JP2008524104A - Process for producing chemically modified fillers - Google Patents

Abstract

A specific combination of functionalizing agent and hydrophobizing agent in an aqueous suspension of inorganic oxide having a pH of 2.5 or less is used, and the pH of the suspension is adjusted after chemical treatment of the filler. An improved process for producing chemically modified fillers by raising is described. In particular, the present invention provides at least a reduced carbon content and mercapto content or lowest carbon content and mercapto content, at least a reduced silane conversion index or lowest silane conversion index, and at least a reduced standard strengthening index or lowest A process for producing a granular or amorphous filler having a standard reinforcement index is provided.

Description

(Description of the invention)
The present invention relates to a method for making a chemically modified filler. More specifically, the present invention provides at least reduced carbon content and mercapto content or lowest carbon content and mercapto content, at least reduced silane conversion index or lowest silane conversion index, and at least reduced standard enhancement. It relates to a process for producing a granular or amorphous filler having an index or a minimum standard strengthening index. Furthermore, the present invention provides at least a reduced carbon content and sulfur content or minimum carbon content and sulfur content, at least a reduced silane conversion index or minimum silane conversion index, and at least a reduced 300% elongation standard. It relates to a process for producing a granular or amorphous filler having a tensile stress or a standard tensile stress at a minimum 300% elongation. In addition, the present invention provides hydrophobization and functionality that improves the efficiency of producing polymer compositions (eg, in rubber mixing) and the performance of polymerized or cured products (eg, but not limited to tires). The present invention relates to a process for producing a base filler (hereinafter “modified filler”).

  In the production of polymer compositions, it is common to incorporate reinforcing fillers to improve the physical properties of the polymer. The surface of such fillers is often modified to increase the reactivity of the fillers in the polymer composition and thus the two-dimensional and three-dimensional bonds. It has been conventional in the rubber industry to incorporate carbon black and other reinforcing fillers into natural and synthetic rubbers to enhance the physical properties of cured rubber vulcanizates. Fillers used to reinforce such polymer compositions include natural fillers and synthetic fillers.

  One of the major non-black fillers used in the rubber industry is amorphous precipitated silica. This silica-containing filler is used to provide rubber vulcanizates with improved tensile strength, tear resistance, and abrasion resistance. Silica filler can also be combined with carbon black to obtain maximum mileage for passenger car tires and tires used outside roads (eg, tires for mining and logging operations, and tires for road construction equipment). Used for. Such applications are already well established. When used as a sole reinforcing filler, silica fillers that are not well dispersed and / or bonded in the rubber provide improved overall performance obtained by using carbon black alone. do not do. This is most easily observed with rubber vulcanizates used for tires (eg, tire treads).

  Various coupling agents (eg, titanates, zirconates and silanes) may be used with such fillers when the filler is incorporated into a polymer composition (eg, rubber) to improve the performance of the rubber vulcanizate. It has been proposed for use. Among the various organosilane coupling agents proposed for such use are mercaptoalkyltrialkoxysilanes (eg, mercaptopropyltrimethoxysilane). The high cost of mercaptoalkyltrialkoxysilanes, the pungent odors associated with neat materials, and the time and energy required to mix them into the rubber composition are the same as the bulk of rubber containing fillers containing silica. It has prevented the more general use as the primary reinforcing filler in applications.

  One drawback in using alkoxysilanes as coupling agents for silica fillers is that they produce exhaust gases. In particular, hydrolysis of alkoxy groups results in the release of alcohol, a portion of which will be retained in the surrounding elastomeric matrix. The alcohol portion retained in the surrounding elastomeric matrix may form surface defects in the resulting rubber article and / or impair the dimensional stability of the tread during extrusion and tire molding. Can produce a zone or blister. This generation and outgassing of alcohol continues throughout the life of a product made from an elastomer mixed with an alkoxysilane coupling agent.

  Bis (alkoxysilylalkyl) -polysulfides can be used in place of mercaptoalkyltrialkoxysilanes. The preparation of silica-filled rubber compositions using bis (alkoxysilylalkyl) -polysulfides generally needs to be carried out within a narrow operating temperature range. This mixing temperature is high enough for the silica-silane reaction to occur rapidly, but is sufficient to avoid irreversible thermal decomposition of the polysulfane functionality of the coupling agent and premature curing (scorch) of the rubber mixture. Should be. These limitations can result in reduced production and increased costs to achieve acceptable dispersion of silica in the rubber matrix.

  Carbon content higher than 1 wt%, mercapto content higher than 0.15 wt%, silane conversion index of at least 0.3 (described below), and standard strengthening index of 4 or higher (also described below) It has now been found that improved modified fillers characterized by (e.g. granular or amorphous inorganic oxides) can be prepared. In addition, a carbon content higher than 1% by weight, a sulfur content higher than 0.1% by weight, a silane conversion index of at least 0.3 (described below), and a standard tensile stress at 300% elongation of 7 or more It has been found that improved fillers (eg, granular or amorphous inorganic oxides) characterized by (also described below) can be prepared. The modified filler of the present invention utilizes a specific combination of a functionalizing agent and a hydrophobizing agent in an aqueous suspension of an inorganic oxide having a pH of 2.5 or less. It can be produced by treating the suspension with an acid neutralizing agent to raise the pH of the suspension to the range of 3.0-10.

  As used herein, a functionalizing agent is a reactive chemical that can covalently bond an inorganic oxide to the polymer composition in which the inorganic oxide is used. The hydrophobizing agent binds to the inorganic oxide to the extent that it causes a decrease in the affinity of the inorganic oxide for water while increasing the affinity of the inorganic oxide for the organic polymer composition in which the inorganic oxide is used. A chemical substance that can associate.

  The standard tensile stress at 300% elongation of at least 7 or above (ie STS @ 300%) indicates improved reinforcement of the rubber composition. Improved reinforcement can be interpreted as an improvement in the mechanical durability of the product, which is evidenced by an increase in tear strength, an increase in hardness and an increase in wear resistance. In addition to improved properties, the modified filler has the advantage of requiring less time and energy to be incorporated into the polymer composition.

  The standard reinforcement index (SRI) of at least 4 above indicates an interaction or bond modification between the components of the filler-polymer composition. In particular, there is a stronger interaction between the filler and the polymer and / or between the polymer and the polymer than is normally present for a given amount of interaction between the filler and the filler. In other words, there is a weaker interaction between filler and filler than is normally present for a given amount of interaction between filler and polymer and / or between polymer and polymer. is there. Appropriate improvements in these interactions in rubber compositions are reported to result in better tire performance (eg, improved tread wear life, lower rolling resistance, better snow traction, and lower noise generation). It was done. In addition to improved properties, the modified filler has the advantage of requiring less time and energy to be incorporated into the polymer composition.

(Detailed description of the invention)
It is understood that all numbers representing amounts, ratios, ranges, etc., as used herein, are modified in all cases by the term “about” unless otherwise specified or otherwise specified. Should be.

The modified filler of the present invention has a carbon content higher than 1% by weight, or at least 1.5% by weight, or at least 2.0%; higher than 0.15% by weight, or at least 0.3% by weight, Or a mercapto content of at least 0.5% by weight; a silane conversion index of at least 0.3, or at least 0.4, or at least 0.5, and at least 4.0, or at least 4.5, or at least 5.0. Can be produced by any method that yields a filler (ie, an inorganic oxide) having a standard reinforcement index of The modified filler of the present invention may also be characterized by a tensile stress at 300% elongation of at least 6.2, or at least 7.0, or at least 7.5, or at least 8.0. Further, the modified filler of the present invention has a carbon content of greater than 1% by weight, or at least 1.5% by weight, or at least 2.0% by weight; greater than 0.1% by weight, or at least 0.3% A sulfur content of wt%, or at least 0.6 wt%; a silane conversion index of at least 0.3, or at least 0.4, or at least 0.5, and at least 7.0, or at least 7.5, or It can be produced by any method that yields a filler (ie, inorganic oxide) having a standard tensile stress at 300% elongation of at least 8.0. Modified filler of the present invention, further, 20~350m ² / g, or 40 to 300 m ² / g, or 100 to 200 m ² / g of Brunauer-Emmett-Teller (BET) single point surface area of 5 to 10, or A pH of 5.5 to 9.5, or 6.0 to 9.0, or a pH of 6.5 to 7.5, or the pH of the product is any of these values, including the stated range. The range of combinations can range; it can be characterized by a percent Soxhlet extractable carbon of less than 30 percent, or less than 25 percent, or less than 20 percent (eg, 15%). Methods for determining the above properties of the modified filler are described in Example 15 and Example 35.

  A wide variety of fillers known to those skilled in the art can be used to prepare the modified fillers of the present invention. Suitable fillers can include, but are not limited to, inorganic oxides selected from precipitated silica, colloidal silica, or mixtures thereof. In addition, inorganic oxides can be used in various molding processes, mixing processes, or coating processes (injection molding, lamination, transfer molding, compression molding, rubber mixing, coating (eg, dipping, brushing, knife coating, roller coating, silkscreening). The material may be suitable for use in (including but not limited to painting, printing, spraying, etc.), casting and the like.

  In a non-limiting embodiment, the inorganic oxide used to produce the modified filler of the present invention can be a type of precipitated silica commonly used for mixing with rubber. Various commercially available silica materials can be used in the present invention. In an alternative non-limiting embodiment, the silica includes silica commercially available from PPG Industries under the trademark Hi-Sil with names 210, 243, etc .; available from Rhone-Poulenc, for example, the names Mention may be made of silica of Z165GR; and silicas available from Degussa AG, for example the names VN2 and VN3.

  The precipitated silica used to produce the modified filler of the present invention can be prepared by various methods known to those skilled in the art. In a non-limiting embodiment, the precipitated silica can be prepared by acidic precipitation from a solution of silicate (eg, sodium silicate). The method of preparing the precipitated silica can be selected based on the desired properties of the silica, such as the surface area and particle size required for a given application.

In alternate non-limiting embodiments of the present invention, BET surface area of the precipitated silica used to prepare the modified filler of the present invention are ^generally, 50m ² / ^g~1000m 2 / g or 100 m, ^It exists in the range of ² / g-500m < ² > / g.

  In an alternative non-limiting embodiment, the precipitated silica used to form the modified filler is in the form of an aqueous suspension from the manufacturing stage prior to the drying process (e.g., a slurry formed during precipitation, Or a reliquefied filter cake); alternatively, the suspension can be formed by redispersing the dried silica in an aqueous and / or organic solvent. The concentration of hydrophilic precipitated silica in the aqueous and / or organic suspension is not critical and can be in the range of 1% to 90% by weight or the concentration of hydrophilic precipitated silica is 1 It can be in the range of wt% to 50 wt%, or 1 wt% to 20 wt%.

The silane conversion index can be defined by the formula T ³ / (T ¹ + T ² + T ³ ). The values of T ¹ , T ² and T ³ are determined by solid state ²⁹ Si NMR and may represent reacted silane units. This silane conversion index can provide an indication of the degree of reaction or crosslinking of silanes on adjacent Si atoms and the reaction or crosslinking of silanes. In general, the higher the index number, the greater the amount of crosslinking between the silane, the silica surface and the adjacent silane. T ¹ represents a silane unit chemically bonded to the silica surface or another silane at one site. T ² is chemically bonded to the Si atom on the silica surface and one adjacent silane, two adjacent silanes, or two adjacent surface Si atoms (ie, a partially crosslinked structure) at two sites. Represents a silane unit bonded to T ³ represents one Si atom and two adjacent silanes on the silica surface, two Si atoms and one silane, or a silane unit chemically bonded to three silane units at three sites .

  Organometallic reactant conversion index comparable to silane conversion index provides an indication of the extent of reaction or crosslinking of zirconate and / or titanate (alone or in combination with silane) with inorganic oxides and their own reaction or crosslinking To do so, it is believed that it can be developed and used by one skilled in the art of coupling agents.

  The standard enhancement index can be determined using a standard mixing protocol. The standard mixing protocol described herein does not involve the addition of free or unbound coupling agent to the rubber batch. Typically, the addition of such a coupling agent to a rubber batch may require a longer time to mix with the compounder.

  The standard tensile stress at 300% elongation can be determined using a standard mixing protocol. The standard mixing protocol described herein does not involve the addition of free or unbound coupling agent to the rubber batch. Typically, the addition of such a coupling agent to a rubber batch may require more time to mix with a compounder.

  Organic polymer compositions (eg, plastics and / or resins) in which a modified filler can be present include essentially any organic plastic and / or resin. Included in this definition is a rubber compound. Such polymers are described in Kirk Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1996, Volume 19, pp 881-904, the description of which is incorporated herein by reference. In a non-limiting embodiment, the modified filler can be mixed with the polymer or polymerizable component thereof, and the physical form of the polymer or polymerizable component can be any liquid or miscible form (eg, solution Suspensions, latexes, dispersions, etc.). The polymer composition comprising the modified filler can be pulverized, mixed, molded and cured by any method known in the art to form a polymer article. In a non-limiting embodiment, the polymer article can have 10-150 parts modified filler dispensed in the article for every 100 parts of polymer. Suitable polymers can include, but are not limited to, thermoplastics, thermosetting resins, rubber compounds, and other polymers having elastomeric properties.

  These polymers include alkyd resins, oil-modified alkyd resins, unsaturated polyesters, natural oils (eg, linseed oil, tung oil, soybean oil), epoxides, nylon, thermoplastic polyesters (eg, polyethylene terephthalate, polybutylene terephthalate). , Polycarbonate (ie, thermoplastic and thermosetting), polyethylene, polybutylene, polystyrene, polypropylene, ethylene propylene copolymer and ethylene propylene terpolymer, acrylic (acrylic acid, acrylate, methacrylate, acrylamide, salts thereof, halogen Homopolymers and copolymers such as hydrohalides), phenolic resins, polyoxymethylenes (homopolymers and copolymers) , Polyurethane, polysulfone, polysulfide rubber, nitrocellulose, vinyl butyrate, vinyl (polymer containing vinyl chloride and / or vinyl acetate), ethyl cellulose, cellulose acetate, and cellulose butyrate, viscose rayon, shellac, wax, ethylene copolymer (for example , Ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene acrylate copolymer), organic rubber and the like.

  The amount of modified filler that can be used in the polymer composition can vary. In a non-limiting embodiment, the amount of modified filler can be 5% to 70% by weight based on the total weight of the plastic composition. For example, typical amounts of modified fillers used in ABS (acrylonitrile-butadiene-styrene) copolymers can be from 30 wt% to 60 wt%, and in acrylonitrile-styrene-acrylate copolymers, from 5 wt% to In aliphatic polyketones, from 15% to 30% by weight, in alkyd resins (for paints and inks), from 30% to 60% by weight in thermoplastic olefins Can be from 10% to 30% by weight, in epoxy resins from 5% to 20% by weight, in ethylene vinyl acetate copolymers up to 60% by weight, in ethylene ethyl acetate copolymers 80% by weight, in liquid crystal polymer (LCP), 30% to 70% by weight, in phenolic resin Obtained was 30 wt% to 60 wt%, the amount in the polyethylene may be a large amount than 40% by weight.

  In a non-limiting embodiment, the polymer can be an organic rubber. Non-limiting examples of such rubbers include natural rubber; butadiene and homologues and derivatives thereof (eg: cis-1,4-polyisoprene; 3,4-polyisoprene; cis-1,4-polybutadiene; Rubbers formed from the homopolymerization of trans-1,4-polybutadiene; 1,2-polybutadiene), and one or more copolymerizable monomers containing ethylenic unsaturation with butadiene and its homologues and derivatives Examples include, but are not limited to, rubbers formed from copolymerization with styrene and its derivatives, vinyl-pyridine and its derivatives, acrylonitrile, isobutylene and alkyl-substituted acrylates such as methyl methacrylate. Further non-limiting examples include styrene-butadiene copolymer rubber (hereinafter “SBR”), including various percentages of styrene and butadiene, and using various isomers of butadiene, if desired; Terpolymers of isoprene and butadiene polymers, and various isomers thereof; acrylonitrile-based copolymer rubber compositions and terpolymer rubber compositions; and isobutylene-based rubber compositions; or mixtures thereof. Obtained, for example, U.S. Pat. Nos. 4,530,959; 4,616,065; 4,748,199; 4,866,131; 4,894,420; 4,925,894; 5,082,901; and 5,162,409. It is as mounting.

  Non-limiting examples of suitable organic polymers may include copolymers of ethylene, other higher alpha olefins (eg, propylene, butene-1 and pentene-1) and diene monomers. These organic polymers can be block polymers, random polymers or sequential polymers and can be obtained by methods known in the art (eg, emulsion polymerization processes (eg, e-SBR) or solution polymerization processes (eg, s-SBR)). But not limited thereto). Additional non-limiting examples of polymers for use in the present invention can include partially or fully functionalized polymers, including bound polymers or star-branched polymers. Additional non-limiting examples of functionalized organic rubbers can include polychloroprene, chlorobutyl and bromobutyl rubbers, and brominated isobutylene-co-paramethylstyrene rubbers. In a non-limiting embodiment, the organic rubber can be polybutadiene, s-SBR, and mixtures thereof.

  In a non-limiting embodiment, the polymer composition can be a curable rubber. The term “curable rubber” is intended to include natural rubber, as well as various raw and reclaimed forms thereof, and various synthetic rubbers. In an alternative non-limiting embodiment, the curable rubber may include a combination of SBR and butadiene rubber (BR), a combination of SBR, BR and natural rubber, and other materials disclosed above as organic rubbers. Any combination may be mentioned. In the description of the present invention, the terms “rubber”, “elastomer” and “rubbery elastomer” may be used interchangeably unless otherwise indicated. The terms “rubber composition”, “mixed rubber” and “rubber compound” are used interchangeably to refer to a rubber blended or mixed with various ingredients and materials, such terms are used for rubber mixing or rubber mixing. Well known to those skilled in the art.

  The modified filler of the present invention can be prepared using various methods known to those skilled in the art. In an alternative non-limiting embodiment, the modified filler comprises hydrophobic silica and fumed silica, as disclosed in US Pat. Nos. 5,908,660 and 5,919,298, respectively. Step A for preparation alone or both steps A and B can be prepared using the following modifications, the relevant disclosures of which are hereby incorporated by reference. The amount of acid used results in a pH of 2.5 or lower, or a pH of 2.0 or lower, or a pH of 1.0 or lower, or a pH of 0.5 or lower in an aqueous suspension; used The modifying chemical is a combination of a mercapto organometallic reactant and a sulfur-free organometallic compound (hereinafter referred to as a non-sulfur organometallic compound). The weight ratio to the organometallic compound is at least 0.05: 1, or 0.05: 1 to 10: 1, or 0.1: 1 to 5: 1, or 0.2: 1 to 2: 1, or 0.5: 1 to 1: 1, and this weight ratio can range between any combination of these values, including the stated values; and, after the chemical treatment reaction is complete, acidic (Added or halogenated organometallic compounds Generated in situ) it is neutralized by hydrolysis. In a non-limiting embodiment, after completing the chemical treatment reaction, the pH of the resulting aqueous suspension is raised to a pH range of 3-10. The neutralizing agent can be selected from a wide variety of materials as are known in the art for raising the pH of acidic solutions. This neutralizing agent should be selected so that the properties of the modified filler are not adversely affected. Non-limiting examples of suitable neutralizing agents can include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, and sodium bicarbonate. In another non-limiting embodiment, neutralization of the modified filler can be accomplished by adding gaseous ammonia to the aqueous solution during spray drying.

  The acid used in step (A) can be selected from a wide variety of acids including organic and / or inorganic acids. In a non-limiting embodiment, the acid catalyst can be an inorganic acid catalyst. Non-limiting examples of suitable acid catalysts can include, but are not limited to, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, and benzenesulfonic acid. One acid catalyst or a mixture of two or more acid catalysts may be used as desired. In a non-limiting embodiment, when the organometallic reactant is chlorosilane, a catalytic amount of acid can be generated in situ by hydrolysis of chlorosilane or by direct reaction of chlorosilane with an inorganic oxide hydroxyl.

  The temperature at which step (A) is carried out is not critical and can be in the range of 20 ° C to 250 ° C, although slightly lower or slightly higher temperatures can be used if desired. The reaction temperature depends on the reactants used (eg, organometallic compound, acid, and cosolvent, if used). In a non-limiting embodiment, step (A) is performed at a temperature in the range of 30 ° C to 150 ° C. In another non-limiting embodiment, step (A) can be performed at the reflux temperature of the slurry used in step (A).

  In the above reaction, the modifying chemical or coupling agent can be a combination of a functionalizing agent instead of a mercapto organometallic compound and a hydrophobizing agent instead of a non-sulfur organometallic compound. This combination of functionalizing agent and hydrophobizing agent can be used at the same weight ratio specified for the combination of mercapto organometallic compound and non-sulfur organometallic compound. Non-limiting examples of reactive groups that the functionalizing agent can include include, but are not limited to, vinyl, epoxy, glycidoxy and (meth) acryloxy. Further non-limiting examples can include sulfide groups, polysulfide groups, and mercapto groups, provided that these are associated with the reactants represented by Formulas I and VI included herein. Absent. Hydrophobizing agents include, as suitable materials, natural or synthetic oils and fats, and chemicals such as non-sulfur organometallic compounds represented by Formulas II, III, IV, V, and mixtures of such hydrophobizing agents Can be mentioned, but is not limited thereto.

  The initial step of contacting the acidic aqueous suspension of the inorganic oxide with a combination of a mercapto organometallic compound and a non-sulfur organometallic compound (eg, a non-sulfur organosilicon compound) further comprises those with the inorganic oxide. Adding a sufficient amount of a water-miscible solvent to promote the reaction. This solvent can act as a phase transfer agent that accelerates the interaction between the combination of the hydrophobic sulfur compound and the non-sulfur organometallic compound and the hydrophilic inorganic oxide. In an alternative ratio limiting embodiment, when a water miscible organic solvent is used, the amount of the water miscible organic solvent is at least 5% by weight of the aqueous suspension, or 15% by weight of the aqueous suspension. May constitute -50 wt%, or 20 wt% -30 wt%, or the wt% may vary between any combination of these values, including the stated values. Non-limiting examples of suitable water-miscible solvents can include, but are not limited to, alcohols such as ethanol, isopropanol, and tetrahydrofuran. In a non-limiting embodiment, isopropanol can be used as a water miscible organic solvent.

  In an alternative non-limiting embodiment, the surfactant is combined with a water miscible organic solvent or in place of a water miscible organic solvent instead of inorganic oxide chemistry with mercapto organometallic compounds and non-sulfur compounds. It can be used in the first step in an amount sufficient to facilitate modification. This surfactant may be selected from nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, or a mixture of such surfactants. The surfactant can be selected so that it does not have a detrimental effect on the performance of the resulting chemically modified inorganic oxide for its intended use. In an alternative non-limiting embodiment, when used, the surfactant is 0.05% to 10%, or 0.1% to 5%, or 0. It can be present in an amount of 1% to 3% by weight, or this weight% can vary between any combination of these values, including the stated value.

  Non-limiting examples of suitable surfactants include alkylphenol polyglycol ethers (eg, p-octylphenol polyethylene glycol (20 units) ether, p-nonylphenol polyethylene glycol (20 units) ether), alkyl polyethylene glycol ethers (eg, , Dodecyl polyethylene glycol (20 units) ether), polyglycol (eg, polyethylene glycol 2000), alkyltrimethylammonium salt (eg, cetyltrimethylammonium chloride or cetyltrimethylammonium bromide), dialkyldimethylammonium salt (eg, dichloride chloride) Lauryldimethylammonium), alkylbenzyltrimethylammonium salts, alkylbenzenesulfonates (eg If, sodium p- dodecylbenzenesulfonate, p- nonyl sodium benzenesulfonate), alkyl hydrogen sulfate (e.g., hydrogen sulfate lauryl), and alkyl sulfates (such as, but lauryl sulfate) may include, but are not limited to. In a non-limiting embodiment, the surfactant can include a polysiloxane polymer or polysiloxane copolymer having an allyl endblocked polyethylene oxide.

  In a non-limiting embodiment, the mercapto organometallic compound used to produce the modified filler of the present invention is represented by formula I:

によって表され得、ここで、Ｍはケイ素であり得、Ｌは、ハロゲンまたは−ＯＲ^７であり得、Ｑは、水素、Ｃ_１〜Ｃ_１２アルキル、またはハロ置換Ｃ_１〜Ｃ_１２アルキルであり得、Ｒ^６は、Ｃ_１〜Ｃ_１２アルキレンであり得、Ｒ^７は、Ｃ_１〜Ｃ_１２アルキル、または２個〜１２個の炭素原子を含むアルコキシアルキルであり得、上記ハロゲンもしくは（ハロ）基は、クロロ、ブロモ、ヨード、またはフルオロであり、そして、ｎは、１、２または３であり得る。さらなる非限定的な実施形態において、Ｒ^６は、Ｃ_１〜Ｃ_３アルキレン（例えば、メチレン、エチレン、およびプロピレン）であり得、Ｒ^７は、Ｃ_１〜Ｃ_４アルキル（例えば、メチルおよびエチル）であり得、Ｌは−ＯＲ^６であり得、そしてｎは３であり得る。別の非限定的な実施形態において、２個のメルカプト基を有するメルカプト有機金属反応物が使用され得る。

Where M can be silicon, L can be halogen or —OR ⁷ , Q is hydrogen, C ₁ -C ₁₂ alkyl, or halo-substituted C ₁ -C ₁₂ alkyl. R ⁶ can be C ₁ -C ₁₂ alkylene, R ⁷ can be C ₁ -C ₁₂ alkyl, or alkoxyalkyl containing 2 to 12 carbon atoms, the halogen or (halo) The group can be chloro, bromo, iodo, or fluoro, and n can be 1, 2, or 3. In further non-limiting embodiments, R ⁶ can be C ₁ -C ₃ alkylene (eg, methylene, ethylene, and propylene) and R ⁷ is C ₁ -C ₄ alkyl (eg, methyl and ethyl). L can be -OR ⁶ and n can be 3. In another non-limiting embodiment, a mercapto organometallic reactant having two mercapto groups can be used.

  In an alternative non-limiting embodiment, a mercapto organometallic compound may be used in which the mercapto group is blocked, ie, the mercapto hydrogen atom is replaced by another group. These blocked mercapto organometallic compounds may have unsaturated heteroatoms or carbons that are bonded directly to sulfur by a single bond. Non-limiting examples of blocking groups may include, but are not limited to, thiocarboxylic acid esters, dithiocarbamic acid esters, thiosulfonic acid esters, thiosulfuric acid esters, thiophosphoric acid esters, thiophosphonic acid esters, thiophosphinic acid esters, and the like. .

  In a non-limiting embodiment, a deblocking agent can be present in the mixture to deblock the blocked mercapto organometallic compound when reaction of the mixture to bind the filler to the polymer is desired. If water and / or alcohol is present in the mixture, a catalyst (e.g., a first catalyst) may be used to initiate and promote the removal of the blocking group by hydrolysis or alcoholysis to liberate the corresponding mercaptoorganometallic compound. Tertiary amines, Lewis acids, or thiols) can be used. Various procedures for preparing and using such compounds (eg, blocked mercaptosilanes) are known in the art, including those described in PCT application number WO 99/09036, as well as US patents. The procedures disclosed in US Pat. Nos. 3,692,812 and 3,922,436 may be mentioned, and relevant portions of these documents are incorporated herein by reference.

  Non-limiting examples of suitable mercapto organometallic compounds include mercaptomethyltrimethoxysilane, mercaptoethyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptoethyltripropoxysilane, mercaptopropyltriethoxysilane. , (Mercaptomethyl) dimethylethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and mixtures thereof, but are not limited to these. In an alternative non-limiting embodiment, the mercapto organometallic compound can include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, or mixtures thereof.

  Non-limiting examples of suitable blocked mercaptosilanes include 2-triethoxysilyl-1-ethyl thioacetate, 3-trimethoxy-silyl-1-propyl thiooctanoate, bis- (3-triethoxysilyl- 1-propyl) -methyldithiophosphonate, 3-triethoxysilyl-1-propyldimethylthiophosphinate, 3-triethoxysilyl-1-propylmethylthiosulfate, 3-triethoxysilyl-1-propyltoluenethiosulfonate, and Mixtures of these may be mentioned, but are not limited to these.

  In the above reaction, the modifying chemical or coupling agent may be a combination of a functionalizing agent instead of bis- (alkoxysilylalkyl) polysulfide and a hydrophobizing agent instead of a non-sulfur organometallic compound. . The combination of functionalizing agent and hydrophobizing agent can be used at the same weight ratio specified for the combination of bis (alkoxysilylalkyl) polysulfide and non-sulfur organometallic compound. Non-limiting examples of reactive groups that the functionalizing agent may include include, but are not limited to, vinyl, epoxy, glycidoxy, and (meth) acryloxy. Further non-limiting examples can include sulfide groups, polysulfide groups, and mercapto groups, provided that these are associated with the reactants represented by Formulas I and VI included herein. Absent. As hydrophobizing agents, suitable substances include chemicals such as natural or synthetic oils and fats, and non-sulfur organometallic compounds represented by the formulas II, III, IV, V, and mixtures of such hydrophobizing agents. Can be mentioned, but is not limited thereto.

  The initial step of contacting the acidic aqueous suspension of precipitated silica with a combination of a bis (alkoxysilylalkyl) polysulfide and a non-sulfur organometallic compound (eg, a non-sulfur organosilicon compound) is further performed with the precipitated silica. Adding a sufficient amount of a water miscible solvent to accelerate the reactions can be included. This solvent can act as a phase transfer agent that accelerates the interaction between the combination of the hydrophobic sulfur compound and the non-sulfur organometallic compound and the hydrophilic inorganic oxide. In an alternative non-limiting embodiment, when a water miscible organic solvent is used, the amount of the water miscible organic solvent is at least 5% by weight of the aqueous suspension, or 15% by weight of the aqueous suspension. May constitute -50 wt%, or 20 wt% -30 wt%, or the wt% may vary between any combination of these values, including the stated values. Non-limiting examples of suitable water-miscible solvents can include, but are not limited to, alcohols such as ethanol, isopropanol, and tetrahydrofuran. In a non-limiting embodiment, isopropanol can be used as a water miscible organic solvent.

  In an alternative non-limiting embodiment, the surfactant can be combined with a water miscible organic solvent or in place of a water miscible organic solvent, inorganic oxidation with bis (alkoxysilylalkyl) polysulfides and non-sulfuric compounds. It can be used in the first step in an amount sufficient to facilitate chemical modification of the product. This surfactant may be selected from nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, or a mixture of such surfactants. This surfactant may be selected so that it does not have a detrimental effect on its intended use on the performance of the resulting chemically modified inorganic oxide. In an alternative non-limiting embodiment, when used, the surfactant is 0.05% to 10%, or 0.1% to 5%, or 0. It can be present in an amount of 1% to 3% by weight, or this weight% can vary between any combination of these values, including the stated value.

  Non-limiting examples of suitable surfactants include alkylphenol polyglycol ethers (eg, p-octylphenol polyethylene glycol (20 units) ether, p-nonylphenol polyethylene glycol (20 units) ether), alkyl polyethylene glycol ethers (eg, , Dodecyl polyethylene glycol (20 units) ether), polyglycol (eg, polyethylene glycol 2000), alkyltrimethylammonium salt (eg, cetyltrimethylammonium chloride or cetyltrimethylammonium bromide), dialkyldimethylammonium salt (eg, dichloride chloride) Lauryldimethylammonium), alkylbenzyltrimethylammonium salts, alkylbenzenesulfonates (eg If, sodium p- dodecylbenzenesulfonate, p- nonyl sodium benzenesulfonate), alkyl hydrogen sulfate (e.g., hydrogen sulfate lauryl), alkyl sulfates (e.g., although lauryl sulfate) may include, but are not limited to. In a non-limiting embodiment, the surfactant can include a polysiloxane polymer or polysiloxane copolymer having an allyl endblocked polyethylene oxide.

In a non-limiting embodiment, bis (alkoxysilylalkyl) -polysulfides used to produce the modified fillers of the present invention include US Pat. Nos. 3,873,489, and 5,580, 919, the relevant disclosure of which is incorporated herein by reference, the bis (alkoxysilylalkyl) -polysulfide can be represented by the following formula VI:
Z-alk-S _{n ′} -alk-Z VI
Where alk can be a divalent hydrocarbon radical having 1 to 18, or 1 to 6, or 2 to 3 carbon atoms; n ′ is 2 Can be an integer of -12, or 2-6, or 3-4, and Z is:

であり得、ここで、Ｒは、１個〜４個の炭素原子を有するアルキル基、またはフェニルであり得、そしてＲ’は、１個〜８個、もしくは１個〜４個、もしくは１個〜２個の炭素原子を有するアルコキシ基、５個〜８個の炭素原子を有するシクロアルコキシ基、または１個〜８個の炭素原子を有する直鎖もしくは分枝鎖のアルキルメルカプト基であり得る。Ｒ基およびＲ’基は、同じであっても異なってもよい。二価のａｌｋ基は、直鎖もしくは分枝鎖であって、飽和もしくは不飽和の脂肪族炭化水素基、または環状炭化水素基であり得る。非限定的な実施形態において、式ＶＩ中のｎ’の８０％が２であることを必要とする、米国特許第５，５８０，９１９号に開示された高純度の有機シランジスルフィドが使用され得る。

Where R can be an alkyl group having 1 to 4 carbon atoms, or phenyl, and R ′ can be 1 to 8, or 1 to 4, or 1 It can be an alkoxy group having ˜2 carbon atoms, a cycloalkoxy group having 5-8 carbon atoms, or a linear or branched alkyl mercapto group having 1-8 carbon atoms. The R group and R ′ group may be the same or different. The divalent alk group may be a straight chain or branched chain, a saturated or unsaturated aliphatic hydrocarbon group, or a cyclic hydrocarbon group. In a non-limiting embodiment, a high purity organosilane disulfide disclosed in US Pat. No. 5,580,919, which requires that 80% of n ′ in Formula VI be 2, can be used. .

  Non-limiting examples of suitable bis (alkoxysilylalkyl) -polysulfides include: Bis (2) where the trialkoxy group can be from trimethoxy, triethoxy, tri (methylethoxy), tripropoxy, tributoxy, etc. to trioctyloxy -Trialkoxysilylethyl) -polysulfides, which can be disulfides, trisulfides, tetrasulfides, pentasulfides, and hexasulfides. From the corresponding bis (3-trialkoxysilylpropyl)-, bis (3-trialkoxysilylisobutyl), -bis (4-trialkoxysilylbutyl)-and the like to bis (6-trialkoxysilylhexyl) polysulfide, Can be used. In non-limiting embodiments, bis (3-trimethoxysilyl-propyl) polysulfide, bis (3-triethoxysilyl-propyl) polysulfide, and bis (3-tripropoxysilyl-propyl) polysulfide; Organosilanes including sulfides and tetrasulfides can be used.

Further non-limiting examples of suitable bis- (alkoxysilylalkyl) -polysulfides include US Pat. No. 3,873,489, column 6, lines 5 to 55, and US Pat. No. 5,580. 919, column 11, line 11 to line 41. Non-limiting representative examples of such compounds include:
3,3′-bis (trimethoxysilylpropyl) disulfide,
3,3′-bis (triethoxysilylpropyl) tetrasulfide,
3,3′-bis (trimethoxysilylpropyl) tetrasulfide,
2,2′-bis (triethoxysilylethyl) tetrasulfide,
3,3′-bis (trimethoxysilylpropyl) trisulfide,
3,3′-bis (triethoxysilylpropyl) trisulfide,
3,3′-bis (tributoxysilylpropyl) disulfide,
There are 3,3′-bis (trimethoxysilylpropyl) hexasulfide and 3,3′-bis (trioctoxysilylpropyl) tetrasulfide, and mixtures thereof. The most preferred compound is 3,3′-bis (triethoxysilylpropyl) tetrasulfide (TESPT).

TESPT is a commercial name of Si-69 under the name of Degussa Corp. Is available from TESPT is
3,3′-bis (triethoxysilylpropyl) monosulfide 3,3′-bis (triethoxysilylpropyl) disulfide 3,3′-bis (triethoxysilylpropyl) trisulfide 3,3′-bis (triethoxy Silylpropyl) tetrasulfide, and a mixture of higher sulfide homologs with an average of 3.5 sulfides.

In an alternative non-limiting embodiment, the non-sulfur organometallic compound that can be used to produce the modified filler of the present invention includes at least one non-sulfur organometallic compound, or:
Formula II:
R ¹ _a MX _(4-a) II
An organometallic compound represented by
Formula III:
_{^{R 2 2c + 2 Si c O}} (c-1) III
An organometallic compound represented by
Formula IV:
R ³ _2d Si _d O _d IV
An organometallic compound represented by the formula V:
(R ² ₃ Si) _k NR ⁴ _(3-k) V
And a mixture of non-sulfur organometallic compounds selected from the group consisting of organometallic compounds represented by: wherein each M may independently be silicon, titanium or zirconium; each R ¹ Can independently be a hydrocarbon group of 1 to 18 carbon atoms, or R ¹ can be an organofunctional hydrocarbon group having 1 to 12 carbon atoms, where For example, the functionality can be amino, carboxylic acid, carbinol ester or amide; each X is independently halogen, amino, alkoxy group having 1 to 12 carbon atoms, and one May be selected from the group consisting of acyloxy groups having ˜12 carbon atoms, a may be an integer 1, 2 or 3; each R ² is independently halo, hydroxy, or 1-18 Charcoal containing carbon atoms While may be a hydrogen group, provided that at least 50 mole% of the ^{R 2} substituent may be a hydrocarbon group containing 1 to 18 carbon atoms, c is an integer 2 to 10,000 obtained; Each R ³ can independently be halo, hydroxy, or a hydrocarbon group containing 1 to 18 carbon atoms, and d can be an integer from 3 to 20; each R ⁴ can be independently Hydrogen, or a hydrocarbon group containing 1 to 18 carbon atoms, and k can be 1 or 2; and a halogen or (halo) group is chloro, bromo, iodo, or It may be selected from fluoro. In the definitions of substituents shown in formulas II, III, IV and V, the same symbols have the same meanings unless otherwise indicated.

In an alternative non-limiting embodiment, each R ¹ in Formula II can be a saturated or unsaturated monovalent hydrocarbon group, or a substituted or unsubstituted monovalent hydrocarbon group. R ¹ is an alkyl group (eg, methyl, ethyl, propyl, iso-propyl, iso-butyl, t-butyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl); an alkenyl group (Eg, vinyl, allyl, and hexenyl); substituted alkyl groups (eg, chloromethyl, 3,3,3-trifluoropropyl, and 6-chlorohexyl); cycloalkyl groups (eg, cyclohexyl, and cyclooctyl); Can be aryl groups (eg, phenyl and naphthyl); and substituted aryl groups (eg, benzyl, tolyl, and ethylphenyl).

  In a further alternative non-limiting embodiment, when X in Formula II is a halogen, the halogen can be chloro; when X is an alkoxy group, X can be methoxy, ethoxy, and propoxy; When X is an acyloxy group, X can be acetoxy. In another non-limiting embodiment, each X can be selected from chloro and methoxy.

  The viscosity of the organometallic compound is non-limiting and can range from fluid viscosity to gum viscosity. In general, higher molecular weight organometallic compounds should be cleaved by the acidic conditions of the chemical modification step to react with hydrophilic inorganic oxides.

In non-limiting embodiments, in Formulas III, IV, and V, each of R ² , R ³ , and R ⁴ can be the same as the hydrocarbon group described for R ¹ . For the purposes of the present invention, silicon is considered a metal when the organometallic reactant is an organosilicon reactant.

In further non-limiting embodiments, the non-sulfur organometallic compound can be represented by Formulas II, III, IV, V, or can be a mixture of those organometallic compounds, where each M is It can be silicon. In a non-limiting embodiment, the non-sulfur organometallic compound can be represented by Formula II, where R ¹ can be C ₁ -C ₆ alkyl, X can be chloro, and a is Can be 2.

  Non-limiting examples of suitable organosilicon compounds include diethyldichlorosilane, allylmethyldichlorosilane, methylphenyldichlorosilane, phenylethyldiethoxysilane, 3,3,3-trifluoropropylmethyldichlorosilane, trimethylbutoxysilane , Sym-diphenyltetramethyldisiloxane, trivinyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaethyldisiloxane, pentylmethyldichlorosilane, divinyldipropoxysilane, vinyldimethylchlorosilane, vinylmethyldichlorosilane, vinyldimethylmethoxysilane , Trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methylto Ethoxysilane, hexamethyldisiloxane, hexenylmethyldichlorosilane, hexenyldimethylchlorosilane, dimethylchlorosilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexamethyldisilazane, trivinyltrimethylcyclotrisilazane, 3 to about 20 Selected from polydimethylsiloxanes containing dimethylsiloxy units and poly (dimethylsiloxane) polymers end-blocked with trimethylsiloxy or hydroxydimethylsiloxy having an apparent viscosity in the range of 1 mPa · s to 1000 mPa · s at 25 ° C. Compounds, and mixtures of these compounds, but are not limited to these.

Non-limiting examples of suitable organotitanium compounds, tetra titanate _(C 1 _{~C 18)} alkoxy, methyl triethoxy titanium (iv), methyl titanium (iv) triisopropoxide, methyl titanium (iv) tri Butoxide, methyl titanium (iv) tri-t-butoxide, isopropyl titanium (iv) triethoxide, butyl titanium (iv) tributoxide, butyl titanium (iv) tributoxide, phenyl titanium (iv) triisopropoxide, phenyl titanium (iv) ) Tributoxide, phenyltitanium (iv) triisobutoxide, [Ti (CH ₂ Ph) ₃ (NC ₅ H ₁₀ )] and [Ti (CH ₂ SiMe ₃ ) ₂ (NEt ₂ ) ₂ ]. It is not limited to these.

Non-limiting examples of suitable organozirconium compounds include tetra (C ₁ -C ₁₈ ) alkoxyzirconate, phenylzirconium (iv) trichloride, methylzirconium (iv) trichloride, ethylzirconium (iv) trichloride, propylzirconium ( iv) trichloride, methylzirconium (iv) tribromide, ethylzirconium (iv) tribromide, propylzirconium (iv) tribromide, chlorotripentylzirconium (iv) may be mentioned but are not limited thereto. In an alternative non-limiting embodiment, zirconium compounds similar to those described above for organotitanium compounds and vice versa are also contemplated.

  The amount of mercapto organometallic compound and non-sulfur organometallic compound used in the chemical modification process described above is greater than 1 wt% carbon content, greater than 0.15 wt% mercapto content, at least 0.3%. Sufficient to produce a modified filler characterized by a silane conversion index of 5 and a standard reinforcement index of at least 4.0. Such an amount herein refers to a coupling amount, ie, an amount sufficient to bind to the filler and allow the modified filler to bind to the polymer composition.

  In an alternative non-limiting embodiment, the weight ratio of mercaptoorganosilane to non-sulfur organometallic compound is at least 0.05: 1, or 0.05: 1 to 10: 1, or 0.1: 1. Can vary from ˜5: 1, or from 0.2: 1 to 2: 1, or from 0.5: 1 to 1: 1, or the weight ratio of these values, including the stated values It can vary between any combination. Individual organometallic reactants can be added together or sequentially in any order. In a non-limiting embodiment, the organometallic reactant may be present in an amount that provides an excess of organometallic units relative to the hydroxyl groups available for reaction on the inorganic oxide particles. The upper limit on the amount of organometallic reactant added to the process is not critical. Excess mercapto organometallic compounds and non-sulfur organometallic compounds can be removed by filtration, distillation, solvent washing, or other known separation techniques.

  In an alternative non-limiting embodiment, the mercapto organometallic reactant is at least greater than 1: 1, or 1.01: 1, or 1 by a combination of a mercapto organometallic compound and a different sulfur-containing organometallic compound. .01: 1 to 100: 1, or 5: 1 to 50: 1, or 10: 1 to 30: 1 of a mercapto organometallic compound and a sulfur-containing organometallic compound, which can be substituted by weight ratio, Can vary between any combination of these values, including the stated values. In general, any sulfur-containing organometallic compound (other than the mercapto organometallic compound represented by Formula I) that can act as a coupling agent in the vulcanization of the filler-containing rubber may be suitable for use in the present invention.

  Non-limiting examples of suitable sulfur-containing organometallic compounds may include bis (alkoxysilylalkyl) -polysulfides as previously described herein.

  The amount of bis (alkoxylsilylalkyl) polysulfide and non-sulfur organometallic compound used in the chemical modification process described above is greater than 1 wt% carbon content, greater than 0.1 wt% sulfur content, at least An amount sufficient to produce a modified filler characterized by a silane conversion index of 0.3 and a standard tensile stress at 300% elongation of at least 7.0. Such an amount herein refers to a coupling amount, ie, an amount sufficient to bind to the filler and allow the modified filler to bind to the polymer composition.

  In an alternative non-limiting embodiment, the weight ratio of bis (alkoxylsilylalkyl) polysulfide to non-sulfur organometallic compound is at least 0.05: 1, or 0.05: 1 to 10: 1, or 0. .1: 1 to 5: 1, or 0.2: 1 to 2: 1 (eg 0.5: 1 to 1: 1), or this weight ratio includes the stated values , And can vary between any combination of these values. Individual organometallic reactants can be added together or sequentially in any order. In a non-limiting embodiment, the organometallic reactant may be present in an amount that provides an excess of organometallic units relative to the hydroxyl groups available for reaction on the inorganic oxide particles. The upper limit on the amount of organometallic reactant added to the process is not critical. Excess bis (alkoxylsilylalkyl) polysulfide and non-sulfur organometallic compounds can be removed by filtration, distillation, washing with a solvent, or other known separation techniques.

  In an alternative non-limiting embodiment, the bis (alkoxylsilylalkyl) polysulfide can be replaced by a combination of a bis (alkoxylsilylalkyl) polysulfide and a different sulfur-containing organometallic compound, the bis (alkoxylsilylalkyl) polysulfide And the weight ratio of the sulfur-containing organometallic compound is at least greater than 1: 1, ie 1.01: 1, or 1.0: 1 to 100: 1, or 5: 1 to 50: 1, or 10: 1. It can be 30: 1 or this weight ratio can vary between any combination of these values, including the stated values. In general, any sulfur-containing organometallic compound (other than the bis (alkoxylsilylalkyl) polysulfide represented by Formula VI) that can act as a coupling agent in the vulcanization of the filler-containing rubber may be suitable for use in the present invention.

  Non-limiting examples of suitable sulfur-containing organometallic compounds can include the mercapto organometallic reactants described hereinabove.

  In an alternative non-limiting embodiment, after the chemical modification process is essentially complete, the pH of the aqueous suspension of the modified inorganic oxide is 3.0 to 10 from a treatment pH of 2.5 or less. 0.0, or 3 or more, or 4 or more, or 5 or more, or 6 or more, and can be raised to a pH of 10 or less, 9 or less, or 8 or less, or 7 or less. The pH of the aqueous suspension can vary between any combination of these levels, including the levels described. This pH can be raised to neutralize the added or generated acidity to produce a final product having a pH of 5.0-10.0 (after drying).

  In an alternative non-limiting embodiment, the modified inorganic oxide is greater than one to one by filtration and drying, or an aqueous suspension of the modified inorganic oxide with a water-immiscible organic solvent, Alternatively, it can be recovered by contacting at a weight ratio of solvent and inorganic oxide greater than 5: 1. The modified inorganic oxide recovered in the solvent phase may be used without further treatment or may be dried. In a non-limiting embodiment, the present invention can include a composition comprising a slurry of modified filler in a water immiscible solvent. The concentration of the modified filler in the slurry can range from 1% to 90% by weight based on the total weight of the slurry.

  Non-limiting examples of suitable water-immiscible organic solvents include low molecular weight siloxanes (eg, hexamethyldisiloxane fluid, octamethylcyclotetrasiloxane fluid, diphenyltetramethyldisiloxane fluid, and endblocks with trimethylsiloxy Non-limiting polydimethylsiloxane fluids). When siloxane is used as a solvent, the siloxane can act both as a solvent and as a reactant with an inorganic oxide. Further non-limiting examples of suitable water-immiscible organic solvents include aromatic hydrocarbons (eg, toluene and xylene; heptane and other aliphatic hydrocarbon solvents; cycloalkanes (eg, cyclohexane); ethers (eg, , Diethyl ether and dibutyl ether); halohydrocarbon solvents (eg, methylene chloride, chloroform, ethylene chloride, and chlorobenzene); and ketones (eg, methyl isobutyl ketone).

  In an alternative non-limiting embodiment, the water-immiscible organic solvent that can be used to contact the aqueous suspension of the hydrophobic particulate inorganic oxide is one dissolved in the water-immiscible organic solvent. The above substances may or may not be included. Non-limiting examples of such materials can include, but are not limited to, one or more rubbers, oils, coupling agents, antioxidants and vulcanization accelerators.

  At least one advantage of the chemically modified filler of the present invention is that the generation of alcohol can be substantially suppressed when mixed with a polymer (eg, a rubber composition). Reaction of the silica particles with the coupling agent of the present invention can yield the chemically modified filler and alcohol by-product of the present invention. For example, ethoxysilane reacts with silica to produce an ethanol byproduct. The process of the invention can be carried out in an aqueous environment under conditions that can result in essentially complete hydrolysis of the alkoxy group. Alcohol by-products produced by the reaction of the coupling agent with silica can be retained in the aqueous phase. Chemically modified fillers can be isolated from the aqueous phase (including the alcohols described above), resulting in no substantial liberation of alcohol by the filler. In a non-limiting embodiment, the filler can release less than 4000 ppm alcohol. In another non-limiting embodiment, the filler can be mixed with the rubber composition in conventional amounts, and the mixed rubber composition can result in no substantial liberation of alcohol. In a further non-limiting embodiment, the mixed rubber composition can release less than 4000 ppm alcohol. In a non-limiting embodiment, the rubber composition comprises 10 to 150 parts of filler per 100 parts of rubber composition. “There is no substantial liberation of alcohol” and similar phrases mean that the filler and / or rubber composition does not continue to release the alcohol; of the alcohol from the filler and / or rubber composition. Any release is the result of physically entrapped alcohol leaking out of it.

  In a non-limiting embodiment, the rubber composition mixed with the modified filler of the present invention and free of bis (alkoxysilylalkyl) polysulfide has a conventional filler and the presence of bis (alkoxysilylalkyl) polysulfide. May release at least 20% less alcohol than the rubber composition.

  In a non-limiting embodiment, the modified filler of the present invention (as a powder, granule, pellet, slurry, aqueous suspension, or solvent suspension) is a base material (ie ready-made to be manufactured). In combination) to form a mixture called a masterbatch. In the masterbatch, the modified filler can be present at a higher concentration than in the final product. An aliquot of this mixture is produced during the mixing operation to facilitate uniform dispersion of very small amounts of such additives into polymer compositions (eg, plastics, rubbers, and coating compositions). Can be added to the amount of size.

  In another non-limiting embodiment, the modified filler is combined with an emulsion and / or solution polymer (eg, organic rubber (SBR) containing solution styrene / butadiene, polybutadiene rubber, or mixtures thereof) to form a masterbatch. Can be formed. In a further non-limiting embodiment, a masterbatch can be formed that includes a combination of an organic rubber, a water immiscible solvent, a modified filler, and optionally a process oil. Such products can be supplied by the rubber producer to the tire manufacturer. At least one advantage of using a masterbatch for tire manufacturers is that the modified filler can be uniformly dispersed in the rubber, which substantially reduces or minimizes the mixing time to produce the mixed rubber. Can be limited. In an alternative non-limiting embodiment, the masterbatch contains 10 to 150 parts (phr) of modified silica, ie 20 to 130 phr, or 30 to 100 phr, or 50 to 80 phr silica, per 100 parts rubber. May be included.

  In an alternative non-limiting embodiment of the present invention, the polymer article is 10 to 150 parts modified filler for 100 parts polymer, or 20 to 130 parts, or 30 to 100 parts for 100 parts polymer. Part, or 50-80 parts of modified filler may be dispersed therein. The amount of modified filler can vary between any combination of these values, including the stated ranges. As described herein, the polymer may be selected from thermoplastic resins, thermosetting resins, and organic rubbers. In a non-limiting embodiment, the polymer can be a curable organic rubber.

  Non-limiting examples of curable rubbers suitable for use in combination with the modified fillers of the present invention are well known to those skilled in rubber chemistry and are vulcanizable rubber and sulfur curable rubber. Can be mentioned, but is not limited thereto. In a further non-limiting embodiment, the curable rubber includes materials typically used for mechanical rubber articles.

  In another non-limiting embodiment, the modified filler of the present invention is about 100 ° F. and about 400 ° F. (38 ° C. to 200 ° C.) by conventional means such as in a Banbury mixer or rubber mill. Can be mixed with uncured rubber elastomers used to prepare vulcanizable rubber compositions. In an alternative non-limiting embodiment, the vulcanizable rubber composition is based on 100 parts vulcanizable rubber polymer, 10-150 parts modified filler, or 20-130 phr, or 30-100 phr, Alternatively, 50-80 phr modified filler may be included. Non-limiting examples of other conventional rubber additives that may be present include, but are not limited to, conventional sulfur cure systems or peroxide cure systems.

  In a non-limiting embodiment, the sulfur cure system can include 0.5-5 parts sulfur, 2-5 parts zinc oxide, and 0.5-5 parts vulcanization accelerator. In a further non-limiting embodiment, the peroxide cure system can include 1 to 4 parts peroxide (eg, dicumyl peroxide). A wide variety of other conventional rubber additives can also be used. Non-limiting examples of such additives include other fillers (eg, carbon black), oils, plasticizers, vulcanization accelerators, antioxidants, thermal stabilizers, light stabilizers, zone stabilizers. (Zone stabilizer), organic acids (such as stearic acid, benzoic acid, or salicylic acid), other activators, extenders, and color pigments may be mentioned, but are not limited to these. Individual mixing recipes vary with the particular vulcanizate prepared; however, such recipes are well known to those having skill in the rubber mixing art.

  Another advantage of the chemically modified filler of the present invention is its stability at high temperatures and / or mixing with the filler at temperatures up to at least 200 ° C. when mixed for at least one-half to 60 minutes. There may be no cure of the rubber being made. In alternative non-limiting embodiments, the mixing process can be performed in batches or continuously. In a non-limiting embodiment of the present invention, at least a portion of the rubber composition and the chemically modified composition can be continuously fed to the first part of the mixing path to produce a blend, which blend is Can be continuously fed to the second part of the mixing path.

  The rubber composition mixed with the chemically modified filler of the present invention has improved performance characteristics over conventional sulfur vulcanized bond performance characteristics mixed with conventional fillers and bis (alkoxysilylalkyl) -polysulfides. Can bring Improved properties may include a higher 300% modulus, a higher 300% to 100% modulus ratio, a lower ΔG ′, and a lower tangent δ at 60 ° C.

  Another advantage of the present invention may be the ability to achieve the desired cure kinetics, as well as the physical properties of the rubber mixed with the chemically modified filler of the present invention and certain curing components. In a non-limiting embodiment, the desired cure reaction rate includes a scorch time greater than 2.5 minutes, wherein the mixed product has a 300% modulus of at least 6.5 mPa (determined according to ASTM D412-98a), and Mention may be made of cure times shorter than 30 minutes (TS2 and TC90, respectively, determined according to ASTM D5289-95). These curing kinetics and physical properties may be achievable when one or more curing components are included. Suitable curing components can include, but are not limited to, a wide variety of materials known to those skilled in the art, such as vulcanization accelerators and retarders.

Non-limiting examples of suitable vulcanization accelerator compositions may include the following:
Benzothiazole, for example:
2-mercaptobenzothiazole,
2-mercaptobenzothiazole zinc,
2,2-dithiobisbenzothiazole,
2-morpholinothiobenzothiazole,
2- (4-morpholinothio) -benzothiazole,
2- (4-morpholinodithio) -benzothiazole,
2- (4-morpholinothio) -5-methylbenzothiazole,
2- (4-morpholinothio) -5-chlorobenzothiazole,
2- (2,6-dimethyl-4-morpholinothio) -benzothiazole,
2- (3,6-dimethyl-4-morpholinothio) -benzothiazole,
2,2′-dibenzothiazole disulfide, and 2-mercaptobenzothiazyl disulfide;
Benzothiazole sulfenamide, for example:
N-cyclohexyl-2-benzothiazole sulfenamide,
N-tert-butyl-2-benzothiazole sulfenamide,
N, N′-dicyclohexyl-2-benzothiazole sulfenamide,
N, N-diisopropyl-2-benzothiazole sulfenamide,
N, N-diethyl-2-benzothiazole sulfenamide,
N-oxydiethylene-2-benzothiazole sulfenamide, and N-oxydiethylenethiocarbamyl-N-oxydiethylene sulfenamide;
Dithiocarbamates, for example:
Bismuth dimethyldithiocarbamate,
Copper dimethyldithiocarbamate,
Cadmium diethyldithiocarbamate,
Lead diamyldithiocarbamate,
Lead dimethyldithiocarbamate,
Selenium diethyldithiocarbamate,
Selenium dimethyldithiocarbamate,
Tellurium diethyldithiocarbamate,
Zinc dimethyldithiocarbamate,
Zinc diethyldithiocarbamate,
Zinc diamyldithiocarbamate,
Zinc di-n-butyldithiocarbamate,
Zinc dimethylpentamethylenedithiocarbamate,
Piperidinium pentamethylenedithiocarbamate,
2-benzothiazyl-N, N-diethyldithiocarbamate, and dimethylammonium dimethyldithiocarbamate;
Thiomorpholine, for example:
4,4′-dithiodimorpholine,
4-mercaptomorpholine,
4-mercapto-2,6-dimethylmorpholine,
4-[(4-morpholinylthio) thiomethyl] morpholine (4-[(4-morpholinylthio) thixomethyl] morpholine),
2,6-dimethylmorpholine disulfide (2,6-dimethylmorpholine sulphide),
Methylmorpholine disulfide,
Propyl 2,6-dimethylmorpholine disulfide,
Alkylmorpholine disulfide, and phenylmorpholine disulfide;
Thiourea, for example:
Trimethylthiourea,
1,3-diethylthiourea,
1,3-dibutylthiourea,
N, N′-dibutylthiourea,
Dimethylethylthiourea,
Diphenylthiourea and tetramethylthiourea;
Xanthate, for example:
Sodium isopropylxanthate,
Zinc isopropylxanthate and zinc dibutylxanthate;
Thiuram sulfide, for example:
Tetramethylthiuram monosulfide,
Tetramethylthiuram disulfide,
Tetraethylthiuram disulfide,
Tetrabutyl thiuram disulfide,
Tetrabenzylthiuram disulfide,
Dipentamethylene thiuram tetrasulfide,
Dimethyldiphenyl thiuram disulfide, and dipentamethylene thiuram monosulfide; and amines such as:
Cyclohexylethylamine,
Dibutylamine,
An acetaldehyde-aniline condensation product,
Heptaldehyde-aniline condensation products; and guanidines such as:
N, N′-diphenylguanidine,
N, N′-di-o-tolylguanidine,
Orthotrilbiguanidine,
A blend of N, N ′, N ″ -triphenylguanidine (N, N ′, N ″ -triphenylguanidine) and diarylguanidine.

Non-limiting examples of suitable retarders can include at least one of the following:
N- (cyclohexylthio) -phthalimide,
Phthalic anhydride, and aromatic sulfenamide.

  Vulcanizable rubber compositions can be vulcanized or cured into rubber vulcanizates according to conventional procedures known in the rubber industry. Non-limiting examples of industrial rubber vulcanizates (articles) that can be produced using the modified filler of the present invention include wire and cable jackets, hoses, gaskets and seals, industrial and automotive drives. Belts, engine racks, V-belts, conveyor belts, roller coatings, tires and tire components (eg, automotive tire treads, subtreads, tire carcass, tire sidewalls, tire belt wedges, tire bead fillers, and tire wires) Skim coat), sole materials, packing rings, braking elements, and many others.

  The present invention is more specifically described in the following discussion of standard mixing protocols, examples and comparative examples, which are exemplary because numerous modifications and changes therein will become apparent to those skilled in the art. Only intended.

(Standard mixed protocol)
Test samples of formulated rubber compositions containing the silica of the Examples and Comparative Examples (CE) were prepared using a standard mixing protocol.

(Part A)
The following components in parts per hundred rubber (phr) were added in the order listed to a polyethylene bag upright in a 500 milliliter (mL) plastic cup.

（１）Ｓｕｎｄｅｘ（登録商標）８１２５ 芳香族炭化水素プロセスオイル、Ｓｕｎ Ｃｏｍｐａｎｙ，Ｉｎｃ．，Ｒｅｆｉｎｉｎｇ ａｎｄ Ｍａｒｋｅｔｉｎｇ Ｄｉｖｉｓｉｏｎから市販されているものを入手
（２）Ｋａｄｏｘ（登録商標） 表面処理された酸化亜鉛、Ｚｉｎｃ Ｃｏｒｐｏｒａｔｉｏｎ ｏｆ Ａｍｅｒｉｃａから市販されているものを入手
（３）Ｗｉｎｇｓｔａｙ（登録商標）１００ オゾン分解防止剤、ジアリールｐ−フェニレンジアミンの混合物、Ｔｈｅ Ｇｏｏｄｙｅａｒ Ｔｉｒｅ ＆ Ｒｕｂｂｅｒ Ｃｏ．から市販されているものを入手
（４）ゴムグレードのステアリン酸、Ｃ．Ｐ．Ｈａｌｌから市販されているものを入手。

(1) Sundex® 8125 aromatic hydrocarbon process oil, Sun Company, Inc. (2) Kadox (registered trademark) surface-treated zinc oxide, commercially available from Zinc Corporation of America (3) Wingstay (registered trademark) 100 ozone Decomposition inhibitors, mixtures of diaryl p-phenylenediamines, The Goodyear Tire & Rubber Co. (4) Rubber grade stearic acid, C.I. P. Get commercially available from Hall.

(Part B)
A 1.89 liter (L) Farrel Banbury mixer ("BR" model) was used to mix the various ingredients. Just prior to adding the batch ingredients to the mixer, 800 grams (g) of CV-60 grade natural rubber is applied to the mixer to remove any residue from the previous run from the mixer and the temperature to about 93 ° C (200 ° F). Raised. After removing the rubber, the mixer was cooled to about 65 ° C. (150 ° F.), after which the ingredients were added to obtain rubber test samples.

  A rubber composition is prepared using the test filler, then the other ingredients listed, and the procedure described below.

（５）Ｓｏｌｆｌｅｘ（登録商標）１２１６ 溶液スチレン−ブタジエンゴム（ＳＢＲ）、Ｔｈｅ Ｇｏｏｄｙｅａｒ Ｔｉｒｅ ＆ Ｒｕｂｂｅｒ Ｃｏ．から市販されているものを入手
（６）Ｂｕｄｅｎｅ １２０７ ブタジエンゴム（ＢＲ）、Ｔｈｅ Ｇｏｏｄｙｅａｒ Ｔｉｒｅ ＆ Ｒｕｂｂｅｒ Ｃｏ．から市販されているものを入手
（７）Ｓａｎｔｏｆｌｅｘ（登録商標）１３ オゾン分解防止剤、Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミンとして記載される、Ｆｌｅｘｓｙｓから市販されているものを入手
（８）Ｏｋｅｒｉｎ（登録商標）７２４０ 微結晶性蝋／パラフィン蝋のブレンド、Ａｓｔｏｒ Ｃｏｒｐｏｒａｔｉｏｎから市販されているものを入手
（９）Ｒｕｂｂｅｒ Ｍａｋｅｒｓ（ＲＭ）硫黄、１００％活性、Ｔａｂｅｒ，Ｉｎｃ．から市販されているものを入手
（１０）Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾールスルフェンアミド、Ｍｏｎｓａｎｔｏから市販のものを入手
（１１）ジフェニルグアニジン、Ｍｏｎｓａｎｔｏから市販されているものを入手。

(5) Solflex® 1216 solution styrene-butadiene rubber (SBR), The Goodyear Tire & Rubber Co. (6) Budene 1207 butadiene rubber (BR), The Goodyear Tire & Rubber Co. (7) Santoflex® 13 Ozone decomposition inhibitor, described as N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, commercially available from Flexsys (8) Okerin® 7240 microcrystalline wax / paraffin wax blend, available commercially from Astor Corporation (9) Rubber Makers (RM) Sulfur, 100% active, Taber , Inc. (10) N-tert-butyl-2-benzothiazolesulfenamide, commercially available from Monsanto (11) diphenylguanidine, commercially available from Monsanto.

  The first path was started by adding rubber, ie SBR and BR, to the mixer and mixing for 0.5 minutes at 116 rpm. The rotor speed was maintained at 116 rpm and 57.5 phr of treated filler sample was added. 1.5 minutes later, the ram was raised and the chute was swept, that is, the cover on the entrance chute was raised and any material in the chute was swept back to the mixer. One minute later, the sample from Part A was added. After another minute, he raised the ram and swept the shot. The contents of the mixer were mixed for an additional minute to achieve a maximum temperature in the range of 145 ° C. to 150 ° C. (293 ° F. to 302 ° F.), completing the first pass in the mixer. Depending on the type of sample, the rotor speed of the mixer can be increased or decreased after 4 minutes to achieve the above range of temperatures within the specified mixing time.

  After completing the first pass, the temperature of this material was determined with a thermoelectric thermometer to ensure that the temperature did not exceed a maximum temperature of 150 ° C. The removed material was weighed and formed into 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch) sheets on a Farrel 12 inch two-roll rubber mill. The resulting rolled stock was cut into strips for the second path in the mixer.

  A minimum of 1 hour was allocated between the completion of the first pass in the mixer and the start of the second pass to allow the rolling stock to cool. If necessary, the above cleaning and preheating procedure with CV-60 grade natural rubber was completed before the second route was started. The mixer temperature was adjusted to about 49 ° C. (120 ° F.). A mixer in which the strip of the raw material of the first path was operated at 77 rpm while flowing cooling water, and a Santoflex® 13 ozonolysis inhibitor and Okerin® 7240 microcrystalline wax / paraffin wax. The second path was initiated by adding to the pre-weighed combination with the blend. After 0.5 minutes, the second additive, RM sulfur, TBBS, and DPG combination was added. 1.5 minutes later, he raised the ram and swept the shot. This second pass was completed by mixing the stock for an additional 2.0 minutes while maintaining the temperature below 125 ° C (257 ° F).

(Part C)
A Farrel 12 inch two roll rubber mill was heated to about 60 ° C. (140 ° F.). Stock from the second path of Part B was fed to a rolling mill operating with a roll gap setting of 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch). The resulting sheet was placed on a flat surface until the sheet temperature reached room temperature. Typically, the sheet cooled within about 30 minutes. Thereafter, the rolled sheet was supplied to a rubber rolling mill with a roll gap setting of 3.81 mm ± 0.51 mm (0.15 inch ± 0.02 inch). In order to maintain a uniform thickness, a rolling bank was adjusted if necessary. The resulting material was subjected to 16 side cuts and then 8 end passes. The roll gap of the rubber mill was adjusted to produce a sheet thickness of 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch). The sheet stock recovered from the rolling mill was placed on a clean plane. Using a stencil, a rectangular sample of 203.2 mm x 152.4 mm (8 inches x 6 inches) was cut from the sheet stock. The sample was conditioned, i.e., stored between clean polyethylene sheets and maintained at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50% ± 5% for 15-18 hours.

  After conditioning, the sample was placed in a standard mechanical steel compression mold having a polished surface of 203.2 mm × 152.4 mm × 2.286 mm (8 inches × 6 inches × 0.09 inches). This sample is T90, or 90 percent cure, in a 890 kilonewton (100 ton) 4-post electrothermal compression press of 61 centimeter by 61 centimeter (24 inches by 24 inches). Cured at 150 ° C. (302 ° F.) under 13.79 megapascals (2000 pounds per cubic inch) according to ASTM D-2084 for a period of 5 minutes plus It was. Typically, curing was complete within about 10 minutes. The resulting cured rubber sheet is removed from the mold and, prior to testing in Part D, 15 ° C. ± 2 ° C. (73.4 ° F. ± 3.6 ° F.) and 15% relative humidity 50% ± 5%. Maintained for time to 18 hours.

(Part D)
The test was performed according to ASTM D412-98a-Test Method A. Dumbbell test specimens were prepared using Die C. An Instron 4204 model equipped with an automatic contact extensometer for measuring elongation was used. The crosshead speed was found to be equal to 508 mm / min. All calculations were performed using the Series IX automated material testing software supplied by the manufacturer. The strengthening index is equal to the tensile stress (MPa) at 300% elongation divided by the tensile stress (MPa) at 100% elongation. When samples were prepared using a standard mixing protocol, the results were reported as a standard enhancement index.

(Preparation of precipitated silica)
Precipitated silica was produced by acidifying the sodium silicate solution with sulfuric acid. Most of the sediment was formed at a pH higher than 8.5. Further sediment was generated by continuing the acid addition until the pH of the solution reached a level of 3.3-4.0.

  A sample of precipitated silica for surface area analysis was prepared by filtering and washing portions of silica as described in Example 15 until the rinse water exhibited a conductivity level of about 300-800 micromho. . The resulting filter cake was reliquefied using a high shear agitator to form a solid suspension in liquid. This suspension was dried with a Niro spray dryer (inlet temperature about 360 ° C. and outlet temperature about 110 ° C.). Listed in Table 1 are the surface areas of the precipitated silica used to prepare the modified silicas of the Examples and Comparative Examples.

(Examples 1-6)
About 50 kilograms (kg) of precipitated silica suspension, about 3.25 kg of silica and 15.2 kg to 15.9 kg of isopropyl alcohol, was added to a 30 gallon glass-lined container with a bottom drain. The vessel was also equipped with a temperature recorder, mechanical stirrer, heating means and condenser.

  While stirring the contents of the vessel and initiating heating, 3-mercaptopropyltrimethoxysilane (MPTMS) is listed for the weight percentage of MPTMS per silica on a dry basis for the examples listed in Table 1. Was added over a period of time (typically about 10 minutes) to produce an approximate amount to be achieved. After completion of the MPTMS addition, dimethyldichlorosilane (DMDCS) was added in the same manner to obtain the approximate amounts listed for wt% DMDCS per silica on a dry basis in Table 1. MPTMS / DMDCS weight ratios are also listed in Table 1. The resulting pH of the solution ranged from about 1.5 to about 2.2.

  After completion of the DMDCS addition, concentrated, ie, about 37% by weight, hydrochloric acid was added in an amount necessary to reduce the pH of the solution to about 0.3. The mixture was heated to about 68 ° C. and kept at this temperature for about 30 minutes. While cooling, 50 wt% NaOH sufficient to adjust the pH to about 3.5 was added to the mixture over a period of time. After completion of the NaOH addition, sufficient toluene (typically 6.75 kg to 7.75 kg) was added to the stirred mixture to separate the hydrophobic precipitated silica from the aqueous phase without forming an emulsion. . The aqueous phase was drained from the container. The stirred mixture in a vessel containing hydrophobic precipitated silica was then washed with about 30 kg of water. Sufficient additional toluene (typically 6.5 kg to 8.0 kg) was added to the stirred mixture to separate the hydrophobic precipitated silica from the aqueous phase without forming an emulsion. The aqueous phase was drained. The stirred mixture containing the hydrophobic precipitated silica was then washed two more times with about 30 kg of water per wash. After each wash, the aqueous phase was drained from the container before the next wash was added.

  After washing is complete, enough toluene (typically 12.5 kg to 15.3 kg) is added to the stirred mixture to obtain a flowable solid-in-liquid suspension that can be easily drained from the vessel. It was. The resulting suspension was dried at a minimum of 140 ° C. under reduced pressure (minimum 23 inches of mercury) in a rotocone dryer. Drying continued until the sample was exposed to 160 ° C. for 10 minutes and showed a weight percent reduction of less than 4%.

(Example 7)
The procedure described for Examples 1-6 was followed with the following exceptions: 80 g of 3-mercaptopropyltrimethoxysilane (MPTMS) was added over about 10 minutes; 487 g of dimethyldichlorosilane was added over about 10 minutes. Without using isopropyl alcohol and toluene, the three individual batch slurries were combined, filtered, and washed with water until the rinse water exhibited a conductivity level of about 300 micromolar to about 800 micromolar. The “treated” silica sample was allowed to dry until exposed to 160 ° C. for 10 minutes, showing a <2 wt% reduction.

  The approximate weight percentages of MPTMS and DMDCS per silica on a dry basis for the modified silica sample of Example 7 and the weight ratio of MPTMS / DMDCS are listed in Table 2.

(Example 8)
The procedure described for Examples 1-6 was used with the following exceptions: 40 kg of re-liquefied solid precipitated silica suspension in liquid (3.3 kg of silica) and 12.2 kg of isopropyl alcohol were used. 171 g 3-mercaptopropyltrimethoxysilane (MPTMS) was added over about 7 minutes; 506 g dimethyldichlorosilane (DMDCS) was added over about 2 minutes; concentrated hydrochloric acid was added over 24 minutes; This solution was heated at about 68 ° C. for 30 minutes and then sufficient 50 wt% NaOH was added to adjust the pH to about 7.0; sufficient toluene (about 7. 1 kg) was added to separate the hydrophobic silica from the aqueous phase without forming an emulsion. The recovered product was not subjected to water washing, but after draining the aqueous phase, about 2.2 kg of toluene was added to the product to make a flowable solid-in-liquid suspension. The treated silica sample was dried until the treated silica sample was exposed to 160 ° C. for 10 minutes and showed a <1.5 wt% reduction.

  The approximate weight percentages of MPTMS and DMDCS per silica on a dry basis for the modified silica sample of Example 8 and the weight ratio of MPTMS / DMDCS are listed in Table 2.

Example 9
The procedure of Example 8 was followed except that 86.5 g of 3-mercaptopropyltrimethoxysilane (MPTMS) was used. The approximate weight percentages of MPTMS and DMDCS per silica on a dry basis and the weight ratio of MPTMS / DMDCS for the modified silica sample of Example 9 are listed in Table 2.

(Examples 10 to 13)
A freshly prepared silica slurry having a temperature of about 65 ° C. to 85 ° C. just prior to adding both silanes (DMDCS and MPTMS) and acid (enough acid to provide a pH of about 0.3) to the vessel. Mixed with. The acid used in all examples except for Example 13 using concentrated hydrochloric acid was concentrated sulfuric acid, ie about 96% by weight sulfuric acid. The resulting mixture was allowed to stand for at least 15 minutes. Water was added, stirring was applied, and the pH was adjusted to 3.5 with 50 wt% aqueous NaOH. The resulting aqueous suspension of hydrophobic silica was filtered and washed with water until the rinse water exhibited a conductivity level of about 300 to about 800 micrometers. The hydrophobic silica was dried until the sample showed less than 2.5 wt% reduction when exposed to 106 ° C for 10 minutes. The approximate amount of silane added to the slurry is reported in Table 2 along with the MPTMS / DMDCS weight ratio in weight percentages based on dry silica.

(Example 14)
The procedures of Examples 10-13 were followed except that no acid was added and only the acid produced by hydrolysis of DMDCS was present. Sufficient (MPTMS) and sufficient dimethyldichlorosilane (DMDCS) were added to give an approximate weight percent for each silica on a dry basis listed in Table 2. The pH of the obtained solution was 1.6.

(Comparative Examples 1-3)
The procedure described for Examples 1-6 was followed. The approximate amount of silane added to the slurry is reported in Table 2 along with the MPTMS / DMDCS weight ratio in weight percentages based on dry silica.

(Comparative Example 4)
Only mercaptopropyltrimethoxysilane was added to obtain an approximate weight percent of MPTMS per silica on a dry basis listed in Table 2, and sufficient concentrated sulfuric acid was added to obtain a pH of about 0.0. Except this, the procedures of Examples 10 to 13 were followed.

(Comparative Example 5)
Except that only dimethyldichlorosilane was added to obtain an approximate weight percent of DMDCS per silica on a dry basis listed in Table 2, and sufficient concentrated sulfuric acid was added to obtain a pH of about 0.4. Followed the procedure of Comparative Example 4.

(Example 15)
The surface areas of the treated and untreated test silica samples of Examples 1-14 and Comparative Examples (CE) 1-5 were measured using a dynamic single point surface area technique, ASTM D3037-93, using a Horiba 6200 series instrument. , Determined by Procedure C (modified version). This procedure, 30% nitrogen in helium was used as adsorbate _gas, simulating Brunauer-Emmett-Teller (BET) method at P / P o = 0.294. The ASTM procedure was modified as follows: a gas mixture of 30% nitrogen in helium was used; a flow rate of about 40 mL / min was maintained; 1 hour at 180 ± 5 ° C. in an analysis cell under nitrogen flow The sample was then dried; and the nitrogen adsorbed on the sample was desorbed by removing the dewar of liquid nitrogen and warming the sample to room temperature without an external heat source. The results for the untreated test silica samples are listed in Table 1, and the results for the treated test silica samples are listed in Table 3.

The percentage of carbon was determined by CHN analysis using a Carlo Erba 1106 model elemental analyzer. A 1 mg to 2 mg sample in a sealed tin capsule was burned in an oxygen-enriched atmosphere with a helium carrier at 1040 ° C., quantitatively burned with Cr ₂ O ₃ , and then the combustion gas was Cu at 650 ° C. Pass over to remove excess oxygen and reduce the oxide of nitrogen to nitrogen. These gases were then passed through a chromatographic column, separated and eluted as N ₂ , CO ₂ , and H ₂ O. The eluted gas was measured by a heat conduction level detector. The instrument was calibrated by burning a standard compound. The results are listed in Table 3.

The percentage of mercapto (SH) listed in Table 3 was accurately weighed to 2-3 g of treated silica in an Erlenmeyer flask to the nearest 0.001 g, 75 ml of isopropyl alcohol was added, and nitrogen was added. Washed off, sealed with a wet stopper and determined by magnetic stirring for 30 minutes. This stirred solution was added to LabChem Inc. Was titrated rapidly to a slightly yellow endpoint using a standard 0.01 N iodine solution commercially available from. Blank titration was also performed by following the same procedure except that no treated silica was added. If a blocked mercaptosilane is used to modify the filler, the blocked mercaptosilane must be deblocked prior to titration. The final value was obtained using the following formula:
% SH = (V1-V2) × N × 3.3 / W
here:
V1 is the volume of iodine solution used with the sample,
V2 is the volume of iodine solution used in the blank,
N is the normality of the iodine solution,
W is the weight of silica in grams.

The silane conversion index reported as SCI in Table 3 was determined by solid state ²⁹ Si NMR. This data was collected at ambient temperature on a Bruker AM-300 NMR using a narrow bore magnet and a Doty 7 mm standard speed MAS probe. The sample was packed in a 7 mm outer diameter zirconia rotor and sealed with a short Kel-F cap. These rotors were rotated at a magic angle at a speed of about 5.0 kHz. Cross-polarization (CP / MAS) data was converted to 90 ° ¹ H pulse, 5600-8400 scans per spectrum, 5 ms contact time, high power proton decoupling during data acquisition, and 3 second relaxation delay. ). The Hartmann-Hahn condition was achieved using kaolinite samples (J. Rocha and J. Klinowski, J. Magn. Reson., 90.567 (1990)). All chemical shifts were referenced to tetramethylsilane (TMS).

All spectra were analyzed using the non-linear curve fitting program (LINESIM) on an Aspect 3000 computer, relative to the peaks of T ¹ (−49 ppm), T ² (−57 ppm), and T ³ (−65 ppm). Area% was determined. Area% values for T ¹ , T ² , and T ³ were determined by curve fitting over the region from −30 ppm to −80 ppm.

  The pH determination was made for the treated fillers of the examples and comparative examples by the following procedure: 5.0 g silica (in powder form) was added to a 150 mL beaker containing a magnetic stir bar; 50 mL isopropanol and 50 mL Of deionized water; and stir vigorously without splashing until the silica is suspended. Place the calibrated pH electrode into the vigorously stirred solution and record the pH reading after 1 minute (± 5 seconds). These results are listed in Table 3.

  The standard strengthening index reported in Table 3 was determined by dividing the tensile stress at 300% elongation by the tensile stress at 100% elongation. Table 4 contains the values of tensile stress at 300% elongation and values of tensile stress at 100% elongation.

  The percentage of Soxhlet extractable carbon in the treated silica of Examples 1, 2 and 7 was 43 mm x 123 mm (inner diameter x outer) with approximately 5 grams of each material placed in a suitably sized Soxhlet extraction tube fitted with a condenser. To the cellulose extraction cylindrical filter paper). The Soxhlet extractor and condenser system was attached to a round bottom flask containing 700 mL of toluene. The flask was heated to the reflux temperature of toluene. After refluxing for a minimum of 19 hours (typically 19-26 hours), the used toluene is replaced with unused toluene and refluxed for a minimum of 19 hours (typically 19-24 hours). Continued. The resulting extracted treated silica was recovered and the sample was dried until it showed a reduction of less than 1.2% by weight when exposed to 160 ° C. for 10 minutes. The percentage of carbon in each sample extracted was determined using the procedure described herein. The percentage of Soxhlet extractable carbon was determined using the following formula: :

これらの結果を表５に列挙する。

These results are listed in Table 5.

（１２）合成沈降シリカであり、３重量％のγ−メルカプトプロピルトリメトキシシランで予め被覆されていると報告されており、ＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ，Ｉｎｃ．から入手可能である。

(12) Synthetic precipitated silica, which has been reported to be pre-coated with 3% by weight γ-mercaptopropyltrimethoxysilane, and is described in PPG Industries, Inc. Is available from

表１の結果は、実施例および比較例を作製するプロセスで使用した未処理のシリカサンプルの表面積が、１７２ｍ^２／ｇ〜２１４ｍ^２／ｇの範囲に及んだことを示す。

The results in Table 1 show that the surface area of the untreated silica samples used in the process of making the Examples and Comparative Examples are ranged from 172m 2 ^/ g~214m 2 ^{/ g.}

  The MPTMS / DMDCS ratio listed in Table 2 for Examples 1-14 ranged from 0.05: 1 to 0.40: 1. The ratios for Comparative Examples 2 and 3 containing both silanes were 0.08: 1 and 0.03: 1, respectively. The MPTMS / DMDCS ratio of Comparative Example (CE) 2 was within the desired range of 0.05: 1 to 10: 1, but the mercapto (SH) listed in Table 3 for CE-2 treated silica. The result for wt% was less than the required amount of more than 0.15 wt%.

The results in Table 3 show that the modified silica samples of the present invention (ie, Examples 1-14) have a standard reinforcement index of at least 4.0, a carbon weight percent greater than 1.0, a mercapto weight percent greater than 0.15, And a silane conversion index of at least 0.3 (ie, T ³ / (T ¹ + T ² + T ³ )). Comparative examples have a carbon weight percent and / or mercapto weight percent below the carbon weight percent and / or mercapto weight percent of Examples 1-14, and a standard strengthening index of less than 4.0 (eg, 3.6) Had.

  The results in Table 4 indicated that all modified silicas of the present invention (ie, Examples 1-14) exhibited a tensile stress at 300% elongation of 6.2 or greater. The tensile stress at 300% elongation for the comparative example was 6.1 or less.

  The results in Table 5 show that the percentage of Soxhlet extractable carbon ranged from as low as 1.82% for Example 7 to as high as 18.33% for Example 2. Yes.

(Example 16: Rubber alcohol release)
The effect of the chemically modified filler of the present invention on the release of alcohol was compared with a rubber composition (compound number 16.1) containing the chemically modified filler of the present invention (filler A), conventional untreated precipitated silica (filler B) Rubber composition comprising (compound number 16.2), rubber composition comprising conventional untreated precipitated silica (filler B) in combination with alkoxysilane 3,3′-bis (triethoxysilylpropyl) tetrasulfide (Compound No. 16.3) was tested by comparing the alcohol release before curing with the subsequent alcohol release.

  The properties of these fillers are listed in Table 6. Surface area, carbon and pH were tested using the representative procedure described in Example 15. The amount of SH was determined using the following procedure. Using an analytical balance, a 2 g ± 0.5 g sample was weighed and recorded by subtracting the tare of the 150 mL Erlenmeyer flask (to the nearest 0.1 mg). Using a stir bar, 75 mL of IPA (using a graduated cylinder) and 10 mL of 0.1 N iodine (using a 10 mL pipette) were added. The flask was flushed with a moderate flow of nitrogen for about 30 seconds and immediately stoppered with a rubber stopper. A small amount of IPA was applied to the tapered portion of the stopper to help create an air tight seal. The flask was placed on a stir plate and stirred moderately for 15 minutes. After 15 minutes of stirring time, remove this rubber stopper and use standardized 0.1N ± 0.0005N sodium thiosulfate to give a colorless end point (no color change for 1 minute) An “A” 10 mL burette was used to titrate immediately. The final volume of 0.1N sodium thiosulfate titration was recorded. By following the above procedure exactly and excluding only the sample, a blank titer value was determined for calculation.

The amount of SH in weight percent was calculated using the following formula:
((Sodium thiosulfate for a blank (mL)-sodium thiosulfate for a sample (mL)) x (N of sodium thiosulfate) x (3.3)) / sample weight (g).

表７に示す列挙した成分、および以後に記載される手順を使用して、ゴム組成物を調製した。列挙した成分についての情報は、標準混合プロトコルに見出され得る。３，３’−ビス（トリエトキシシリルプロピル）テトラスルフィドは、商用名Ｓｉ−６９の下でＤｅｇｕｓｓａ Ｃｏｒｐｏｒａｔｉｏｎから市販されているものを入手したことに留意されたい。

Rubber compositions were prepared using the listed components shown in Table 7 and the procedures described below. Information about the listed components can be found in standard mixing protocols. Note that 3,3′-bis (triethoxysilylpropyl) tetrasulfide was obtained commercially from Degussa Corporation under the trade name Si-69.

（パートＡ）
ゴム１００重量部当たりの重量部（ｐｈｒ）の量で以下の成分を、記載される順に、５００ミリリットル（ｍＬ）プラスチックカップ中に直立させたポリエチレンバッグに加えた。

(Part A)
The following ingredients, in the order of parts by weight per 100 parts by weight of rubber (phr), were added to a polyethylene bag upright in a 500 milliliter (mL) plastic cup in the order listed:

１．８９リットル（Ｌ）Ｆａｒｒｅｌ Ｂのバンバリーミキサー（「ＢＲ」モデル）を、種々の成分を混合するために使用した。バッチ成分をミキサーに加える直前に、８００グラム（ｇ）のＣＶ−６０グレード天然ゴムをミキサーにかけ、ミキサーから先の運転のあらゆる残留物を清掃し、温度を約９３℃（２００°Ｆ）に上昇させた。このゴムを取り出した後、このミキサーを約６５℃（１５０°Ｆ）に冷却し、その後、成分を加えてゴム試験サンプルを得た。

A 1.89 liter (L) Farrel B Banbury mixer ("BR" model) was used to mix the various ingredients. Just prior to adding the batch ingredients to the mixer, 800 grams (g) of CV-60 grade natural rubber is applied to the mixer to clean any residue from the previous run from the mixer and raise the temperature to about 93 ° C (200 ° F). I let you. After removing the rubber, the mixer was cooled to about 65 ° C. (150 ° F.), after which the ingredients were added to obtain rubber test samples.

  The first path was started by adding rubber, ie sSBR and BR, to the mixer and mixing at 116 rpm for 0.5 minutes. The rotor speed was maintained at 116 rpm and an appropriate amount of the specific filler shown in Table 7 was added. 1.5 minutes later, the ram was raised and the chute was swept, that is, the cover on the entrance chute was raised, and any material found in the chute was swept back to the mixer. One minute later, the sample from Part A was added. After another minute, he raised the ram and swept the shot. The mixer contents were mixed for the addition time (dump time) to the maximum temperature (dump temperature) shown in Table 7 to complete the first path in the mixer. The mixer rotor speed was increased or decreased to achieve maximum temperature (dump temperature) within the specified mixing time (dump time).

  After completing the first path, the temperature of this material was determined with a thermoelectric thermometer to ensure that the temperature did not exceed the indicated maximum temperature (dump temperature). The removed material was weighed and formed into sheets at 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch) on a Farrel 12 inch two roll rubber rolling mill. The resulting rolled stock was cut into strips for the second path in the mixer.

  A minimum of 1 hour was allocated between the completion of the first pass in the mixer and the start of the second pass to allow the rolling stock to cool. If necessary, the above cleaning and preheating procedure with CV-60 grade natural rubber was completed before the second path was started. The mixer temperature was adjusted to about 49 ° C. (120 ° F.). While flowing cooling water, the strips of the first path stock were added to a mixer operating at 77 rpm, and Santoflex® 13 ozonolysis inhibitor and Okerin® 7240 microcrystalline wax / paraffin wax. The second route was started by adding to the blend with and to the pre-weighed combination. After 0.5 minutes, a second additive of a combination of RM sulfur, TBBS and DPG was added. 1.5 minutes later, he raised the ram and swept the shot. This second pass was completed by mixing the stock for an additional 2.0 minutes while maintaining the temperature below 125 ° C (257 ° F).

  A Farrel 12 inch two roll rubber mill was heated to about 60 ° C. (140 ° F.). Stock from the second path of Part B was fed to a rolling mill operating with a roll gap setting of 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch). The resulting sheet was placed on a flat surface until the sheet temperature reached room temperature. Typically, the sheet cooled within about 30 minutes. Thereafter, the rolled sheet was supplied to a rubber rolling mill with a roll gap setting of 3.81 mm ± 0.51 mm (0.15 inch ± 0.02 inch). In order to maintain a uniform thickness, the rolling bank was adjusted if necessary. The resulting material was subjected to 16 side cuts and then 8 end passes. The roll gap of the rubber mill was adjusted to produce a sheet thickness of 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch). The sheet stock recovered from the rolling mill was placed on a clean plane. Using a stencil, a rectangular sample of 203.2 mm x 152.4 mm (8 inches x 6 inches) was cut from the sheet stock. This sample (compound A) was conditioned, i.e., the sample was stored between clean polyethylene sheets and maintained at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50% ± 5% for 15-18 hours. A portion of this compound was used in the alcohol release test as described below.

  After conditioning, the sample was placed in a standard mechanical steel compression mold having a polished surface of 203.2 mm × 152.4 mm × 2.286 mm (8 inches × 6 inches × 0.09 inches). This sample was placed in a 61 cm x 61 cm (24 inch x 24 inch) 890 kilonewton (100 ton) 4-post electrothermal compression press according to T90, or ASTM D-2084. Cured at 150 ° C. (302 ° F.) under a pressure of 13.79 megapascals (2000 pounds per cubic inch) for a time of 5 minutes plus 90 minutes to cure. It was. Typically, curing was complete within about 10 minutes. The resulting cured rubber sheet is removed from the mold and, prior to testing, at a temperature of 23 ° C. ± 2 ° C. (73.4 ° F. ± 3.6 ° F.) and a relative humidity of 50% ± 5% for 15 hours-18. Maintained for hours. These sheets (Compound B) were used to generate test specimens for determination of alcohol release, 300% modulus, and 300% / 100% modulus ratio.

  Alcohol release (methanol and ethanol) was determined by analyzing the samples using headspace-GC according to the conditions described in Example 23 herein below. A pre-cure (BC) sample (ie, Compound A) was heated at 150 ° C. for 20 minutes prior to analysis. After curing (AC) samples (ie, Compound B) were heated at 100 ° C. for 60 minutes prior to analysis. The sample size was about 35 mg. Each compound was analyzed in triplicate using a sample taken diagonally across the sample. To account for the difference in sample weight between runs, the peak area was divided by the sample weight. Relative concentrations are based on compound 16.3BC with the maximum amount present.

  The 300% modulus and 300% / 100% modulus ratio were determined according to ASTM D412-98a—Test Method A. Dumbbell test specimens were prepared using Die C. An Instron 4204 model equipped with an automatic contact extensometer to measure elongation was used. The crosshead speed was found to be equal to 508 mm / min. All calculations were performed using Series IX automatic material testing software supplied by the manufacturer. The 300% / 100% modulus ratio is equal to the tensile stress (MPa) at 300% elongation divided by the tensile stress (MPa) at 100% elongation.

  These results are summarized in Table 8. These results show that the compound (16.1) of the present invention is equivalent to the compound (16.2) in which only the silica is added while maintaining the same curing characteristics as the in-situ silane technology (16.3). It shows essentially no alcohol release.

（実施例１７：早期硬化）
この実施例は、本発明によって生成されたコンパウンドが本質的に早期硬化を起こさないことを示している。配合物を表１０に示す。両方の配合物を、下記の手順に従って、バンバリーブレードを備えたブラベンダーミキサーで混合した。それぞれのコンパウンドからの個々のサンプルを、示された試験温度（すなわち、増分１０℃で１２０℃〜１９０℃）を用い、ＭＤＲレオメーター（下記）を使用して評価した。これらの結果を、それぞれ図１および図２にグラフによって示す。示されるように、本発明のプロセスにより生成されるコンパウンド（コンパウンド１７．１、図１）は、早期硬化を起こさない（すなわち、少なくとも１９０℃までのいずれの温度においても、時間経過に伴うトルク顕著な増加を全く示していない）。比較すると、公知の技術を用いて生成されたコンパウンドは、１３０℃〜１４０℃という低い温度にて早期硬化を起こす（コンパウンド１７．２、図２）。

(Example 17: Early curing)
This example shows that the compound produced by the present invention does not inherently undergo premature curing. The formulations are shown in Table 10. Both formulations were mixed in a Brabender mixer equipped with a Banbury blade according to the following procedure. Individual samples from each compound were evaluated using the MDR rheometer (below) using the indicated test temperatures (ie, 120 ° C. to 190 ° C. in 10 ° C. increments). These results are shown graphically in FIGS. 1 and 2, respectively. As shown, the compound produced by the process of the present invention (compound 17.1, FIG. 1) does not undergo premature curing (ie, torque over time at any temperature up to at least 190 ° C.). No significant increase). In comparison, compounds produced using known techniques cause premature curing at temperatures as low as 130 ° C. to 140 ° C. (Compound 17.2, FIG. 2).

(Characteristics of filler)
The filler properties are listed in Table 9. Surface area, carbon, and pH were tested using the respective procedures specified in Example 15. The amount of SH was determined using the procedure described in Example 16.

（混合）
列挙された混合成分についての情報は、標準混合プロトコルに見出され得る。混合成分Ｘ５０−Ｓ（登録商標）は、二官能性の硫黄含有有機シランＳｉ ６９（登録商標）（ビス−（トリエトキシシリルエトキシテトラスルフィド））と、Ｎ３３０型カーボンブラックとの１：１のブレンドであり、Ｄｅｇｕｓｓａから市販のものが入手される。

(mixture)
Information about the listed mixing components can be found in standard mixing protocols. Mixed component X50-S® is a 1: 1 blend of difunctional sulfur-containing organosilane Si 69® (bis- (triethoxysilylethoxytetrasulfide)) and N330 type carbon black. Commercially available from Degussa.

  A rubber composition was prepared using the components shown and listed in Table 10 and the procedures described herein below.

  C. equipped with Banbury blades and oil heated 350-420 ml mixing chamber. W. A Brabender mixer EPL2-5501 type was used to mix the various ingredients. The mixer was warmed between 70 ° C. and 80 ° C. for about 30 minutes.

  The first path was started by adding rubber, ie sSBR and BR, to the mixer and mixing for 0.5 minutes at 85 rpm. The rotor speed was maintained at 85 rpm and the appropriate amount of specific filler was added. One minute later, the ram was raised and an additional amount of specific filler was added, for compound 17.2, 13.0 phr of X-50S. After an additional 1.5 or 2.0 minutes, Part A. 1 or A.1. Samples from 2 were added. The contents of the mixer were mixed for an additional 2.5 or 3.0 minutes to the maximum temperature indicated. During this further mixing time, the ram was periodically raised and swept to ensure that all material was incorporated into the mixture. The mixer rotor speed was increased or decreased to achieve maximum temperature within the specified mixing time.

  After completing this first path, the temperature of the material was determined with a thermoelectric thermometer to ensure that the temperature did not exceed the indicated maximum temperature. The removed material was weighed and formed into sheets at 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch) on a Farrel 12 inch two roll rubber rolling mill. The resulting rolled stock was cooled to room temperature.

（Ａ．１）
ゴム１００重量部当たりの重量部（ｐｈｒ）の量の以下の成分を、記載された順に、５００ミリリットル（ｍＬ）プラスチックカップ中に直立させたポリエチレンバッグに加えた：

(A.1)
The following ingredients in parts per hundred parts by weight rubber (phr) were added, in the order listed, to a polyethylene bag upright in a 500 milliliter (mL) plastic cup:

（Ａ．２）
ゴム１００重量部当たりの重量部（ｐｈｒ）の量の以下の成分を、記載された順に、５００ミリリットル（ｍＬ）プラスチックカップ中に直立させたポリエチレンバッグに加えた：

(A.2)
The following ingredients in parts per hundred parts by weight rubber (phr) were added, in the order listed, to a polyethylene bag upright in a 500 milliliter (mL) plastic cup:

（パートＣ−試験）
硬化プロフィールを、ローターレス硬化計量器を用いるゴム特性（加硫）についての標準試験方法（ＡＳＴＭ名：Ｄ５２８９−９５）に従い、ＭＤＲ２０００（Ｍｏｖｉｎｇ Ｄｉｅ Ｒｈｅｏｍｅｔｅｒ）を使用して決定した。個々のサンプルを、増分１０℃で１２０℃〜１９０℃の温度にて試験した。本発明のコンパウンド（１７．１）についての硬化プロフィールを図１にグラフで示し、比較コンパウンド（１７．２）についての硬化プロフィールを図２に示す。

(Part C-Test)
The cure profile was determined using MDR2000 (Moving Die Rheometer) according to the standard test method for rubber properties (vulcanization) using a rotorless cure meter (ASTM name: D5289-95). Individual samples were tested at temperatures from 120 ° C. to 190 ° C. in increments of 10 ° C. The cure profile for the inventive compound (17.1) is shown graphically in FIG. 1 and the cure profile for the comparative compound (17.2) is shown in FIG.

(Example 18: Dump time / temperature)
The effect of dump time and dump temperature of a rubber composition incorporating the chemically modified filler of the present invention was tested using filler A from Example 16 (Table 6). This filler is described in Example 16 (Table 7, Compound 16.1) except that the dump time and dump temperature used in the first path are the dump time and dump temperature shown in Table 11. Were mixed using the same ingredients and procedures. The rotor temperature was increased or decreased to achieve the dump temperature within the specified dump time.

標準混合プロトコルのパートＣを、コンパウンド１〜８について実施した。これらのシートを使用して、２００％時モジュラス、３００％時モジュラス、２００％／１００％モジュラス比、および３００％／１００％モジュラス比の決定のための試験標本を生成した。

Part C of the standard mixing protocol was performed for compounds 1-8. These sheets were used to generate test specimens for determination of 200% modulus, 300% modulus, 200% / 100% modulus ratio, and 300% / 100% modulus ratio.

  The material was applied to 16 side cuts and then to 8 end passes, and a rebound button was generated by sheeting at 3.81 mm ± 0.13 mm (0.150 inch +/− 0.005 inch). . The resulting sheet was removed from the rolling mill and folded in half to a sheet stock thickness of 7.62 mm ± 0.13 mm (0.300 inch +/− 0.005 inch). Three samples were punched from this sheet stock using a 1 inch punch. These samples were then stacked on top of each other. The total weight of the sample was 12 grams +/- 1 gram. These samples were cured in a 11/8 inch circle x 1/2 inch thick cavity with flat plates on the top and bottom. These samples were cured in a T90 or 90 percent cure in accordance with ASTM D-2084 in an 890 kilonewton (100 ton) four column electrothermal compression press measuring 61 centimeters by 61 centimeters (24 inches by 24 inches). Cured at 150 ° C. (302 ° F.) under a pressure of 13.70 megapascals (2000 pounds per cubic inch) for a period of 10 minutes plus the time it took for Typically, curing was completed within about 15 minutes. The resulting cured rubber sheet is removed from the mold and, prior to testing in Part D, 15 ° C. ± 2 ° C. (73.4 ° F. ± 3.6 ° F.) and 15% relative humidity 50% ± 5%. Maintained for time to 18 hours.

  Mooney scorch (T5) was determined using a Mooney viscometer MV2000 model with a small rotor, following standard test methods (ASTM name: D 1646-98a) for early cure properties of rubber.

  Mooney viscosity ML4100 ° C. was determined using the Mooney Viscosity MV2000 model with a large rotor according to the standard test method (ASTM name: D 1646-98a) for the early cure properties of rubber.

  The scorch time (TS2) is determined using a MDR 2000 (Moving Die Rheometer) according to a standard test method for rubber vulcanization properties (ASTM name: D 5289-95) using a rotorless cure meter. did.

  The 200% modulus, 300% modulus, 200% / 100% modulus ratio, and 300% / 100% modulus ratio were determined according to ASTM D412-98a (Test Method A). The dumbbell test specimen was prepared using Die C. An Instron 4204 model equipped with an automatic contact extensometer to measure elongation was used. The crosshead speed was found to be equal to 508 mm / min. All calculations were performed using Series IX automatic material testing software supplied by the manufacturer. The 200% / 100% modulus ratio is equal to the tensile stress (MPa) at 200% elongation divided by the tensile stress (MPa) at 100% elongation. The 300% / 100% modulus ratio is equal to the tensile stress (MPa) at 300% elongation divided by the tensile stress (MPa) at 100% elongation.

Elastic modulus or memory at 1% strain (G ′, 1% strain) was determined using rheometer kinetic analyzer 2 according to ISO method 2856 elastomer (general requirements for kinetic testing). Cylindrical specimens with a diameter of 11 mm and a weight of 0.86 ± 0.01 g are compression molded and cured between two 25 mm appropriately prepared side-by-side sample plates at 150 ° C. for T90 + 10 minutes. Elastic modulus or memory modulus (G ′) is measured at 1 HZ and 30 ° C. with strain ranging from 0.1% to 20%. The elastic modulus or storage rate at 1% strain (G ′, 1% strain) is calculated from a polynomial fitted to the data (r ² > 0.99).

  Rebound resilience at 23 ° C. and rebound resilience at 100 ° C. are determined using a Zwick 5109 rebound resilience tester according to the standard test method for rubber property resilience using pendulum rebound resilience (ASTM name used: D 1054-91) did.

Tangent δ at 60 ° C. and tangent δ at 0 ° C. were determined using rheometer kinetic analyzer 2 according to ISO method 2856 elastomer (general requirements for kinetic testing). Cylindrical specimens with a diameter of 11 mm and a weight of 0.86 g ± 0.01 g are compression molded and cured between two 25 mm appropriately prepared side-by-side sample plates at 150 ° C. for T90 + 10 minutes. Tangent δ is measured at temperatures ranging from −45 ° C. to 75 ° C. at 1 HZ and 2% strain. The tangent δ at 60 ° C. and the tangent δ at 0 ° C. are calculated from the polynomial fitted to the data (r ² > 0.99).

表１２のデータは、コンパウンドの性能特性に対する一定のダンプ温度におけるダンプ時間の効果を示している。これらの結果は、４分から７分へのダンプ時間の上昇が、１％の歪みにおけるＧ’および６０℃における正接δを低下させる一方で、スコーチ時間、３００％／１００％モジュラス比、および１００℃における反発弾性を増大させることを示している。これらの結果は、本発明の充填材で強化され、一定のダンプ温度にてより長いダンプ（混合）時間で生成されたコンパウンドが、硬化中のスコーチ安全性を改善させ得ること、および硬化したコンパウンドが、タイヤにおいて、改善されたトレッド磨耗およびより低い転がり抵抗を提供し得たことを示している。

The data in Table 12 shows the effect of dump time at a constant dump temperature on the performance characteristics of the compound. These results show that while increasing dump time from 4 to 7 minutes decreases G ′ at 1% strain and tangent δ at 60 ° C., scorch time, 300% / 100% modulus ratio, and 100 ° C. It shows that the rebound resilience is increased. These results show that a compound reinforced with the filler of the present invention and produced with a longer dump (mixing) time at a constant dump temperature can improve scorch safety during curing, and the cured compound Shows that the tire could provide improved tread wear and lower rolling resistance.

  The data in Table 13 shows the effect of dump temperature at a constant dump time on compound performance. These results show that increasing the dump temperature from 130 ° C to 170 ° C increases the scorch time, 300% / 100% modulus ratio, and rebound resilience at 100 ° C. It shows that G ′ at 1% strain and tangent δ at 60 ° C. are reduced. These results show that the compound reinforced with the filler of the present invention and produced at a higher dump temperature at a constant dump time can improve the scorch stability during curing, and the cured compound is It has been shown that it could provide improved tread wear and lower rolling resistance. This improved performance was obtained without loss of productivity because the dump time was the same and remained unchanged.

  The data in Table 14 shows that there can be a combined benefit of increased dump time and dump temperature. Compounds 7 and 8 show scorch time, modulus at 200% elongation and 300% elongation, 200% / 100% modulus ratio and 300% / 100% modulus ratio, and increased resilience at 23 ° C and 100 ° C On the other hand, Mooney viscosity, G ′ at 1% strain, and decrease in tangent δ at 0 ° C. and 60 ° C. are shown. These results show that the compound, reinforced with the filler of the present invention, produced with a combination of higher dump times and higher dump temperatures, has improved processing characteristics that improved scorch stability during curing. This indicates that it can provide improved tread wear with higher static friction and lower rolling resistance in the tire.

(Example 19)
The effect of mixing the chemically modified filler of the present invention with the main vulcanization accelerator was tested using Filler A (Table 6) from Example 16.

  Filler A was mixed using the ingredients and first path procedure described in the standard mixing protocol to produce Part A shown in Table 15. The following procedure and the components listed in Table 15 were used for the second route. C. equipped with Banbury blades and oil heated 350-420 ml mixing chamber. W. A Brabender mixer type EPL2-5501 was used to mix the various ingredients in the second path. The mixer was warmed to 50 ° C. for about 30 minutes. In a second path, a 205.5 phr strip of the first path material is added to a mixer operating at 50 rpm, and the Santoflex® 13 ozonolysis inhibitor and Okerin® 7240 microcrystalline wax. / Started by adding pre-weighed combination with paraffin wax blend. After 0.5 minutes, a combination of the second additive, RM sulfur and vulcanization accelerator, was added. The second route was completed by mixing the ingredients while maintaining the temperature below 125 ° C. (257 ° F.) for an additional 2.0 minutes. After completing the second path, the temperature of this material was determined with a thermoelectric thermometer to ensure that the temperature did not exceed 125 ° C. Cured sheets were produced according to Part C of the standard mixing protocol.

スコーチ時間（ＴＳ２）および硬化時間（ＴＣ９０）を、ＭＤＲ ２０００レオメーターを使用して、ＡＳＴＭ Ｄ ５２８９−９５に従って決定した。モジュラス３００％のさらなる試験を、標準混合プロトコルのパートＤに従って実施した。表１６に報告されるこれらの結果は、サンプル９（ＴＢＢＳおよびＤＰＧ加硫促進剤を使用）が、許容し得るＴＳ２と、ＴＣ９０と、３００％モジュラスとの最良の組み合わせを有したことを示している。

Scorch time (TS2) and cure time (TC90) were determined according to ASTM D 5289-95 using an MDR 2000 rheometer. Further testing with a modulus of 300% was performed according to Part D of the standard mixing protocol. These results reported in Table 16 indicate that Sample 9 (using TBBS and DPG vulcanization accelerator) had the best combination of acceptable TS2, TC90, and 300% modulus. Yes.

（実施例２０）
本発明の化学修飾充填材を種々の加硫促進剤と混合することの影響を試験した。表１７〜１９に示されるように第二経路において加えられる加硫促進剤以外は、実施例１９を繰り返した。

(Example 20)
The effect of mixing the chemically modified filler of the present invention with various vulcanization accelerators was tested. Example 19 was repeated except for the vulcanization accelerator added in the second route as shown in Tables 17-19.

（２０）Ｍｅｔｈｙｌｔｕａｄｓ テトラメチルチウラムジスルフィド、Ｒ．Ｔ．Ｖａｎｄｅｒｂｉｌｔ Ｃｏ．，Ｉｎｃ．から市販されているものを入手
（２１）Ｕｎａｄｓ テトラメチルチウラムモノスルフィド、Ｒ．Ｔ．Ｖａｎｄｅｒｂｉｌｔ Ｃｏ．，Ｉｎｃ．から市販されているものを入手
（２２）ジ−ｏ−トリルグアニジン
（２３）硫黄ドナー ジペンタメチレンチウラムテトラスルフィド、Ｄｏｗ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙから市販されているものを入手
（２４）硫黄ドナー ４，４’−ジチオジモルホリン、Ｒ．Ｔ．Ｖａｎｄｅｒｂｉｌｔ Ｃｏ．，Ｉｎｃ．から市販されているものを入手
（２５）メチルクメート（ｍｅｔｈｙｌ ｃｕｍａｔｅ） ジメチルジチオカルバミン酸銅、Ｒ．Ｔ．Ｖａｎｄｅｒｂｉｌｔ Ｃｏ．，Ｉｎｃ．から市販されているものを入手
（２６）Ｖｕｌｋｏｃｉｔ 亜鉛Ｎ−ジメチルジチオカルバミン酸、Ｌａｎｘｅｓｓから市販されているものを入手
（２７）Ｖｕｌｋｏｃｉｔ ジエチルジチオカルバミン酸亜鉛、Ｌａｎｘｅｓｓから市販されているものを入手
（２８）Ｖｕｌｋｏｃｉｔ Ｎ−ジブチルジチオカルバミン酸亜鉛、Ｌａｎｘｅｓｓから市販されているものを入手
（２９）Ｖｕｌｋｏｃｉｔ エチルフェニルジチオカルバミン酸亜鉛、Ｌａｎｘｅｓｓから市販されているものを入手
（３０）Ｖｕｌｋｏｃｉｔ ジベンジルジチオカルバミン酸亜鉛、Ｌａｎｘｅｓｓから市販されているものを入手
（３１）ジメチルジチオカルバミン酸ビスマス
（３２）ジエチルジチオカルバミン酸カドミウム
（３３）ジエチルジチオカルバミン酸テルル。

(20) Methyltuads tetramethylthiuram disulfide, R.I. T.A. Vanderbilt Co. , Inc. (21) Unads tetramethylthiuram monosulfide, R.I. T.A. Vanderbilt Co. , Inc. (22) Di-o-tolylguanidine (23) Sulfur donor Dipentamethylene thiuram tetrasulfide, commercially available from Dow Chemical Company (24) Sulfur donor 4,4'- Dithiodimorpholine, R.I. T.A. Vanderbilt Co. , Inc. (25) Methyl cumate, copper dimethyldithiocarbamate, R.I. T.A. Vanderbilt Co. , Inc. (26) Vulkocit zinc N-dimethyldithiocarbamic acid, commercially available from Lanxess (27) Vulkocit zinc diethyldithiocarbamate, commercially available from Lanxess (28) Vulkocit N-dibutyldithiocarbamate zinc, commercially available from Lanxess (29) Vulkocit zinc ethylphenyldithiocarbamate, commercially available from Lanxess (30) Vulkocit zinc dibenzyldithiocarbamate, commercially available from Lanxess (31) Bismuth dimethyldithiocarbamate (32) Cadmium diethyldithiocarbamate (33) Tellurium diethyldithiocarbamate.

  Scorch time (TS2), cure time (TC90), and 300% modulus were tested as in Example 19. The results reported in Table 20 show that the preferred combinations of properties are benzothiazole sulfenamide vulcanization accelerator and dithiocarbamate vulcanization accelerator in samples 2, 11, 17-24, 27 and 29-31, respectively. Shows that achieved using.

（実施例２１）
本発明の化学修飾充填材を遅延剤と混合することの影響を試験した。表２１に示されるように第二経路において加えられる遅延剤以外は、実施例１９を繰り返した。

(Example 21)
The effect of mixing the chemically modified filler of the present invention with a retarder was tested. Example 19 was repeated except for the retarder added in the second route as shown in Table 21.

（３４）Ｓａｎｔｏｇａｒｄ ＰＶＩ Ｎ−（シクロヘキシルチオ）フタルイミド、Ｆｌｅｘｓｙｓから市販されているものを入手
（３５）Ｒｅｔａｒｄｅｒ ＡＫ、改良無水フタル酸、Ａｋｒｏｃｈｅｍ Ｃｏｒｐｏｒａｔｉｏｎから市販されているものを入手
（３６）Ｖｕｌｋａｌｅｎｔ Ｅ／Ｃ Ｎ−フェニル−Ｎ−（トリクロロメチルスルホニル）ベンゼンスルホンアミド、Ｌａｎｘｅｓｓから市販されているものを入手。

(34) Santogard PVI N- (cyclohexylthio) phthalimide, commercially available from Flexsys (35) Retarder AK, modified phthalic anhydride, commercially available from Akrochem Corporation (36) Vulkalent E / C N-phenyl-N- (trichloromethylsulfonyl) benzenesulfonamide, commercially available from Lanxess.

  Scorch time (TS2), cure time (TC90), and 300% modulus were tested as in Example 19. The results reported in Table 22 show that the addition of retarder improves scorch time with acceptable cure time and 300% modulus.

（比較例２２）
米国特許第４，００２，５９４号で使用される加硫促進剤との混合を、表２３に示される通りであること以外は実施例１９のプロセスに従うことにより、本発明の加硫促進剤との混合と比較した。

(Comparative Example 22)
By following the process of Example 19 except that the mixing with the vulcanization accelerator used in US Pat. No. 4,002,594 is as shown in Table 23, the vulcanization accelerator of the present invention and Compared with the mixture.

スコーチ時間（ＴＳ２）、硬化時間（ＴＣ９０）、および３００％モジュラスを、実施例１９と同様に試験した。表２４で報告される結果は、米国特許第４，００２，５９４号に記載される硬化剤（比較サンプル１〜９）の特定の組み合せが、本発明で使用される硬化剤（サンプル１０）の実施形態と比較して、所望の硬化反応速度および物理的性質を生まないことを示している。

Scorch time (TS2), cure time (TC90), and 300% modulus were tested as in Example 19. The results reported in Table 24 show that the specific combination of curing agents (Comparative Samples 1-9) described in US Pat. Compared to the embodiment, it does not produce the desired cure kinetics and physical properties.

（実施例２３−充填材アルコール放出）
本発明の化学修飾充填材（充填材Ａ）を、実施例１１において記載される手順に従って調製した。％ＭＰＴＭＳ／ＳｉＯ_２は、５．５０％であり、そして％ＤＭＤＣＳ／ＳｉＯ_２は、１９．６％であった。充填材Ａは、以下の特性を有した：Ｎ_２ １ｐｔ．ＢＥＴ表面積＝１３６ｍ^２／ｇ、ｐＨ＝６．４、炭素＝２．８重量％、およびＳＨ＝０．５３重量％。比較充填材Ｂは、従来の未処理の沈降シリカであった。比較充填材Ｃを、従来の未処理のシリカ粉末とメルカプトプロピルトリメトキシシラン（ＭＰＴＭＳ）とを物理的にブレンドすることによって調製した。％ＭＰＴＭＳ／ＳｉＯ_２は、３．０％であった。比較充填材Ｄを、従来の未処理のシリカ粉末をメルカプトプロピルトリエトキシシラン（ＭＰＴＥＳ）とを物理的にブレンドすることにより調製した。％ＭＰＴＥＳ／ＳｉＯ_２は、６．０％であった。比較充填材Ｅを、従来の未処理のシリカ粉末と３，３’−ビス（トリエトキシシリルプロピル）テトラスルフィド（ＴＥＳＰＴ）とを物理的にブレンドすることにより調製した。％ＴＥＳＰＴ／ＳｉＯ_２は、８．０％であった。各充填材の本質的に等しい分を、以下の条件の下でヘッドスペース−ＧＣ分析を用いて、アルコール放出について分析した：
ヘッドスペースオーブン：１５０℃
バイアル平衡時間：２０分
カラム：３０Ｍ×０．５３ｍｍ ＩＤ ＤＢ−ＷＡＸ（１．０ｍｍフィルム）
温度プログラム：３５℃−５分−１０℃／分−２２０℃−８．５分
注入ポート温度：２００℃。

Example 23-Filler alcohol release
A chemically modified filler of the present invention (Filler A) was prepared according to the procedure described in Example 11. % MPTMS / SiO ₂ was 5.50% and% DMDCS / SiO ₂ was 19.6%. Filler A had the following properties: N _{2 1} pt. BET surface area = 136 m ^{2 /} g, pH = 6.4, carbon = 2.8 wt%, and SH = 0.53 wt%. Comparative filler B was conventional untreated precipitated silica. Comparative filler C was prepared by physically blending conventional untreated silica powder and mercaptopropyltrimethoxysilane (MPTMS). % MPTMS / SiO ₂ was 3.0%. Comparative filler D was prepared by physically blending conventional untreated silica powder with mercaptopropyltriethoxysilane (MPTES). % MPTES / SiO ₂ was 6.0%. Comparative filler E was prepared by physically blending conventional untreated silica powder with 3,3′-bis (triethoxysilylpropyl) tetrasulfide (TESPT). % TESPT / SiO ₂ was 8.0%. An essentially equal portion of each filler was analyzed for alcohol release using headspace-GC analysis under the following conditions:
Headspace oven: 150 ° C
Vial equilibration time: 20 minutes Column: 30M x 0.53mm ID DB-WAX (1.0mm film)
Temperature program: 35 ° C.-5 minutes-10 ° C./minute-220° C.-8.5 minutes Injection port temperature: 200 ° C.

  These results are summarized in Table 25 below.

これらの結果は、本発明のサンプル（充填材Ａ）が、関連するアルコキシシランを沈降シリカとブレンドすることにより、生成された充填材よりもかなり低いアルコール放出を有することを示している。

These results show that the inventive sample (filler A) has a significantly lower alcohol release than the filler produced by blending the relevant alkoxysilane with precipitated silica.

(Examples 24 to 25)
About 40 kilograms (kg) of precipitated silica suspension, about 5.2 kg of silica, and about 11.7 kg of isopropyl alcohol were added to a 30 gallon glass lined container with a bottom drain. The vessel was also equipped with a temperature recorder, mechanical stirrer, heating means and condenser.

  While stirring the contents of the vessel and initiating heating, the Si-69 toughener, referred to herein as TESPT, was weighted to the TESPT per silica on a dry basis for the examples listed in Table 28. It was added over a period of time (typically about 10 minutes) that produced the approximate amounts listed for percent. After completion of the TESPT addition, dimethyldichlorosilane (DMDCS) was added in the same manner to obtain the approximate amount listed in Table 28 for the weight percent DMDCS per silica on a dry basis. The TESPT / DMDCS weight ratio is also listed in Table 28. The resulting solution had a pH of about 0.8.

  After completion of the DMDCS addition, the mixture was heated to about 68 ° C. and left at this temperature for about 10 minutes. While cooling, sufficient toluene (typically 15 kg) was added to the stirred mixture to separate the hydrophobic precipitated silica from the aqueous phase without forming an emulsion. The aqueous phase was drained from this container. The stirred mixture in the vessel containing the hydrophobic precipitated silica is then mixed with about 400 grams for Example 24, about 500 grams of sodium bicarbonate for Example 25, about 30 kg of water for Example 24. Thus, Example 25 was washed twice with about 40 kg of water. The aqueous phase was drained.

  After washing is complete, enough additional toluene (about 13.9 kg for Example 24, about 23.7 kg for Example 25) can be added to the stirred mixture to allow easy drainage from the vessel. A solid suspension in liquid was obtained. The resulting suspension was dried in a rotocone dryer under reduced pressure (at least 23 inches of mercury) at a minimum of 140 ° C. Drying was continued until the sample was exposed to 160 ° C. for 10 minutes and showed a weight percent loss of less than 4.5%.

(Examples 26 to 31)
About 19 kg of precipitated silica suspension, about 1.5 kg of silica, was added to a 40 liter glass container with a bottom drain. The vessel was also equipped with a temperature recorder, mechanical stirrer, heating means and condenser.

  While stirring the contents of the vessel, the surfactants listed in Table 27 were added at about 1 weight percent per silica on a dry basis. After completion of the surfactant addition, the resulting mixture was stirred for 5 minutes. TESPT was added to the stirred mixture over 5 minutes to give about 10 weight percent TESPT per silica on a dry basis. The resulting solution had a pH of about 3.0. After completion of the TESPT addition, dimethyldichlorosilane (DMDCS) was added in the same manner to obtain about 15 weight percent DMDCS per silica on a dry basis. The pH of the resulting solution ranged from about 0.9 to about 1.6. The mixture was heated to about 61 ° C. to about 68 ° C. and held at this temperature typically for about 20 minutes. The suspensions of Example 28 and Example 31 were heated for about 40 minutes and about 16 minutes, respectively. During cooling, sufficient 50% by weight NaOH was added to the mixture over a period of time (typically 10-15 minutes) to adjust the pH to about 7.0. A 20 L stirred mixture containing hydrophobic precipitated silica was drained from the vessel, vacuum filtered using a Buchner funnel, and then washed three times with about 8 kg of water for each wash. After washing was complete, sufficient deionized water and high shear agitation were applied to the filter cake to obtain a flowable solid-in-liquid suspension. The resulting suspension was spray dried with a Niro spray dryer (inlet temperature about 400 ° C. and outlet temperature about 150 ° C.) to form the treated silica samples of Examples 26-31.

(Examples 32-34)
17 L of untreated precipitated silica used in Examples 24-25 containing 820 grams of silica was added to a vessel equipped with a mechanical stirrer. The pH of this slurry before treatment was about 6.5. While the stirrer is mixing this suspension, sufficient TESPT is added and listed for the weight percent of TESPT per silica on a dry basis for Comparative Examples 32-34 listed in Table 28. An approximate amount was obtained. The resulting treated suspension was dried with a Niro spray dryer (suction temperature about 360 ° C. and discharge temperature about 110 ° C.).

(Example 35)
The surface areas of the treated test silica samples of Examples 24-31 and Comparative Examples 32-34 and untreated test silica samples were compared to the Horiba 6200 series according to the dynamic single point surface area technique, ASTM D3037-93, Procedure C (modified). Determined using equipment. This procedure, 30% nitrogen in helium was used as adsorbate _gas, simulating Brunauer-Emmett-Teller (BET) method at P / P o = 0.294. The ASTM procedure was modified as follows: a gas mixture of 30% nitrogen in helium was used; a flow rate of about 40 mL / min was maintained; 1 hour at 180 ± 5 ° C. in an analysis cell under nitrogen flow The sample was then dried; and the nitrogen adsorbed on the sample was desorbed by removing the dewar of liquid nitrogen and allowing the sample to warm to room temperature without an external heat source. The results for the untreated test silica samples are listed in Table 26, and the results for the treated test silica samples are listed in Table 29.

The percentage of carbon was determined by CHN analysis using a Carlo Erba 1106 model elemental analyzer. A 1-2 mg sample in a sealed tin capsule was burned in an oxygen-enriched atmosphere with a helium carrier at 1040 ° C., quantitatively burned with Cr ₂ O ₃ , and then the combustion gas was Cu at 650 ° C. Pass over to remove excess oxygen and reduce the nitrogen oxides to nitrogen. These gases were then passed through a chromatographic column, separated and eluted as N ₂ , CO ₂ , and H ₂ O. The eluted gas was measured by a heat conduction level detector. The instrument was calibrated by burning a standard compound. The results are listed in Table 29.

  The percentage of sulfur was determined by X-ray fluorescence analysis (XRF) using a Rigaku RIX 2000 wavelength dispersive spectrometer. Samples were mixed with a SpectroBlend® binder (Chemplex Industries, Tuckahoe, NY) at a 1: 1 weight ratio, followed by an aluminum support cup at a pressure of 344.75 megapascals (25 tons / square inch). Briquetting inside. NIST and NBS traceable secondary standards (PPG-generated silica, or equivalent) were used for empirical XRF calibration. Detection was performed with a gas proportional flow counter using a germanium crystal monochromator. The results are listed in Table 29.

The silane conversion index reported as SCI in Table 29 was determined by solid state ²⁹ Si NMR. This data was collected at ambient temperature with a Bruker AM-300 NMR using a narrow bore magnet and a Doty 7 mm standard speed MAS probe. The sample was packed in a 7 mm outer diameter zirconia rotor and sealed with a short Kel-F cap. These rotors were rotated at a magic angle at a speed of about 5.0 kHz. Cross polarization (CP / MAS) data using 90 ° ¹ H pulse, 5600-8400 scans per spectrum, 5 ms contact time, high power proton decoupling during data acquisition, and 3 s relaxation delay. Collected. The Hartmann-Hahn condition was achieved using kaolinite samples (J. Rocha and J. Klinowski, J. Magn. Reson., 90.567 (1990)). All chemical shifts were referenced to tetramethylsilane (TMS).

All spectra were analyzed on the Aspect 3000 computer using the non-linear curve fitting program (LINESIM), relative area% for the T ¹ (−49 ppm), T ² (−57 ppm), and T ³ (−65 ppm) peaks. Was analyzed. Area% values for T ¹ , T ² , and T ³ were determined by curve fitting over the region from −30 ppm to −80 ppm.

  The pH determination was performed on the treated silica of the examples and comparative examples by the following procedure: 5.0 g silica (in powder form) was added to a 150 mL beaker containing a magnetic stir bar; 50 mL isopropanol and 50 mL Of deionized water is added; and stirred vigorously without splashing until the silica is suspended. Place the calibrated pH electrode into the vigorously stirred solution and record the pH reading after 1 minute (± 5 seconds). These results are listed in Table 29.

  The percentage of Soxhlet extractable carbon of the treated silica of Example 1 is 43 mm × 123 mm (inner diameter × external length) cellulose in which 5.44 grams of material is placed in a suitably sized Soxhlet extraction tube attached to a condenser. Determined by adding to extraction cylindrical filter paper. The Soxhlet extractor and condenser system was attached 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 refluxing was continued for 22.5 hours. The resulting treated silica was recovered and the sample was dried until it showed a 1.0 wt% reduction when exposed to 160 ° C. for 10 minutes. The percent carbon of the extracted sample was determined using the procedure described herein. The percentage of Soxhlet extractable carbon was determined using the following formula:

。

.

  The percentage of carbon before extraction was 3.50, and the percentage of carbon after extraction was 3.02. Therefore, the percentage of Soxhlet extractable carbon of the treated silica of Example 24 was 13.7.

Alcohol release was determined using headspace-GC analysis under the following conditions:
Headspace oven: 150 ° C
Vial equilibration time: 20 minutes Column: 30M x 0.53mm ID DB-WAX (1.0mm film)
Temperature program: 35 ° C-5 minutes-10 ° C / minute-220 ° C-8.5 minutes Injection port temperature: 200 ° C

（１２）両性界面活性剤、コカミドプロピルアミノベタインをベースにしていると報告される、ＢＡＳＦから入手可能
（１３）非イオン性界面活性剤、エトキシ化シリコーンをベースにしていると報告される、ＢＡＳＦから入手可能
（１４）非イオン性界面活性剤、アルキルクロリドで末端をキャップした酸化エチレンをベースにしていると報告される、ＢＡＳＦから入手可能
（１５）非イオン性界面活性剤、グリコールエーテルをベースにしていると報告される、ＢＡＳＦから入手可能
（１６）非イオン性界面活性剤、ポリオキシエチレン（ｐｏｌｙｏｘｅｔｈｙｌｅｎｅ）ラウリルエーテルをベースにしていると報告される、Ａｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ Ｃｏ．から入手可能
（１７）非イオン性／カチオン性、エトキシ化（５０）ステアリルアミンをベースにしていると報告される、ＡＫＺＯ Ｃｈｅｍｉｃａｌ，Ｉｎｃ．から入手可能。

(12) Reported to be based on the amphoteric surfactant, cocamidopropylaminobetaine, available from BASF (13) Nonionic surfactant, reported to be based on ethoxylated silicone, Available from BASF (14) Nonionic surfactant, reported from BASF, reported to be based on alkyl chloride end-capped ethylene oxide (15) Nonionic surfactant, glycol ether Available from BASF, reported to be based (16) Aldrich Chemical Co., reported to be based on a nonionic surfactant, polyoxyethylene lauryl ether. (17) Non-ionic / cationic, ethoxylated (50) reported to be based on stearylamine, AKZO Chemical, Inc. Available from

ＮＤ^＊は、試験を行わなかったことを示す；
ＳＣＩ^＊＊は、シラン変換指数を表す；
ＳＴＳ＠３００％^＊＊＊は、３００％伸び時の標準引張り応力を表す。

ND ^* indicates that the test was not performed;
SCI ^** represents the silane conversion index;
STS @ 300% ^*** represents standard tensile stress at 300% elongation.

The results in Table 26, untreated silicas used in the process of generating the modified silica of the Examples and Comparative Examples have shown that a surface area ranging from 180m 2 ^/ g~198m 2 ^{/ g} .

  The results in Table 29 show that the treated silica samples of the present invention have a standard tensile stress at 300% elongation of at least 7.0, a carbon weight percent greater than 1.0, a weight percent sulfur greater than 0.1, and 0. It shows a silane conversion index higher than .3.

  Comparative Example 32 had a carbon weight percent lower than required and exhibited an STS at 300% of 3.6. Both Comparative Example 33 and Comparative Example 34 had carbon and sulfur levels within the required range, but both had a 300% STS at less than 7.0. Comparative Example 34 also had a SCI value lower than that required.

  Although the invention has been described with reference to specific details for specific embodiments thereof, such details are considered a limitation on the scope of the invention, except as included in the claims. Not intended to be.

FIG. 1 is a graph of the cure profile for the composition of Example 17. FIG. 2 is a graph of the cure profile for the comparative composition of Example 17.

Claims (36)

  An acidic aqueous suspension of an amorphous or particulate inorganic oxide selected from precipitated silica, colloidal silica or mixtures thereof is optionally added in the presence of a surfactant and / or a water-miscible solvent in a cup. A process of forming an acidic aqueous suspension of a chemically modified filler in contact with a ring agent and recovering the filler to produce a chemically modified filler, the improvement being as the coupling agent, A weight ratio of (a) :( b) of at least 0.05: 1 in an aqueous suspension of an inorganic oxide having a pH of 2.5 or less, (a) a mercapto organometallic compound and (b) non- Using a combination with a sulfurous organometallic compound and treating the acidic aqueous suspension of the chemically modified filler with an acid neutralizer to raise the pH of the suspension to a range of 3.0-10 Process, including .   The process of claim 1, wherein the step of producing an alcohol by-product; the step of recovering the filler and aqueous phase from the suspension; and the substantial release of alcohol from the filler. Further comprising the step of retaining the alcohol by-product in the aqueous phase.   The process of claim 1, wherein the step of producing an alcohol by-product; the step of recovering the filler and aqueous phase from the suspension; and the alcohol released from the filler is less than 4000 ppm. Further comprising the step of retaining the alcohol by-product in the aqueous phase.   The process of claim 2, further comprising the step of mixing the filler with a rubber composition so that there is substantially no release of alcohol from the mixed rubber composition. .   The process of claim 2, further comprising the step of mixing the filler with a rubber composition so that the alcohol release from the mixed rubber composition is less than 4000 ppm. 2. The process of claim 1, wherein the mercapto organometallic compound has the following formula I:

Wherein M is silicon, L is halogen or —OR ⁷ , Q is hydrogen, C ₁ -C ₁₂ alkyl or halo-substituted C ₁ -C ₁₂ alkyl, and R ⁶ is , C ₁ -C ₁₂ alkylene, R ⁷ is C ₁ -C ₁₂ alkyl or alkoxyalkyl containing 2 to 12 carbon atoms, wherein the halogen or (halo) group is chloro, bromo, iodo or Process where fluoro and n is 1, 2 or 3.   7. The process of claim 6, wherein the mercapto group of the mercapto organometallic compound is blocked.   The process of claim 1, wherein the non-sulfur organometallic compound is an alkyl silane. 9. The process of claim 8, wherein the alkyl silane is of formula II, III, IV, and V:

And each R ¹ is independently a hydrocarbon group having 1 to 18 carbon atoms, or R ¹ is selected from the group consisting of compounds represented by: ¹ is an organofunctional hydrocarbon group having 1 to 12 carbon atoms, where the functionality is amino, carboxylic acid, carbinol ester, or amide; each X is independently Selected from the group consisting of halogen, amino, an alkoxy group having 1 to 12 carbon atoms, and an acyloxy group having 1 to 12 carbon atoms, and a is an integer 1, 2 or 3 Each R ² is independently halo, hydroxy, or a hydrocarbon group containing from 1 to 18 carbon atoms, provided that at least 50 mole percent of the R ² substituents are from 1 to 18 Carbon field A hydrocarbon group containing a child, c is an integer from 2 to 10,000; each R ³ is independently a halo, hydroxy, or a hydrocarbon group containing from 1 to 18 carbon atoms D is an integer from 3 to 20; each R ⁴ is independently hydrogen or a hydrocarbon group containing 1 to 18 carbon atoms, k is 1 or 2, and A process wherein the halo or halogen is selected from chloro, fluoro, bromo or iodo.   2. The process according to claim 1, wherein the mercapto organometallic compound is a mercapto organometallic compound and bis (alkoxysilylalkyl) in a weight ratio of at least 1: 1 mercapto organometallic compound: bis (alkoxysilylalkyl) -polysulfide. )-Process substituted by combination with polysulfide. 11. The process according to claim 10, wherein the bis (alkoxysilylalkyl) -polysulfide has the following formula VI:
Z-alk-S _{n ′} -alk-Z VI
Where alk is a divalent hydrocarbon radical having 1 to 18 carbon atoms; n ′ is an integer from 2 to 12 and Z is:

Where R is a C ₁ -C ₄ alkyl or phenyl group, and R ′ is a C ₁ -C ₈ alkoxy, C ₅ -C ₈ cycloalkoxy, or C ₁ -C ₈ alkyl mercapto group. Is the process.   The product of the process of claim 1.   The product of claim 11, wherein the product is a tire. A process for producing a sulfur vulcanized composition comprising:
(I) a step of mixing a curable elastomer and a chemically modified filler without precuring to form a vulcanizable elastomer composition;
(Ii) adding a sulfur-containing curing agent to the vulcanizable elastomer composition; and (iii) curing the vulcanizable elastomer composition, wherein the chemically modified filler comprises An acidic aqueous suspension of an amorphous or particulate inorganic oxide selected from precipitated silica, colloidal silica or mixtures thereof, optionally in the presence of a surfactant and / or a water-miscible solvent, Formed by contacting with a coupling agent to form an acidic aqueous suspension of chemically modified filler, and recovering the filler, wherein the coupling agent is an inorganic oxide having a pH of 2.5 or less. A combination of (a) a mercapto organometallic compound and (b) a non-sulfur organometallic compound in an aqueous suspension in a weight ratio of at least 0.05: 1 (a) :( b); and The Treating the acidic aqueous suspension of chemically modified filler with an acid neutralizer to raise the pH of the suspension to a range of 3.0-10;
process.   15. The process of claim 14, wherein the elastomer is selected from homopolymers of conjugated diene monomers and copolymers and terpolymers of conjugated diene monomers with monovinyl aromatic monomers and trienes. 15. The process of claim 14, wherein the chemically modified filler is:
(I) a carbon content greater than 1 weight percent;
(Ii) a mercapto content greater than 0.15 weight percent;
(Iii) a process having a silane conversion index of at least 0.3; and (iv) a standard enhancement index of at least 4. A process for producing a sulfur vulcanized composition comprising:
(I) mixing together a curable elastomer, a chemically modified filler, a vulcanization accelerator composition, and optionally a retarder composition to produce a vulcanizable elastomer composition; and (ii) Adding a curing agent to the vulcanizable elastomer composition to cure the elastomer, wherein the cured elastomer has a scorch time longer than about 2.5 minutes, a curing time shorter than about 30 minutes, And having a 300% modulus greater than about 6.5 Mpa, wherein the chemically modified filler is an amorphous or particulate inorganic oxide selected from precipitated silica, colloidal silica, or mixtures thereof. The acidic aqueous suspension is contacted with a coupling agent, optionally in the presence of a surfactant and / or a water-miscible solvent, to produce acidic water of the chemically modified filler A coupling suspension is formed by recovering the filler and the coupling agent is at least 0.05: 1 in an aqueous suspension of an inorganic oxide having a pH of 2.5 or less. A combination of (a) a bis (alkoxysilylalkyl) -polysulfide compound and (b) a non-sulfur organometallic compound in a weight ratio of (a) :( b) and the acidic modified filler Treating the aqueous suspension with an acid neutralizing agent to raise the pH of the suspension to a range of 3.0-10,
process.   18. The process of claim 17, wherein the vulcanization accelerator composition is of benzothiazole, benzothiazole sulfenamide, dithiocarbamate, dithiophosphate, thiomorpholine, thiourea, xanthate, thiuram sulfide, and amine. A process comprising at least one of   18. The process of claim 17, wherein the retarder composition comprises N- (cyclohexylthio) -phthalimide, phthalic anhydride, benzoic acid, salicylic acid, stearic acid, N-nitrosodiphenylamine, sodium acetate, aromatic sulfone. A process comprising at least one of an amide, dioctyl phthalate, and magnesium oxide.   18. The process according to claim 17, wherein the elastomer is selected from the group of homopolymers of conjugated diene monomers and copolymers and terpolymers of conjugated diene monomers with monovinyl aromatic monomers and trienes.   An acidic aqueous suspension of an amorphous or particulate inorganic oxide selected from precipitated silica, colloidal silica or mixtures thereof is optionally added in the presence of a surfactant and / or a water-miscible solvent in a cup. A process for producing a chemically modified filler by contact with a ring agent to form an acidic aqueous suspension of the chemically modified filler and recovering the filler, the improvement being as the coupling agent (A) a bis (alkoxysilylalkyl) polysulfide in an aqueous suspension of inorganic oxide having a pH of 2.5 or less and a weight ratio of (a) :( b) of at least 0.05: 1; b) using a combination with a non-sulfur organometallic compound, and treating the acidic aqueous suspension of the chemically modified filler with an acid neutralizer to adjust the pH of the suspension to 3.0-10. Rise to range Including the Rukoto, process.   23. The process of claim 21, wherein the step of producing an alcohol by-product; the step of recovering the filler and aqueous phase from the suspension; and the substantial release of alcohol from the filler. Holding the alcohol by-product in the aqueous phase.   23. The process of claim 21, wherein the step of producing an alcohol byproduct; the step of recovering the filler and aqueous phase from the suspension; and the alcohol released from the filler is less than 4000 ppm. Holding the alcohol by-product in the aqueous phase.   23. The process of claim 22, further comprising the step of mixing the filler with a rubber composition so that substantially no alcohol is released from the mixed rubber composition.   23. The process of claim 22, further comprising the step of mixing the filler with a rubber composition so that the alcohol release from the mixed rubber composition is less than 4000 ppm. The process of claim 21, wherein the bis (alkoxysilylalkyl) polysulfide has the following formula VI:
Z-alk-S _{n ′} -alk-Z VI
Where alk is a divalent hydrocarbon radical having 1 to 18 carbon atoms; n ′ is an integer from 2 to 12 and Z is:

Where R is a C ₁ -C ₄ alkyl or phenyl group, and R ′ is a C ₁ -C ₈ alkoxy, C ₅ -C ₈ cycloalkoxy, or C ₁ -C ₈ alkyl mercapto group. Is the process.   The process of claim 21, wherein the non-sulfur organometallic compound is an alkyl silane. 28. The process of claim 27, wherein the alkyl silane is of Formula II, III, IV, and V:

Or a mixture of said alkylsilane compounds; wherein each R ¹ is independently a hydrocarbon group having 1 to 18 carbon atoms, or R ¹ is an organofunctional hydrocarbon group having 1 to 12 carbon atoms, where the functionality is amino, carboxylic acid, carbinol ester, or amide; each X is independently And a is selected from the group consisting of halogen, amino, an alkoxy group having 1 to 12 carbon atoms, and an acyloxy group having 1 to 12 carbon atoms, and a is an integer 1, 2 or 3 Yes; each R ² is independently halo, hydroxy, or a hydrocarbon group containing from 1 to 18 carbon atoms, provided that at least 50 mole percent of the R ² substituents are from 1 to 18 Carbon fields A hydrocarbon group containing a child, c is an integer from 2 to 10,000; each R ³ is independently a halo, hydroxy, or a hydrocarbon group containing from 1 to 18 carbon atoms D is an integer from 3 to 20; each R ⁴ is independently hydrogen or a hydrocarbon group containing 1 to 18 carbon atoms, k is 1 or 2, and A process wherein the halo or halogen is selected from chloro, fluoro, bromo or iodo.   The process of claim 21, wherein the bis (alkoxysilylalkyl) polysulfide is a bis (alkoxysilylalkyl) polysulfide in a weight ratio of at least 1: 1 bis (alkoxysilylalkyl) polysulfide: mercaptoorganometallic material. A process that has been replaced by a combination with a mercapto organometallic material. 30. The process of claim 29, wherein the mercapto organometallic material is represented by the following formula I:

Wherein M is silicon, L is halogen or —OR ⁷ , Q is hydrogen, C ₁ -C ₁₂ alkyl or halo-substituted C ₁ -C ₁₂ alkyl, and R ⁶ is , C ₁ -C ₁₂ alkylene, R ⁷ is C ₁ -C ₁₂ alkyl or alkoxyalkyl containing 2 to 12 carbon atoms, wherein the halogen or (halo) group is chloro, bromo, iodo Or fluoro, wherein n is 1, 2 or 3.   31. The process of claim 30, wherein the mercapto group of the mercapto organometallic material is blocked.   The product of the process of claim 21.   The product of claim 32, wherein the product is a tire. A process for producing a sulfur vulcanized composition comprising:
(I) mixing together a curable elastomer, a chemically modified filler, a vulcanization accelerator composition, and optionally a retarder composition to produce a vulcanizable elastomer composition; and (ii) Adding a curing agent to the vulcanizable elastomer composition to cure the elastomer, wherein the cured elastomer has a scorch time greater than about 2.5 minutes and a cure time less than about 30 minutes. And having a 300% modulus greater than about 6.5 Mpa, wherein the chemically modified filler is an amorphous or particulate inorganic oxide selected from precipitated silica, colloidal silica, or mixtures thereof Of the chemically modified filler is brought into contact with a coupling agent in the presence of a surfactant and / or a water-miscible solvent, if necessary. Forming an acidic aqueous suspension and recovering the filler, wherein the coupling agent is at least 0.05 in an aqueous suspension of an inorganic oxide having a pH of 2.5 or less: A combination of (a) a bis (alkoxysilylalkyl) -polysulfide compound and (b) a non-sulfur organometallic compound in a weight ratio of 1 (a) :( b), and the chemically modified filler Treating the acidic aqueous suspension with an acid neutralizing agent to raise the pH of the suspension to a range of 3.0-10,
process.   35. The process of claim 34, wherein the retarder composition comprises N- (cyclohexylthio) -phthalimide, phthalic anhydride, benzoic acid, salicylic acid, stearic acid, N-nitrosodiphenylamine, sodium acetate, aromatic sulfone. A process comprising at least one of an amide, dioctyl phthalate, and magnesium oxide.   35. The process of claim 34, wherein the elastomer is selected from the group of homopolymers of conjugated diene monomers and copolymers and terpolymers of conjugated diene monomers with monovinyl aromatic monomers and trienes.

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