TW502054B - Process for producing a chemically treated filler and the chemically treated filler - Google Patents

Abstract

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

Description

502054 A7 _______B7 1、發明説明（1 ~~' ~ 相關申請案的交叉參老警 本申請案係請求在2000年5月10曰所提申之美國臨時 申請案號60/203,428，在1999年12月17日所提申之美國臨時 申請案號60/172,309與在1999年18月19日所提申之美國臨時 申請案號60/149,757的權益。 發明之說明 本發明係有關於製造化學處理填料的方法。更特別的 是，本發明係有關於一種製造具有最低碳及巯基含量、最 低的矽烷轉換指數以及最低標準強力指數之顆粒或不定形 填料的方法。最特別的是，本發明係有關一種製造經疏水 化與官能化之填料的方法，在此所稱之“改質填料，，改進 生成聚合組成物的效率（例如，在橡膠中之複合化）以及該 經聚合化或固化產物（例如，輪胎）之效能。 該生成聚合組成物上，一般係加入強化填料，以改質 該聚合物的物理特性。該填料的表面常被改質以增高該填 料反應性以及在該聚合組成物中二度或三度空間中的偶合 作用。傳統上。在橡膠工業中，是將碳黑以及其它強化填 料加入天然或合成的橡膠中，以增加該經固化之橡膠的硫 化橡膠之物理特性。用來強化該等聚合組成物之填料係包 含天然與合成填料。 使用於橡膠工業中之一種主要非黑色的填料係為不 定形之沈澱矽石。此等含矽填料係用於給予該橡膠之硫化 橡膠改良的張力強度、抗撕裂性與耐磨性。石夕石填料亦用 來與碳黑相結合，以得到在小客車以及非道路用的輪胎（例 本紙張尺度翻巾關家鮮（CNS) A4規格（210X297公釐)^ (請先閲讀背面之注意事项再填寫本頁) •訂· ΓΙί、 502054 A7 —一_---— 67 _ 五、發明説明（2 ) 如，用於挖礦或採木操作或用於道路建設的設備者）具有最 大里魟數。此4應用業已建立的相當好了。當矽石填料使 用作為唯一的強化填料，該等未被分散以及/或偶合於橡膠 内之矽石填料無法提供出該等僅使用碳黑所獲致之整體改 進的功效。此一填料最容易在用於輪胎中之橡膠的硫化橡 膠中，例如，輪胎胎面上，觀察到。 各種偶合劑，例如，鈦酸鹽、鉻酸鹽與矽烷係被建議 當填料係被加入聚合組成物中（例如，橡膠），是與填料一 起使用，俾以改進該橡膠之硫化橡膠的效能。在各種有機 矽烷偶合劑中，建議如此使用者係為巯基烷基三烷氧基矽 烷，例如，酼基丙基三曱氧基矽烷。己被報導出，在經含 矽填料-強化合成橡膠中使用適量該等偶合劑，特別是疏基 丙基二甲氧基矽烷，在幾個重要的物理特性可提供至少相 s於經碳黑-強化合成橡膠的效能，例如，300%模量、張 力強度、耐磨性以及熱累積性。 酼基烷基三烷氧基矽烷之成本、與該純物質相結合之 刺激性臭味以及其等混合至橡膠組成物中所需之時間與能 量，係有害於一般使用含矽填料在高量體積橡膠之應用上 作為主要強化填料。美國專利第4,436,847號揭示矽烷偶合 劑，特別是巯基矽烧偶合劑之效率，其使用烷氧基係烷與 矽烷組合而形成一偶合組成物。在揭示於‘847專利之特定 的貫施例中，該石夕烧偶合組成物在對偶合組成物與含石夕填 料呈惰性之適當非反應性液體中與該含矽填料相配製，以 製得一橡膠複合添加劑，例如，矽石_矽烷濃縮物。 本紙張尺度翻中國國詳（CNS) A4规格（210X297公釐） '—一 · r!· (請先閲讀背面之注意事項再填寫本頁) 訂| 502054 A7 _______ _B7 _ 五、發 一) ^ 〜s -：— 美國專利第5,116,886號揭示一種二步驟方法，其中該 天然、合成、氧化物或矽酸鹽填料的表面，係藉由使用一 些有機矽化合物而被改質。在第一步驟中，該有機矽化合 物在一低於60°C之溫度下被緊密地與填料混合。在第二步 驟中，該均相混合物係經歷一60至16(TC之溫度，以完成嗲 填料表面改質。 美國專利第5,908,660號揭示一種用於製備疏水性矽 石的二步驟方法。在第一步驟中，該經沈澱的水性懸浮液 係在一催化劑之酸存在下，與一有機矽化合物相接觸，以 達成該經沈澱之矽石的疏水化作用。在第二步驟中，該疏 水沈澱矽石的水性懸浮液係與一種與水不可混合的有機溶 劑在溶劑對矽石的重量比大於5:1的比例下相接觸，以達成 源自於該水相之該疏水沈澱矽石的分離。 現今發現，可製得一種改良的填料，例如，顆粒或不 定形無機氧化物，其特徵係在於碳含量大於彳重量百分比、 巯基含量大於0·15重量百分比、矽烷轉換指數（如後所述者） 至少為0.3且標準強化指數（亦如後所述者）係為4或更高。揭 不於美國專利第5,908,660號的方法可以被改進並用來製造 出本發明之改質填料，此係利用在具有2_5或更低ρΗ之無機 氧化物水性懸浮液中，應用官能化劑與疏水化劑之一些組 合，並以一種酸中性劑來處理該改質填料之酸性水性懸浮 液，以增加該懸浮液之pH到一3.0至1〇之範圍内來達成。 在此所使用者，官能化劑係為一可以造成一無機氧化 物係被共價結合至其中所使用之聚合物上的反應性化學 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 、τ Ψ 502054 A7 B7 五、發明説明（ ................ (請先閲讀背面之注意事項再填寫本頁) 品。疏水化劑係為一種化學品，其可結合至無機氧化物以 及’或與無機氧化物相結合，而達一可造成該無機氧化物對 水的親和性的降低同時增高該無機氧化 機聚合物之親和性的程度。 中所使用有 _、tr— 前述之至少4或更高的標準強化指數，係指示在填料一 聚合物組成物成份間的相互反應或結合之改質作用。詳言 之，相較於一般存在於填料與填料之所給予量之相互作 用，在該填料與聚合物以及/或該聚合物與聚合物之間存在 有一更強的相互作用。換言之，較於一般存在於填料與聚 合物以及/或聚合物與聚合物之所給予量之相互作用，在該 填料與填料之間存在有一較弱的相互作用。在橡膠組成物 中此等相互反應的改質被報導出可造成較佳的輪胎效 能，例如，經改進的胎面磨損壽命、較低的轉動抗性、在 雪地上較佳的磨擦力以及較低的噪音生成。除了該等改進 特性，該改質填料具有需要較少的時間與能量來將其加入 聚合組成物中之優點。 本發明的謀細說明 除了非該等操作實施例或另外有指示，所有在表示 里、比例、範圍等數字皆可了解在所有的情況下皆可為 “約” 一字所變化。 本發明之改質填料係可以任何可製造此一填料的方 法來製造，該填料即為一種具有大於彳重量百分比，更佳為 至少1.5重量百分比且最佳係為〇 2重量百分比之碳含量；大 於〇·15重量百分比、更佳是至少為〇 3重量百分比且最佳為502054 A7 _______B7 1. Description of the invention (1 ~~ '~ Cross-referenced veterans in related applications This application is requesting US Provisional Application No. 60 / 203,428 filed on May 10, 2000, in December 1999 Interests in US Provisional Application No. 60 / 172,309 filed on May 17 and US Provisional Application No. 60 / 149,757 filed on August 19, 1999. DESCRIPTION OF THE INVENTION The present invention relates to the manufacture of chemically treated fillers More specifically, the present invention relates to a method for manufacturing granular or amorphous fillers having the lowest carbon and sulfhydryl content, the lowest silane conversion index, and the lowest standard strength index. Most particularly, the present invention relates to A method of making a hydrophobized and functionalized filler, referred to herein as "modified filler, to improve the efficiency of forming a polymeric composition (eg, compounding in rubber) and the polymerized or cured product ( (For example, tires). The resulting polymer composition is generally added with a reinforcing filler to modify the physical properties of the polymer. The surface of the filler is often modified to increase the filler. Material reactivity and coupling in the second or third degree space in the polymer composition. Traditionally, in the rubber industry, carbon black and other reinforcing fillers are added to natural or synthetic rubbers to increase the cured Physical properties of vulcanized rubber of rubber. The fillers used to strengthen these polymeric compositions include natural and synthetic fillers. One of the main non-black fillers used in the rubber industry is amorphous precipitated silica. These silicon-containing The filler is used to give the rubber vulcanized rubber improved tensile strength, tear resistance and abrasion resistance. Shixi stone filler is also used in combination with carbon black to obtain tires for passenger cars and off-roads (examples Paper Size Turning Towel (CNS) A4 Specification (210X297mm) ^ (Please read the notes on the back before filling out this page) • Order · ΓΙί, 502054 A7 — 一 _---— 67 _ V. Invention Explanation (2) For example, those used in mining or timber mining operations or road construction equipment) have the largest mileage. These 4 applications have been established quite well. When silica filler is used as the sole reinforcement It is expected that the silica fillers that are not dispersed and / or coupled to the rubber cannot provide the overall improved efficacy obtained by using only carbon black. This filler is most easily used in vulcanized rubber for rubber in tires. For example, tire treads are observed. Various coupling agents, such as titanate, chromate, and silane systems are suggested when filler systems are added to the polymer composition (for example, rubber), and are used with fillers,改进 In order to improve the performance of the vulcanizate of this rubber. Among various organic silane coupling agents, it is recommended that such users be mercaptoalkyltrialkoxysilanes, for example, propylpropyltrimethoxysilane. It has been reported that The use of appropriate amounts of these coupling agents in silicone-filled-reinforced synthetic rubber, especially sulfopropyldimethoxysilane, can provide at least the same properties as carbon black-reinforced synthetic rubber in several important physical properties. Efficiency, such as 300% modulus, tensile strength, abrasion resistance, and heat buildup. The cost of fluorenylalkyltrialkoxysilane, the irritating odor combined with the pure substance, and the time and energy required to mix it into the rubber composition are harmful to the general use of silicon-containing fillers in high amounts Bulk rubber is used as the main reinforcing filler. U.S. Patent No. 4,436,847 discloses the efficiency of a silane coupling agent, particularly a mercaptosilane coupling agent, which uses a combination of an alkoxy-based alkane and a silane to form a coupling composition. In a specific embodiment disclosed in the '847 patent, the Shiiyaki coupling composition is formulated with the silicon-containing filler in a suitable non-reactive liquid that is inert to the coupling composition and the Shii-containing filler to produce A rubber compound additive is obtained, for example, silica-silane concentrate. The size of this paper is translated into Chinese National Detailed (CNS) A4 specifications (210X297 mm) '—I · r! · (Please read the notes on the back before filling out this page) Order | 502054 A7 _______ _B7 _ V. Send 1) ^ ~ S-:-US Patent No. 5,116,886 discloses a two-step method in which the surface of the natural, synthetic, oxide or silicate filler is modified by using some organic silicon compounds. In the first step, the organosilicon compound is intimately mixed with the filler at a temperature below 60 ° C. In the second step, the homogeneous mixture is subjected to a temperature of 60 to 16 ° C. to complete the surface modification of the rhenium filler. US Patent No. 5,908,660 discloses a two-step method for preparing hydrophobic silica. In one step, the precipitated aqueous suspension is contacted with an organosilicon compound in the presence of a catalyst acid to achieve the hydrophobization of the precipitated silica. In the second step, the hydrophobic precipitate The aqueous suspension of silica is contacted with an organic solvent that is immiscible with water at a solvent to silica weight ratio of more than 5: 1 to achieve the separation of the hydrophobic precipitated silica originating from the aqueous phase. It is now found that an improved filler can be prepared, for example, particulate or amorphous inorganic oxides, which is characterized by a carbon content greater than 彳 by weight, a mercapto content greater than 0.15 by weight, and a silane conversion index (as described later) (Or) is at least 0.3 and the standard strengthening index (also described later) is 4 or higher. The method disclosed in US Patent No. 5,908,660 can be improved and used to make the present invention The modified filler of the Ming Dynasty uses the combination of a functionalizing agent and a hydrophobizing agent in an inorganic oxide aqueous suspension having a pH of 2-5 or lower, and uses an acid neutral agent to treat the modified filler. An acidic aqueous suspension is achieved by increasing the pH of the suspension to a range of 3.0 to 10. For the users here, the functionalizing agent is one that can cause an inorganic oxide to be covalently bound to it. Reactive chemistry on the polymer used This paper is sized according to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page), τ Ψ 502054 A7 B7 V. Description of the invention ( (Please read the notes on the back before filling out this page). Hydrophobizing agent is a chemical that can be combined with inorganic oxides and 'or In combination with inorganic oxides, it can reach a degree that can reduce the affinity of the inorganic oxides for water and increase the affinity of the inorganic oxidizing organic polymers. _, Tr— used in at least 4 or Higher standard strengthening index Modification of the mutual reaction or combination of filler-polymer composition components. In detail, the filler and polymer and / or the There is a stronger interaction between the polymer and the polymer. In other words, there is a relationship between the filler and the filler compared to the amount of interaction typically present between the filler and the polymer and / or the polymer and the polymer. There is a weaker interaction. These interacting modifications in the rubber composition have been reported to result in better tire performance, such as improved tread wear life, lower rotational resistance, on snow Better friction and lower noise generation. In addition to these improved properties, the modified filler has the advantage of requiring less time and energy to add it to the polymeric composition. Detailed description of the present invention Except for such operating examples or other instructions, all numbers in the representation, ratio, range, etc. can be understood to be changed by the word "about" in all cases. The modified filler of the present invention can be manufactured by any method capable of manufacturing such a filler, that is, a filler having a carbon content of more than 彳 by weight, more preferably at least 1.5 by weight, and most preferably 0 by weight; More than 0.15 wt.%, More preferably at least 0. 3 wt.% And most preferably

-7- 502054 A7 ______B7 五、發明説明（5 ) 至少0.5重量百分比之巯基含量；至少為〇 3、更佳是至少 0.4、最佳為至少0.5之矽烷轉換指數；以及，至少為4〇、 更佳為至少4.5且最佳係為5.0之標準強化指數的無機氧化 物。本發明之改質填料具有下列特徵：在3〇〇%延伸度下至 少為6.2、較佳為至少7.〇、更佳為至少75且最隹係為8〇之 張應力。本發明之改質填料可進一步具有下列特徵：具有 20至350 m2/g、較佳為40至300 m2/g且最佳係為彳〇〇至2〇() m2/g之Brunauer-Emmett-TelleqBET)單點表面面積，·在5至 10，較佳係在5.5至9.5，更佳係為6·0至9 〇之卟值且最佳 係為6.5至7.5的pH值，或者該產物的叫落在該等值組合的 範圍内，包含所載述的範圍；以及低於3〇百分比，較佳係 為低於25百分比，更佳係為低於2〇百分比（例如，15百分比） 之索格利（S〇X_可萃取碳百分比。用以決定改質填料前 述特性之方法係揭示於實施例15。 用來製備本發明改質填料之填料係為選自於沈澱矽 石、膠狀矽石或其等混合物之無機氧化物❶此外，該無機 氧化物係為適合使用於各種模製、複合或塗覆方法中之物 質，該等方法包含有射出模製、層合作用、轉移模製、壓 縮膜製、橡膠複合、塗覆（例如浸人、刷上、刮刀塗覆、輥 塗覆專）、鑄造以及其類似方法。 較佳的是，該等用來製造本發明改質料填料之益機氧 化物係為-用來與橡膠複合型式之沈殿石夕石。被認為可使 用於本發明之各種商業上可取得的石夕石包含有得自於㈣ Industries且商品名為theHj-S丨·丨而編號為21〇 243,咖之矽 本紙張尺度適用中國國家標準(CNs):4規格(2歌297公釐) ----—-7- 502054 A7 ______B7 V. Description of the invention (5) Mercapto group content of at least 0.5% by weight; a silane conversion index of at least 0.3, more preferably at least 0.4, and most preferably at least 0.5; and at least 40, more It is preferably an inorganic oxide having a standard strengthening index of at least 4.5 and most preferably 5.0. The modified filler of the present invention has the following characteristics: a tensile stress of 300% elongation of at least 6.2, preferably at least 7.0, more preferably at least 75, and at most 80. The modified filler of the present invention may further have the following characteristics: Brunauer-Emmett- having 20 to 350 m2 / g, preferably 40 to 300 m2 / g, and most preferably 彳 200 to 20 () m2 / g TelleqBET) single point surface area, in the range of 5 to 10, preferably 5.5 to 9.5, more preferably a porosity of 6.0 to 90, and most preferably a pH of 6.5 to 7.5, or Called to fall within the range of such value combinations, including the stated range; and less than 30%, preferably less than 25%, and more preferably less than 20% (for example, 15%) Soxley (SOX_percentage of extractable carbon. The method used to determine the aforementioned characteristics of the modified filler is disclosed in Example 15. The filler used to prepare the modified filler of the present invention is selected from the group consisting of precipitated silica, gum Inorganic oxide of silica-like silica or its mixture. In addition, the inorganic oxide is a substance suitable for use in various molding, compounding or coating methods. These methods include injection molding, lamination, and transfer. Molding, compression film, rubber compounding, coating (such as dipping, brushing, doctor blade coating, roller coating Special), casting and the like. Preferably, the beneficial organic oxides used to make the modified fillers of the present invention are-Shen Dian Shi Xi Shi used for compounding with rubber. It is considered that it can be used in the present invention. The various commercially available Shi Xi Stones invented include those obtained from ㈣ Industries and traded under the trade name theHj-S 丨 · 丨 with the number 21〇243. The size of the silicon paper is applicable to Chinese national standards (CNs): 4 Specifications (2 songs 297 mm) ------

.......... (請先閲讀背面之注意事項再填窝本頁) •訂！： 502054.......... (Please read the notes on the back before filling in this page) • Order! : 502054

發明説明 的 石·，得自於Rh〇ne-Poulenc，且具有例如，編號Z11請血 Z165GR之矽石以及得自於DegussaAG且具有例如，編號， VN2 and VN3之矽石等。 儿’ 用來製造本發明之改質填料的沈澱矽石可利用由矽 酸鹽（例如，矽酸鈉）溶液酸性沈澱而生成。製備該 矽石的方法並不限於本發明所揭示者，且是依所欲之梦石 特性，例如，一特定應用所需之表面面積與顆粒尺寸，而 變化。 使用於製備本發明改質填料之沈澱矽石的bet表面積 一般係落在50 m2/g至1〇〇〇 m2/g之範圍内，且較佳是在1〇〇 m2/g至500 m2/g的範圍内。 用來形成該改質矽石的沈澱矽石係可為在其乾燥步 驟之前的生成階段所呈現之水性懸浮液，例如，在沈激中 形成的漿液或再液化的過濾濾餅。該懸浮液亦可利用將經 乾燥石夕石再分散於水性以及/或有機溶劑中而形成。在該水 性以及/或有機變浮液中之該親水性沈澱矽石，並不重要且 可在約1至to 90重量百分比的範圍内。較佳的是，該親水性 沈殿石夕石的濃度係在1至5〇重量百分比的範圍内，且更佳 是在1至20重量百分比的範圍内。The stone of the invention is obtained from Rhone-Poulenc, and has, for example, the silica of the number Z11 and Z165GR, and the silica of DegussaAG and has, for example, the numbers, VN2 and VN3. The precipitated silica used to make the modified filler of the present invention can be formed by acid precipitation from a silicate (e.g., sodium silicate) solution. The method of preparing the silica is not limited to the one disclosed in the present invention, and it varies depending on the desired characteristics of the dream stone, such as the surface area and particle size required for a particular application. The bet surface area of the precipitated silica used in the preparation of the modified filler of the present invention generally falls within the range of 50 m2 / g to 1,000 m2 / g, and is preferably 100 m2 / g to 500 m2 / g. The precipitated silica series used to form the modified silica may be an aqueous suspension that appears in the formation stage before its drying step, for example, a slurry formed in a sink or a reliquefied filter cake. The suspension may also be formed by redispersing the dried stone spar in an aqueous and / or organic solvent. The hydrophilic precipitated silica in the aqueous and / or organic floatant is not critical and can be in the range of about 1 to 90 weight percent. Preferably, the concentration of the hydrophilic Shen Dian Shi Xi Shi is in the range of 1 to 50 weight percent, and more preferably in the range of 1 to 20 weight percent.

矽烷轉換指數係以公式τ3/(τι+τ2+π)來定義。τ'卩與 Τ3值係利用固態29Sj NMR來決定，且代表經反應之矽烷單 元。矽烷轉換指數提供在鄰近的Si原子之矽烷與其彼此之 間的反應或交聯的程度之指示。較高的指數，在石夕烧、石夕 石表面以及鄰近矽烷之間有較高量的交聯作用。Γ代表石J 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)The silane conversion index is defined by the formula τ3 / (τι + τ2 + π). The values of τ '卩 and Τ3 are determined using solid state 29Sj NMR and represent the reacted silane units. The silane conversion index provides an indication of the degree of reaction or crosslinking between the silanes of adjacent Si atoms and each other. The higher the index, the higher the amount of cross-linking between the stone sinter, the surface of the stone and the adjacent silane. Γ stands for Stone J. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

燒單元在一侧化學結合至石夕石表面或另一個石夕燒上。了2代 表一矽烷單元在其二側化學結合至一在矽石表面上的S|原 子且結合至一鄰近矽烷、二個鄰近矽烷，或者結合至二個 鄰近表面Si原子，即部分交聯結構。T3代表一石夕燒單元在 其三側化學結合至一在矽石表面上的Si原子且二個鄰近石夕 烧，二個Si原子以及一個矽烧，或結合至三個石夕燒單元。 一般相信’與矽烷轉換指數可相比擬且被熟習偶合劑 技藝人士所發展與使用的有機金屬反應轉換指數，可提供 鉻酸鹽以及/或鈦酸鹽（單獨或與矽烷相結合）與無機氧化物 及其本身之反應或交聯之程度的指示。 標準強化指數係使用一標準複合步驟來決定出者。在 此所揭示之標準複合步驟並不包含有加入該橡膠批次中之 自由或未結合的偶合劑。此係為一重要的區別處，蓋因， 其它者近來已被報導出具有大於4之強化指數，即3〇〇百分 比模數/100百分比模數比例。參見美國專利第5 846 311與 5,876,494號。在此二專利中，於橡膠複合期間，加入矽烷 X50-S、矽石/橡膠偶合劑。一般而言，該等偶合劑加入至 橡膠批次中是需要更多的’時間以供複合器來混合。 可被加入改質填料之有機聚合組成物，例如，塑膠以 及/或树知，係基本上包含任何的塑膠以及/或樹脂。被該 界定涵蓋者係為橡膠化合物。該等聚合物係為揭示於 Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1996, Volume 19, PP 881-904中者，其揭示内容列為參考資料 而被併入本案。該改質填料可與聚合物或其可聚合之成份 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公 -10- A7The firing unit is chemically bonded to the surface of Shi Xishi or on the other side. 2 represents that a silane unit is chemically bonded to an S | atom on the surface of silica on its two sides and to a neighboring silane, two neighboring silanes, or two neighboring surface Si atoms, that is, a partially cross-linked structure . T3 stands for a stone yaki unit chemically bonded to one Si atom on the surface of silica and two adjacent yaki cells, two Si atoms, and one silicon yaki unit, or bonded to three stone yaki cells on its three sides. It is generally believed that the organometallic reaction conversion index, which is comparable to the silane conversion index and developed and used by those skilled in coupling agents, can provide chromate and / or titanate (alone or in combination with silane) and inorganic oxidation. An indication of the extent to which the substance and its own reaction or cross-linking. The standard enhancement index uses a standard compound step to determine the winner. The standard compounding steps disclosed herein do not include free or unbound coupling agents added to the rubber batch. This is an important difference. Gein, others have recently been reported to have a strengthening index greater than 4, that is, a 300% modulus / 100% modulus ratio. See U.S. Patent Nos. 5,846,311 and 5,876,494. In these two patents, silane X50-S and silica / rubber coupling agent are added during rubber compounding. Generally speaking, adding these coupling agents to the rubber batch requires more time for the compounder to mix. Organic polymer compositions, such as plastics and / or dendrimers, to which modified fillers can be added, essentially comprise any plastic and / or resin. Those covered by this definition are rubber compounds. These polymers are disclosed in the Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1996, Volume 19, PP 881-904, and their disclosures are incorporated herein by reference. The modified filler can be combined with polymer or its polymerizable ingredients. The paper size is applicable to China National Standard (CNS) A4 (210X297) -10- A7

相捧合’而該聚合物或可聚合之成份的物理形式可為任意 的液體或可複合的形式，例如，溶液、懸浮液、乳膠、分 散液等。含有改質填料之聚合組成物可利用此技術中已知 的方式加以磨碾、混合、模製或固化，以形成一其中每1000 伤聚合物被分散有1〇至150份改質填料之聚合物件。適合的 聚合物’舉例來說，包含有熱塑性與熱固性樹脂、橡膠化 合物以及其它具有彈性體特性之聚合物。 該聚合物可為醇酸樹脂、經油改質之醇酸樹脂、不飽 和聚i旨、天然油脂（例如，亞麻油、桐油、大豆油）、過氧 化物、耐龍、熱塑性聚酯（例如，聚乙烯對苯二甲酸、聚丁 烯對苯二甲酸）、聚碳酸酯，即熱塑性與熱固性聚乙烯、聚 丁烯、聚苯乙烯、聚丙烯、乙烯丙烯共聚物與三聚物、丙 烯酸（丙烯酸、丙烯酸酯、甲代丙烯酸酯、丙烯醯胺、其鹽 類與_化氫鹽等之同聚物與共聚物）、酚樹脂、聚氧乙撐基 (同聚物與共聚物），聚胺基甲酸酯、聚颯、多硫橡膠、硝基 纖維素、丁酸乙烯酯、乙烯類（含有乙烯氯以及或乙酸乙烯 _之聚合物）、乙基纖維素、纖維素乙酸酯以及丁酸酯、黏 液絲、蟲膠、蠟、乙烯共·聚物（例如，乙烯·乙酸乙烯酯共 聚物、乙烯-丙烯酸共聚物、乙烯丙烯酸酯共聚物）、有機 橡膠等。 可使用於聚合組成物中改質填料量係在5至70重量百 分比的範圍内（以該塑膠組成物之總重為準）。例如，使用 於ABS(丙烯腈-丁二烯-苯乙烯）共聚物中之改質填料量係為 30至60重量百分比，用於丙烯腈-苯乙烯-丙烯酸酯共聚物中 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐） ......... (請先閲讀背面之注意事項再填窝本頁) 、^τ— # -11 - 五、發明説明（ — — — — — — — — — — — — — — — — — — — — — I — I I I (請先閲讀背面之注意事項再填寫本頁) 則為5至20重量百分比，用於脂族聚酮則為15至3〇重量百分 比’用於醇酸樹脂（例如，塗料與墨水）中則為3〇至6〇重量百 分比’用於熱塑性烯烴類中則為1〇至3〇重量百分比，用於 %氧樹脂則為5至20重量百分比，用於乙撐基乙酸乙烯酯共 I物為至多60重量百分比、用於乙撐基乙酸乙酯共聚物係 為至多80重量百分比，用於液體結晶聚合物（LCP)係為30至 70重量百分比，用於酚類樹脂係為3〇-6〇重量百分比，且在 聚乙烯中，該量係大於4〇重量百分比。 *可— 更特別的是’有機橡膠是較佳的。該等橡膠的例子包 含有天然橡膠，由丁二烯及其類似物或衍生物同聚化反應 而形成者，例如：順式-1,4-聚異間戊二烯；3,4_聚異間戊二 烯；順式-1,4-聚丁二烯；反式·彳,4_聚丁二烯；彳义聚丁二烯； 以及由丁二烯及其類似物或衍生物與一或多種包含有烯類 不飽和之可共聚化單體共聚化反應而形成者，該等可共聚 化單體例如，本乙稀及其衍生物、乙稀比淀及其衍生物、 丙烯腈、異丁烯與經烧基取代之丙烯酸酯，例如甲基甲代 丙烯酸酯。該等例子包含有由各種苯乙烯與丁二烯百分比 且使用各種所欲之丁二烯異構物所組成之苯乙烯_丁二烯 共聚物橡膠（其後稱為"SBFn;苯乙烯、異戊二烯與丁二烯 聚合物之三聚物以及其等各種異構物；丙烯腈為主之共聚 物與三聚物橡膠組成物；以及以異丁烯為主的橡膠組成 物，或其等混合物，此等係如在美國專利案第4,咖，㈣； 4,616,065 ； 4,748,199 ； 4,866,131 ； 4,894,420 ; 4,925,894 ； 5,〇82,901 以及 5,162,409 中所述者。 12- 五 、發明說明（10 如，其它適當的有機聚合物係為乙烯與其它高I稀烴（例 機平：婦、丁小烯與戊烯以及二烯單體之共聚物。該有 二物係為嵌段、隨機或有順序者且可利用乳化或溶液 方法來製備（例如，s-SBR)。其它可使用的聚合物包含 =等部份地或完全地被官能化者，其包含被偶合化或星 =^化的聚合物。官能化有機橡膠之其它特定例子包含 聚氣戊二烯、氯丁基以及溴丁基橡膠以及經溴化之異丁 烯/、對甲基笨乙烯橡膠。較佳的有機橡膠係為聚丁二 婦、S-SBR及其等混合物。 “較佳的是，該聚合組成物係為一種可固化橡膠。該 盥可固化橡膠一詞係意指天然及其各種粗製與再生形式 與各種合成橡膠。例如，可固化橡膠包含有sbr與丁二晞 橡膠(BR)、SBR、BR以及天然橡膠的組合以及其它先前揭 示作為有機橡膠之物質的組合。在本發明之揭示内容中， 除，非另有指示，否則“橡膠”、“彈性體，，以及橡膠彈性 體”等詞係可互換地使用。“橡膠組成物，，、‘複合橡膠 及“橡膠複合物”是可互換使用的，以指與各種成分與 物質相摻合或混合的橡膠，且該等詞係為熟習該橡膠混合 與橡膠複合技術者所了解。 本發明之改質填料係可使用單獨步驟A或步驟六與8 二者來製備，以供製備出分別揭示於美國專利第5 9〇8 66() 與5,919,298號疏水性矽石與煙霧矽石，該二專利之揭示内 谷以參考資料而被併入本發明，但有下列的改變。所使用 的酸製成該水性懸浮液為2.5或更低之PH，且較佳是2.0或更 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公贊） -13- 502054 A7 ----- -- B7 丨·"丨丨丨丨丨丨丨丨 ...........................................丨…丨 丨丨_丨丨丨丨丨 五、發明説明（11 ) 低之pH，更佳是1.〇或更低之卟，而最佳是〇·5或更低之 ΡΗ ;所使用之改質化學品係為一種巯基有機金屬反應物與 一種不含有機金屬化合物的組合，後者其後係被稱為無硫 之有機金屬，該Μ基有機金屬反應物對該無硫有機金屬化 合物之重量比係至少為〇.〇5:1，較佳為〇〇5:1至1〇:1，更佳 係為〇.1·Ί至5:1 ’最佳係為0·2:1至2:1，例如，〇.5:1至1:1，或 该重量比可在該等數值之任何組合的範圍内，其包含所載 述之數值；且在該化學處理反應完成後，該酸性（其是被加 入或因該鹵化有機金屬化合物水解而原位生成）係被中 和。一般而言，在化學處理反應完全後，所得水性懸浮液 之pH係在3至10之範圍内。該中和劑可為一般任何用來增 加酸性溶液pH的型式，只要改質填料之特性並未受到不利 的影響。適合的中和劑包含氫氧化納、氫氧化鉀、氣氧化 銨以及碳酸氫納。該等改質填料的中和作用亦可利用在喷 霧乾燥期間加入氨來完成。 使用於步驟(A)之酸可為任何型式、有機以及/無機 酸。較佳的酸催化劑係為無機酸。適合酸催化劑的例子包 含鹽酸、氫溪酸、氫蛾酸.、硫酸、硝酸、碟酸以及苯石黃酸。 若有需要，亦可使用一種酸催化劑或二種或多種酸催化劑 之混合物。當有機金屬反應物係為，例如，氣石夕院，時， 該酸催化量可為該石夕院水解或者該氣錢直接與無機氧化 物之經基反應所原位生成的。 在進行步驟（A)之溫度並不重要且_般係在耽至挪 t的範圍内’雖然低-點或高一點的溫度若有需要亦可使 本紙張尺度細巾關家標準（CNS) A4規格（210X297公釐)' ----- -14-The physical form of the polymer or polymerizable component can be any liquid or compoundable form, for example, a solution, a suspension, a latex, a dispersion, and the like. Polymeric compositions containing modified fillers can be milled, mixed, molded, or cured in a manner known in the art to form a polymerization in which 10 to 150 parts of modified fillers are dispersed per 1,000 polymers. object. Suitable polymers' include, for example, thermoplastic and thermosetting resins, rubber compounds, and other polymers having elastomeric properties. The polymer may be an alkyd resin, an oil-modified alkyd resin, unsaturated polyimide, natural oils and fats (eg, linseed oil, tung oil, soybean oil), peroxides, nylon, thermoplastic polyesters (eg , Polyethylene terephthalic acid, polybutylene terephthalic acid), polycarbonate, namely thermoplastic and thermosetting polyethylene, polybutene, polystyrene, polypropylene, ethylene propylene copolymers and terpolymers, acrylic acid ( Homopolymers and copolymers of acrylic acid, acrylates, methacrylic esters, acrylamide, their salts and hydrogen chloride salts, etc.), phenol resins, polyoxyethylene groups (homopolymers and copolymers), polymers Urethane, polyfluorene, polysulfide rubber, nitrocellulose, vinyl butyrate, ethylene (polymer containing vinyl chloride and / or vinyl acetate), ethyl cellulose, cellulose acetate, and Butyrate, viscose, shellac, wax, ethylene copolymers (for example, ethylene · vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene acrylate copolymer), organic rubber, and the like. The amount of the modified filler used in the polymer composition can be in the range of 5 to 70 weight percent (based on the total weight of the plastic composition). For example, the amount of modified filler used in ABS (acrylonitrile-butadiene-styrene) copolymer is 30 to 60% by weight. It is used in acrylonitrile-styrene-acrylate copolymer. National Standard (CNS) Α4 specification (210X297 mm) ......... (Please read the precautions on the back before filling in this page), ^ τ— # -11-V. Description of the invention (— — — — — — — — — — — — — — — — — — — — — I — III (Please read the notes on the back before filling out this page) is 5 to 20% by weight, for aliphatic polyketones 15 to 30 weight percent 'for alkyd resins (for example, coatings and inks), 30 to 60 weight percent' for thermoplastic olefins, 10 to 30 weight percent, for% Oxygen resin is 5 to 20% by weight, up to 60% by weight for ethylene vinyl acetate co-I, and up to 80% by weight for ethylene acetate copolymers, for liquid crystalline polymers (LCP) is 30 to 70% by weight, and for phenol resins is 30. -60% by weight, and in polyethylene, the amount is greater than 40% by weight. * Can — more particularly, 'organic rubber is preferred. Examples of such rubbers include natural rubber, made from butadiene And its analogs or derivatives formed by homopolymerization, such as: cis-1,4-polyisoprene; 3,4_polyisoprene; cis-1,4-poly Butadiene; trans-fluorene, 4-polybutadiene; polyisobutadiene; and butadiene and its analogs or derivatives with one or more copolymerizable monomers containing ethylenic unsaturation The copolymerizable monomers are formed by polymer copolymerization reactions, such as, for example, ethylidene and its derivatives, ethylidene and its derivatives, acrylonitrile, isobutylene, and acrylates substituted with alkyl groups, such as methyl Methacrylic esters. These examples include styrene-butadiene copolymer rubbers (hereinafter referred to as "SBFn; terpolymers of styrene, isoprene, and butadiene polymers and their various isomers; acrylonitrile-based copolymers Polymer and trimer rubber compositions; and isobutene-based rubber compositions, or mixtures thereof, such as in US Patent No. 4, Café, ㈣; 4,616,065; 4,748,199; 4,866,131; 4,894,420; 4,925,894; 5, 〇82,901 and 5,162,409. 12- V. Description of the invention (10 For example, other suitable organic polymers are ethylene and other high-I dilute hydrocarbons (e.g., chlorin, butadiene and pentene, and Copolymers of diene monomers. The dimers are block, random, or ordered and can be prepared using emulsification or solution methods (eg, s-SBR). Other polymers that can be used include polymers that are partially or fully functionalized, including polymers that are coupled or starved. Other specific examples of functional organic rubbers include polyprene, chlorobutyl, and bromobutyl rubbers and brominated isobutylene / p-methylstyrene rubber. Preferred organic rubbers are polybutene, S-SBR and mixtures thereof. "Preferably, the polymeric composition is a curable rubber. The term curable rubber means natural and its various crude and recycled forms and various synthetic rubbers. For example, curable rubber includes sbr and dioxin The combination of rubber (BR), SBR, BR and natural rubber and other previously disclosed substances as organic rubber. In the present disclosure, unless otherwise indicated, "rubber", "elastomer," And rubber elastomers "are used interchangeably." Rubber composition, "" composite rubber and "rubber compound" are used interchangeably to refer to rubbers that are blended or mixed with various ingredients and substances, And these words are understood by those familiar with the rubber mixing and rubber compounding technology. The modified fillers of the present invention can be prepared using separate step A or both steps 6 and 8 for the preparation of hydrophobic silica and fumed silica disclosed in U.S. Pat. Nos. 5,098,66 () and 5,919,298, respectively. The disclosure of these two patents is incorporated into the present invention by reference, but with the following changes. The acid used makes the aqueous suspension to have a pH of 2.5 or lower, and preferably 2.0 or higher. Paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 praise) -13- 502054 A7- -----B7 丨 · " 丨 丨 丨 丨 丨 丨 丨 丨 ............... ......... 丨 丨 丨 丨 _ 丨 丨 丨 丨 丨 V. Description of the invention (11) Low pH, more preferably 1.0 or lower, and the best is 0.5 or lower; the modified chemical used is a combination of a mercapto organometallic reactant and an organometallic-free compound, the latter being referred to as a sulfur-free organometal, the M group The weight ratio of the organometallic reactant to the sulfur-free organometallic compound is at least 0.05: 1, preferably 0.05: 1 to 10: 1, and more preferably 0.1 · Ί to 5: 1 'best is from 0.2: 1 to 2: 1, for example, 0.5: 1 to 1: 1, or the weight ratio may be in the range of any combination of these values, including the stated Value; and after the chemical treatment reaction is completed, the acidity (which is added in situ due to hydrolysis of the halogenated organometallic compound) To) system is neutralized. Generally, after the chemical treatment reaction is completed, the pH of the obtained aqueous suspension is in the range of 3 to 10. The neutralizing agent may be any type generally used to increase the pH of an acidic solution, as long as the properties of the modified filler are not adversely affected. Suitable neutralizing agents include sodium hydroxide, potassium hydroxide, ammonium oxide and sodium bicarbonate. The neutralization of these modified fillers can also be accomplished by adding ammonia during spray drying. The acid used in step (A) may be any type, organic and / or inorganic acid. A preferred acid catalyst is an inorganic acid. Examples of suitable acid catalysts include hydrochloric acid, hydroxidic acid, hydrolysic acid, sulfuric acid, nitric acid, dishic acid, and benzoic acid. If necessary, an acid catalyst or a mixture of two or more acid catalysts may also be used. When the organometallic reactant is, for example, Kishiyoshiin, the acid catalyzed amount may be generated in situ by hydrolysis of the Shiyewon or by direct reaction of the gas with the inorganic oxide. The temperature at which step (A) is carried out is not important and is generally within the range of delay t '. Although the low-point or higher temperature can also make the paper size fine towels close to the standard (CNS) if necessary A4 size (210X297 mm) '----- -14-

(請先閲讀背面之注意事項再填寫本頁〕 ------------ 馨 12 502054 五、發明説明 用。該反應溫度係依所使用的反應物，例如，有機金屬化 合物；酸以及共溶劑（若有使用），而變化。較佳的是，牛 驟（A)係在一落在30°C至150°C之範圍内的溫度下進行，雖然 若有需要，步驟（A)可在步驟（A)中所使用漿液之迴流溫度下 進行。 在前述的反應中，該改質化學品或偶合劑可為取代巯 基有機金屬化合物的官能化劑且為取代無硫有機金屬化合 物之疏水化劑。官能化劑與疏水化劑之組合可使用相同於 載述在Μ基有機金屬化合物對無硫有機金屬化合物之組合 中的重量比。官能化劑可以含有之反應性基團的例子包含 有’但不限於’乙烯基、環氧基、縮水甘油氧基以及(甲代) 丙烯氧基。硫化物、多硫化物以及巯基亦可為該官能化劑， 但規定其不可與在此所揭示之以化學通式⑴與⑺丨)表示的 反應物相結合。而疏水化劑、物質可包含，但不限於，該 等例如天然或合成脂肪與油脂之類的化學品以及具有通式 ⑴）、⑴丨）、（ιν)、（V)之無硫有機金屬化合物以及該等疏水劑 的混合物。 令该無機氧化物之酸性水性懸浮液與一由酼基有機 金屬化合物與無硫有機金屬化合物（較佳為無硫有機矽化 口物）所構成之組合袓接觸的最初步驟，係可進一步包含有 加入水可相溶劑’其量係足以有助於其與無機氧化物之反 應。該溶劑係作為-相轉移劑，加速該疏水硫有機金屬化 口物與無硫有機金屬化合物之組合與疏水性無機氧化物的 相互反應。當使用水可混之有機溶劑，其一般係包含有至 本紙張尺細中國BW(CNS) 再 頁 訂 -15- 502054 A7(Please read the precautions on the back before filling this page] ------------ Xin 12 502054 V. For explanation of the invention. The reaction temperature depends on the reactants used, for example, organometallic compounds. ; Acid and co-solvent (if used), and change. Preferably, the step (A) is performed at a temperature falling in the range of 30 ° C to 150 ° C, although if necessary, the step (A) can be carried out at the reflux temperature of the slurry used in step (A). In the aforementioned reaction, the modified chemical or coupling agent may be a functionalizing agent replacing a mercaptoorganometallic compound and a substituted sulfur-free organic Hydrophobicizing agent for metal compounds. The combination of the functionalizing agent and the hydrophobing agent can be used in the same weight ratio as described in the combination of the M-based organometallic compound and the sulfur-free organometallic compound. The reactive group that the functionalizing agent may contain Examples of the group include 'but not limited to' vinyl, epoxy, glycidyloxy, and (meth) propenyloxy groups. Sulfides, polysulfides, and mercapto groups can also be functionalizers, but it is stipulated that And the chemistry revealed here The reaction was represented by the formula ⑴ and Shu ⑺) combined. The hydrophobizing agent and substance may include, but are not limited to, such chemicals as natural or synthetic fats and oils, and sulfur-free organic metals having the general formulas ⑴), ⑴ 丨), (ιν), (V) Compounds and mixtures of such hydrophobic agents. The initial step of contacting the acidic aqueous suspension of the inorganic oxide with a combination of a fluorene-based organometallic compound and a sulfur-free organometallic compound (preferably a sulfur-free organosilicide) may further include: The water-compatible solvent is added in an amount sufficient to facilitate its reaction with the inorganic oxide. The solvent acts as a phase transfer agent to accelerate the interaction between the combination of the hydrophobic sulfur organometallic compound and the sulfur-free organometallic compound and the hydrophobic inorganic oxide. When using a water-miscible organic solvent, it usually contains up to the paper rule of China BW (CNS). -15- 502054 A7

(請先閲讀背面之注意事項再填寫本頁) •訂丨 • 16 - 502054 A7 ---_ B7 五、發明説明（14 ) ^ '：— 氫硫酸鹽；以及硫酸烷酯，例如，硫酸月桂酯。該表面活 性劑亦包含，例如，具有烯丙基終端_阻礙之聚環氧乙基的 聚矽氧烷聚合物或共聚物。 用以生成本發明改質填料之髄基有機金屬化合物係 為以具有下列通式者來表示： /(Dn HS—Rs—M’ \ Q(3-n) j 其中M係為矽、L係為鹵素或-0R7，Q為氫、a·。2烷基或 經齒基取代之Ci-C12烷基、R6係為Ci-C12烷撐基，R7係為 h-C12烷基或含有2至12個碳原子之烷氧基烷基，該鹵素（齒 基）係為氯、溴、碘或氟，且n係為彳，2或3、Re較佳係為匕·。 烷撐基，例如，甲撐基、乙撐基與丙撐基，R7較佳係為以七々 烷基，更佳係為甲基與乙基，L較佳係為-〇R6，且η較佳係 為3。亦可使用具有二個巯基之酼基有機金屬反應物。 亦可使用其上酼基係被阻礙之巯基有機金屬化合 物’即，酼基氫原子係被另一基團所取。該阻礙之疏基有 機金屬化合物可具有一經·由一單鍵而直接結合至硫上之不 飽和的雜原子或碳原子。特定的阻礙基團之例子包含有硫 代羧基酯、二硫代胺基甲酸酯、硫代磺酸酯、硫代硫酸酯、 硫代磷酸酯、硫代膦酸酯、硫代次膦酸酯等。 當用以偶合填料至聚合物之混合物反應是所欲的，一 去阻礙劑係加入該混合物中，以去除該經阻礙之巯基有機 金屬化合物上的阻礙。若在該混合物中存在有水以及/或 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公贊）(Please read the precautions on the back before filling this page) • Order 丨 • 16-502054 A7 ---_ B7 V. Description of the Invention (14) ^ ': — Hydrogen sulfate; and alkyl sulfate, such as laurel sulfate ester. The surfactant also contains, for example, a polysiloxane polymer or copolymer having an allyl-terminated polyoxyethylene. The fluorene-based organometallic compound used to form the modified filler of the present invention is represented by the following formula: / (Dn HS—Rs—M '\ Q (3-n) j where M is silicon and L Is halogen or -0R7, Q is hydrogen, a..2 alkyl or Ci-C12 alkyl substituted with dentyl, R6 is Ci-C12 alkylene, R7 is h-C12 alkyl or contains 2 to An alkoxyalkyl group of 12 carbon atoms, the halogen (dentate) is chlorine, bromine, iodine or fluorine, and n is fluorene, 2 or 3, and Re is preferably d. Methylene, ethylene, and propylene, R7 is preferably heptadecyl, more preferably methyl and ethyl, L is preferably -0R6, and η is preferably 3 . It is also possible to use a fluorenyl organometallic reactant having two mercapto groups. It is also possible to use a sulfhydryl organometallic compound whose fluorenyl group is blocked, that is, a fluorenyl hydrogen atom system is taken by another group. The phosphine organometallic compound may have an unsaturated hetero atom or a carbon atom which is directly bonded to sulfur via a single bond. Examples of specific blocking groups include thiocarboxylates, dithioaminocarboxylic acids Ester, sulfur Sulfonates, thiosulfates, thiophosphates, thiophosphonates, thiophosphinates, etc. When reacting a mixture of fillers with a polymer is desirable, remove the inhibitor system Add to the mixture to remove the hindrance on the hindered mercaptoorganometallic compound. If water is present in the mixture and / or the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public praise)

. (請先閲讀背面之注意事項再填寫本頁) A7 -—~ ________B7__ 五、發明説明（15 ) "~— ' -- 醇時，可使用一催化劑，例如，三級胺、路易士酸或硫醇， 以利用水解或醇解作用引發並促進該阻礙基團的消失，俾 釋出對應的疏基有機金屬化合物。用以製備與使用該等化 合物之步驟，例如，經阻礙之酼基石夕烧，係揭示於心申 清案W0 99/09036中。其它用以製備經阻礙之疏基石夕烷的步 驟係揭示於美國專利第3>692 812與3 922 436中，該等專利 以參考資料而被併入本發明中。 可使用的鲸基有機金屬化合物的例子係包含，但不限 於疏基甲基三甲氧基石夕烧、酼基乙基三甲氧基石夕燒、疏基 丙基三甲氧基矽烷、巯基甲基三乙氧基矽烷、巯基乙基三 丙氧基矽烷、巯基丙基三乙氧基矽烷、（酼基甲基）二甲基 乙氧基矽烷、（酼基曱基）甲基二乙氧基矽烷、巯基丙基· 曱基二甲氧基矽烷以及其等混合物。最佳的化合物係為酼 基丙基二甲氧基矽烷，巯基丙基三乙氧基矽烷或其等混合 物0 可使用之阻礙之疏基石夕烧的、例子係包含有，但不限 於，2·三乙氧基矽烷基小乙基硫代乙酸酯、3-三甲氧基-矽 烧基-1-丙基硫代辛酸酯、雙三乙氧基矽烷基小丙基卜 甲基二硫代膦酸酯、3-三乙氧基矽烷-1-丙基二甲基硫代次 膦酸酯、3-三乙氧基矽烷-1-丙基甲基硫代硫酸酯、三乙 氧基矽烷-1·丙基甲苯磺酸酯及其等混合物。 可使用來生成本發明之改質填料之無硫有機金屬化 合物可為或一由選自於下列之無硫有機金屬化合物所構成 群中之至少一種無硫有機金屬化合物或混合物·· 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公楚〉 (請先閲讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page) A7 -— ~ ________B7__ V. Description of the Invention (15) " ~ — '-For alcohol, a catalyst can be used, for example, tertiary amine, Lewis acid Or thiol, in order to use hydrolysis or alcoholysis to initiate and promote the disappearance of the hindering group, and release the corresponding sulfo organometallic compound. The steps used to prepare and use these compounds, for example, the obstructed sillstone scuttle, are disclosed in Xinshen Case WO 99/09036. Other steps for the preparation of hindered phosphinoxane are disclosed in U.S. Patent Nos. 3 > 692 812 and 3 922 436, which are incorporated by reference into the present invention. Examples of cetyl organometallic compounds that can be used include, but are not limited to, sulphydrylmethyltrimethoxylite, fluorenylethyltrimethoxysilyl, thiopropyltrimethoxysilane, mercaptomethyltriethyl Oxysilane, mercaptoethyltripropoxysilane, mercaptopropyltriethoxysilane, (fluorenylmethyl) dimethylethoxysilane, (fluorenylmethyl) methyldiethoxysilane, Mercaptopropyl · fluorenyldimethoxysilane and mixtures thereof. The most preferred compounds are fluorenylpropyldimethoxysilane, mercaptopropyltriethoxysilane, or mixtures thereof. Examples of obstructive sulfonyl sintered materials that can be used include, but are not limited to, 2 · Triethoxysilyl small ethylthioacetate, 3-trimethoxy-silyl-1-propylthiocaprylate, bistriethoxysilyl small propylmethyldithio Phosphonates, 3-triethoxysilane-1-propyldimethylthiophosphinate, 3-triethoxysilane-1-propylmethylthiosulfate, triethoxysilane -1 · propyl tosylate and mixtures thereof. The sulfur-free organometallic compound that can be used to form the modified filler of the present invention may be or at least one sulfur-free organometallic compound or mixture selected from the group consisting of the sulfur-free organometallic compounds below. Applicable to China National Standard (CNS) A4 specification (210X297). (Please read the precautions on the back before filling this page)

502054 A7 ____B7__ 五、發明説明（16 ) 具有通式丨丨之有機金屬化合物：502054 A7 ____B7__ 5. Description of the invention (16) Organometallic compounds having the general formula 丨 丨:

RlaMX(4-a) I' 具有通式丨丨丨之有機金屬化合物： R22c+2Sic〇(c-1) "丨 具有通式丨V之有機金屬化合物：RlaMX (4-a) I 'Organometallic compound having the general formula 丨 丨 丨: R22c + 2Sic〇 (c-1) " 丨 Organometallic compound having the general formula 丨 V:

R32dSid〇d IV 以及具有通式V之有機金屬化合物：R32dSidOd IV and organometallic compounds having the general formula V:

(R23Si)kNR4(3-k) V 其中每個Μ各自為矽、鈦或鉻；每個R1係各自為具有1至18 個碳原子之烴基，或R1可為一具有1至12個碳原子之有機官 能基fe基’其中，例如，該官能基係為胺基、鲅酸、甲醇 酯或醯胺類；每個X係各自選自於鹵素、胺基、具有彳Μ 2 個碳原子之烷氧基與具有1-12個碳原子之醯氧基所構成的 群中，a係為1、2或3之整數；每個R2係各自為鹵基、經基 或具有1至18個碳原子之烴基，但規定至少50莫耳百分比之 R2取代基係為具有1至18個碳原子、之烴基，c係為2至iqoqq 之整數，母個R3係各自為_基、經基或具有1至18個碳原子 之烴基，且，d係為3至20之整數；每個R4係各自為氫或具 有1至18個碳原子之烴基，且k係為彳或2;且，該齒素或齒 基係選自於氣、溴、碘或氟。在顯示於通式丨丨、丨u、以與乂 中之取代基的定義中，除非另有相說明，否則同的符號具 有相同的意義。 ；' 在通式II中，每個R1係可為飽和或不飽和單價烴基或 一經取代或未經取代之單價烴基。Ri可為，例如:二二 Ιϊϊλ度適用中國國家標準（CNS) A4規格（210 X 297公楚) ----^~丨一 (請先閲讀背面之注意事項再填寫本頁) •訂— 19- 、發明説明（17 諸如甲基、乙基、丙基、異丙基、異丁基、t-丁基,η· 丁基、 戊基、己基、庚基、辛基、壬基、癸基以及十二烧基；烧 烯基諸如，乙烯基、烯丙基與己烯基；經取代之烷基， 例如，氯甲基、3,3,3.三敦丙基以及6_氯己基；環烷基，諸 如，環已基與環辛基；以及，芳基，諸如，苯基與萘基； W及經取代之燒基，諸如，笨甲基、甲苯基、乙基苯基。 當在通式丨丨中之X係為_素時，其較佳係為氯。當χ係 =氧基時’ X可為’例如，甲氧基、乙氧基與丙氧基。 田係為醯氧基時，X可為，例如，乙醯氧基。更佳的是X 選自於由氣與甲氧基所構成的群中。 前述有機金屬化合物之黏度並是不限制，且可為呈流 體至膠體之黏度範圍内。一般而言，較高分子量的有機金 屬化合物應會為化學改質步驟之酸性條件所裂解，而容許 其等與親水性無機氧化物起反應。 一在通式丨丨丨、IV與V中，各個R2、R3與R4係可與Ri所述之 ^基相同者。為了本發明之目的，#該有機金屬反應物係 為有機矽反應物時，該矽被視為一金屬。 較佳的疋，该無硫有機金屬化合物係以通式丨|，丨丨丨，IV， V來表示或者為該等有機金屬化合物之混合物，其中每個M 係為石夕。更佳的是，該無硫有機金屬係以通式II表示，其 中R1係為c”c6烷基，x係為氣，而3為2。 可使用有機矽的例子包含有，但不限於，選自於下列 的化合物與該等混合物之混合物··二乙基二氯石夕燒、埽丙 基甲基二氯矽烷、甲基苯基二氯矽烷、苯基乙基二乙氧基 (CNS) A4m (210X297^) .........t… (請先閲讀背面之注意事項再填寫本頁) •訂— # 502054 A7 B7 五、發明説明（ (請先閲讀背面之注意事項再填窝本頁) 3Λ3·三_基甲基二氣我、三甲基丁氧基石夕烧 sym-二苯基四甲基二矽氧烷、三乙烯基三甲基·環三矽氧 烧八甲基環四石夕氧燒、六乙基二石夕氧燒、五甲基二氣石夕 烷、二乙烯基二丙氧基矽烷、乙烯基二曱基氣矽烷、乙烯 乙基二氯矽烷、乙烯二甲基甲氧基矽烷、^甲基氯矽烷、 三甲基甲氧基矽烷、三甲基乙氧基矽烷、甲基三氣矽烷、 訂| 甲基三甲氧基㈣、甲基三乙氧基㈣、六f基二石夕氧烧 己烯基甲^氯矽烷、乙烯基二甲基氯矽烷、二甲基氯矽烷、 二甲基二氯矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基 矽烷、六甲基二矽氨烷、三乙烯基三甲基環三矽氨烷、包 含有0至約20個二甲基石夕氧基單元之聚二甲基石夕氧烧以及 經二甲基矽氧基或羥基二甲基矽氧基終端阻礙之聚（二甲 基矽氧烷）聚合物，其在25°C下具有一在1至1000之範圍内 的表觀黏度。 可使用之有機鈦化合物包含，但不限於，四（Ci_Ci8) 烷氧基鈦酸鹽、甲基三乙氧基鈦（iv)、甲基鈦（iv)三異丙化 物、甲基鈦（iv)三丁氧化物、甲基鈦（iv)三+丁氧化物、異 丙基鈦（iv)二丁氧化物、卞基鈦（jv)三乙氧化物、丁基鈦（I" 二丁氧化物、苯基鈦（ίν)三異丙化物、苯基鈦（jv)三丁氧化 物、苯基鈦（iv)三異丁氧基、[T丨(CH2Ph)3(NC5Hl〇)]與 m(CH2(R23Si) kNR4 (3-k) V where each M is each silicon, titanium or chromium; each R1 is a hydrocarbon group having 1 to 18 carbon atoms, or R1 may be a group having 1 to 12 carbon atoms Organic functional group of the 'fe group' wherein, for example, the functional group is an amine group, an acetic acid, a methanol ester, or an amine group; each X series is independently selected from the group consisting of a halogen, an amine group, and 2 carbon atoms. In the group consisting of an alkoxy group and a fluorenyl group having 1 to 12 carbon atoms, a is an integer of 1, 2, or 3; each R2 is a halogen group, a radical, or having 1 to 18 carbons Atomic hydrocarbon groups, but the R2 substituents requiring at least 50 mole percent are hydrocarbon groups having 1 to 18 carbon atoms, c is an integer from 2 to iqoqq, and the parent R3 groups are each A hydrocarbon group of 1 to 18 carbon atoms, and d is an integer of 3 to 20; each R 4 is a hydrogen group or a hydrocarbon group of 1 to 18 carbon atoms, and k is 彳 or 2; and Voxels or dentin are selected from gas, bromine, iodine or fluorine. In the definitions of the substituents shown in the general formulas 丨 丨, 丨 u, and 乂, the same symbols have the same meaning unless otherwise stated. ; 'In Formula II, each R1 may be a saturated or unsaturated monovalent hydrocarbon group or a substituted or unsubstituted monovalent hydrocarbon group. Ri can be, for example: 222 ϊϊ λ degrees are applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 Gongchu) ---- ^ ~ 丨 One (please read the precautions on the back before filling this page) • Order — 19-, description of the invention (17 such as methyl, ethyl, propyl, isopropyl, isobutyl, t-butyl, η-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl And dodecyl groups; alkenyl groups such as vinyl, allyl, and hexenyl; substituted alkyl groups, for example, chloromethyl, 3,3,3. Tripentyl, and 6-chlorohexyl ; Cycloalkyl, such as cyclohexyl and cyclooctyl; and aryl, such as phenyl and naphthyl; and substituted alkyl, such as benzyl, tolyl, ethylphenyl. When X in the general formula is a prime, it is preferably chlorine. When χ is an oxygen group, 'X may be', for example, methoxy group, ethoxy group, and propoxy group. When it is an ethoxy group, X may be, for example, an ethoxy group. More preferably, X is selected from the group consisting of gas and a methoxy group. The viscosity of the aforementioned organometallic compound is not limited, and may be Fluid-to-colloid In general, higher molecular weight organometallic compounds should be cleaved by the acidic conditions of the chemical modification step, allowing them to react with hydrophilic inorganic oxides.-In the general formula 丨 丨 丨 IV In V, each of R2, R3, and R4 may be the same as those described in Ri. For the purpose of the present invention, when the organometallic reactant is an organosilicon reactant, the silicon is regarded as a metal. Preferably, the sulfur-free organometallic compound is represented by the general formula 丨 |, 丨 丨 丨, IV, V or a mixture of such organometallic compounds, where each M is Shi Xi. More preferably The sulfur-free organic metal system is represented by the general formula II, wherein R1 is a c ”c6 alkyl group, x is a gas, and 3 is 2. Examples of usable organic silicon include, but are not limited to, selected from the following Compounds of these compounds and these mixtures ·· Diethyldichlorosulphite, 埽 propylmethyldichlorosilane, methylphenyldichlorosilane, phenylethyldiethoxy (CNS) A4m (210X297 ^) ......... t ... (Please read the notes on the back before filling this page) • Order — # 502054 A 7 B7 V. Description of the invention ((Please read the precautions on the back before filling in this page) 3Λ3 · Tris-methyldigas, trimethylbutoxylithium sym-diphenyltetramethyldisilazine Oxane, trivinyltrimethyl · cyclotrisiloxane, octamethylcyclotetraoxane, hexaethyldioxazine, pentamethyldioxane, divinyldipropoxy Silane, vinyl dihydrazine, ethylene ethyl dichlorosilane, ethylene dimethylmethoxysilane, methylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, methyl Three gas silane, order | methyltrimethoxyfluorene, methyltriethoxyfluorene, hexafyl dioxanylhexenylmethyl ^ chlorosilane, vinyl dimethylchlorosilane, dimethylchlorosilane , Dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexamethyldisilazane, trivinyltrimethylcyclotrisilazine, containing 0 to Polydimethylxanthine fired with about 20 dimethylxanthoxy units and poly (dimethylsiloxane) polymerization hindered by dimethylsiloxy or hydroxydimethylxyloxy termination Having an apparent viscosity in the range of 1 to 1000 at 25 ° C. Organic titanium compounds that can be used include, but are not limited to, tetra (Ci_Ci8) alkoxytitanates, methyltriethoxytitanium (iv), methyltitanium (iv) triisopropylate, methyltitanium (iv ) Tributoxide, methyl titanium (iv) tri + butoxide, isopropyl titanium (iv) dibutoxide, fluorenyl titanium (jv) triethoxide, butyl titanium (I " dibutoxide Compounds, phenyl titanium (ίν) triisopropylate, phenyl titanium (jv) tributoxide, phenyl titanium (iv) triisobutoxy, [T 丨 (CH2Ph) 3 (NC5H10)] and m (CH2

SiMe3)2(NEt2)2]。 可使用之有機鉻化合物包含，但不限於四（Cl-Cl8)烷 氧基鉻酸鹽、苯基鉻（iv)三氯化物、甲基鉻（jv)三氯化物、 乙基鉻（iv)三氯化物、丙基鉻（丨v)三氯化物、甲基鉻（jv)三漠SiMe3) 2 (NEt2) 2]. Organic chromium compounds that can be used include, but are not limited to, tetra (Cl-Cl8) alkoxychromate, phenylchromium (iv) trichloride, methylchromium (jv) trichloride, ethylchromium (iv) Trichloride, propyl chromium (丨 v) trichloride, methyl chromium (jv) three desert

化物乙基鉻（ιν)二溴化物、丙基絡（⑺三演化物、氯三戊 基鉻㈣。與前述有機鈦化合物相似的絡化合物亦是認為可 行的，反之亦然。 用於前述化學改質步驟中之魏基有機金屬化合物與 無硫有機金屬化合物的量，係為一足以生成具有下列特徵 之改質填料的量，該特徵為具有大於1重量百分比之碳含 量、大於0.15重量百分比之巯基含量、至少為〇3之矽烷轉 換和數以及至少4.0之標準強化指數。該等量在此係指偶合 篁，即足以結合至該填料且能夠使改質填料結合至聚合組 成物中之量。 酼基有機金屬矽烷對無硫有機金屬化合物之重量比 係至少0.05:1，較佳係為〇.〇5:1至1〇:1，更佳係為〇彳：彳至^， 且最佳係為0.2:1至2:1，例如，在〇.5:1至1:1中變化，或者該 重量比係落在該等數值之組合的範圍，包含所載述的數 值。各個有機金屬反應物係可一起加入或以任何的次序加 入。較佳的是，該有機金屬反應係以一相對於在該無機氧 化物粒子上之供反應的羥基提供過量的有機金屬單元之量 來加入。加入該方法之有金屬反應物之量的上限並不重 要。過量之酼基有機金屬化合物與無硫有機金屬化合物係 可利用過濾、蒸餾、以溶劑清洗或其它已知的分離技術加 以去除。 在另一個實施例中，該酼基有機金屬反應物可為被一 由巯基有機金屬化合物與一含有硫之不同有機金屬化合物 的組合所取代，該組合之酼基有機金屬化合物對該含有硫 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公釐） 發明説明（20 ) 之不同有機金屬化合物之重量比係為至少大於彳：1 ,例如， 1·01:1。該比例係可在1.01:1至100:1間變化，較佳係在5:1至 5〇:1 ’且最佳係在10:1至30:1之間變化，或該重量比係落在 該等數值任意組合之範圍，包含有該等數值。其可使用在 该含填料之橡膠之硫化反應中作為偶合劑功用之任何含硫 有機金屬化合物（具有通式丨之酼基有機金屬化合物除外）。 可使用之含硫有機金屬化合物的例子包含有揭示於 美國專利第3,873,489與5,580,919號中之雙（烷氧基矽烷基烷 基卜多硫化物（該二專利之揭示内容以參考資料併入本發明 中），其係以具有下列通式VM者為代表：Compounds of ethyl chromium (ιν) dibromide, propyl complexes (three evolutions, chlorotripentylchromium). Complex compounds similar to the aforementioned organic titanium compounds are also considered feasible, and vice versa. Used in the aforementioned chemistry The amount of the Weiji organometallic compound and the sulfur-free organometallic compound in the upgrading step is an amount sufficient to produce a modified filler having the following characteristics, which is a carbon content greater than 1 weight percent and greater than 0.15 weight percent The thiol content, the silane conversion sum of at least 0 3, and the standard strengthening index of at least 4.0. These amounts refer to coupling hydrazones, that is, those that are sufficient to bind to the filler and enable the modified filler to be incorporated into the polymeric composition. The weight ratio of the fluorenyl organometallic silane to the sulfur-free organometallic compound is at least 0.05: 1, preferably 0.05: 1 to 10: 1, and more preferably 〇 :: 彳 to ^, and The optimal range is 0.2: 1 to 2: 1, for example, it varies from 0.5: 1 to 1: 1, or the weight ratio falls within the range of the combination of these values, including the stated values. Each Organometallic reactants can be added together or What is the order of addition. Preferably, the organometallic reaction is added in an amount that provides an excess of organometallic units relative to the hydroxyl groups available for reaction on the inorganic oxide particles. The metal reactant added to the method The upper limit of the amount is not important. Excess fluorenyl organometallic compounds and sulfur-free organometallic compounds can be removed by filtration, distillation, solvent washing or other known separation techniques. In another embodiment, the hydrazone The organometallic reactant may be replaced by a combination of a mercaptoorganometallic compound and a different organometallic compound containing sulfur, and the fluorenyl organometallic compound of the combination applies the Chinese National Standard (CNS) to the sulfur-containing paper size A4 size (210 X 297 mm) Description of the invention (20) The weight ratio of different organometallic compounds is at least greater than 彳: 1, for example, 1 · 01: 1. The ratio can be from 1.01: 1 to 100: 1 The change is preferably between 5: 1 and 50: 1 ', and the best is between 10: 1 and 30: 1, or the weight ratio falls within the range of any combination of these values, including These values can be used for any sulfur-containing organometallic compound (except fluorene-based organometallic compounds having the general formula 丨) that functions as a coupling agent in the vulcanization reaction of the filler-containing rubber. Available sulfur-containing organometallic compounds Examples include bis (alkoxysilyl alkyl polysulfide disclosed in US Patent Nos. 3,873,489 and 5,580,919 (the disclosures of these two patents are incorporated into the present invention by reference), which are provided with the following The general formula VM is represented:

Z-alk-Sn，-alk-Z, VII 其中alk係為具有1至18個碳原子，較佳為具1至6個破原子， 更佳為具有2至3個碳原子之雙價烴基團n，係為2至彳2之整 數，較佳為2至6，且更佳為3至4之整數；而ζ為： R» _Si· 或 —S1—R, \， 其中R係為具有1至4個碳原子之烷基或苯基，且R，係為具 1至8個，較佳為具有1至4個且更佳係為具有彳至2個碳原子 的烷氧基，具有5至8個碳原子之環烷氧基，或一具有彳至丨 個碳原子之直鏈或分支烷巯基。該[^與尺，基團可為相同者」 不同者。該二價alk基團可為直鏈或分支、飽和或不飽和# 脂族烴基或環烴基。揭示於美國專利第5,58〇,919號中之高 純度有機矽烷二硫化物需要在通式丨中8〇百分比之卩，係為2 〜054 A7 ^^ __ 五、發明説明（21 ) 該雙（烧氧基石夕烧基烧基）-多硫化物的例子包含有：雙 (2-三烧氧基石夕烧基乙基）·多硫化物，其中三烧氧基係為= 甲氧基、三乙氧基、三（甲基乙氧基），三丙氧基、三丁氧基， 例如’直至二辛氧基’而该多硫化物係為二、三、四、五 與六硫化物。該對應之雙（3·三烷氧基矽烷基丙基）_、雙（3-二燒氧基石夕烧基異丁基）-、雙（3-三烧氧基石夕烧基丁基卜等， 直型雙（6-三烷氧基矽烷基己基）多硫化物皆可使用。較佳者 係為相當簡早地建構之有機碎烧，其包含雙（3 -三甲氧基_ 二乙氧基-，以及-三丙氧基石夕烧丙基）多硫化物；即，二、 三與四硫化物。 雙（烧氧基碎烧基烧基）·多硫化物之特定例子係揭示 於刖述美國專利第3,873,489號第6攔第5-55行以及美國專利 弟5,580,919號第11欄11-14行。該等化合物之代表性之例子 係為：3,3’-雙（三甲氧基石夕烧基丙基）二硫化物、3,3，-雙（三乙 氧基矽烷基丙基）四硫化物、3,3，-雙（三甲氧基矽烷基丙基） 四硫化物、2,2’-雙（三乙氧基石夕烧、基乙基）四硫化物、3,3_-雙 (三甲氧基矽烷基丙基）三硫化物、3,3，-雙（三乙氧基石夕烷基 丙基）三硫化物、3,3'-雙（三丁氧基石夕烧基丙基）二硫化物、 3,3'-雙（三曱氧基矽烧基丙基）六硫化物以及3,3，·雙（三辛氧 基矽烷基丙基）四硫化物與其等混合物。最佳的化合物係為 3,3’-雙（三乙氧基矽烷基丙基）四硫化物（TESPT)。 TESPT係可以商品名稱Si-69而自Degussa Corp取得。其 被報導係為3,3，-雙（三乙氧基矽烷基丙基）單硫化物、3,3，-雙 (三乙氧基矽烷基丙基）三硫化物、3,3，·雙（三乙氧基矽烷基 本紙張尺度適用中國國家標準（CNS) A4规格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)Z-alk-Sn, -alk-Z, VII where alk is a divalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 6 broken atoms, more preferably 2 to 3 carbon atoms n is an integer from 2 to 彳 2, preferably from 2 to 6, and more preferably from 3 to 4; and ζ is: R »_Si · or —S1—R, \, where R is 1 An alkyl or phenyl group of 4 to 4 carbon atoms, and R is an alkoxy group having 1 to 8, preferably 1 to 4 and more preferably an alkoxy group having 彳 to 2 carbon atoms, having 5 A cycloalkoxy group of up to 8 carbon atoms, or a straight-chain or branched alkylthiol group having 彳 to 碳 carbon atoms. The [^ and ruler, the groups may be the same "different. The divalent alk group may be a linear or branched, saturated or unsaturated # aliphatic or cyclic hydrocarbon group. The high-purity organic silane disulfide disclosed in U.S. Patent No. 5,58〇, 919 needs 80% of the general formula, which is 2 to 054 A7 ^^ __ V. Description of the invention (21) This Examples of bis (oxothiocarbyl) -polysulfides include: bis (2-trioxoyloxanylethyl) · polysulfides, where the trialkyloxy group is methoxy , Triethoxy, tri (methylethoxy), tripropoxy, tributoxy, such as 'up to dioctyloxy' and the polysulfides are di-, tri-, tetra-, penta-, and hexa-sulfide Thing. The corresponding bis (3-trialkoxysilylpropyl) _, bis (3-dialkoxysilylisobutyl)-, bis (3-trialkoxysilylbutyl), etc. Straight bis (6-trialkoxysilylhexyl) polysulfides can be used. The preferred one is the organic calcined, which is constructed relatively early, which contains bis (3-trimethoxy_diethoxy -, And -tripropoxy sulfonyl propyl) polysulfides; that is, di-, tri-, and tetra-sulfides. Specific examples of bis (carboxy alkynyl) -polysulfides are disclosed in 刖The U.S. Patent No. 3,873,489, No. 6 and No. 5, Line 55 and the U.S. Patent No. 5,580,919, No. 11, Column No. 11, and No. 11-14 are mentioned. Representative examples of these compounds are: Alkylpropyl) disulfide, 3,3, -bis (triethoxysilylpropyl) tetrasulfide, 3,3, -bis (trimethoxysilylpropyl) tetrasulfide, 2, 2'-bis (triethoxylithium, ethyl ethyl) tetrasulfide, 3,3_-bis (trimethoxysilylpropyl) trisulfide, 3,3, -bis (triethoxyoxy stone) Alkylpropyl) trisulfide, 3,3 ' -Bis (tributoxylithiumpropyl) disulfide, 3,3'-bis (trimethoxysilylpropyl) hexasulfide and 3,3, · bis (trioctyloxysilane) Propyl) tetrasulfide and its mixtures. The best compound is 3,3'-bis (triethoxysilylpropyl) tetrasulfide (TESPT). TESPT is available under the trade name Si-69. Acquired by Degussa Corp. It is reported to be 3,3, -bis (triethoxysilylpropyl) monosulfide, 3,3, -bis (triethoxysilylpropyl) trisulfide, 3 , 3, · bis (triethoxysilyl) This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

24- 50205424- 502054

發明説明 丙土）、瓜化物、3-雙二乙氧基石夕烧基丙基）四硫化物以及 具有平均3.5之硫化程度之較高硫化物同類物的混合物。 (請先閲讀背面之注意事項再填寫本頁) 在化學改質方法完成後，該經改質無機氧化物之水性 懸净液的pH係自處理之pH 2.5或更低增加至pH 3 〇至1〇 〇。 一般而言，所得之水性懸浮液之卟增加至3或更佳，較佳 疋4或更同，更佳是5或更高，最佳是6或更高，且一般係為 1〇更低、車交佳係為9或更低、更佳係為8或更低且最佳係為7 或更低忒水性懸浮液之PH係可在上述量之任何組合範圍 内’包含該等所載述之量。此係被進行以中和所加入或生 成的I性，生成一具有5_〇至1〇〇之卟的最終產物（在乾燥 後）。 •訂丨 忒經改質之無機氧化物係利用過濾與乾燥來回收或 令該改質無機氧化物水性懸浮液係與一水不可相混的有機 溶劑在溶劑對無機氧化物重量比係為大於彳比彳（較佳係大 於5比1)下相接觸而回收。在溶劑相中回收之改質無機氧化 物係可使用，而無庸進一步的處理或乾燥。本發明一種的 可能實施例係為一種組成物，其包含有一配置在與水不相 混之溶劑中之改質填料的漿液。在該漿液中該改填料的濃 度以該漿液的總重為準係在彳至卯重量百分比的範圍内。 可使用之與水不相混之溶劑的例子包含有低分子量 矽氧烷、諸如，六甲基二矽氧烷、六甲基環四矽氧烷以及 三甲基矽氧烷基終端阻礙之聚二甲基矽氧烷流體。當使用 矽氧烷作為溶劑時。其可作為溶劑以及有無機氧化物之反 應物二者。此外，可使用之與水不相混之溶劑包含有芳族DESCRIPTION OF THE INVENTION A mixture of propionite), melons, 3-bisdiethoxylithium propyl) tetrasulfide, and higher sulfide congeners with an average degree of vulcanization of 3.5. (Please read the notes on the back before filling this page) After the chemical modification method is completed, the pH of the aqueous suspension of the modified inorganic oxide is increased from the treated pH 2.5 or lower to pH 3 to 100%. Generally speaking, the porosity of the obtained aqueous suspension is increased to 3 or better, preferably 疋 4 or more, more preferably 5 or higher, most preferably 6 or higher, and generally 10 or lower. , Che Jiao Jia is 9 or lower, more preferably 8 or lower and the best is 7 or lower. The pH of the aqueous suspension can be included in any combination of the above amounts. Mentioned amount. This line is carried out to neutralize the added or generated I nature, resulting in a final product (after drying) with a porphyry of 5 to 100. • Ordered 忒 忒 The modified inorganic oxide system is recovered by filtration and drying or the modified inorganic oxide aqueous suspension system and mono-water immiscible organic solvent in the solvent to inorganic oxide weight ratio is greater than彳 ratio 彳 (preferably greater than 5 to 1) is recovered by contact. Modified inorganic oxides recovered in the solvent phase can be used without further processing or drying. A possible embodiment of the present invention is a composition comprising a slurry of a modified filler disposed in a solvent immiscible with water. The concentration of the modified filler in the slurry is in the range of 彳 to 彳 by weight based on the total weight of the slurry. Examples of water-immiscible solvents that can be used include low-molecular-weight siloxanes, such as hexamethyldisilazane, hexamethylcyclotetrasiloxane, and trimethylsilyl-terminated barrier polymers. Dimethicone fluid. When using siloxane as solvent. It can be used both as a solvent and as a reactant with an inorganic oxide. In addition, solvents that are immiscible with water include aromatics.

-25- A7 〜 ------ B7___ 五、發明説明（23 ) ~ L，諸如甲苯與二甲苯，以及其它脂族烴類溶劑；環烷類， 諸如’環己烷；醚類，例如，***、二丁；函化烴類，諸 如一氣曱烷、氣像、二氣乙烷以及氣苯；以及酮類，諸如， 甲基異丁酮。 用來接觸一疏水顆粒無機氧化物水性懸浮液之與水 不可相混的有機溶劑，亦可含有或不含有溶解於其中一或 多種物質（若有需要）。該等質物之例子包含有，但不限於， 一或多種橡膠、油脂、偶合劑、抗氧化劑以及加速劑。 本發明之改質填料（呈粉末、顆粒、丸塊、漿液、水 f生懸浮液或溶劑懸浮液）可與主要物質，即使用於該欲製造 產物中之物質，相結合，以形成在此所稱之“批次母料” 之混合物。在該批次母料中，該改質填料係可以高於最終 產物之濃度存在者。在混合操作期間，一般該混合物之等 刀试料係被加入該製造大小的量，以有助於十分少量之該 等添加劑被均勻地分散於至該聚合組成物中，例如，塑膠、 橡膠與塗層組成物中。 改質之填料係可與乳化以及/或溶液聚合物，例如， 含有溶液笨乙苯/丁二烯（SBR)、聚丁二烯橡膠或其等混合 物，相結合，以形成一批次母料。一個可行之實施態樣係 為一種批次母料，其包含有機橡膠、與水不可相混之溶劑、 改夤填料以及任擇地含有的加工油。如此的生成可由橡勝 製造者至輪船製造者所供應。使用如批次母料對輪胎製造 者之益處係在於該改質填料係可均勻地分散於該橡膠中， 其可使得用以產生經複合之橡膠所需的混合時間被降至最 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐〉 (請先閱讀背面之注意事項再填寫本頁) 訂丨 502054-25- A7 ~ ------ B7___ V. Description of the invention (23) ~ L, such as toluene and xylene, and other aliphatic hydrocarbon solvents; naphthenes, such as' cyclohexane; ethers, for example Diethyl ether, dibutyl; functional hydrocarbons, such as monotrimethane, gas, diethane, and benzene; and ketones, such as methyl isobutyl ketone. Water-immiscible organic solvents used to contact an aqueous suspension of hydrophobic particulate inorganic oxides may or may not contain one or more of these substances, if required. Examples of such materials include, but are not limited to, one or more rubbers, greases, coupling agents, antioxidants, and accelerators. The modified filler of the present invention (in the form of powder, granules, pellets, slurry, aqueous suspension or solvent suspension) can be combined with the main substance, even the substance used in the product to be manufactured, to form here A mixture of so-called "batch master batches". In this batch of masterbatch, the modified filler may be present at a higher concentration than the final product. During the mixing operation, generally, a knife sample of the mixture is added in an amount of the manufacturing size to help a very small amount of the additives be uniformly dispersed in the polymer composition, such as plastic, rubber and In a coating composition. Modified fillers can be combined with emulsified and / or solution polymers, for example, containing solution styrene / butadiene (SBR), polybutadiene rubber, or mixtures thereof to form a batch of master batch . One possible implementation is a batch masterbatch that contains organic rubber, a water-immiscible solvent, modified fillers, and optionally contained processing oils. Such a production can be supplied from the manufacturer of the oak to the manufacturer of the ship. The benefit to tire manufacturers using batch master batches is that the modified filler is evenly dispersed in the rubber, which can reduce the mixing time required to produce a compounded rubber to the minimum paper size. Applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order 丨 502054

發明説明 低。該批次母料每伽份橡膠可包含有1Q至⑽份的填料， #^i^20^l3〇phr^^^30^l〇〇phr,xt^^5〇^8〇phr〇 .......•… (請先閲讀背面之注意事項再填寫本頁) 在本發明另一可行的實施例中，其具有-種聚合物 件，其中每1。。份聚合物分散有，。至15〇份的填料，：佳每 ⑽f刀聚合物是20至13G份，更佳是3〇至⑽份，最佳是別至 8〇份。或者’ I亥改質_之量係落在該等數值之任何組合 之範圍内，包含該等載述之範圍。如在此所述者，該聚合 物可選自於由熱塑性樹脂、熱固性樹脂以及有機橡膠所構 成的群中。較佳的是，該聚合物係為一種可固化有機橡膠。 主要被認為與本發明之改質填料一起使用的可固化 橡膠係為熟習橡膠化學之技術者所熟知者，且包含有可硫 訂丨 化與硫可固化橡膠。特別是，該等被認為一般供機械橡膠 產品用者。 本發明之改質填料係可與一種用來以傳統構件製造 可硫化之橡膠組成物的未固化橡膠彈性體相混合，該組成 物係利用傳統構件，例如，Banbur^l合器或在橡膠磨碾器 上。而在100°F與300°F之間（38°C-150°C)下製得。可硫化之 橡膠組成物，以1〇〇份可硫化橡膠聚合物為準，包含有忉 至150伤的改質填料，較佳是2〇至13〇 phr，更佳是3〇至1 〇〇 phr，且最佳是50至8〇ph卜存在之其它傳統橡膠添加劑係為 傳統之硫或過氧化物固化系統。 該硫固化系統包含有0.5至3份硫、2至5份氧化鋅以及 0.5至2份加速劑。該過氧化物-固化系統可包含有1至4份之 過氧化物，例如二枯基過氧化物。其亦可使用其它傳統的Description of the invention Low. This batch of master batch can contain 1Q to ⑽ parts of filler, # ^ i ^ 20 ^ l3〇phr ^^^ 30 ^ l00〇phr, xt ^^ 5〇 ^ 8〇phr .. ..... • ... (Please read the notes on the back before filling out this page) In another feasible embodiment of the present invention, it has a polymer piece, each of which is 1. . Parts of polymer are dispersed. Filler to 150 parts, preferably 20 to 13 G parts per polymer, more preferably 30 to 8 parts, and most preferably 80 parts. Alternatively, the amount of the 'IH modified quality' falls within the range of any combination of these values, including the stated range. As described herein, the polymer may be selected from the group consisting of a thermoplastic resin, a thermosetting resin, and an organic rubber. Preferably, the polymer is a curable organic rubber. The curable rubbers which are mainly considered to be used with the modified fillers of the present invention are well known to those skilled in rubber chemistry and include sulfur curable and sulfur curable rubbers. In particular, these are considered to be generally used for mechanical rubber products. The modified filler system of the present invention can be mixed with an uncured rubber elastomer used to make a vulcanizable rubber composition from a conventional component, which uses a conventional component such as a Banbur ^ l combiner or a rubber mill. On the mill. It is made between 100 ° F and 300 ° F (38 ° C-150 ° C). The vulcanizable rubber composition is based on 100 parts of a vulcanizable rubber polymer, and contains a modified filler having 忉 to 150 wounds, preferably 20 to 130 phr, and more preferably 30 to 100 phr. The other traditional rubber additives, which are preferably 50 to 80 ph, are traditional sulfur or peroxide curing systems. The sulfur curing system contains 0.5 to 3 parts of sulfur, 2 to 5 parts of zinc oxide, and 0.5 to 2 parts of an accelerator. The peroxide-curing system may contain 1 to 4 parts of peroxide, such as dicumyl peroxide. It can also use other traditional

502054 A7 __— B7___ 五、發明説明（25 ) 橡膠添加劑。該等添加劑包有諸如炭黑之其它填料、油脂、 塑化劑、加速劑、抗氧化物、熱安定劑、光安定劑、臭氧 安定劑、諸如硬脂酸、苯甲酸或水揚酸之類的有機酸、其 它活化劑、增充劑以及呈色色素。最終的複合配方係隨著 所製備之硫化橡膠而變化，但該等配方係為熟習橡膠複合 技術者所熟知者。 该可硫化橡膠組成物係利用在橡膠工業上所熟知之 傳統步驟而被硫化或固化成一硫化橡膠。可使用本發明填 料來生成之工業上硫化橡膠（物件）之例子包含有電線與纜 線外套、軟管、墊圈與密封件、工業與自動驅動帶、引擎 安裝件、V-帶、輸送帶、滾筒塗層、輪胎以及輪胎組件， 例如，汽車輪胎胎面、次胎面（subtreads)、胎殼、輪胎侧壁、 輪始胎帶楔形物、胎唇填料與胎去渣面層⑴re wireskim coat)、鞋底物質、包裝環、傾倒元件與許多其它元件。 本發明係特別地揭示於以下討論之標準複合步驟、實 施例與比較實施例中，其等係僅用來例示說明本發明，因 為記多的修飾與變化對熟習該項技術者係為顯然的。 標準複合步驄 標準複合步驟係用來製備出含有實施例與比較例（ce) 之矽石所配製出橡膠組成物的測試樣品。502054 A7 __— B7___ V. Description of the invention (25) Rubber additives. These additives include other fillers such as carbon black, greases, plasticizers, accelerators, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, such as stearic acid, benzoic acid or salicylic acid. Organic acids, other activators, extenders and pigments. The final compound formula varies with the vulcanizate produced, but these formulas are well known to those skilled in rubber compound technology. The vulcanizable rubber composition is vulcanized or cured into a vulcanized rubber using conventional procedures well known in the rubber industry. Examples of industrially vulcanized rubber (objects) that can be produced using the filler of the present invention include wires and cable jackets, hoses, gaskets and seals, industrial and automatic drive belts, engine mounts, V-belts, conveyor belts, rollers Coatings, tires, and tire components, such as automotive tire treads, subtreads, tire casings, tire sidewalls, wheel starter wedges, bead fillers, and tire degreasing layers (re wireskim coat), Sole material, packing rings, pouring elements and many other elements. The present invention is specifically disclosed in the standard compound steps, examples, and comparative examples discussed below, which are only used to illustrate the present invention, because many modifications and changes are obvious to those skilled in the art. . Standard compounding step The standard compounding step is used to prepare a test sample of a rubber composition prepared from the silica of the examples and comparative examples (ce).

部分A 以對每百分橡膠重量_之量所示下列成份係以所 述的次序加入被直立在500毫升（mL)塑膠杯中之聚乙烯袋 内： ^ 本紙張尺度適用中國國家標準A4規格（210\297公|) 丨 — — — — — — — — — — — — — — 丨 — II 丨 — I — I I I » 鳴 (請先閲讀背面之注意事項再填寫本頁) 、一1T— 眷 -28- 502054 發明説明（ ⑴ 物質 加工油⑴ 氧化鋅⑺ 抗氧化劑(3) 硬脂酸⑷ 矽石樣品 Sundex@8125芳香族烴 類加工油 量(Dhr)30.0 2.52.0 1.0 12.5 商業上得自於SunThe following ingredients are shown in part A in terms of the weight of rubber per hundred. The following ingredients are added in the stated order to a polyethylene bag standing upright in a 500 ml (mL) plastic cup: ^ This paper size applies to China National Standard A4 (210 \ 297 公 |) 丨 — — — — — — — — — — — — — 丨 II 丨 — I — III »Ming (please read the notes on the back before filling this page), 1T— -28- 502054 Description of the invention (⑴ Substance processing oil ⑺ Zinc oxide ⑺ Antioxidant (3) Stearic acid ⑷ Silica sample Sundex @ 8125 Aromatic hydrocarbon processing oil (Dhr) 30.0 2.52.0 1.0 12.5 Commercially available from Sun

Company, lnc_粗煉與銷售部門。 Kadox@表面處理之氧化辞，其係商業上得自於ZincCorporation of America。w_ay”。。抗臭氧劑，其係為二芳基p苯撐基二胺 之此a物，商業上得自於The Goodyear Tire & Rubber Co.橡膠級硬脂酸，商業上得自於C p Ha|| 部分B 1 ·89升（L)Faire丨Banbury混合器（“BR”型）係用於混合各 種成份。再將該批料成分加入該混合物之前，馬上將8〇〇 克（g) of cv-60級天橡膠提經該混合器以清除掉任何前次運 行之殘餘物同時增加溫度至約93艽（2〇〇卞）。在去除橡膠 後，在加入該等成份以生成橡膠測試樣品之前，將該混合 器係被冷卻至約65°C(150°F)。使用所測試的矽石製得橡膠組成物，以下稱所之成份 與步驟係在其後揭示·· (2) (3) (4) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） — — — — — — — — — — — — — — — — — — — I·匿 I I I (請先閲讀背面之注意事項再填寫本頁) 訂丨 -29- A7 〜^^_ B7 五、發明說明（27 ) 物質加入混合器 量灿『1_ 70.0 或（自混合器去除) 分鐘 η 橡膠(6) 30.0 V 〇 剩試石夕石 57.5 V 0.5 源自部分A的 全部 3.0 樣品 廢料量 > 竭 Μη ((5.0)) 弟一通道物之 產物 全部 0 抗氧化劑(7) 2.0 0 石油蠛⑷ 1.5 0 硫（9) 1.4 0.5 TBBS (1〇) 1.7 0.5 DPG (11) 2.0 0.5 廢料量 ((4.0)) (5) Solflex® 1216溶液笨乙烯-丁二烯橡膠（SBR),商業上 旋轉速 度 imip) 116 116 116 116 7 7 7 7 7 7 7 7 7 7 7 7 (請先閲讀背面之注意事項再填寫本頁) 得自於The Goodyear Tire & Rubber Co。 (6) Budene 1207丁二烯橡膠（BR),商業上得自於TheCompany, lnc_ Crude & Sales Department. Kadox @ Surface-treated oxidation term, which is commercially available from Zinc Corporation of America. w_ay ".. Antiozonant, which is a substance of diaryl p phenylene diamine, commercially available from The Goodyear Tire & Rubber Co. rubber grade stearic acid, commercially available from C p Ha || Part B 1 · 89 liter (L) Faire 丨 Banbury mixer ("BR" type) is used to mix various ingredients. Before adding the batch ingredients to the mixture, 800 grams (g ) of cv-60 grade rubber is lifted through the mixer to remove any residue from previous runs while increasing the temperature to about 93 艽 (200 卞). After removing the rubber, add these ingredients to produce rubber Before testing the sample, the mixer was cooled to about 65 ° C (150 ° F). A rubber composition was prepared using the tested silica, and the ingredients and steps hereinafter referred to are disclosed later ... (2 ) (3) (4) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) — — — — — — — — — — — — — — — — — — (Please first Read the notes on the back and fill in this page) Order 丨 -29- A7 ~ ^^ _ B7 V. Description of the invention (27) Measure the amount of "1_ 70.0 or (remove from the mixer) minutes η Rubber (6) 30.0 V 〇 Remaining test stone Xi Shi 57.5 V 0.5 Total 3.0 sample waste amount from part A > exhaustion Mη ((5.0)) Siyi All products of the channel 0 Antioxidant (7) 2.0 0 Petroleum Rhenium 1.5 0 Sulfur (9) 1.4 0.5 TBBS (1〇) 1.7 0.5 DPG (11) 2.0 0.5 Waste ((4.0)) (5) Solflex® 1216 Solution Styrene Butadiene Rubber (SBR), commercial rotation speed imip) 116 116 116 116 7 7 7 7 7 7 7 7 7 7 7 7 (Please read the notes on the back before filling this page) Available from The Goodyear Tire & Rubber Co. (6) Budene 1207 Butadiene Rubber (BR), commercially available from The

Goodyear Tire & Rubber Co。 (7) Santoflex® 13 抗臭氧劑，係為 N-(1,3-二曱基丁基）-N，- 苯基-P-苯撐二胺，商業上得自於Flexsys。 (8) Okerin® 7240微結晶蠟/石蠟摻合物，商業上得自於Goodyear Tire & Rubber Co. (7) Santoflex® 13 antiozonant, N- (1,3-difluorenylbutyl) -N, -phenyl-P-phenylenediamine, commercially available from Flexsys. (8) Okerin® 7240 microcrystalline wax / paraffin blend, commercially available from

Astor Corporation 〇 (9) Rubber Makers (RM)硫，100 %活性，商業上得自於Taber，Astor Corporation 〇 (9) Rubber Makers (RM) sulfur, 100% active, commercially available from Taber,

Inc. 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公釐） 502054 A7 B7 28 五、發明説明 (10) N-第三丁基冬苯並嗔唑亞續醯胺，商業上得自於Inc. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 502054 A7 B7 28 V. Description of the invention (10) N-Third-Butylbenzobenzoxazolidine, commercially available Derived from

Monsanto 〇 (11) 二苯基脈，商業上得自於M〇nsant〇. 第一通道物係由加入橡膠，即SBR與BR ,至該混合器 並在116rpm下混合〇·5分鐘而引發。該旋轉速度係保持在116 rpm，且再加入57.5 phr之經處理之矽石樣品。在另一個）5 分鐘後，昇起撞錘，且導槽活塞，即導槽人口覆蓋物，係 被昇起，任何在該導槽内的物質皆會被掃回該混合器中。 在另一分鐘後，加入源自於部份A的樣品。在另一個一分 鐘後，昇起該撞錘並清掃導槽。在該混合器内的内含物係 混合另外一分鐘，以達成一在145至150°C(293至302°F)之最 咼溫度，並完全該混合物之第一通道物。依該樣品的型式， 在4分鐘後，該混合物器的旋轉速度係可增加或減少，以在 特定之混合期間達成在前述範圍内之溫度。 在完成第一通道物後，該物質的溫度係利用一熱偶合 器來決定’以確認其超過最高溫1501：。該經去除的物質係 被稱重，且在FarreM2吋二滾筒橡膠磨碾機内薄片化為 2.032 mm±0.127 mm (0.080吋±〇·〇〇5吋）。所得之經研碾之原 料係被切成長條，以用於供在第二混合物之第二通道物的 製備。 在該混合器中之第一通道物完成與第二通道開始之 間係配有1小時之最低量，以容許該經磨碾之原料冷卻。若 有必要，在引發第二通道物之前，使用CV-60級天然橡膠完 成前述的清潔與溫熱步驟。該混合物之溫度係被調敕成約 (請先閲讀背面之注意事項再填窝本頁) i U- I-----t· 、訂| -31- 502054 A7 ____ B7_ 五、發明説明（29 ) 49°C(120°F)。隨著冷卻水的運轉，該第二通道物係利用將 第一通道物原料之長條加入在77rpm下運作之混合器中而 引發’且摻合預稱重之Santoflex®13抗臭氧劑以及Okerin 7240微結晶蠟/石蠟的組合。在0.5分鐘後，加入由rm硫、 TBBS與DPG構成之組合的第二加入物。在另一個彳5分鐘 後’昇起該撞錘並清掃導槽。該第二道通物係利用混.合該 原料經另外的2.0分鐘且同時保持溫度在125。〇(257卞）或低 於該溫度而完全。Monsanto (11) diphenyl vein, commercially available from Monsant. The first channel system was initiated by adding rubber, namely SBR and BR, to the mixer and mixing at 116 rpm for 0.5 minutes. The rotation speed was maintained at 116 rpm, and an additional 57.5 phr of the treated silica sample was added. After another 5 minutes, the ram is raised, and the guide groove piston, the guide cover covering, is raised, and any substance in the guide groove is swept back into the mixer. After another minute, the sample derived from Part A was added. After another minute, raise the ram and clean the guide groove. The contents of the mixer are mixed for another minute to reach a maximum temperature of 145 to 150 ° C (293 to 302 ° F) and complete the first passage of the mixture. According to the type of the sample, after 4 minutes, the rotation speed of the mixer can be increased or decreased to achieve a temperature within the aforementioned range during a specific mixing period. After the completion of the first passage, the temperature of the substance was determined using a thermal coupler 'to confirm that it exceeded the maximum temperature of 1501 :. The removed material was weighed and thinned in a FarreM 2-inch two-roller rubber mill to 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch). The resulting milled raw material is cut into strips for use in the preparation of a second channel in a second mixture. A minimum amount of 1 hour is provided between the completion of the first passage in the mixer and the start of the second passage to allow the milled material to cool. If necessary, complete the aforementioned cleaning and warming steps with CV-60 grade natural rubber before initiating the second channel. The temperature of the mixture is adjusted to about the agreement (please read the precautions on the back before filling in this page) i U- I ----- t ·, order | -31- 502054 A7 ____ B7_ V. Description of the invention (29 ) 49 ° C (120 ° F). With the operation of the cooling water, the second channel system is initiated by adding a strip of the raw material of the first channel to a mixer operating at 77 rpm, and mixed with a pre-weighed Santoflex® 13 antiozonant and Okerin 7240 microcrystalline wax / paraffin combination. After 0.5 minutes, a second addition consisting of a combination of rm sulfur, TBBS and DPG was added. After another 5 minutes, the ram is raised and the guide groove is cleaned. The second pass utilizes mixing the materials for another 2.0 minutes while maintaining the temperature at 125. 〇 (257 卞) or below this temperature and complete.

部分C AFaiTeM2吋二滾筒橡膠磨碾機係被加熱至約60°C (140°F )。源自於部分B之第二通道物的原料係被饋送至一 具有設定在2.032 mm±0.127 mm (0.080吋± 0.005吋）之縫隙 的運行磨碾機。所得的薄片係被置於一平坦表面，直至該 薄片的溫度到達室溫。一般而言，該薄片係在約3〇分鐘内 冷卻。而後，該經磨碾的薄片係被饋送至一具有設定在3.81 mm±(h51_ (〇.15对± 〇 〇2对）之縫隙的橡膠磨碾機。若有必 #該滾筒組是可調整的，以保持一均勻的厚度。所得的物 質經過16次的侧切割而後經過8次的端通道。該橡膠磨礙 機縫隙係可調整以生成2.032 mm ± 〇·i27 _ (〇._对± 乂才）之薄片厚度。該由該磨碾器所收集出之薄片原料 係被置於平坦乾淨之表面上。使用印刷模版，而由該薄 原料中切出長方形樣品M3 2 mm X 152.4 mm (8对x6对）。 4樣口口係受條件限制的，即儲存在清潔聚乙烯薄片之間並 保持在2rc±代且5, 5%相對溼度下達15錢小時。 ^張尺度_ _^^^τ^Χ297公嫠）--- -32- ....................、可..... (請先閲讀背面之注意事項再填寫本頁) 502054 A7 B7 五、發明説明（30 ) 在該條件限制後，該樣品係置於一具有拋光表面之 203·2 mm X 152.4 mm X 2.286 mm (8吋X 6 吋χθ.09吋）標準框 架機器鋼壓縮模具。該樣品係於一 公分X 61公分（24对X 24 叶）890千牛頓（1〇〇领)之4-後電加熱壓縮壓機固化達T9〇，此 即，依六3丁1\/|〇-2084，其係為在外加150。(：（302。？）下且在13.79 百萬巴斯卡（每平方吋2〇〇〇磅）的壓力下5分鐘而發生有 90%固化作用所需之時間。典型地，固化作用係在約1〇分 鐘内完成。所得之固化橡膠薄片係自該模具中去除，並於 在部分D測試前，在23°C± 2°C(73.4T± 3.6°F)溫度且50%土 5%的相對溼度下保持15至18小時。Part of the C AFaiTeM 2-inch two-roller rubber mill is heated to approximately 60 ° C (140 ° F). The raw material originating from the second channel of Part B is fed to a running mill with a gap set at 2.032 mm ± 0.127 mm (0.080 inch ± 0.005 inch). The resulting sheet was placed on a flat surface until the temperature of the sheet reached room temperature. Generally, the sheet is cooled in about 30 minutes. Then, the milled sheet is fed to a rubber mill with a gap set at 3.81 mm ± (h51_ (0.15. ± 0.02 pairs). If necessary, the roller set is adjustable. To maintain a uniform thickness. The obtained material was subjected to 16 side cuts and then 8 end channels. The gap between the rubber grinder and the machine was adjusted to produce 2.032 mm ± 〇 · i27 _ (〇._ 对 ±乂 才). The sheet material collected by the mill is placed on a flat and clean surface. Using a printing stencil, a rectangular sample M3 2 mm X 152.4 mm ( 8 pairs x 6 pairs). The 4 sample mouths are conditionally limited, that is, stored between clean polyethylene sheets and kept at 2rc ± generation and 5,5% relative humidity for 15 money hours. ^ 张 平面 _ _ ^^ ^ τ ^ Χ297 公 嫠) --- -32- .........., may ... (Please read the notes on the back before filling (This page) 502054 A7 B7 V. Description of the invention (30) After the conditions are limited, the sample is placed on a polished surface of 203.2 mm X 152.4 mm X 2.286 mm (8 inches X 6 inches x θ.09 inches) standard Frame machine steel compression mold. The sample was cured on a 4-post electric heating compression press of 1 cm X 61 cm (24 pairs X 24 leaves) 890 kilonewtons (100 collars) to T90, that is, according to Liu 3 3 1 // | 〇-2084, which is an additional 150. (: (302.?) And the time required for 90% curing to occur for 5 minutes under a pressure of 13.79 million Baska (2,000 pounds per square inch). Typically, curing is at Completed in about 10 minutes. The resulting cured rubber sheet was removed from the mold and was tested at 23 ° C ± 2 ° C (73.4T ± 3.6 ° F) and 50% soil 5% before Part D testing. Keep at a relative humidity of 15 to 18 hours.

部分D 依據ASTM D 412-98a _測試方法A進行測試。使用模子 C製備Dumbbel丨測試樣本。使用一種用以測定延伸度之具 有自動接觸延伸計算器的Instron型4204。該十字頭 (cross-head)速度係等於508 mm/min。且使用由製造商所提供 之Series IX自動物質測試軟體來進行計算。該強化指數係 等於在300%延伸度（MPa)下之張應力除以在100%延伸度 (MPa)下之張應力。當該當品是使用標準複合步驟來製備 時’所得的結果係以標準強化指示來表示。 沈澱矽石的f舞 沈澱矽石係以一硫酸來酸化一矽酸鈉溶液而生成。該 沈澱物之主要部分係在高於8.5之pH下形成。進一步的沈 澱物則利用持續地加入酸直到該溶液？!^到達3 3至4 〇之位 準所生成。 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公紫） (請先閲讀背面之注意事項再填寫本頁)Part D is tested according to ASTM D 412-98a _ Test Method A. Dumbbel test specimens were prepared using mold C. An Instron Model 4204 with an automatic contact elongation calculator for measuring elongation was used. The cross-head speed is equal to 508 mm / min. And use the Series IX automatic substance test software provided by the manufacturer for calculation. The strengthening index is equal to the tensile stress at 300% elongation (MPa) divided by the tensile stress at 100% elongation (MPa). When the current product is prepared using standard compounding steps, the results obtained are indicated by standard strengthening instructions. The f dance of precipitated silica is formed by acidifying a sodium monosilicate solution with sulfuric acid. A major part of the precipitate is formed at a pH above 8.5. Further sedimentation is made by continuously adding acid until the solution? ! ^ Generated by reaching 3 3 to 4 〇. This paper size applies to China National Standard (CNS) A4 (210 X 297 male purple) (Please read the precautions on the back before filling this page)

502054502054

(請先閲讀背面之注意事項再填寫本頁) 一種用於表面分析之沈澱矽石樣品，即實施例15所述 者，係利用下述方式製備，即過濾並清洗一部分的矽石， 直至該清洗水顯示出一約300 10 800微歐姆量的導電性。 所得的渡餅係使用較高的攪動器而被再液化，因而形成一 配置於液體懸浮液中之固體。該懸浮液係在Nir〇喷霧乾燥 器上（入口溫度約36(rc且出口溫度約11〇。〇乾燥。在第工 表中所列出者係為為沈澱矽石，其等被用來製備實施例與 比較實施例之改質石夕石。 實施例1 6 •訂， 其中約3.25 kg係為矽石之約50公斤（kg)之沈澱矽石懸 浮液與15.2至5.9 kg異丙醇係被加入3〇加崙具有一底部排 出管之設有管線的玻璃容器。該容許亦設有一溫度記錄 器、機場攪拌器、加熱構件與冷凝器。 該開始攪拌並加熱該容器的内含物，3-酼基丙基三甲 氧基矽烷（MPTMS)係被在一時間内（一般約彳〇分鐘）加入其 中’會生成基於所列第1表中之實施例的乾重，各個石夕石 所列示之MPTMS百分比適當量。在MPTMS加入完成後，二 甲基二氣矽烷係以相同的方式加入，以生成基於第1表之乾 重每矽石產生所列之DMDCS百重百分之適當量。該 MPTMS/DMDCS之重量比係列於第1表中。該溶液所得之pH 係落在約1_5至約2·2的範圍内。 在完成DMDCS加入後，加入需將該溶液之pH降低至約 0.3之約37wt%之鹽酸。該混合物係被加熱至約68°C，並保 持在該溫度下達約30分鐘。當冷卻時，將足夠之5〇 wt.% 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公釐） 34- 502054 A7 __ B7_ 五、發明説明（32 )(Please read the precautions on the back before filling this page.) A precipitated silica sample for surface analysis, as described in Example 15, was prepared by filtering and cleaning a portion of the silica until the The washing water showed a conductivity of about 300 10 800 microohms. The resulting cake was reliquefied using a higher agitator, thereby forming a solid disposed in a liquid suspension. The suspension was dried on a Niro spray dryer (inlet temperature of about 36 ° C and outlet temperature of about 11.0 °. The ones listed in the worksheet are Shendian silica, which are used to Preparation Example and Comparative Example of Modified Shixite. Example 16 • Order, of which about 3.25 kg is about 50 kg (kg) of precipitated silica suspension of silica and 15.2 to 5.9 kg of isopropanol It is added to 30 gallons of glass container equipped with a pipe with a bottom discharge tube. The allowance is also provided with a temperature recorder, airport stirrer, heating means and condenser. The contents of the container shall be stirred and heated, 3-Methinopropyltrimethoxysilane (MPTMS) is added to it over a period of time (generally about 100 minutes), which will generate a dry weight based on the examples in Table 1 listed. Appropriate amount of the listed percentage of MPTMS. After the addition of MPTMS is completed, dimethyl digas silane is added in the same way to generate the DMDCS 100% listed per silica based on the dry weight of Table 1 The weight ratio series of MPTMS / DMDCS is shown in Table 1. The resulting pH is in the range of about 1-5 to about 2.2. After the addition of DMDCS is complete, add about 37% by weight of hydrochloric acid that reduces the pH of the solution to about 0.3. The mixture is heated to about 68 ° C, and kept at this temperature for about 30 minutes. When cooling, it will be enough 50wt.% This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 34- 502054 A7 __ B7_ Five Description of the invention (32)

NaOH以一段時間加入該混合物中，以調整該卟至約35。 在Na〇H加入完成後，足夠的甲苯（一般係為6 75至7j5kg) 係加入該攪拌混合物中，以達成自該水相中分離出疏水性 沈澱矽石，而不用形成一乳化劑。該水相係自該容器中排 出，在該容器中之含有疏水性沈澱矽石的水相，而後係以 約30kg的水清洗。另外足夠之甲苯（一般係為6 5至8 〇叻)係 被加入該攪拌混合物中，以達成自該水相中分離出疏水性 沈澱矽石，而不用形成一乳化劑。該水相係自該容器中排 出。而後含有該疏水性沈澱矽石之攪拌混合物係以每次約 30 kg的水清洗二次或更多次。在各個清洗後且在其後清潔 液加入之前，將該水相自該容器中排出。 在清洗完成後，將足夠的甲苯（一般係為12.5至15.3 kg) 加入該攪拌混合物中，以製得一固體在液體中之可流動懸 浮液’該懸浮液係可容易地自該容器中釋出。所得到的懸 浮液係在一旋轉角錐乾燥器在真空下（最低值係為23对水 銀柱）且在最低14(TC下乾燥。持讀乾燥直至該樣品暴露於 160°C下達1〇分鐘顯示出低於4%之wt·%的損失。 實施例7 除了下列外，依照實施例1-6所述的步驟進行：8〇g之 3-巯基-丙基三甲氧基矽烷（MPTMS)係在約10分鐘的期間内 加入；487 g之二曱基二氯矽烷係在約10分鐘的時間内加 入；不使用異丙醇與甲苯，且三個批次的漿液係被結合、 過濾並以水清洗，直至該清洗液顯示出約300至8〇〇微歐姆 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)NaOH was added to the mixture over a period of time to adjust the porphyry to about 35. After the addition of NaOH, sufficient toluene (generally 675 to 7j5kg) was added to the stirred mixture to achieve the separation of the hydrophobic precipitated silica from the aqueous phase without forming an emulsifier. The aqueous phase was discharged from the container, and the aqueous phase containing hydrophobic precipitated silica in the container was then washed with about 30 kg of water. In addition, sufficient toluene (usually 65 to 800 Å) was added to the stirring mixture to achieve the separation of the hydrophobic precipitated silica from the aqueous phase without forming an emulsifier. The water phase was discharged from the container. The stirred mixture containing the hydrophobic precipitated silica is then washed twice or more with about 30 kg of water each time. The water phase was drained from the container after each washing and before the subsequent cleaning liquid was added. After the washing is completed, sufficient toluene (generally 12.5 to 15.3 kg) is added to the stirring mixture to obtain a flowable suspension of a solid in a liquid. The suspension can be easily released from the container Out. The resulting suspension was dried in a rotary cone drier under vacuum (minimum value was 23 pairs of mercury columns) and dried at a minimum of 14 (TC. Keep reading dry until the sample was exposed to 160 ° C for 10 minutes and showed Loss of less than 4% wt.%. Example 7 Except the following, the procedure described in Examples 1-6 was followed: 80 g of 3-mercapto-propyltrimethoxysilane (MPTMS) was added at about Added over a period of 10 minutes; 487 g of difluorenyldichlorosilane was added over a period of about 10 minutes; isopropyl alcohol and toluene were not used, and three batches of the slurry system were combined, filtered, and washed with water Until the cleaning solution shows about 300 to 800 microohms. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

502054 A7 ----- - B7_ 五、發明説明（33 ) 的導電位準。該經處理的矽石樣品係被乾燥，直至該樣品 暴露於160°C下達10分鐘顯示出<2%之wt·%的損失。 以乾重為準每矽石之MPTMS與DMDCS的大約重量百分 比與MPTMS/DMDCS對實施例7之改質矽石的重量比係列於 第2表中。 實施例8 除了下列外，依照實施例1 -6所述的步驟進行：其係使 用40 kg之再液化之固體在液體中的沈澱石夕石懸浮液（3 3 之矽石）與12.2 1^異丙醇；1719之3-酼基丙基三甲氧基矽烷 (MPTMS)係以約7分鐘的時間加入；506 g之二甲基二氣石夕院 (DMDCS)係以約2分鐘的時間加入；以約24分鐘的時間加入 濃鹽酸，而造成一 pH約為0.4的溶液；在約68°C加熱達30 分鐘後，加入足夠之50 wt.% NaOH，以調整該pH至約7.0 ; 加入足夠之曱苯（約7.1 kg)，以達成自該水相中分離出疏水 性矽石，而不用形成乳化液。該經回收之產物係經過水清 洗’但在該水相排出後，加入約、2.2 kg之甲苯至該產物，以 製造一種固體在液體之可流動懸浮液。該處理之石夕石樣品 係被乾燥，直至該樣品暴露於160°C下達10分鐘顯示出 <1.5%之wt·%的損失。 以乾重為準每石夕石之MPTMS與DMDCS的大約重量百分 比與MPTMS/DMDCS對實施例8之改質矽石的重量比係列於 第2表中。 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) #丨 •36- 502054 A7 ------------ 五、發明説明（34 ) 贵施例9 依照實施例8之步驟，除了是使用86.5g之3-疏基丙基 三甲氧基矽烷（MPTMS)。以乾重為準每矽石之MpTMS與 DMDCS的大約重量百分比與MpTMS_DCS對實施例9之改 質矽石的重量比係列於第2表中。 實施侧10.13 矽烷（DMDCS & MPTMS)以及酸（足以製造約〇 3之州）二 者在被加入一容器之前馬上係與一新鮮製得之具有約65至 68°C矽石漿液共混合。在所有之實施例使用的酸係為濃硫 酸（即約96 wt%)，除了實施例13是使用濃鹽酸。所得的混 合物靜置至少15分鐘。加入水並施以攪拌，同時以5〇wt.% 之水性氫氧化鈉調整pH至約3_5。所得之疏水性水性懸浮 液係被過濾並以水清洗，直至該清洗水顯示出一在3〇〇至 800微歐姆之位準間的導電性。該疏水性矽石係被乾燥，直 至0亥樣σα暴露於1 〇 6 C下達1 0分鐘顯示出< 2.5 %之wt · %的損 失。以乾矽石重量百分比為準，、加入至該漿液中之矽烷大 約量以及MPTMS/DMDCS的重量比係列於第2表中。 實施例14 依照實施例10-13之步驟，除了無有酸的加入，而存在 僅有DMDCS水解所生成之酸。將足夠之（MPTms)與足夠之二 甲基二氯矽烷（DMDCS)加入，以製造基於乾重每矽石的大 約重量百分比係為列於第2表者。所得溶液之pH係為彳6。 比較實施例1 · 3 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) •訂— 502054 A7 B7 五、發明説明（35 ) (請先閱讀背面之注意事項再填寫本頁) 依照揭示於實施例1-6之步驟。加入漿液中之矽烷大約 量係係與MPTMS/DMDCS重量比一起基於乾矽重量百分比 而列於第2表中。 比較實施例4 依照實施例10-13之步驟，除了其加入酼基丙基三甲氧 基矽烷，以造成以乾重為準為列於第2表之每矽石MPTMS 的大約重量百分比，且加入足夠的濃硫酸以製成約0.0之 pH 〇 比較實施例5 依照比較實施例4之步驟，除了其加入二甲基二氯矽 烷，以造成以乾重為準為列於第2表之每矽石DCDMS的大約 重量百分比，且加入足夠的濃硫酸以製成約0.4之pH。 實施例15 使用Horiba 6200系列儀器，並利用動態單點表面積技 術ASTM D3037-93，步驟C經修改）而決定出實施例1-14與比 較實施例（CE)1-5之經處理與未處理測試矽石樣品的表面 積。此步驟在 P/P。= 0.294下仿效 Brunauer-Emmett-Teller (BET) 方法，且使用在氦氣中30%氮氣作為吸收氣體。ASTM步驟 係被修改如下：使用在氦氣中30%氮氣；維持約40 mL/min 的流動性；在氮氣流下於180± 5°C下在一分析小室内乾燥 樣品達1小時；以及在樣品上吸收之氮氣係利用液態氮之杜 爾作用（dewar)且容許該樣品在外在熱源溫熱至室溫而被釋 出。未經處理之測試矽石樣品結果係顯示於第1表，而經處 理之測試矽石樣品結果係顯示於第3表。 本紙張尺度適用中國國家標準（CNS) A4规格（210X297公釐） 502054 A7 B7 五、發明説明（ 石反百分比係使用Carlo Erba modeM 106元素分析儀並 利用CHN分析來決定的。在錫密封膠囊中之1-2mg樣品係 在一具有氦載氣之富含氧大氣壓且於i〇4(rc燃燒，在Cr2〇3 上定量燃燒，而後燃燒氣體在65(rc下流經過。，以消除過 量氧並還原氮氧化物為氮。而後該氣體流經一層析管柱， 將之分離並溶析成N2、C〇2與hbO。經溶析的氣體係利用熱 傳導性檢測試來測量。該儀器係利用標準化合物之燃燒來 才父正。其結果係顯示於第3表。 列於第3表之疏基（SH)百分比係利用下述方式決定 者在丨enmeyer—角瓶中，精確地將2-3克經處理之石夕稱 重出最接近0.001g，加入75ml異丙醇、以氮清點之，以一溼 的密封器密封並磁性攪拌達30分鐘。該經攪拌之溶液係利 用商業上得自於LabChem lnc之標準〇 1N碘溶液來進行快 速滴定至一微黃色終點。除了不加入經處理之矽石外，其 亦利用相同步驟進行一空白滴定。若使用經阻礙之疏基矽 燒來改質填料，在滴定前必須去除經阻礙之疏基石夕烧上的 阻礙。下列方程式係使用來得到最終值。502054 A7 ------B7_ V. Conduction level of invention description (33). The treated silica sample was dried until the sample was exposed to 160 ° C for 10 minutes and showed a loss of < 2% wt.%. Table 2 lists the approximate weight percentages of MPTMS and DMDCS per silica based on dry weight and the weight ratio of MPTMS / DMDCS to the modified silica of Example 7. Example 8 Except for the following, the procedure described in Examples 1 to 6 was performed: it used 40 kg of re-liquefied solids in the liquid precipitated stone suspension (silica of 3 3) and 12.2 1 ^ Isopropanol; 3-Methylpropyltrimethoxysilane (MPTMS) of 1719 was added over a period of about 7 minutes; 506 g of dimethyl digassine (DMDCS) was added over a period of about 2 minutes Add concentrated hydrochloric acid over a period of about 24 minutes, resulting in a solution with a pH of about 0.4; after heating at about 68 ° C for 30 minutes, add enough 50 wt.% NaOH to adjust the pH to about 7.0; add Sufficient toluene (approximately 7.1 kg) to achieve the separation of hydrophobic silica from the aqueous phase without forming an emulsion. The recovered product was washed with water 'but after the aqueous phase was discharged, about 2.2 kg of toluene was added to the product to make a solid, liquid, flowable suspension. The treated stone evening stone sample was dried until the sample was exposed to 160 ° C for 10 minutes and showed a loss of < 1.5% wt.%. Table 2 lists the approximate weight percentages of MPTMS and DMDCS per stone evening stone and the weight ratio of MPTMS / DMDCS to the modified silica of Example 8. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) # 丨 • 36- 502054 A7 ------------ 5 Explanation of the invention (34) Gui Example 9 The procedure of Example 8 was followed, except that 86.5 g of 3-sulfopropyltrimethoxysilane (MPTMS) was used. Table 2 lists the approximate weight percentages of MpTMS and DMDCS per silica and the weight ratio of MpTMS_DCS to the modified silica of Example 9 based on dry weight. Implementation side 10.13 Silane (DMDCS & MPTMS) and acid (enough to make about 03) were blended with a freshly prepared silica slurry having a temperature of about 65 to 68 ° C immediately before being added to a container. The acid used in all examples was concentrated sulfuric acid (i.e., about 96 wt%), except that in Example 13, concentrated hydrochloric acid was used. The resulting mixture was allowed to stand for at least 15 minutes. Water was added and stirred while adjusting the pH to about 3-5 with 50 wt.% Aqueous sodium hydroxide. The resulting hydrophobic aqueous suspension was filtered and washed with water until the washing water exhibited a conductivity between 300 and 800 microohms. The hydrophobic silica series was dried until exposure to 0 ° C-like σα for 10 minutes at 10 ° C showed a loss of < 2.5% wt.%. Based on the weight percentage of dry silica, the approximate amount of silane added to the slurry and the weight ratio of MPTMS / DMDCS are listed in Table 2. Example 14 In accordance with the procedure of Examples 10-13, except that no acid was added, there was only an acid formed by the hydrolysis of DMDCS. Enough (MPTms) and sufficient dimethyldichlorosilane (DMDCS) are added to make the approximate weight percentages per silica based on dry weight as listed in Table 2. The pH of the resulting solution was 彳 6. Comparative Example 1 · 3 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) • Order — 502054 A7 B7 V. Description of the invention (35) ( (Please read the notes on the back before filling out this page) Follow the steps disclosed in Example 1-6. The approximate amount of silane added to the slurry is listed in Table 2 together with the weight ratio of MPTMS / DMDCS based on the dry silicon weight percentage. Comparative Example 4 The procedure of Example 10-13 was followed, except that fluorenylpropyltrimethoxysilane was added so as to cause the dry weight to be approximately the weight percentage of each silica MPTMS listed in Table 2, and added Sufficient concentrated sulfuric acid to make a pH of about 0.0. Comparative Example 5 The procedure of Comparative Example 4 was followed, except that dimethyldichlorosilane was added to cause each silicon listed in Table 2 based on the dry weight. Approximately weight percent of the stone DCDMS, and sufficient concentrated sulfuric acid was added to make a pH of about 0.4. Example 15 Using Horiba 6200 series instruments and using dynamic single-point surface area technology (ASTM D3037-93, step C modified) to determine the treated and untreated examples 1-14 and comparative example (CE) 1-5 Test the surface area of the silica sample. This step is in P / P. The Brunauer-Emmett-Teller (BET) method was followed at 0.294, and 30% nitrogen in helium was used as the absorption gas. The ASTM procedure was modified as follows: using 30% nitrogen in helium; maintaining a flowability of about 40 mL / min; drying the sample in an analytical cell under nitrogen flow at 180 ± 5 ° C for 1 hour; and in the sample The absorbed nitrogen gas is released by using the dewar of liquid nitrogen and allowing the sample to warm to room temperature from an external heat source. The results of untreated test silica samples are shown in Table 1 and the results of treated test silica samples are shown in Table 3. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 502054 A7 B7 V. Description of the invention (The percentage of anti-stone is determined by using Carlo Erba modeM 106 elemental analyzer and using CHN analysis. In tin sealed capsule A sample of 1-2 mg was at an oxygen-rich atmospheric pressure with a helium carrier gas and was burned at 100 ° C, and was quantitatively burned on Cr203, and the combustion gas was passed at 65 ° C to eliminate excess oxygen and The nitrogen oxides are reduced to nitrogen. The gas then passes through a chromatography column, which is separated and eluted into N2, Co2, and hbO. The dissolved gas system is measured using a thermal conductivity test. The instrument system The standard compound is used to burn the flames. The results are shown in Table 3. The sulphur (SH) percentages listed in Table 3 are determined by the following method in the enmeyer-angle bottle, which is exactly 2 -3 grams of treated Shi Xi weighed out to the nearest 0.001g, added 75ml of isopropanol, counted with nitrogen, sealed with a wet sealer and magnetically stirred for 30 minutes. The stirred solution was obtained commercially using Standard 0N iodine from LabChem lnc Liquid to perform a rapid titration to a slightly yellow end point. In addition to not adding treated silica, it also uses a blank titration using the same procedure. If a hindered succinic silica is used to modify the filler, it must be removed before titration. Obstacles that are blocked by the obstruction of the stone. The following equations are used to get the final value.

% SH = (V1-V2) X N X 3.3 / W 其中：V1係為與該樣品一起使用的碘溶液的體積 ▽2係為與該空白組一起使用的碘溶液的體積 N係為碘溶液之當量濃度 W係為矽石重量（克） 在第3表中為SCI之矽烷轉換指數係利用固態之巧引 來决定出者。此資料係於室溫下在一具有窄孔磁體與 本紙張尺度適用中國國家檩準（CNS)人4規格⑵〇X297公釐） (請先閲讀背面之注意事項再填寫本頁) 、tr— 39- 502054 A7 B7 37 五、發明説明（% SH = (V1-V2) XNX 3.3 / W where: V1 is the volume of the iodine solution used with the sample ▽ 2 is the volume of the iodine solution used with the blank group N is the equivalent concentration of the iodine solution W is the weight of silica (g) The silane conversion index of SCI in Table 3 is determined by the cleverness of the solid state. This information is at room temperature on a magnet with a narrow hole and the paper size is applicable to China National Standards (CNS) Standard 4 (× 297mm) (Please read the precautions on the back before filling this page), tr— 39- 502054 A7 B7 37 V. Description of the invention (

Doty 7 mm標準速度之MAS探針的a Bruker AM-300 NMR上收 (請先閲讀背面之注意事項再填窝本頁) 集。樣品係被包裝至7 mm o.cl.鉻轉子且以短Ke|_F蓋子密封 之。該轉子係在具有約5.0 kHz之幻角度（Magic Angle)轉動。 该父叉極化（CP/MAS)資料係使用a 90。1H脈衝、每光譜 5600-8400掃描、5 msec接觸時間、在資料取得期間之高功 率偶合作用以及3秒的鬆弛延遲作用來收集。Hartmann_Hahn 條件係使用高嶺 土樣品（J. Rocha and J. Klinowski, J· Magn. Reson·, 90，567 (1990))所達成。所有的化學移動皆是參考外 在的四甲基矽烷（TMS)。 所有的光譜值係使用在Aspect 3000電腦上之非線性曲 線配合程式（LINESIM)來分析，以決定出r (_49 ppm)、了2 (_57 ppm)與T3 (-65 ppm)峰之相對面積％。了1、丁2與丁3面積％值係 利用在-30 ppm至-80 ppm之内的曲線配合而決定出者。 利用下方法而對實施例與比較實施例之經處理石夕作 pH測定：加入5.0 g矽石（粉末形式）至一含有磁性攪拌子之 150 mL燒杯；加入50 mL異丙醇以及50 mL去離子水；並在 不濺出下劇烈攪拌，直至該矽石被散浮於其中。將一經校 正的PH電極置於劇烈攪拌溶液中，並在1分鐘（± 5耖）後， 記錄該pH數值。其結果列於第3表。 在第3表中之標專強化指數係利用將在3〇〇%延伸度下 的張應力除以在1000%延伸度下的張應力而測出者。該在 300%與100%延伸度下的張應力之值數係在第4表中。 實施例1、2與7之經處理石夕石的索袼利特可萃取碳百分 比係利用將約5克的各個物質加入至43 mm χ 123 mm (内徑 -40- 502054 A7 _ B7 五、發明説明（38 ) X外徑）纖維素可萃取嵌環，該嵌環則被置入一適當大小且 配有一冷凝器的索格利特萃取管。此索格利特萃取器與冷 凝器系統係被連接至一含有7〇〇mL甲苯的圓底三角瓶。該 三角瓶被加熱至該甲苯的迴流溫度。在迴流至少19小時（一 般係為19至26小時）後，所使用的甲苯係以未使用過的甲苯 取代之’再持續迴流至少19小時（一般係為19至24小時）。回 收所付之經卒取之處理過的砍石並乾燥，直至該樣品暴露 於160°C下達10分鐘顯示出低於1_2%之wt·%的損失。使用在 此所述的步驟測定出各個經萃取之樣品的碳百分比。該索 格利特可萃取碳百分比T係使用下列方程式來決定出者： (萃取前的碳％)-(萃取後的碳。/。）X 100 (%萃取前的碳) 其結果顯示於第5表中 第1表 使用於實施例中 表面積（IP/g) 未經處的矽石 (請先閲讀背面之注意事項再填寫本頁) 、^T— 1-7 & CE1-3 0 12 3 4 i· i— i· i* ii 191 193 172 187 182 214 188 199 本紙張尺度適用中國國家標準（CNS) A4规格（210 X 297公釐〉 502054 A7 B7 五、發明説明 39 例 趣 0 12 3 4 1. X— ii 1 1— %MPTMS/Si 〇2 2.5 2.5 1.0 5.0 2.5 4.0 2.5 5.22.6 4.0 4.06.0 4.0 4.0 第2表 DMDCS/Si〇2 15.0 27.1 22.0 15.0 15.0 22.2 15.0 15.3 15.3 22.210.0 15.0 22.220.0 MPTMS/DMD cs比例 0.17:1 0.09:1 0.05:1 0.33:1 0.17:1 0.18:1 0.17:1 0.34:1 0.17:1 0.18:1 0.40:1 0.40:1 0.18:1 0.20:1 實施例# 第2表（接續> %MPTMS/Si % MPTMS/DMD 〇1 DMDCS/Si〇2 CS比例 CE1 0.0 15.0 0:15 CE2 1.0 12.0 0.08:1 CE3 0.5 15.0 0.03:1 CE4 4.0 0.0 4:0 CE5 0 22.0 0:22 CiptaneD1(12) 3.0 0.0 3:0 (12)係為合成沈澱矽石，其被報導被預塗覆有3重量百分 比之7 -巯基丙基三甲氧基矽烷，且得自於PPG Industries, Inc。 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公爱〉 (請先閱讀背面之注意事項再填窝本頁) 502054 A7B7 五、發明説明（4Q ) 表 3 第 例 施 實 #Ι1234567891011121314ΕΕ C € 2 表面積 132 112 119 128 128 113 126 103 108 118 146 123 115 139 137 149 碳A Bruker AM-300 NMR of a Doty 7 mm standard speed MAS probe was collected (please read the precautions on the back before filling this page). Samples were packed into 7 mm o.cl. chrome rotors and sealed with short Ke | _F caps. The rotor is rotated at a magic angle of about 5.0 kHz. The CP / MAS data was collected using a 90.1H pulse, 5600-8400 scans per spectrum, 5 msec contact time, high power coupling during data acquisition, and a relaxation delay of 3 seconds. The Hartmann_Hahn condition was achieved using kaolin samples (J. Rocha and J. Klinowski, J. Magn. Reson., 90, 567 (1990)). All chemical movements are referenced to external tetramethylsilane (TMS). All spectral values were analyzed using the Nonlinear Curve Matching Program (LINESIM) on the Aspect 3000 computer to determine the relative area% of the r (_49 ppm), 2 (_57 ppm) and T3 (-65 ppm) peaks. The values of the area percentage values of 1, 2 and 3 were determined by using a curve fit within the range of -30 ppm to -80 ppm. The pH of the treated stone of the Examples and Comparative Examples was measured by the following method: 5.0 g of silica (in powder form) was added to a 150 mL beaker containing a magnetic stir bar; 50 mL of isopropanol and 50 mL were added to Ionized water; stir vigorously without splashing until the silica is floated in it. Place the calibrated pH electrode in a vigorously stirred solution and record the pH value after 1 minute (± 5 耖). The results are shown in Table 3. The standard strengthening index in Table 3 is measured by dividing the tensile stress at 300% elongation by the tensile stress at 1000% elongation. The values of the tensile stresses at 300% and 100% elongation are shown in Table 4. The solutelite extractable carbon percentage of the treated Shixite of Examples 1, 2 and 7 was obtained by adding about 5 grams of each substance to 43 mm x 123 mm (inner diameter -40-502054 A7 _ B7 V. Description of the invention (38) X outer diameter) cellulose extractable insert ring, the insert ring is placed into a Soxhlet extraction tube of an appropriate size and equipped with a condenser. The Soxhlet extractor and condenser system was connected to a round-bottomed triangular flask containing 700 mL of toluene. The Erlenmeyer flask was heated to the reflux temperature of the toluene. After refluxing for at least 19 hours (typically 19 to 26 hours), the toluene system used is replaced with unused toluene 'and continued to reflux for at least 19 hours (typically 19 to 24 hours). The paid processed chopped stones were recovered and dried until the sample was exposed to 160 ° C for 10 minutes and showed a loss of less than 1_2% wt.%. Use the procedure described here to determine the carbon percentage of each extracted sample. The Soxhlet extractable carbon percentage T is determined using the following equation: (carbon before extraction)-(carbon after extraction.) X 100 (% carbon before extraction) The results are shown in The first table in Table 5 is used in the examples. The surface area (IP / g) is untreated silica (please read the precautions on the back before filling this page), ^ T— 1-7 & CE1-3 0 12 3 4 i · i— i · i * ii 191 193 172 187 182 214 188 199 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm> 502054 A7 B7) V. Description of the invention 39 Example interest 0 12 3 4 1. X— ii 1 1—% MPTMS / Si 〇2 2.5 2.5 1.0 5.0 2.5 4.0 2.5 5.22.6 4.0 4.06.0 4.0 4.0 Table 2 DMDCS / Si〇2 15.0 27.1 22.0 15.0 15.0 22.2 15.0 15.3 15.3 22.210 .0 15.0 22.220.0 MPTMS / DMD cs ratio 0.17: 1 0.09: 1 0.05: 1 0.33: 1 0.17: 1 0.18: 1 0.17: 1 0.34: 1 0.17: 1 0.18: 1 0.40: 1 0.40: 1 0.18: 1 0.20: 1 Example # Table 2 (continued)% MPTMS / Si% MPTMS / DMD 〇1 DMDCS / Si〇2 CS ratio CE1 0.0 15.0 0:15 CE2 1.0 12.0 0.08: 1 CE3 0.5 15.0 0.03: 1 CE4 4.0 0.0 4: 0 CE5 0 22.0 0:22 CiptaneD1 (12) 3.0 0.0 3: 0 (12) is a synthetic precipitated silica that has been reported to be pre-coated with 3% by weight of 7-mercaptopropyltrimethoxysilane and is available from PPG Industries, Inc. This paper size applies China National Standard (CNS) A4 specification (210X297 public love) (Please read the precautions on the back before filling in this page) 502054 A7B7 V. Description of the invention (4Q) Table 3 Example implementation # Ι1234567891011121314ΕΕ C € 2 Surface area 132 112 119 128 128 113 126 103 108 118 146 123 115 139 137 149 carbon

Η S wt %) wtΗ S wt%) wt

C SC S

R SR S

•H D 215-3002873009554 2322232223233111 2 0 6*0 5 3 3 * 8 3 8 i— 4 ο 2 331D3646D35 5 4201 Ο.Ο.Ο.ΝΟ.Ο.Ο.Ο.ΝΟ.ΟΟ.Ο.Ο.Ο.Ο• HD 215-3002873009554 2322232223233111 2 0 6 * 0 5 3 3 * 8 3 8 i— 4 ο 2 331D3646D35 5 4201 Ο.Ο.Ο.ΝΟ.Ο.Ο.Ο.ΝΟ.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.Ο.〇. Ο

5 6 2 6 1— * 2 ****** 5 * * 55655D5DDDDDD4DD OOOOONONNNNNNONN 8529633116330176 4 4 4 4 454554444423 078356181-9378651 66676678106666666 (請先閲讀背面之注意事項再填寫本頁) 、^τ— 續 (# 表 3 第 實施例 # CE 3 CE 4 CE 5 CiptaneQ 1 表面積 (m2/q) 碳 (wt, %) 9 4 4 2 3 9 3 3 1— 4— 1 6 6 6 5 1.0.2 ο SH (wt. %)0.1 0.34 <0.001 0.4 SCI” ND* ND* ND* 0.275 6 2 6 1— * 2 ****** 5 * * 55655D5DDDDDD4DD OOOOONONNNNNNONN 8529633116330176 4 4 4 454554444423 078356181-9378651 66676678106666666 (Please read the precautions on the back before filling this page), ^ τ— continued (# Table 3 实施 例 # CE 3 CE 4 CE 5 CiptaneQ 1 Surface area (m2 / q) Carbon (wt,%) 9 4 4 2 3 9 3 3 1— 4— 1 6 6 6 5 1.0.2 ο SH (wt. %) 0.1 0.34 < 0.001 0.4 SCI ”ND * ND * ND * 0.27

R S 5 9 6 2 3 2 2 3R S 5 9 6 2 3 2 2 3

Η D 8 7 6 0 5 6 6 7 ND*指示該測試未進行。 SCI»代表矽烷轉換指數。 SRI”*代表標準強化指數。 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐） -43- 502054 A7 B7 五、發明説明（ 41 實施例# 1 2 3 4 5 6 7 8 9 10 11 12 13 14 CE1 CE2 CE3 CE4 CE5 CiptaneDl 第4表 在300%下張應力模氩 8.9 8.2 7.0 10.8 8.7 12.0 7.8 11.1 9.9 9.3 8.0 10.2 6.2 7.4 2.8 6.1 5.5 5.5 3.8 4.8 在100%下張應力模氩 1.8 (請先閲讀背面之注意事項再填寫本頁) .訂_ 表 5 第 %JL 碳之 %後| 碳之 %取 碳萃 8 10 112 2 3 2 14 6 8 -Ku -1 7 3 9 3 6 8 第1表的結果顯示，使用於製備實施例與比較實施例之 方法中的未經處理矽石樣品表面積係落在172至214 m2/g的 範圍内。 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -44- 502054 A7 B7 五、發明説明（ 列於第2表中之實施例[14的MPTMS/DMDCS比例係落 在0.05:1至0.40:1之間。含有石夕烧之比較實施例2與3之該比 例則分別為0.08:1與0.03:1。雖然比較實施例（ce)的 MPTMS/DMDCS比例是落在所欲之0.05:1至1〇:1的範圍内，但 列於第3表中之CE-2經處理矽石的酼基（SH)重量百分比結 果是比需要之大於0.15重量百分量之量為低^ 第3表顯示，本發明之改質矽石，即實施例M4，顯示 出至少為4.0的標準強化指數，大於1 〇的碳重量百分，大於 〇·15之巯基重量百分比以及至少為〇 3之矽烷轉換指數，即 Τ /(Τ + Τ2 + Τ3)。该比較實施例具有一低於實施例1 _ι4所具 有之碳重量百分比以及/或酼基重量百分比，且具有一低於 4.0之標準強化指數，例如，為3 6。 第4表的結果顯示，本發明所有改質矽石，即實施例 1-14，在300%延伸度下顯示出6 2或更高的張應力。比較實 施例在300%延伸度下的張應力則是6彳或更低。 第5表的結果顯示索格利特可萃取碳百分比係落在實 施例7之低值1.82%與實施例2之高值18.33%之間。 本發月雖參照了一些貫施態樣的詳述而被揭示，但本發明 除了在此所具有之申請專利範圍之外，並不想要將該等詳 述内谷視作為對本發明之範圍的限制。 (請先閲讀背面之注意事項再填寫本頁) -響· 、^τ—Η D 8 7 6 0 5 6 6 7 ND * indicates that the test was not performed. SCI »stands for Silane Conversion Index. "SRI" * stands for Standard Strengthening Index. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -43- 502054 A7 B7 V. Description of the invention (41 Example # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 CE1 CE2 CE3 CE4 CE5 CiptaneDl Table 4 Tensile stress argon at 300% 8.9 8.2 7.0 10.8 8.7 12.0 7.8 11.1 9.9 9.3 8.0 10.2 6.2 7.4 2.8 6.1 5.5 5.5 3.8 4.8 Tensile stress argon at 100% 1.8 (Please read the precautions on the back before filling out this page). Order_ Table 5 After% JL Carbon% | Carbon% Take Carbon Extraction 8 10 112 2 3 2 14 6 8 -Ku -1 7 3 9 3 6 8 The results in Table 1 show that the surface area of the untreated silica samples used in the methods of the Preparation Examples and Comparative Examples falls within the range of 172 to 214 m2 / g. This paper size is applicable to the Chinese National Standard (CNS ) A4 specification (210X297 mm) -44- 502054 A7 B7 V. Description of the invention (Examples listed in Table 2 [MPTMS / DMDCS ratio of 14 falls between 0.05: 1 to 0.40: 1. Contains stone The ratio of the evening burns of Comparative Examples 2 and 3 is 0.08: 1 and 0.03: 1, respectively. Although the MPTMS / DMDCS of Comparative Example (ce) Examples are within the desired range of 0.05: 1 to 10: 1, but the weight percent of fluorene (SH) of CE-2 treated silica listed in Table 3 results in greater than 0.15 weight than required The percentage amount is low ^ Table 3 shows that the modified silica of the present invention, Example M4, shows a standard strengthening index of at least 4.0, a carbon weight percentage greater than 10, and a mercapto group greater than 0.15 The weight percentage and the silane conversion index of at least 0, that is, T / (T + Τ2 + Τ3). The comparative example has a carbon weight percentage and / or a fluorene-based weight percentage lower than that of Example 1-4. Has a standard strengthening index below 4.0, for example, 3 6. The results in Table 4 show that all of the modified silicas of the present invention, Examples 1-14, show 6 2 or more at 300% elongation. High tensile stress. The tensile stress of the comparative example at 300% elongation is 6 Torr or less. The results in Table 5 show that the percentage of Soxhlet extractable carbon falls at 1.82%, which is the lowest in Example 7. And 18.33% of the highest value of Example 2. Although this hair month was revealed with reference to some detailed descriptions of the implementation However, the present invention is in addition to the scope of this patent has, does not want to be described later in detail within the restrictions of the valley regarded as the scope of the invention. (Please read the notes on the back before filling out this page)-响 · ， ^ τ—

Claims (1)

502054502054 申請專利範園 第089i丨6783號專利申請案申請專利範圍修正本 修正日期：91年5巧 1 一種製造經化學處理的填料之方法，其係任擇地在一 表面活性劑以及或一水可相混的溶劑存在下，令一種 選自於沈澱矽石、膠狀矽石或其等混合物中之不定形 或顆粒無機氧化物的酸性水性懸浮液係與一偶合劑相 接觸，以形成一種經化學處理填料之酸性水性懸浮 液，並回收該填料，其改良處係包含將一由⑻酼基有 機金屬化合物與⑻無硫有機金屬化合物所構成之組 合使用於一具有pH 2.5或更低之無機氧化物的水性 懸浮液中作為該偶合劑，且該㈤對⑻之重量比係為至 少0.05:1 ’並以一中和劑處理該經化學處理填料之水 性懸浮液，以增高該懸浮液之pH至3.0至1〇的範圍 内0 如申請專利範圍第1項之方法，其中該酼基有機金屬 物質係具有下列通式I者： 2. Ah), (請先閲讀背面之注意事項再填寫本頁) 訂， HS-R1 ε 其中Μ係為矽、L係為鹵素或-(^7,〇為氫、〇1412烷 基或經鹵基取代之CVC12烷基、R6係為Ci-Cu烷撐基， R7係為Ci_Ci2烧基或含有2至12個碳原子之烧氧基 烧基’該鹵素或鹵基係為氯、溴、碘或氟，且η係為 1，2 或 3 〇 本紙張尺度適用中國國家檩準（CNS) Α4規格（21〇><297公爱） 502054 4. 5. 6. A8 B8 C8 D8 六、申請專利範圍 3.如申凊專利範圍第2項之方法，其中L係為_〇R7、R6 係為烷撐基，R7係為烷基，且n係為3。 如申請專利範圍第2項之方法，其中該酼基有機金屬 物質之疏基係被阻礙。 如申請專利範圍第1項之方法，其中該巯基有機金屬 物質係選自於巯基甲基三甲氧基矽烷、疏基乙基三甲 氧基矽烷、酼基丙基三甲氧基矽烷、酼基甲基三乙氧 基矽烷、巯基乙基三丙氧基矽烷、巯基丙基三乙氧基 矽烷、（M基甲基）二甲基乙氧基矽烷、（酼基甲基）曱基 一乙氧基矽烧、3_巯基丙基-甲基二甲氧基石夕烧以及其 等混合物。 如申請專利範圍第1項之方法，其中該無硫有機金屬 化合物係選自於下列群中： 具有通式丨I之有機金屬化合物： R1aMX(4-a) II 具有通式III之有機金屬化合物： ^^2c+2^ic〇(c-1) HI 具有通式IV之有機金屬化合物： R32dSid〇d IV 以及具有通式V之有機金屬化合物·· (R23Si)kNR4(3-k) V 以及該等有機金屬化合物之混合物，其中每個M各自 為梦、敛或鉻；每個R1係各自為具有1至18個碳原 子之烴基，或R1可為一具有1至12個碳原子之有機 -2- 本紙張尺度適用中國國家標準（哪）A4規格（2i〇x297公釐） (請先閱讀背面之注意事項再填寫本頁)Patent Application Fanyuan No. 089i 丨 6783 Patent Application Application Amendment to the Patent Scope Amendment Date: 1991 Wuqiao 1 A method for manufacturing a chemically treated filler, which is optionally a surfactant and / or water In the presence of a mixed solvent, an acidic aqueous suspension of amorphous or particulate inorganic oxides selected from precipitated silica, colloidal silica, or a mixture thereof is contacted with a coupling agent to form a warp An acidic aqueous suspension of a filler is chemically treated, and the filler is recovered. The improvement includes the use of a combination of a fluorene-based organometallic compound and a sulfide-free organometallic compound in an inorganic material having a pH of 2.5 or lower. The coupling agent is used in an aqueous suspension of oxide, and the weight ratio of rhenium to rhenium is at least 0.05: 1 ′ and the chemically-treated filler aqueous suspension is treated with a neutralizing agent to increase the suspension ’s In the range of pH to 3.0 to 10, as in the method of claim 1 in the patent application, wherein the fluorenyl organometallic substance has the following general formula I: 2. Ah), (Please read the note on the back first (Please fill in this page on the matter of interest), HS-R1 ε where M is silicon, L is halogen or-(^ 7, 0 is hydrogen, 01412 alkyl or halogen substituted CVC12 alkyl, R6 is Ci-Cu alkylene group, R7 is Ci_Ci2 alkyl or oxyalkyl alkyl having 2 to 12 carbon atoms, the halogen or halogen is chlorine, bromine, iodine or fluorine, and η is 1, 2 Or 3 〇 This paper size is applicable to China National Standards (CNS) A4 specifications (21〇 > < 297 public love) 502054 4. 5. 6. A8 B8 C8 D8 6. Scope of patent application 3. If you apply for patent scope The method of item 2, wherein L is _〇R7, R6 is an alkylene group, R7 is an alkyl group, and n is 3. The method of item 2 in the scope of patent application, wherein the fluorenyl organometallic substance The thiol group is hindered. For example, the method of claim 1 in which the mercaptoorganometallic substance is selected from the group consisting of mercaptomethyltrimethoxysilane, thioethyltrimethoxysilane, and propylpropyltrimethoxy Silane, fluorenylmethyltriethoxysilane, mercaptoethyltripropoxysilane, mercaptopropyltriethoxysilane, (M-methyl) dimethyl Oxysilane, (fluorenylmethyl) fluorenyl-ethoxysilane, 3-mercaptopropyl-methyldimethoxylithium oxide, and mixtures thereof. For example, the method of claim 1 in the patent scope, wherein The sulfur-free organometallic compound is selected from the following groups: Organometallic compounds having the general formula 丨 I: R1aMX (4-a) II Organometallic compounds having the general formula III: ^^ 2c + 2 ^ ic〇 (c- 1) HI Organometallic compounds of general formula IV: R32dSidOd IV and organometallic compounds of general formula V. (R23Si) kNR4 (3-k) V and mixtures of these organometallic compounds, where each M Each is dream, convergence, or chromium; each R1 is a hydrocarbon group with 1 to 18 carbon atoms, or R1 can be an organic group with 1 to 12 carbon atoms-2- This paper size applies Chinese national standards (which ) A4 specification (2i0x297 mm) (Please read the precautions on the back before filling this page) g能基烴基’其中’該官能基係為胺基、㈣、甲醇 酿或醯胺類；每個X係各自選自於處素、胺基、具秀 彳-12個碳原子之烧氧基與具有彳_12個碳原子之醯氧基 所構成的群中，a係為1、2或3之整數；每個R2係 各自為鹵基、羥基或具有1至18個碳原子之烴基， 但規定至少50莫耳百分比之R2取代基係為具有1至 18個碳原子之烴基，c係為2至1〇 〇〇〇之整數；每個 R3係各自為_基、羥基或具有1至18個碳原子之烴 基’且’ d係為3至20之整數；每個R4係各自為氫 或具有1至18個碳原子之烴基，且k係為1或2;且， 該鹵素或鹵基係選自於氯、溴、碘或氟。 7.如申請專利範圍第1項之方法，其中該無硫有機化合 物係選自於下列群中：二乙基二氯矽烷、烯丙基甲基 二氯矽烷、甲基苯基二氣矽烷、苯基乙基二乙氧基矽 烧、3,3,3·三氟丙基甲基二氯矽烷、三甲基丁氧基矽 烷、sym_二笨基四甲基二矽氧烷、三乙烯基三甲基_環 三矽氧烷、八曱基環四矽氧烷、六乙基二矽氧烷、五 甲基二氣矽烷、二乙烯基二丙氧基矽烷、乙烯基二甲 基氣矽烷、乙烯基甲基二氯矽烷、乙烯二甲基甲氧基 石夕烧、三甲基氣石夕烧、三甲基甲氧基石夕燒、三甲基乙 氧基矽烷、甲基三氯矽烷、甲基三曱氧基矽烷、甲基 三乙氧基矽烷、·六曱基二矽氧烷、己烯基甲基二氣石夕 烷、己烯基二曱基氯矽烷、二甲基氯矽烷、二曱基二 氣矽烷、二甲基二曱氧基矽烷、二甲基二乙氧基矽燒、 本紙張尺度適用中國國家標準（CNS) Μ規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) Φ .、可| 502054 A8 B8 C8 D8 申請專利範園 六甲基二矽氨烧、三乙烯基三甲基環三矽氨烧、包含 有3至約20個二甲基石夕氧基單元之聚二甲基石夕氧烧、 四（Cl-Ci8)烷氧基鈦酸鹽、甲基三乙氧基鈦（iv)、甲基 鈦（ίν)三異丙化物、甲基鈦（jv)三丁氧化物、甲基鈦（iv) 三-t-丁氧化物、異丙基鈦（iv)三丁氧化物、丁基鈦（iv) 三乙氧化物、丁基鈦（iv)三丁氧化物、苯基鈦（iv)三異 丙化物、苯基鈦(iv)三丁氧化物、苯基鈦（iv)三異丁氧 基、[Ti(CH2Ph)3(NC5Hi〇)]、[Ti(CH2SiMe3)2(NEt2)2]、四 (C1-C18)烷氧基鉻酸鹽、苯基鉻（jv)三氯化物、甲基鉻 (丨v)二氯化物、乙基鉻（iv)三氣化物、丙基鉻（ίν)三氯化 物、甲基鉻（iv)三演化物、乙基鉻㈣三溴化物、丙基 鉻(iv)三溴化物、氣三戊基鉻(iv)與該等有機金屬化合 物之混合物。 8. 如申請專利範圍第6項之方法，其中該無硫有機金屬 化合物係為具有通式Μ、ιπ、丨v、v或該等有機金屬化 合物之混合物，其中每個Μ係為矽。 9. 如申請專利範圍第6項之方本甘& 貝之方法，其中該無硫有機金屬 化合物係為具有通式Π者，其中R1係為C1_C6烧基， X係為氣，a為2 ’而無機氧化物係為沈澱石夕石。 1〇.如申請專利範圍第1項之方法，其中該⑻對⑼之重量 比係為0·05:1至1〇:1。 11·:申=專利範圍第9項之方法，其中該⑻對⑻之重量 比係為0.2:1至2:1。 本紙張尺度適用中®^家標準（哪）Α4規格 (請先閲讀背面之注意事項再填寫本頁)The g-energetic hydrocarbon group 'wherein' the functional group is an amine group, amidine, methanol, or ammonium; each X system is independently selected from the group consisting of a sulfonium group, an amine group, and an alkoxy group having 12 carbon atoms. In the group consisting of fluorenyloxy groups having 彳 _12 carbon atoms, a is an integer of 1, 2, or 3; each R2 is a halogen group, a hydroxyl group, or a hydrocarbon group having 1 to 18 carbon atoms, However, it is required that at least 50 mole percent of the R2 substituent is a hydrocarbon group having 1 to 18 carbon atoms, and c is an integer of 2 to 10,000; each R3 is a _ group, a hydroxyl group, or having 1 to 18-carbon hydrocarbon group 'and' d is an integer from 3 to 20; each R4 is hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, and k is 1 or 2; and, the halogen or halogen The radical is selected from chlorine, bromine, iodine or fluorine. 7. The method according to item 1 of the patent application range, wherein the sulfur-free organic compound is selected from the group consisting of diethyldichlorosilane, allylmethyldichlorosilane, methylphenyldiazine, Phenylethyldiethoxysilane, 3,3,3 · trifluoropropylmethyldichlorosilane, trimethylbutoxysilane, sym_dibenzyltetramethyldisiloxane, triethylene Trimethyl_cyclotrisiloxane, octadecylcyclotetrasiloxane, hexaethyldisiloxane, pentamethyldisiloxane, divinyldipropoxysilane, vinyldimethylsiloxane Silane, vinyl methyl dichlorosilane, ethylene dimethyl methoxylite, trimethyl air stone, trimethyl methoxy stone, trimethyl ethoxy silane, methyl trichloro silane , Methyltrimethoxysilane, methyltriethoxysilane, hexamethyldisilaxane, hexenylmethyldiasparoxane, hexenyldifluorinylchlorosilane, dimethyl chloride Silane, difluorenyl disilane, dimethyl dimethoxy silane, dimethyl diethoxy silane, this paper size is applicable to Chinese National Standard (CNS) M specifications (210 X 297 mm) (Please read the precautions on the back before filling this page) Φ. 、 Can | 502054 A8 B8 C8 D8 Patent Application Fanyuan Hexamethyldisilazane, Trivinyltrimethylcyclotrisamine, contains 3 Up to about 20 dimethyllithium oxide units, polydimethyllithium oxide, tetra (Cl-Ci8) alkoxytitanate, methyltriethoxytitanium (iv), methyl titanium ( ίν) Triisopropoxide, methyl titanium (jv) tributoxide, methyl titanium (iv) tri-t-butoxide, isopropyl titanium (iv) tributoxide, butyl titanium (iv) Triethoxide, butyl titanium (iv) tributoxide, phenyl titanium (iv) triisopropoxide, phenyl titanium (iv) tributoxide, phenyl titanium (iv) triisobutoxy, [Ti (CH2Ph) 3 (NC5Hi〇)], [Ti (CH2SiMe3) 2 (NEt2) 2], tetra (C1-C18) alkoxychromate, phenylchromium (jv) trichloride, methylchromium (丨 v) Dichloride, ethyl chromium (iv) trigas, propyl chromium (ίν) trichloride, methyl chromium (iv) tri-evolution, ethyl chromium, tribromide, propyl chromium ( iv) a mixture of tribromide, tritriamyl chromium (iv) and these organometallic compounds. 8. The method according to item 6 of the patent application, wherein the sulfur-free organometallic compound is a compound having the general formula M, ιπ, 丨 v, v or a mixture of these organometallic compounds, where each M is silicon. 9. For example, the method of Fangbengan & Shell in the scope of patent application, wherein the sulfur-free organometallic compound is a compound having the general formula Π, where R1 is a C1_C6 alkyl group, X is a gas, and a is 2 'The inorganic oxide system is Shendian Shixite. 10. The method according to item 1 of the scope of patent application, wherein the weight ratio of rhenium to rhenium is from 0.05: 1 to 10: 1. 11 ·: Shen = The method of item 9 of the patent scope, wherein the weight ratio of the plutonium to the plutonium is 0.2: 1 to 2: 1. This paper size is applicable to the ^ house standard (where) A4 specification (please read the precautions on the back before filling this page) 502054 A8 B8 C8 _____D8 六、申請專利範園 12. 如申請專利範圍第1項之方法，其中該⑻酼基有機金 屬化合物係為酼基有機金屬化合物與雙（烷氧基矽烷 基燒基）多硫化物之組合，該酼基有機金屬化合物對雙 (烧氧基矽烷基烷基）多硫化物之重量比係至少大於 1:1 〇 13. 如申請專利範圍第12項之方法，其中該酼基有機金屬 化合物對雙（烷氧基矽烷基烷基）多硫化物之重量比係 為5:1至50:1，且該無機氧化物係為沈澱矽石。 14. 如申請專利範圍第12項之方法，其中該雙（烷氧基矽 烷基烧基）多硫化物係具有下列通式VII: Z_al k-Sn'-al k-Z, VII 其中alk係為具有1至18個碳原子之雙價烴基團；η· 係為2至12之整數；而Ζ為： /R /R R , —Si「R: —Si「RS 或—sfRt R* R· R· 其中R係為C1_C4烧基或苯基，且R’係為C1-C4烧氧 基，C5-C8環烷氧基，或CiCs烷巯基。 15·如申請專利範圍第12項之方法，其中該雙（烧氧基石夕 烷基烷基)-多硫化物係選自於下列群中：3,3'·雙(三甲 氧基碎烧基丙基一硫化物、3,3 -雙（三乙氧基砍烧基丙 基）四硫化物、3,3'-雙（三甲氧基矽烷基丙基）四硫化 物、2,2’-雙（三乙氧基矽烷基乙基）四硫化物、3,3，-雙（三 甲氧基矽烷基丙基）三硫化物、3,3·-雙（三乙氧基矽烷 基丙基）三硫化物、3,3·-雙（三丁氧基矽烷基丙基）二硫 _ -5- 本紙張尺度適用中國國家標準（) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁)502054 A8 B8 C8 _____D8 VI. Apply for a patent garden 12. If the method of applying for the scope of the first item of the patent, wherein the fluorenyl organometallic compound is a fluorenyl organometallic compound and a bis (alkoxysilyl) For a combination of sulfides, the weight ratio of the fluorenyl organometallic compound to the bis (alkoxysilylalkyl) polysulfide is at least greater than 1: 1. 13. The method according to item 12 of the patent application, wherein the The weight ratio of the organometallic compound to the bis (alkoxysilylalkyl) polysulfide is 5: 1 to 50: 1, and the inorganic oxide is Shendian silica. 14. The method of claim 12 in which the bis (alkoxysilylalkyl) polysulfide system has the following general formula VII: Z_al k-Sn'-al kZ, VII where alk is 1 A bivalent hydrocarbon group of up to 18 carbon atoms; η · is an integer from 2 to 12; and Z is: / R / RR, —Si ″ R: —Si ″ RS or —sfRt R * R · R · where R Is a C1-C4 alkyl group or a phenyl group, and R 'is a C1-C4 alkyl group, a C5-C8 cycloalkoxy group, or a CiCs alkylmercapto group. 15. The method according to item 12 of the application, wherein the bis ( Benzyloxyalkylalkyl) -polysulfide is selected from the group consisting of 3,3 '· bis (trimethoxypalylpropylmonosulfide, 3,3-bis (triethoxy) Carbamoylpropyl) tetrasulfide, 3,3'-bis (trimethoxysilylpropyl) tetrasulfide, 2,2'-bis (triethoxysilylethyl) tetrasulfide, 3 , 3, -bis (trimethoxysilylpropyl) trisulfide, 3,3 · -bis (triethoxysilylpropyl) trisulfide, 3,3 · -bis (tributoxysilane) Propyl) disulfide _ -5- This paper size applies to Chinese national standard (A4) Format (210 X 297 mm) (Please read the back of the precautions to fill out this page) 、申請專利範園 物3,3-雙（二甲氧基發烧基丙基）六硫化物以及3,3匕 雙（二辛氧基矽烷基丙基）四硫化物與其等混合物。 種經化學處理之填料，其係由如申請專利範圍第巧 項之方法所製得。 種經化學處理之填料，其係由如φ請專利範圍第4 項之方法所製得。 一種經化學處理之填料，里a 叶，、係由如申請專利範圍第12 項之方法所製得。 16. 17. _ 18.3. Patent applications: 3,3-bis (dimethoxypyroxypropyl) hexasulfide and 3,3 bis (dioctyloxysilylpropyl) tetrasulfide and mixtures thereof. A chemically-treated filler prepared by a method such as the one described in the patent application. A chemically treated filler, which is prepared by a method such as φ claim patent item 4. A chemically treated filler, a-leaf, is prepared by a method such as the scope of patent application No. 12. 16. 17. _ 18. (請先閱讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)