BS C8 D8 Patent Application No. 89116781 Patent Application Revision No. PCT Application No. PCT Application No. PCT Application No. PCT Application No. Forming a chemically modified filler by contacting an acidic aqueous suspension of an amorphous or particulate inorganic oxide selected from the group consisting of Shengying oxidized granules, colloidal oxidized dreams or mixtures thereof with a coupling agent in the presence of a solvent An acidic aqueous suspension, and the recovery of the filler, the improvement comprising the use of (a) a bis(alkoxycarboxyalkylalkyl) polysulfide in an aqueous suspension of an inorganic oxide having a pH of 2.5 or less (b) a composition of a non-sulfur organometallic compound as a coupling agent, (a) a weight ratio of at least 〇〇5 ··1 relative to (b) and an acidity of the chemically modified filler treated with an acid neutralizing agent An aqueous suspension in which the pH of the suspension is raised to a range from 3.0 to 1 Torr; wherein the bis(alkoxycarboxyalkylalkyl) polysulfide is represented by the following chemical formula I: Z- alk-Sn,-alk-Z I where alk is a Divalent hydrocarbon radicals from 1 to 18 carbon atoms; η' is an integer from 2 to 12; and z is: (Please read the note on the back to write this page) Pack. #- Ministry of Economics Intellectual Property Bureau employee consumption cooperative printing •—' — Table paper size is suitable for R -Si~R, R · R -R' R1 , ^ L-R1, R_ where R is a C ^ C: 4 alkyl or phenyl And r is a CVC8 alkoxy group, a c5_c8 cycloalkoxy group or a _Ci_c8 alkanoyl group: wherein the non-sulfur organometallic compound is selected from the group consisting of organometallic compounds represented by the following formula II: (4) Material (CNS) A4 -44- 1260335 Λ3 B8 CS D8 Six patent application scope Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Rla MX(4-a) 有机 Organometallic compound represented by Chemical Formula III: r22c+2 Si C°(cl) 有机 an organometallic compound represented by the chemical formula IV: R 2d Si d〇d IV an organometallic compound represented by the chemical formula V: (r23 Si )k NR4(3_k) V and the organometallic compound a mixture; each of the "systems are independently of each other, tantalum, titanium or cone; each of the R1 systems is in contact with each other The standing site is a hydrocarbon group having 1 to 18 carbon atoms or R1 is an organofunctional hydrocarbon group having 1 to 12 carbon atoms, wherein the functional group is an amine group, a carboxylic acid, a methanol vinegar or a guanamine group; each X system is independent of each other The ground is selected from the group consisting of: an aryl group, an amine group, an alkoxy group having 1 to 12 carbon atoms, and a decyloxy group having from 12 to 12 carbon atoms, and a is an integer 丨, 2 or 3; each R2 Independently, each other is a halo group, a hydroxyl group or a hydrocarbyl group having from 丨 to "carbon atoms, provided that at least 50 mol% of the R 2 substituents are hydrocarbyl groups having from 1 to 18 carbon atoms, and c is from 2 An integer to 1 〇,000; each R3 is independently a halo group, a hydroxy group or a hydrocarbyl group having from 丨 to 18 carbon atoms, and d is an integer from 3 to 20; each R4 is independent of each other The ground is hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, and k is 1 or 2; and the halogenated group or halogen is selected from a chloro group, a fluoro group, a bromo group or an iodo group; The non-sulfur organometallic compound is represented by the chemical formula II, III, IV V or a mixture of the organometallic compounds, wherein the paper ϋ ϋ ------ Please read the back of the note firstly Fill in the zero 1 本 本 . Page I Book AS B8 C8 D8 1260335, the scope of the patent application is 矽; and wherein the bis(alkoxycarboxarmalkylalkyl group) is substituted with a combination of a bis(alkoxycarboalkylalkyl)polysulfide and a fluorenyl organometallic species. The polysulfide, the weight ratio of the bis(alkoxycarboxyalkylalkyl) polysulfide to the sulfhydryl organometallic species is at least greater than 1··1. 2. The method of claim 1, wherein the bis(alkoxycarboxyalkylalkyl) polysulfide is selected from the group consisting of: 3,3'-bis(trimethoxymethylcarbazide) Propyl) disulfide; 3,3' bis(triethoxymethyl sulfanylpropyl) tetrasulfide; 3,3' bis(trimethoxymethylsulfanylpropyl) tetrasulfide; 2,2' bis(triethoxymethyl sulfonylethyl) tetrasulfide; 3,3' bis(trimethoxymethyl sulfonylpropyl) trisulfide; 3,3' bis (triethoxy A)矽alkylpropyl)trisulfide; 3,3, bis(tributylmethoxymethylpropyl) disulfide; 3,3'-bis(trimethoxydecylalkylpropyl) hexasulfide; And 3,3'-bis(trioctyloxydecylpropyl) tetrasulfide and mixtures thereof. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumption Co., Ltd. 3. The method of claim 1, wherein the non-sulfur organometallic compound is selected from the group consisting of diethyl dichlorodecane, allyl decyl dichloromethane. , nonylphenyl dioxane, phenylethyl diethoxy decane, 3,3,3 -di-propyl propyl decyl dichloride chopping, dimercaptobutoxy chopping, homo-diphenyl Tetradecyldioxane, trivinyltridecylcyclotrioxane, octadecylcyclotetraoxane, hexaethyldioxane, pentyldecyldioxane, divinyldipropene Oxydecane, vinyl dimercaptochloromethane, Intellectual Property Department of the Ministry of Economic Affairs of the Ministry of Economic Affairs, Printed by the Consumer Cooperatives, 1260335, the patent range of alkenyl methyl dichlorodecane, vinyl dimethyl methoxy decane, trimethyl chloride Decane, trimethyl methoxy decane, trimethyl ethoxy decane, methyl dichloro decane, methyl trimethoxy decane, methyl triethoxy decane, hexamethyldioxane, hexylmethyl Dioxane, hexyl dimethyl chlorodecane, dimethyl chlorodecane, dimethyl dioxane, dimethyl di a methoxy decane, dimethyl diethoxy decane, hexamethyldioxane, trivinyltrimethylcyclotriazane, agglomerates having from 3 to about 2 decyl decyloxy units Dimethyl decane, tetrakis(Ci_Ci8) alkoxylate, methyltriethoxytitanium (iv), methyltitanium (iv) triisopropoxide, bismuth titanium tributoxide, A Titanium (iv) tri-tert-butoxide, isopropyl titanium dibutoxide, butyl titanium (iv) triethoxylate, butyl titanium (iv) tributyl oxide, phenyl titanium (iv) Triisopropyl oxide, phenyl titanium (iv) tributyl oxide, phenyl titanium (1V) diisobutylene oxide, [Ti(CH2Ph)3(NC5H^)], [TKCHJiMeA (Net2)2], # Acid tetra (Ci_Ci8 oxy vinegar, phenyl hydrazine (iV) tri-vapor, methyl zirconium (iv) trichloride, ethyl hydrazine (iv) tri-vapor, propyl iv (iv) tri-vapor, A Base error (iv) tribromide, ethyl zirconium (iv) king evolution, propyl zirconium (called tribromide, triphenylphosphonium chloride (iv) and mixtures of such organometallic compounds. a method of the beta, wherein the non-sulfur organometallic compound is The chemical formula is represented by π, wherein R1 is a Ci_c group, χ is a gas group, a is 2, and the inorganic oxide is a precipitated cerium oxide. 5. The method of claim 1 wherein (4) is relatively The weight ratio of (8) is from 0.05:1 to 1〇: i. 6_ The method of claim 4, wherein (4) is relative to the weight of (8) #----- '丨定---- ---------^91. C Please read the notes on the back and fill out this page. A 4 Τ 1260335 Α 8 Β 8 C8 D8 HS 申请 The scope of patent application is from 0.2 : 1 to 2 : 1. 7. The method of claim i, wherein the weight ratio of the bis(alkoxycarboxyalkyl)polysulfide to the sulfhydryl organometallic species is from 5:1 to 50··1, and The inorganic oxide is precipitated cerium oxide. 8. The method of claim 2, wherein the sulfhydryl organometallic material is represented by the following structural formula VII: (L)n VII Q(3-h) wherein M is hydrazine, l is halogen or _0R7 , q is hydrogen, Cl_Cl2 alkyl or melanin substituted iCVCu alkyl, r6 is cKC12 alkylene, R7 is alkyl or is an alkoxyalkyl group having 2 to 12 carbon atoms, the halogen or the substituent is gas a bromo, bromo, iodo or fluoro group, and η is 1, 2 or 3. 9. The method of claim 8, wherein L is _〇R7, R6 is Ci_C3, R, Cl_C4 is burned, and n is 3. 10. The method of claim 8, wherein the base of the bismuth-based organometallic material is a closed D 11. The method of claim 7, wherein the weigen organometallic material is selected from the following In the group: call methyltrimethoxy, thioethyl dimethoxy decane, decyl propyl trimethoxy decane, decyl methyl triethoxy sulphate 6, sulfoethyl tripropoxy sulphur , Wei Ke Cing &amp; triethoxy zexi, 姨 姨 甲基 dimethyl ethoxy ethoxy Xi Xi, (Wilyl methyl) methyl diethoxy decane, 3 巯 propyl propyl dimethyl oxime Base decane and its mixture -------- Γ ^--------- (Please read the back of the note first and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1260335 A8 B8 C8 D8 Patent Application---------- ------ (Please read the notes on the back and fill in this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Cooperatives Printing System