TW200400920A - Precipitated silica containing aluminum with adjustable BET/CTAB ratio - Google Patents

Abstract

The present invention relates to precipitated silica containing aluminum, which has an adjustable BET/CTAB ratio, a process for its manufacture and its use.

Description

200400920 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種含有鋁的沉澱矽石，其具有可調整 的BET/CTAB比，其製法和其用途。 【先前技術】 已經知道沉澱矽石於彈料混合物（如：輪胎）之使用。 高需求針對用於輪胎的矽石。它們必須容易分散於橡膠 中，及視情況地於偶合劑存在時，必須具有與橡膠或其他 塡料中所含的聚合物鏈之良好連接。除了矽石的可分散性 以外，比表面積（BET或CTAB)和吸油性（DBP)亦重要。比 表面積是矽石的總表面積（B E T)或外在表面積（C T A B )指 標，這兩種方法皆利用尺寸有變化的分子作爲吸附劑。這 些表面積係數比（即BET/CTAB表面積商）提供矽石孔洞尺 寸分佈的指標及矽石的’’總"與”外在”表面積關係。矽石的 表面積性質實質上決定它們的可能應用，或者，矽石的特 定應用（如：用於彈料混合物的載體系統或塡料）須要某些 表面性質。 因此，US 6 013 234提出BET和CTAB表面積是100 至3 5 0 m2/g的沉澱矽石之製造。此矽石特別適用以摻入彈 料混合物中，此處，BET/CTAB比介於1和1.5之間。 EP 〇 9 3 7 7 5 5提出各式各樣沉澱矽石，其BET表面積約 180至約430m2/g，CTAB表面積約160至340m2/g。這些 矽石特別適合作爲載體材料且BET/CTAB比是1.1至 1.3。EP 0 647 591提出一種沉澱矽石，其BET/CTAB表 (2) (2)200400920200400920 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a precipitated silica containing aluminum, which has an adjustable BET / CTAB ratio, a preparation method thereof, and a use thereof. [Previous Technology] The use of precipitated silica in ammunition mixtures (such as tires) has been known. High demand is for silica for tires. They must be readily dispersible in rubber, and optionally in the presence of a coupling agent, must have a good connection to the polymer chains contained in the rubber or other rubber. In addition to the dispersibility of silica, specific surface area (BET or CTAB) and oil absorption (DBP) are also important. The specific surface area is an indicator of the total surface area (B E T) or external surface area (C T A B) of silica. Both methods use molecules with varying sizes as adsorbents. These surface area coefficient ratios (ie BET / CTAB surface area quotients) provide an indicator of the distribution of the pore size of the silica and the relationship between the "total" and "external" surface area of the silica. The surface area properties of silica essentially determine their possible applications, or specific applications of silica (such as carrier systems or aggregates for ammunition mixtures) require certain surface properties. Therefore, US 6 013 234 proposes the manufacture of precipitated silica with a BET and CTAB surface area of 100 to 350 m2 / g. This silica is particularly suitable for incorporation into a bullet mixture, where the BET / CTAB ratio is between 1 and 1.5. EP 0 9 3 7 7 5 5 proposes various precipitated silicas having a BET surface area of about 180 to about 430 m2 / g and a CTAB surface area of about 160 to 340 m2 / g. These silicas are particularly suitable as support materials and have a BET / CTAB ratio of 1.1 to 1.3. EP 0 647 591 proposes a precipitated silica whose BET / CTAB table (2) (2) 200 400 920

面積比是0.8至1 . 1 ’此處的這些表面係數絕對値高至 35。m 2/§。EP 〇 643 015提出沉澱矽石，其可作爲牙膏中 的硏磨和/或稠化組份’其BET表面積是10至 1 3 〇 1112 ； ' CT AB 表面積是 10 至 7 0 m2 / g，即，B E T / C T A B 比約1至5.2 1。 輪胎製造中’常使用含鋁的沉澱矽石作爲塡料。 因此，E P 〇 9 8 3 9 6 6提出一種含鋁的沉澱矽石，其具 下列物化性質： BE 丁 表面積 8〇-18〇m2/g CTAB 表面積 80-l39m2/g DBF 數 l〇〇'320g/l〇〇g A 12 Ο 3 含量 &lt; 5 % 此類型沉澱矽石可經改善而作爲彈料塡料。 已經發現到，含鋁且Β Ε Τ表面積高的沉澱矽石特別 適合作爲塡料（如，用於輪胎）。 【發明內容】 本發明的標的因此是沉殿矽石，其 BET表面積在150-400m2/g範圍內，以19〇_3〇〇m2/g爲佳 CTAB 表面積在 140-350m2/g 範圍內，以 145_25〇nl2/g 爲 佳 1 45 -200m2/g A12 0 3含量在0 · 2 - 5重量％範圍內，以1 _ 3重量％爲佳， 可分別調整至較佳範圍。 -6 - (3) (3)200400920 根據本發明之沉澱矽石以具有特定BET/CTAB表面積 比爲佳。此BET/CTAB比可在1 .0- 1 .6範圍內，以1 .2- 1 .6 爲佳。 此外，此沉澱矽石的特徵在於wk係數（無法以超音波 崩解的顆粒之顆粒尺寸分佈在1 .0- 1 00 // m範圍內的最高 含量與尺寸&lt; 1 m的崩解顆粒的最高含量之間的比）$ 3.4，以〇·丨至3.4爲佳，特別佳者是0. 1至3.0和/或 DBP吸收是1 8 0-3 2 0g/100g，其中’本發明的第一個實施 例中的矽石之 DBP在較佳範圍 200-320 g/l〇〇g，250-320 g/l〇〇g和 250-300 g/100g之內，在本發明的另一實施 例中，DBP 於較佳範圍 l80-300g/100g 和 180-250g /1 00g ° 已知沉澱矽石具有明顯較高wk係數和/或顆粒尺寸 分佈最高點出現其他値。 已經知道Wk係數是沉澱矽石分散性的指標’其爲沉 澱矽石崩解性（分散性）指標。wk係數越小’沉澱矽石越 容易分散，即，摻入橡膠中時，更多顆粒分解。 根據本發明之沉澱矽石的BET和CTAB表面積或它 們的比値以在下列範圍內爲佳： (4) (4)200400920 B E T [ m 2 / g ] C T A Β Γ m2 / g ] BET/CTAB t匕 1 95 145 1.34 200 15 0 1 -Ί Λ 1 . j j 2 10 149 1.4 1 2 8 0 14 7 1.90 3 15 1 48 2.13 3 5 0 15 0 2 . j j 3 70 1 52 2.43 根據本發明之沉澱矽石之表面性質使得它們特別適合 作爲彈料的塡料。可藉經修飾的S e a r s數V 2確定，其値 以介於5和3 5 m 1 / 5 g之間爲佳，特別佳者介於2 0和 3 0 m 1 / 5 g 之間。 本發明的另一標的是性質如下的沉澱矽石之製法： BET表面積在150-400m2/g範圍內 CTAB表面積在l 40-3 5 0m2/g範圍內 AI2O3含量在0.2-5重量％範圍內’ 其中 a) 水玻璃水溶液充塡至容器中 b) 於5 5 - 9 5 °C攪拌時，水玻璃和酸化劑同時稱入此容 器中達30-100分鐘， c) 以酸化劑酸化至PH約5，及 d) 過濾和乾燥 -8- (5) (5)200400920 此處’鋁化合物於步驟b )和/或c )添加。 藉根據本發明之方法製得的砂石具有前述較佳參數 BET、CTAB、DBP、Al2〇3 含量和 sears 數。 步驟a)中引入的水玻璃溶劑濃度可以與步驟b )所用 的水玻璃濃度相同（如：密度 i.34%，27.4%，S!02， 8 . 1 % N a 2 Ο )。也可以使用稀釋溶液，如：〇 . 5 - 1 0 % S i Ο 2和 對應的 〇 . 1 5 °/。- 3 % N a 2 0。 步驟b)和c)中添加的構份（g卩，水玻璃和酸化劑）可具 有相同或不同濃度和/或添加速率。程序的變化中，這兩 個步驟中所用的構份濃度相同，在步驟c)中的構份進料速 率是步驟b )中之進料速率的1 2 5 _丨4 〇 %。另—變化中，步 驟c )中的進料速率僅步驟b )中的3 0 - 1 0 0，以5 0 - 8 0 %爲 佳。 除了水玻璃（矽酸鈉溶液）以外，也可以使用其他矽酸 鹽（如：砂酸鉀）。以使用硫酸作爲酸化劑爲佳，但也可以 使用其他酸化劑’如：hci、hno3、H3P〇4、CH3COOH或 C〇2。 銘化合物可於步驟b )和c )添加，亦可僅於步驟b )或c) 添加’其以固體、水溶液或酸化劑/鋁化合物混合溶液形 式添加。 鋁化合物可以是Ah(S〇4)3水溶液形式並以此爲佳， 但也可以是A1(N03)3、A1C13或Al(OAc)3,其於水中之濃 度是50-130g/l’以70-110g/丨爲佳。或者，可以使用酸化 劑/鋁化合物混合溶液。 (6) (6)200400920 專家知道根據本發明之矽石的過濾和乾燥，並可由， 如：前述專利文獻，得知。根據本發明之矽酸以藉短時間 乾燥方式（如：噴霧乾燥（視情況地於噴嘴乾燥機中）、閃 蒸和/或旋轉閃蒸乾燥機）乾燥爲佳。噴霧乾燥可根據， 如：U S 4 0 97 7 7 1進行。此處，於噴嘴乾燥機中製造沉澱 矽石，其顆粒平均直徑超過80，特別是超過90，特別佳 者超過2 0 0 μ m。 乾燥之後，有須要時，使用或不使用滾筒壓縮機硏磨 或粒化。此處，粒化之後之終產物的平均直徑2 1 m m。 據此，根據本發明之矽石可作爲，如：彈料混合物、 可硫化橡膠混合物、其他硫化粒（特別是用於輪胎者）、電 池隔絕物、防結塊劑、漆的無光澤劑、紙塗料、消沫劑、 電腦鍵盤、傳輸帶和/或窗密封劑中的塡料。 根據本發明之矽石可視情況地經式〗至ΠI表示的有 機矽化合物（矽烷）修飾 [R'n(RO)rSi(Alk)m(Ar)p]q[B] (I)， R1 n(R〇)3-nSi(Alkyl) (II)， 或 R'n(R〇)3-nSi(Alkenyl) (III), 其中， B ： -SCN、-SH、-SC(0)CH3、-SC(0)(CH2)6CH3、-C 卜 _NH2、-〇C(0)CHCH2、-〇C(0)C(CH3)CH2(若 q-1 )、 (7) (7)200400920 或- sx-(若 q = 2) ’ R和R1 :具2至3 0 C原子的脂族、稀族、芳族或芳 基芳族基團’其可視情況地經下列基團取代：經基、胺 基、醇基、氰基、硫氛基 '鹵素、磺酸、磺酸酯、硫赶、 苯甲酸、苯甲酸醋、碳酸、碳酸酯、丙烯酸酯 '異丁烯酸 醋、有機砂烷基，其中R和R1可具有相同或不同意義或 取代， n : 0 ; 1 或 2 ’ alk :具1至6個碳原子的二價非支鏈或支鏈烴基， m : 0 或 1， a r :具6至1 2 C原子（以6 C原子爲佳）的芳基’其可 經下列基團取代：經基、胺基、醇基、氰基、硫氰基、鹵 素、磺酸、磺酸酯、硫赶、苯甲酸、苯甲酸酯、碳酸、碳 酸酯、有機砂院基， P : 0或1，但p和η不同時爲0， X : 2 至 8， r ： 1、 2 或 3，但 r+n+m+p=4， a 1 k y 1 :具1至2 0個碳原子（以2至8個碳原子爲佳） 的一價非支鏈或支鏈不飽和烴基’ alkenyl:具2至20個碳原子（以2至8個碳原子爲佳） 的一價非支鏈或支鏈不飽和烴基。 根據本發明之矽石可經組成 R2uSiXn (n=l、2、 3) 、 [SiR2xXyO]z (0&lt;x&lt;2;0&lt;y&lt;2;3&lt;z&lt;10,x+y^2) 、 [SiR2xXyO]z (0&lt;x&lt;2; 0&lt;y&lt;2; 3&lt;z&lt;10, x+y+2) 、 (8) (8)200400920 S1R2nXmOSiR20XP (0&lt;n&lt;3 ; 〇 ^ m &lt; 3 ; 0&lt;〇&lt;3 ; 〇&lt;p&lt;3 , n + m = 3 , 0 + p = 3) ， SiR^Xn^SiR^Xp (0&lt;n&lt;3; 0 &lt; m &lt; 3; 0&lt;o&lt;3; 0&lt;p&lt;3 n + )-0 = 3, o + p = 3) 、SiR-nXm[SiR xXyO]zSiR 〇Xp (0&lt;n&lt;3: 0&lt;m^3； 〇&lt;x&lt;2; 0&lt;y^2; 0&lt;o&lt;3; 0&lt;p&lt;3; l&lt;z&lt;10000, n + m=〇，x + y = 2, 〇 + P = 3)。所示的有機矽化合物修飾。這 些化合物可爲直鏈、環狀和支鏈矽烷、矽氮烷和矽氧烷化 合物。R2可以是具1至20個碳原子的院基和/或芳基， 其可經官能基（如：羥基、胺基、多元醚（如：環氧乙烷和 /或環氧丙院）和鹵素基團（如：氟））取代。R 2亦可含有基 團，如：院氧基、稀基、快基和芳基和含硫基團。X可以 是反應性基團’如：砂院醇、胺基、硫赶、鹵化物、院氧 基、烯基和氫化物基團。 以使用具組成 SiR2nXm[SiR2xXyO]zSiR2QXp (〇SnS3; 〇 ^ m &lt; 3 ; 0 &lt; x &lt; 2 ; 0 &lt; y &lt; 2 ; 0 &lt; ο &lt; 3 ; 0 &lt; ρ &lt; 3 ; 1 &lt; ζ &lt; 1 0 0 0 0 , n + m = 3， x + y = 2, 0 + ρ = 3)的直鏈聚矽氧烷爲佳，其中 R2以代表甲 基爲佳。 特別佳的情況是使用具組成The area ratio is 0.8 to 1.1. These surface coefficients here are absolutely as high as 35. m 2 / §. EP 〇643 015 proposes precipitated silica, which can be used as a honing and / or thickening component in toothpaste 'whose BET surface area is 10 to 1 〇1112;' CT AB surface area is 10 to 70 m 2 / g, ie , BET / CTAB ratio is about 1 to 5.2 1. In tire manufacturing, aluminum-containing precipitated silica is often used as the material. Therefore, EP 0 9 8 3 9 6 6 proposes a precipitated silica containing aluminum, which has the following physical and chemical properties: BE but surface area 80--18m2 / g CTAB surface area 80-139m2 / g DBF number 100'320g / 100% A 12 Ο 3 content &lt; 5% This type of precipitated silica can be improved to be used as an elastic material. It has been found that precipitated silica containing aluminum and a high surface area of Beta E is particularly suitable as a binder (for example, for tires). [Summary of the Invention] The subject of the present invention is therefore Shendian Silica, whose BET surface area is in the range of 150-400m2 / g, and preferably in the range of 19-30m2 / g. The CTAB surface area is in the range of 140-350m2 / g. The content of 145_25〇nl2 / g is preferably 1 45 to 200 m2 / g, and the content of A12 0 3 is in the range of 0.2 to 5% by weight, and the content of 1 to 3% by weight is preferable, and can be adjusted to a better range, respectively. -6-(3) (3) 200400920 The precipitated silica according to the present invention preferably has a specific BET / CTAB surface area ratio. The BET / CTAB ratio can be in the range of 1.0-1.6, and preferably 1.2-1.6. In addition, this precipitated silica is characterized by a wk coefficient (the particle size distribution of particles that cannot be disintegrated by ultrasound is in the range of 1.0- 1 00 // the highest content and size of disintegrated particles <1 m The ratio between the highest content) is $ 3.4, preferably from 0.1 to 3.4, particularly preferably from 0.1 to 3.0 and / or the DBP absorption is 1 8 0-3 2 0g / 100g, of which 'the first The DBP of silica in one embodiment is within a preferred range of 200-320 g / 100 g, 250-320 g / 100 g, and 250-300 g / 100 g. In another implementation of the present invention, In the example, DBP is in the preferred range of 80-300g / 100g and 180-250g / 1 00g ° It is known that precipitated silica has a significantly higher wk coefficient and / or other peaks appear at the highest point of the particle size distribution. It has been known that the Wk coefficient is an index of the dispersibility of precipitated silica, and it is an index of the disintegration (dispersibility) of precipitated silica. The smaller the wk coefficient, the more easily the precipitated silica is dispersed, that is, the more particles are decomposed when incorporated into the rubber. The BET and CTAB surface areas of precipitated silica according to the present invention or their ratios are preferably within the following ranges: (4) (4) 200 400 920 BET [m 2 / g] CTA Γ m 2 / g] BET / CTAB t 1 95 145 1.34 200 15 0 1 -Ί Λ 1 .jj 2 10 149 1.4 1 2 8 0 14 7 1.90 3 15 1 48 2.13 3 5 0 15 0 2 .jj 3 70 1 52 2.43 Precipitated silicon according to the present invention The surface properties of the stones make them particularly suitable as a material for bullets. It can be determined by the modified Se a r s number V 2, and 値 is preferably between 5 and 35 m 1/5 g, and particularly preferably between 20 and 30 m 1/5 g. Another object of the present invention is a method for preparing precipitated silica with the following properties: BET surface area is within the range of 150-400m2 / g, CTAB surface area is within the range of 1-40-150m2 / g, and the AI2O3 content is within the range of 0.2-5% by weight. ' A) Water glass solution is filled into the container b) When stirring at 5 5-9 5 ° C, water glass and acidifier are weighed into the container at the same time for 30-100 minutes, c) acidified with acidifier to about pH 5, and d) filtered and dried -8- (5) (5) 200400920 where the 'aluminum compound is added in steps b) and / or c). The gravel prepared by the method according to the present invention has the aforementioned preferred parameters BET, CTAB, DBP, Al203 content and sears number. The concentration of the water glass solvent introduced in step a) may be the same as the concentration of the water glass used in step b) (eg, density i.34%, 27.4%, S! 02, 8.1% Na 2 0). Dilute solutions can also be used, such as: 0.5-10% S i Ο 2 and the corresponding 0.1 ° °. -3% N a 2 0. The components (g., Water glass and acidulant) added in steps b) and c) may have the same or different concentrations and / or addition rates. In the variation of the procedure, the component concentrations used in the two steps are the same, and the component feed rate in step c) is 1 2 5 4 0% of the feed rate in step b). Another—in a variation, the feed rate in step c) is only 3 0-1 0 0 in step b), and preferably 50-80%. In addition to water glass (sodium silicate solution), other silicates (eg potassium oxalate) can also be used. It is preferred to use sulfuric acid as the acidifying agent, but other acidifying agents' such as hci, hno3, H3P04, CH3COOH, or CO2 may also be used. The compound can be added in steps b) and c), or it can be added only in step b) or c), which is added as a solid, an aqueous solution, or an acidulant / aluminum compound mixed solution. The aluminum compound may be in the form of an aqueous solution of Ah (S〇4) 3, and it may also be A1 (N03) 3, A1C13, or Al (OAc) 3, and its concentration in water is 50-130 g / l 'to 70-110g / 丨 is better. Alternatively, a mixed solution of an acidifying agent / aluminum compound may be used. (6) (6) 200400920 Experts know the filtration and drying of silica according to the present invention, and can be known from, for example, the aforementioned patent documents. The silicic acid according to the present invention is preferably dried by a short-time drying method (such as: spray drying (optionally in a nozzle dryer), flash evaporation and / or rotary flash dryer). Spray drying can be performed according to, for example: U S 4 0 97 7 7 1. Here, the precipitated silica is produced in a nozzle dryer, and the average particle diameter is more than 80, particularly more than 90, and particularly preferably more than 200 μm. After drying, if necessary, honing or granulating with or without a roller compressor. Here, the average diameter of the final product after granulation is 21 mm. According to this, the silica according to the present invention can be used as, for example: elastomer mixtures, vulcanizable rubber mixtures, other vulcanizates (especially for tires), battery separators, anti-blocking agents, paint matting agents, paper Coatings, defoamers, computer keyboards, transmission belts and / or window sealants. The silica according to the present invention may optionally be modified with an organosilicon compound (silane) represented by the formulas [I] to [II] [R'n (RO) rSi (Alk) m (Ar) p] q [B] (I), R1 n (R〇) 3-nSi (Alkyl) (II), or R'n (R〇) 3-nSi (Alkenyl) (III), where B: -SCN, -SH, -SC (0) CH3,- SC (0) (CH2) 6CH3, -C BU_NH2, -〇C (0) CHCH2, -〇C (0) C (CH3) CH2 (if q-1), (7) (7) 200400920 or- sx- (if q = 2) 'R and R1: aliphatic, rare, aromatic or aryl aromatic groups having 2 to 3 0 C atoms' which may optionally be substituted by the following groups: via a group, Amine, alcohol, cyano, thiol, halogen, sulfonic acid, sulfonate, thiophene, benzoic acid, benzoic acid vinegar, carbonic acid, carbonate, acrylate 'methacrylic acid ester, organic sand alkyl group, among which R and R1 may have the same or different meanings or substitutions, n: 0; 1 or 2 'alk: a divalent unbranched or branched hydrocarbon group having 1 to 6 carbon atoms, m: 0 or 1, ar: having 6 An aryl group of 1 to 2 C atoms (preferably 6 C atoms) may be substituted by the following groups: via a amine group, an amine group, an alcohol group, a cyano group, a thiocyano group, a halogen, a sulfonic acid, a sulfonate, Sulfur Benzoic acid, benzoate, carbonic acid, carbonate, organic sand base, P: 0 or 1, but p and η are not 0 at the same time, X: 2 to 8, r: 1, 2 or 3, but r + n + m + p = 4, a 1 ky 1: a monovalent unbranched or branched unsaturated hydrocarbon group having 1 to 20 carbon atoms (preferably 2 to 8 carbon atoms) 'alkenyl: having 2 to A monovalent unbranched or branched unsaturated hydrocarbon group of 20 carbon atoms (preferably 2 to 8 carbon atoms). The silica according to the present invention may be composed of R2uSiXn (n = 1, 2, 3), [SiR2xXyO] z (0 &lt; x &lt;2; 0 &lt; y &lt;2; 3 &lt; z &lt; 10, x + y ^ 2), [SiR2xXyO] z (0 &lt; x &lt;2; 0 &lt; y &lt;2; 3 &lt; z &lt; 10, x + y + 2), (8) (8) 200400920 S1R2nXmOSiR20XP (0 &lt; n &lt;3; 〇 ^ m &lt;3; 0 &lt; 〇 &lt;3; 〇 &p; p &lt; 3, n + m = 3, 0 + p = 3), SiR ^ Xn ^ SiR ^ Xp (0 &lt; n &lt;3; 0 &lt; m &lt;3; 0 &lt; o &lt;3; 0 &lt; p &lt; 3 n +) -0 = 3, o + p = 3), SiR-nXm [SiR xXyO] zSiR 〇Xp (0 &lt; n &lt; 3: 0 &lt; m ^ 3; 〇 &lt; x &lt;2; 0 &lt; y ^ 2; 0 &lt; o &lt;3; 0 &lt; p &lt;3; l &lt; z &lt; 10000, n + m = 〇, x + y = 2, 〇 + P = 3). Modified organosilicon compound shown. These compounds can be linear, cyclic, and branched silanes, silazane, and siloxane compounds. R2 may be an alkyl group and / or an aryl group having 1 to 20 carbon atoms, which may be a functional group (such as a hydroxyl group, an amino group, a polyether (such as ethylene oxide and / or propylene oxide) and Halogen group (such as: fluorine)). R 2 may also contain groups such as: oxo, dilute, fast and aryl, and sulfur-containing groups. X may be a reactive group &apos; such as a saponol, an amine group, a sulfur group, a halide, a oxo group, an alkenyl group, and a hydride group. To use the composition SiR2nXm [SiR2xXyO] zSiR2QXp (〇SnS3; 〇 ^ m &lt;3; 0 &lt; x &lt;2; 0 &lt; y &lt;2; 0 &lt; ο &lt;3; 0 &lt; ρ &lt;3; 1 &lt; ζ &lt; 1 0 0 0 0, n + m = 3, x + y = 2, 0 + ρ = 3) linear polysiloxane is preferred, in which R2 is preferably methyl . A particularly good situation is to use

SiR2nXm[SiR2xXyO]zSiR2〇Xp (0&lt;n&lt;3; 0&lt;m&lt;3; 0&lt;x&lt;2; 0&lt;y&lt;2; 〇S〇S3 ; 0&lt;p&lt; 1 ; l&lt;z&lt;10000, n + m = 3, x + y = 2, o + p = 3)白勺聚石夕 氧烷，其中R2以代表甲基爲佳。 經以一或多種前述有機矽烷粒化、非粒化、硏磨和/ 或未硏磨的前述有機矽烷修飾，有機矽烷之混合物用量可 以是0.5至50份/ 100份沉澱矽石（特別是1至15份/ 1 Q 0份沉澱矽石）’藉此，沉澱矽石和有機矽烷之間的反 200400920 ⑼ 應可於製造混合物（原處）期間內或產製期間之外藉噴霧和 後續的混合物韌化處理、藉由使有機矽烷與矽石懸浮液混 合及後續乾燥和韌化（例如，根據D E 3 4 3 7 4 7 3和 D E 1 9 6 0 9 6 1 9 )或根據 D E 1 9 6 0 9 6 1 9 或 D E - P S 4 0 04 7 8 1 中所述方法進行。 所有的二官能性矽烷（其可一方面偶合至含矽烷醇基 的塡料，另一方面偶合至聚合物）基本上適合作爲有機矽 化合物。相對於沉澱矽石總量，有機矽化合物的一般量是 1至1 0重量％。 這些有機矽化合物的例子有：雙（3 -三乙氧基甲矽烷 基丙基）四硫、雙（3 -三乙氧基甲矽烷基丙基）二硫、乙烯基 三甲氧基矽烷、乙烯基三乙氧基矽烷、3 -锍基丙基三甲氧 基矽烷、3 -毓基丙基三乙氧基矽烷、3 -胺基丙基三甲氧基 矽烷、3 -胺基丙基三乙氧基矽烷。其他有機矽化合物述於 W099/09036、EP 1 108 231、DE 101 37 809、 DE 101 6 3 94 5、DE 1 02 2 3 658。 本發明的較佳實施例中，可以使用雙（3 -三乙氧基甲 矽烷基丙基）四硫和雙（3 -三乙氧基丙基）二硫作爲矽烷。 根據本發明之矽石於彈料混合物中之使用 根據本發明之矽烷可以5至200份/ 1 00份橡膠的 量，以粉末、微粒或顆粒且經矽烷修飾或未經矽烷修飾的 形式混入彈料混合物、輪胎或可硫化橡膠混合物中作爲強 化塡料。 -13 - (10) (10)200400920 前述一或多種矽烷可與矽石加至彈料中，此處，塡料 和砂完之間的反應發生於在提高溫度混合時（原處修飾）或 已修飾的形式中（例如，D E - P S 4 0 0 4 7 8 1 )，亦即，反應參 與者於確實製造反應以外的時候反應。 除了混合物（含有根據本發明之矽石以外，尙含或不 含根據式ί至111的有機矽烷作爲塡料）以外，彈料可以另 含有一或多種或多或少的強化塡料。第一個例子中，可用 於此處的碳黑（如：爐黑、氣體、燄黑 '乙炔碳黑）和根據 本發明之矽石（有和無矽烷）之摻合物，天然塡料（如：黏 土、含矽的白堊）、其他市售矽石和根據本發明之矽石之 摻合物。 此處與有機矽烷的摻合比配合最終橡膠混合物所欲達 到的性質。可以使根據本發明的矽石和其他前述塡料之間 的比爲5 - 9 5 % ’此亦合乎此體制內。 除了根據本發明的矽石以外，有機矽烷和其他塡料、 彈料是橡膠混合物的其他重要構份。根據本發明之矽烷可 用於可以促進劑/硫交聯且亦可以過氧化物交聯的所有彈 料。這些的例子是天然和合成、摻或不摻油的彈料，其爲 單一聚合物或與其他彈料（如：天然橡膠、丁二烯橡膠、 異間戊二烯橡膠、丁二烯苯乙烯橡膠（特別是SBR，藉溶 液聚合法製得）、丁二烯丙烯腈橡膠、丁基橡膠、乙烯/ 丙烯/非共軛二烯的三聚物）之摻合物。下列額外橡膠亦 可列入與前述橡膠之橡膠混合物的考慮範圍內：羧基橡 膠、環氧化物橡膠 '反式- polypentenamer '鹵化丁基橡 -14 - (11) (11)200400920 膠、得自2_氯丁二烯的橡膠、乙烯/乙酸乙烯酯共聚 物 '乙_/丙烯共聚物和選用之天然橡膠的化學衍生物及 經修飾的天然橡膠。 類似的已知者是其他構份，如：適用量的塑化劑、安 疋Μ 活化劑、顏料、抗氧化物和加工助劑。 根據本發明之矽石（有或無矽烷）用於所有橡膠應用， 如·輪胎、運輸帶' 密封、ν -帶、水管、鞋底.·等。 本發明的另一標的是彈料混合物，特別是可硫化的橡 膠混合物，其含有根據本發明之矽石，其量是5至2 0 0份 / 1 0 0份彈料或橡膠。處理此矽石和製造含有此矽石之混 合物係以橡膠工業常用的方式於內部混合機或開口滾筒硏 磨機中進行。可資利用的形式或使用形式可爲粉末、微粒 或細粒。此處，根據本發明之矽石與已知的白塡料並無不 同。 欲達聚合物混合物中之良好的組合値，沉澱矽石於基 質（聚合物）中之分散性有決定性的影響。 根據本發明之沉澱矽石於紙塗覆之使用 目前使用的墨水（用於所有所謂噴墨印刷和其相關方 法之類型者）大多本質爲陰離子性。因此，就固定著色劑 (染料和/或顏料）、顏色輝度、印刷明確和印刷深度而 言，欲印刷的介質表面上或其表面範圍中，顆粒具有至少 部分陽離子性表面。 目前，矽石和矽酸鹽通常用於前述塗覆調合物（如： (12) (12)200400920 紙、膜塗覆）。這些矽石和矽酸鹽之活化修飾（即，可採用 .的陽離子性位置（EP 0 49 2 2 6 3 ))發生於它們的表面上，與 常用陰離子性著色劑的目前要求相符。 因爲內置金屬離子對於折射指數之影響，使用透明介 質（例如’塗料中使用矽石/矽酸鹽用於箔片）有額外優 點。 因此，本發明的目的亦爲使用根據本發明之沉礙砂 石’或經由根據本發明之方法製造沉澱矽石作爲製紙或紙 塗覆之添加物。 特別地，根據本發明之沉澱矽石可用於紙塗覆（如： 噴墨紙）和其他印刷介質（如：完全沒入的膜或可印刷的織 品）之塗覆。 根據本發明之沉澱矽石不僅可爲經乾燥和視情況,經研; 磨的產物，也可以是分散液。根據本發明之沉澱矽石之，經 分散的濾餅用於紙漿或可印刷的介質之塗覆應用時，特別 能獲致進一步處理的優點或成本優點。 用於製紙時，可以在輔助劑（常用於紙工業者，如： 聚醇、聚乙烯醇、合成或天然聚合物）中，使顏料（Ti〇2、 Fe氧化物、A丨金屬濾餅）（也可以是未摻雜矽石者，即， 無鋁添加物（沉澱矽石或氣溶膠））與根據本發明之沉澱矽 石的分散液混合。 以下列方法測定根據本發明之沉澱矽石的物化數據： BET 表面積 Area meter，Strohlein，根據 IS05794/ (13) 200400920 C T A B表面積於ρ Η 9，根據 J a n z e n and Kraus in Rubber 〇gy 44(1971)1287SiR2nXm [SiR2xXyO] zSiR2〇Xp (0 &lt; n &lt;3; 0 &lt; m &lt;3; 0 &lt; x &lt;2; 0 &lt; y &lt;2;〇S〇S3; 0 &lt; p &lt;1; l &lt; z &lt; 10000, n + m = 3, x + y = 2, o + p = 3) Polyoxoxane, where R2 is preferably a methyl group. Modified with one or more of the aforementioned organic silanes, granulated, non-granulated, honed, and / or unhoned, the aforementioned organic silanes can be used in an amount of 0.5 to 50 parts per 100 parts of precipitated silica (especially 1 To 15 parts / 1 Q 0 parts of precipitated silica) 'This will allow the anti-200400920 之间 between the precipitated silica and the organosilane to be sprayed and subsequent mixtures during the manufacturing mixture (in situ) or outside the manufacturing period. Toughening treatment, by mixing the organosilane with the silica suspension and subsequent drying and toughening (for example, according to DE 3 4 3 7 4 7 3 and DE 1 9 6 0 9 6 1 9) or according to DE 1 9 6 0 9 6 1 9 or DE-PS 4 0 04 7 8 1. All difunctional silanes (which can be coupled to silanol-containing compounds on the one hand and to polymers on the other hand) are basically suitable as organosilicon compounds. The typical amount of the organosilicon compound is 1 to 10% by weight relative to the total amount of precipitated silica. Examples of these organosilicon compounds are: bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, vinyltrimethoxysilane, ethylene Triethoxysilane, 3 -fluorenylpropyltrimethoxysilane, 3 -ylpropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane. Other organosilicon compounds are described in W099 / 09036, EP 1 108 231, DE 101 37 809, DE 101 6 3 94 5, DE 1 02 2 3 658. In a preferred embodiment of the present invention, bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxypropyl) disulfide can be used as the silane. Use of silica according to the present invention in a projectile mixture. Silane according to the present invention may be mixed into the bomb in the form of powder, microparticles or granules with or without silane modification in an amount of 5 to 200 parts per 100 parts rubber It is used as a reinforcing material in rubber mixtures, tires or vulcanizable rubber mixtures. -13-(10) (10) 200400920 The aforementioned one or more silanes can be added to the ammunition with silica. Here, the reaction between the aggregate and the sand ends occurs when the temperature is mixed (modified in situ) or In the modified form (for example, DE-PS 4 0 4 7 8 1), that is, the reaction participants reacted when they did not actually make the reaction. In addition to the mixture (with or without the silica according to the invention, with or without the organosilanes according to formulae XI to 111), the bomb may additionally contain one or more reinforced concrete. In the first example, a blend of carbon black (eg, furnace black, gas, flame black 'acetylene carbon black) and silica (with and without silane) according to the present invention, (Eg, clay, silicon-containing chalk), blends of other commercially available silicas, and silicas according to the present invention. The blending ratio with the organosilane here matches the desired properties of the final rubber mixture. It is possible to make the ratio between the silica according to the present invention and the other aforementioned materials to be 5 to 95% ', which is also within this system. In addition to the silica according to the invention, organosilanes and other materials and elastomers are other important constituents of rubber mixtures. The silanes according to the invention can be used for all elastomers which can be accelerator / sulfur crosslinked and also peroxide crosslinked. Examples of these are natural and synthetic, blended or non-blended bullets, which are single polymers or with other bullets (eg natural rubber, butadiene rubber, isoprene rubber, butadiene styrene Blends of rubber (especially SBR, made by solution polymerization), butadiene acrylonitrile rubber, butyl rubber, terpolymer of ethylene / propylene / non-conjugated diene). The following additional rubbers can also be included in the consideration of rubber mixtures with the aforementioned rubbers: carboxylate rubber, epoxy rubber 'trans-polypentenamer' halogenated butyl rubber-14-(11) (11) 200400920 rubber, from 2 _Chloroprene rubber, ethylene / vinyl acetate copolymer 'Ethylene / propylene copolymer and chemical derivatives of selected natural rubber and modified natural rubber. Similar known ones are other components, such as: suitable amounts of plasticizers, AM activators, pigments, antioxidants and processing aids. Silica (with or without silane) according to the invention is used in all rubber applications, such as · tires, conveyor belts' seals, v-belts, hoses, soles, etc. Another object of the present invention is a projectile mixture, especially a vulcanizable rubber mixture, containing silica according to the present invention in an amount of 5 to 200 parts per 100 parts of a projectile or rubber. The processing of the silica and the manufacture of the mixture containing the silica are carried out in an internal mixer or open-drum honing machine in a manner commonly used in the rubber industry. Available forms or forms of use may be powders, granules or granules. Here, the silica according to the present invention is not different from the known white beet. To achieve a good combination of polymer mixtures, the dispersion of precipitated silica in the matrix (polymer) has a decisive effect. Use of Precipitated Silica According to the Invention for Paper Coating The inks currently used (for all types of so-called inkjet printing and related methods) are mostly anionic in nature. Therefore, the particles have at least a part of a cationic surface in terms of fixed colorants (dye and / or pigment), color brightness, print clarity, and print depth on the surface of the medium to be printed or in the surface range thereof. Currently, silica and silicate are commonly used in the aforementioned coating blends (eg: (12) (12) 200 400 920 paper, film coating). The activation modification of these silicas and silicates (ie, cationic sites that can be used (EP 0 49 2 2 6 3)) occur on their surfaces, in accordance with the current requirements for commonly used anionic colorants. Because of the effect of built-in metal ions on the refractive index, the use of transparent media (such as silica / silicates for foils in coatings) has additional advantages. Therefore, the object of the present invention is also to use precipitated sandstone according to the present invention or to manufacture precipitated silica as a paper-making or paper-coating additive by the method according to the present invention. In particular, the precipitated silica according to the present invention can be used for coating paper (for example, inkjet paper) and other printing media (for example, completely immersed film or printable fabric). The precipitated silica according to the present invention may be not only a dried and optionally ground product, a ground product, but also a dispersion. In the case of precipitated silica according to the present invention, the dispersed filter cake is particularly advantageous when it is used for coating applications of pulp or printable media to achieve further processing or cost advantages. When used in paper making, pigments (Ti〇2, Fe oxide, A 丨 metal filter cake) can be used in auxiliary agents (commonly used in the paper industry, such as: polyalcohol, polyvinyl alcohol, synthetic or natural polymers) ( It may also be an undoped silica, that is, an aluminum-free additive (precipitated silica or aerosol) is mixed with the dispersion of precipitated silica according to the present invention. The physical and chemical data of the precipitated silica according to the present invention were determined by the following methods: BET surface area Area meter, Strohlein, according to IS05794 / (13) 200400920 C T A B surface area at ρ Η 9, according to Ja n z e n and Kraus in Rubber ogy 44 (1971) 1287

Chemistry and Techno 測定矽石懸浮液之固體含量 矽石懸浮液（如：漿料）於iR乾燥機中乾燥至穩定重 量。乾燥ί貝失遇常主要包含水氣和僅微量其他揮發性成 份。 執行： 2.0g砂石懸浮液置於經事先稱重的鋁盤中，封住IR 乾燥器單元（M e 111 e r，L Ρ 1 6型）。—旦按下啓動鍵’懸浮 液開始於105 °c乾燥’每單位時間的重量降低量低於 2mg/12 0s時’自動停止。在裝置上選擇〇_1〇〇。/。模式，直 接顯示乾燥損耗（％)。重覆測定。 測定矽石水氣 根據此方法’遵循I S 0 7 8 7 - 2，於1 0 5。(：乾燥2小時 之後’定出砂石的揮發性部分（此處簡稱爲水氣）。此乾燥 損耗通常主要包含水氣。 執行： 1 0g粉末、球狀或粒狀矽石精確稱重至0.〗nig(經稱重 的樣品E) ’裝入經稱重並具有玻璃蓋（直徑8cm，高3cm) 的乾瓶中。此樣品於乾燥箱中於頂部開放的情況下於i 〇 5 -17 - (14) (14)200400920 ± 2 t乾燥2 h。之後，稱量瓶經密封並於使用矽膠作爲乾 燥劑的乾燥箱中冷卻至室溫。以重力計測定經稱重的A 部分。 根據（E ( g ) - A ( g )) X 1 〇 〇 % / E ( g )測得水氣 ％。 重覆測定。 測定D B P吸收 D B P吸收（D B P値）用以測定沉澱矽石的吸收力，此根 據DIN標準5 3 60 1測定： 執行 1 2.5 0 g含0 - 1 0 %水氣（視情況地，於1 〇 5 t：於乾燥箱中 乾燥以調整水氣含量）的粉末或球狀砂石加至 B r a b e n d e r Absorptometer ”E&quot;的捏和槽（物件編號 2 79 0 6 1 )中。以顆 粒爲例，使用3 . 1 5至1 m m (不绣鋼網、R e t s c h )的舗過部分 (使用塑膠抹刀溫和施壓使顆粒通過孔洞尺寸爲3 . 1 5mm的 篩網）。穩定攪拌（捏和槳旋轉速率是1 2 5 rp m)，苯二甲酸 二丁酯經由” D 〇 s i m a t e η B r a b e n d e r T 9 0 / 5 0 ” 以 4 m 1 / m i η 速 率於室溫滴至混合物中。以最小電力消耗混合，此可由數 位顯示器看出。測定終點時，混合物成爲糊狀，此由電力 消耗緩緩提高得知。顯示値爲6 0 0 (扭矩0.6 N m)時，藉電 力接觸關閉捏和機和DBP測定。用於DBP供應測定的同 步馬達連接至數位計數器，以讀取DBP(ml)。 (15) (15)200400920 執行 DBP吸收以g/100g表示，使用下列式自測得的DBP 計算得知。D B P於2 0 °C的密度基本上是1 . 0 4 7 g/m 1。 DBP 吸收（g/100g) = DBP 用量（ml) X DBP 密度（g/ml) X 100/12.5g D B P吸收定義用於無水之經乾燥的矽石。使用含水氣 的沉澱矽石時，此値須經下列校正表校正。經相關水含量 校正的値加至以實驗測得的D B P値；例如，水含量5 . 8 % 將意謂DBP吸收加上33g/100g。 (16) 200400920 用於苯二甲酸二丁酯吸收（無水）的校正表 水％ 水％ .0 .2 .4 .6 • 8 0 0 2 4 5 7 1 9 10 12 13 15 2 16 18 19 2 0 2 2 3 23 24 26 2 7 28 4 28 29 29 3 0 3 1 5 3 1 32 3 2 Ο 〇 Λ -&gt; 6 34 34 3 5 3 5 3 6 7 3 6 3 7 3 8 3 8 3 9 8 39 40 40 4 1 4 1 9 42 43 43 44 44 1 0 45 45 46 46 47Chemistry and Techno Determine the solids content of silica suspensions. Silica suspensions (such as slurries) are dried to a stable weight in an iR dryer. Dried shellfish often contain moisture and only trace amounts of other volatile components. Execution: 2.0g of gravel suspension is placed in a pre-weighed aluminum pan, and the IR dryer unit (M e 111 e r, L P 16 type) is sealed. -Once the start button is pressed, 'the suspension begins to dry at 105 ° C', and the weight reduction per unit time is less than 2mg / 120s, and it automatically stops. Select 0_1〇〇 on the device. /. Mode, directly displays the drying loss (%). Repeat the determination. Determining Silica Water Vapor According to this method ’follow I S 0 7 8 7-2 at 105. (: After 2 hours of drying, the volatile portion of the gravel (herein referred to as water vapor) is determined. This drying loss usually mainly includes water vapor. Execution: 10 g of powder, spherical or granular silica is accurately weighed to 0.〗 nig (weighed sample E) 'Into a dry bottle weighed with a glass lid (diameter 8cm, height 3cm). This sample was placed in a dry box with the top open at i 〇5 -17-(14) (14) 200 400 920 ± 2 t Dry for 2 h. After that, the weighing bottle is sealed and cooled to room temperature in a drying box using silicone as a desiccant. The weighed part A is measured by gravimeter Measured% moisture by (E (g)-A (g)) X 100% / E (g). Repeated measurement. Measurement of DBP absorption DBP absorption (DBP 値) is used to determine the absorption of precipitated silica Force, this is determined according to DIN standard 5 3 60 1: perform 1 2.50 g of powder containing 0-10% water vapor (optionally at 1.05 t: dried in a drying box to adjust the water vapor content) or Spherical sandstone is added to the kneading tank of Brabender Absorptometer "E &quot; (article number 2 79 0 6 1). Taking granules as an example, use 3 15 to 1 mm (non-embossed steel mesh, Retsch) paved part (use a plastic spatula to gently press the particles through a sieve with a hole size of 3. 15 mm). Stable stirring (kneading paddle rotation rate Is 1 2 5 rp m), dibutyl phthalate is dripped into the mixture at room temperature at a rate of 4 m 1 / mi η via "D osimate η Brabender T 9 0/50". Mix with minimal power consumption This can be seen by the digital display. At the end of the measurement, the mixture becomes mushy, which is known from the increase in power consumption. When the display is 6 0 (torque 0.6 N m), the kneader and DBP are turned off by power contact. Measurement. The synchronous motor used for the measurement of DBP supply is connected to a digital counter to read DBP (ml). (15) (15) 200400920 Perform DBP absorption expressed in g / 100g, using the following formula to calculate the self-tested DBP. The density of DBP at 20 ° C is basically 1.04 7 g / m 1. DBP absorption (g / 100g) = DBP dosage (ml) X DBP density (g / ml) X 100 / 12.5g DBP absorption Defined for anhydrous dried silica. When using moisture-precipitated silica, this should be corrected as follows Content corrected by the relevant correction Zhi water was added to the experimentally measured D B P Zhi;.. For example, a water content of 58% The mean DBP absorption plus 33g / 100g. (16) 200400920 Calibration water used for dibutyl phthalate absorption (anhydrous)% Water% .0 .2 .4 .6 • 8 0 0 2 4 5 7 1 9 10 12 13 15 2 16 18 19 2 0 2 2 3 23 24 26 2 7 28 4 28 29 29 3 0 3 1 5 3 1 32 3 2 〇 Λ-&gt; 6 34 34 3 5 3 5 3 6 7 3 6 3 7 3 8 3 8 3 9 8 39 40 40 4 1 4 1 9 42 43 43 44 44 1 0 45 45 46 46 47

藉雷射繞射測定wk係數：附聚尺寸分佈 φ 樣品製備 如果欲測定的矽石是顆粒’那麼將5 g矽石顆粒加至 燒杯中，較粗的顆粒以杵碾碎但非敲碎。1 .〇〇g經粉碎的 粉末或球狀矽石（含5 ± 1 %水氣’視情況地，於乾燥箱中 於1 0 5 °C乾燥以調整水氣或使濕度均勻），其於1 〇天內製 得，稱入具凸面底的3 0 m 1離心管（高7 c m，直徑3 c m，凸 面突出1 c m )中，並與2 0 · 0 m 1分散液（親水性砂石：2 0 · 0 g 六偏磷酸鈉（Baker))混合，以去離子水補足至1 0 00ml ;疏 -20- (17) (17)200400920 水性矽石：2 0 0.0 m 1試藥級乙醇和2 . 〇 m 1濃氣水溶液和 0.50g Triton X-100 (Merck)以去離子水補足至 l〇00ml)混 合。之後，離心管置於雙層壁的玻璃冷卻槽（容S 80ml， 高9 c m，直徑3 . 4 c m )中，此冷卻槽配備冷自來水（2 0 C )的 接頭，樣品以超音波套筒（Bendelin，具 Horn DH 13G的 U W 2 2 0 0型，鑽石板直徑1 3 m m )處理2 7 0秒鐘。此處’超 音波套筒的電力供應單元（Sonopuls，Bendelin ’ HD2200 型）設定於50%電力和80%脈衝（相當於0.8秒電力和0.2 秒脈衝）。懸浮液之加熱以水冷卻調整至不超過8 °C ° — 旦樣品在1 5分鐘之內加至雷射繞射單元的液體模組中’ 懸浮液以磁攪拌器攪拌以避免可能的沉積情況。 執行 測定之前，使雷射繞射單元L S 2 3 0 ( C 〇 u 11 e r )和液體模 組（具整體化超音波套筒 CV 181的 LS Variable Speed F 1 u i d Μ o d u 1 e P 1 u s，C o u 11 e r)熱機 2 小時，模組淸洗 1 〇 分 鐘（功能選單&quot;Control/rinse&quot;)。 單元的工作列中，使用功能選單&quot;M e a s u r e m e n t&quot;以選 擇檔条視窗&quot;C a 1 c u 1 a t e O p t. Μ o d e 1&quot;，折射指數如下列定義 於r ft檔案中：流體折射指數b.I. Real = 1.3 3 2;材料折射 指數 Real=1.46;虛擬=0.1。 檔案視窗中，’’Measuring CyCle”幫浦速率輸出設定於 2 6 %，整體化的超音波套筒c 丁 1 8 1超音波輸出設定於 3。超音波”during sample adding&quot;、&quot;1〇 seconds before (18) (18)200400920 e a c h m e a s u .r e m e n t ” 和&quot;d u r i n g m e a s u r i n g &quot;指不燈壳著。此 外，此檔案視窗中選擇下列指示： 設定補償測定，調整’背景測定’測定濃度’輸入樣 品資訊，輸入測定資訊’啓動2個測定’自動’淸洗和 PIDS數據。 校正之後，以 LS Size Control G15 Standard (Coulter) 測定，將背景測定列入。添加懸浮的矽石，直到達到45-5 5 %輕度吸收且單元顯示&quot;〇 K &quot;。 於室溫以前述定義的.fft檔案的評估模型測定。三次 重覆試驗各6 0秒鐘，各個矽石樣品之間的等待時間是〇 秒鐘。 由原始數據曲線，軟體基於體積分佈地（將Mie理論 和 F r a U n h 〇 f e r的光學模型列入考慮）計算顆粒尺寸分佈。 基本上，兩種統計方式的分佈曲線發現A模型介於〇 - 1 以m之間（最高約0.2 m)，B模型介於1 - 1 0 0 # m之間（最 高約5 μ m)。根據附圖1，可由此測定w k係數，所示者 是6次測定的平均値。 此處的基礎點是經由超音波輸入的能量，代表模擬經 由輪胎工業中之工業混合機中的機械力輸入的能量。 此曲線顯示第一個顆粒尺寸分佈最大値在1 . 0 // m -範圍內，另一最大値範圍cl.O/zm。在1.0-100 # m範圍內的峰是在超音波處理之後一部分仍未粉碎的矽 石顆粒。這些相當粗的顆粒於橡膠混合物中之分散欠佳。 小得多的顆粒尺寸（&lt; 1 0 y m)的第二個峰指出在超音波處 -22 - (19) (19)200400920 理期間內被粉碎的矽石顆粒。這些非常小的顆粒在橡膠混 合物中的分散非常良好。 w k係數是未崩解的顆粒（B )(其最大値出現於1 . 〇 - 1 〇 〇 μ m ( B ')範圍內）的峰高度與崩解的顆粒（a )(其最大値出現 於&lt;1 ·0 # m(A)處）的峰高度之間的比。 測定矽石之經修飾的Sears數 經修飾的Sears數（下文稱爲Sears數V2)是自由羥基 數的指標’其可藉由以pH6至pH9的氫氧化鉀溶液滴定 石夕石而定出。 下列化學反應構成此測定法的基礎，其中以”Si-OH” 代表矽烷醇基： ” S i，’ - Ο H + N a C 1 &quot; S i&quot; - Ο N a + H C 1 HC1 + KOH KCl + H2〇 執行 10.OOg粉末、球狀或粒狀矽石（含5 ± 1 %水氣）於 IKA Μ 20 通用硏磨機中硏磨60秒鐘（ 5 5 0 W ; 20,000rpm)。有 須要時，必須在乾燥槽中於1 0 5 °C乾燥或甚至濕化以調整 水氣含量。2.5 0g經此處理的矽石於室溫稱入2 5 0ml滴定 槽中，與60.0ml試藥級甲醇混合。樣品完全溶解之後， 添加40.〇ml去離子水，全數藉Ultra Turrax T 25 (KV-1 8 G攪样軸，直徑1 8 m m)於1 8，0 0 0 r p m分散3 0秒鐘。以 (20) (20)200400920 1 ο 0 m 1去離水將黏附於槽邊緣和攪拌器的樣品顆粒沖下’ 並置於2 S °c恆溫水浴中。 PH 計（Knick，型號：766 calimatic PH meter ’具溫 度感知器）和p Η電極（單桿測定鏈，S c h 〇 11 ’型號N 7 6 8 0 ) 於室溫以緩衝溶液（p Η 7.0 0和9.0 0)校正。首先，以P H計 測定懸浮液於2 5 r的起始pH値，之後視輸出而定’以氫 氧化鉀溶液（〇 _ 1 m 〇 1 /1)或鹽酸溶液（〇 . 1 m 0 1Π )調整至p Η値 6 . 〇 〇。調整至ρ Η 6 · 0 0的Κ Ο Η或H C 1溶液消耗（m 1)設定爲 V ,,。 之後，添加2 0.0 m 1氯化鈉溶液（2 5 0 . 〇 〇 g試藥級N a C 1 以去離子水加至 11)。持續以 〇. 1 m 〇 1 η κ Ο Η滴定至 ρΗ9·00。至ρΗ9.00的ΚΟΗ消耗設定爲V2’° 之後，先將V !，或V 2，標準化至1 g理論稱重樣品並擴 充至5倍，得到V t和S e a r s値V 2 (m 1 / 5 g )。多次重覆此測 定。 【實施方式】 實例 實例1 5 1.5 1水和 3 . 8 1水玻璃（密度1 . 3 4 6 k g /1 ’ 27.4%Si02、8.1%Na20)引至配備渦輪攪拌傳動裝置和雙殼 加熱器的高級不銹鋼製反應器中。 之後，於8 7 °C劇烈攪拌8 0分鐘時’添加8 · 2 1 / h水玻 璃、0.3451/h硫酸鋁溶液（n〇g/l Ah〇3)和〇.6 Ι/h硫酸 (21) (21)200400920 (9 6 %，密度 1 . 8 4 k g /1)。完成此添加之後，停止供應水坡 璃和硫酸鋁溶液，添加更多硫酸，直到2 0 °C懸浮液達 pH5.0。 所得懸浮液以一般方式過濾’以水淸洗至硫酸鈉濃度 &lt;4重量％。此濾餅以含水的硫酸和切剪單元液化。之後噴 霧乾燥此含1 6 %固體的矽石漿料。 所得粉末產物的BET表面積是195m2/g，CTAB表面 積是 145 m 2/g，DBP 吸收是 306g/l〇〇g，wk 係數是 1.46。 終產物的氧化鋁含量是1 .0%，Sears値V2是2 5.7 m 1/5 g。 實例2 5 1 . 5 1水和 3 . 8 1水玻璃（密度 1 . 3 4 6 k g /1， 27.4^0^02、8 . 1 %Na20)引至配備渦輪攪拌傳動裝置和雙殼 加熱器的高級不銹鋼製反應器中。 之後’於85 °C劇烈攪拌80分鐘時，添加8.21/h水玻 璃、0.8 65 1/h 硫酸鋁溶液（ll〇g/l Ah〇3)和 0.4 7 5 Ι/h 硫酸 (96% ’密度1 .84kg/l)。完成此添加之後，停止供應水玻 璃和硫酸鋁溶液，添加更多硫酸，直到2 0。(：懸浮液達 ρΗ5·0。 所得懸浮液以一般方式過濾，以水淸洗至硫酸鈉濃度 &lt;4重量％。此濾餅以含水的硫酸和切剪單元液化。之後噴 霧乾燥此含1 6 %固體的矽石漿料。 所得粉末產物的BET表面積是2 00 m2/g，C TAB表面 積是 150m2/g’ DBP 吸收是 285g/l〇〇g，wk 係數是 2.78。 -25- (22) (22)200400920 終產物的氧化鋁含量是2.0 %，S e ar s値V 2是2 3 . 2 m 1 / 5 g。 實例3 5 1.5 1水和 3.8 1水玻璃（密度 1 .3 4 6 k g /1 ， 2 7.4 % S i Ο 2 ' 8 . 1 % N a2 〇 )引至配備渦輪攪样傳動裝置和雙殼 加熱器的高級不銹鋼製反應器中。 之後，於8 3 °C劇烈攪拌8 0分鐘時，添加8 · 2 Ι/h水玻 璃、2.170 Ι/h 硫酸鋁溶液（110g/l Al2〇3)和 0.185 Ι/h 硫酸 (9 6 % ’密度1 . 8 4 k g /1)。完成此添加之後，停止供應水玻 璃和硫酸鋁溶液，以〇·475 Ι/h速率添加更多硫酸，直到 2〇°C懸浮液達PH5.〇。 所得懸浮液以一般方式過濾，以水淸洗至硫酸鈉濃度 &lt;4重量％。此濾餅以含水的硫酸和切剪單元液化。之後噴 霧乾燥此含1 8 %固體的矽石漿料。 所得粉末產物的BET表面積是210m2/g，CTAB表面 積是 149 m 2/g，DBP 吸收是 247g/100g，wk 係數是 3.11。 終產物的氧化鋁含量是4.5%，Sears値V2是25.7ml/5g。 實例4 下列實例使用下列物質：Determine the wk coefficient by laser diffraction: agglomeration size distribution φ sample preparation If the silica to be measured is a particle ’, add 5 g of silica particles to the beaker. The coarser particles are crushed with a pestle but not broken. 1.0 g of pulverized powder or spherical silica (containing 5 ± 1% water vapor ', as appropriate, dried in a drying cabinet at 105 ° C to adjust the water vapor or make the humidity uniform). Prepared within 10 days, weighed into a 30 m 1 centrifuge tube with a convex bottom (7 cm high, 3 cm in diameter, 1 cm convex) and mixed with 20 · 0 m 1 dispersion (hydrophilic sandstone) : 2 · 0 g sodium hexametaphosphate (Baker)) mixed with deionized water to make up to 100 ml; Shu-20- (17) (17) 200400920 water-based silica: 2 0 0.0 m 1 test grade ethanol It was mixed with 2.0 ml of a concentrated aqueous solution of gas and 0.50 g of Triton X-100 (Merck) (to make up to 100 ml with deionized water). After that, the centrifuge tube was placed in a double-walled glass cooling tank (capacity S 80ml, height 9 cm, diameter 3.4 cm). This cooling tank was equipped with a cold tap (20 C) connector, and the sample was an ultrasonic sleeve (Bendelin, UW 2 2 0 0 with Horn DH 13G, diamond plate diameter 13 mm) Processed for 2 70 seconds. Here, the power supply unit (Sonopuls, Bendelin 'HD2200 type) of the ultrasonic sleeve is set to 50% power and 80% pulse (equivalent to 0.8 second power and 0.2 second pulse). The heating of the suspension is adjusted by water cooling to no more than 8 ° C ° — once the sample is added to the liquid module of the laser diffraction unit within 15 minutes' the suspension is stirred with a magnetic stirrer to avoid possible deposition . Before performing the measurement, make the laser diffraction unit LS 2 3 0 (Coin 11 er) and the liquid module (LS Variable Speed F 1 uid Μ odu 1 e P 1 us with integrated ultrasonic sleeve CV 181, Co ou 11 er) warm up for 2 hours, clean module for 10 minutes (function menu &quot; Control / rinse &quot;). In the task bar of the unit, use the function menu &quot; M easuremen t &quot; to select the bar window &quot; C a 1 cu 1 ate O p t. Μ ode 1 &quot;, the refractive index is defined in the r ft file as follows: fluid refraction Index bI Real = 1.3 3 2; material refractive index Real = 1.46; virtual = 0.1. In the file window, the "Measuring CyCle" pump speed output is set to 26%, and the integrated ultrasonic sleeve c ding 1 8 1 ultrasonic output is set to 3. Ultrasonic "during sample adding &quot;, &quot; 1〇 seconds before (18) (18) 200400920 eachmeasu .rement ”and“ duringmeasuring ”means that the lamp is not on. In addition, select the following instructions in this file window: Set the compensation measurement, adjust the 'background measurement', and measure the concentration. Enter the measurement information 'Start 2 measurements' 'Automatic' washing and PIDS data. After calibration, use the LS Size Control G15 Standard (Coulter) measurement to include the background measurement. Add suspended silica until it reaches 45-5 5 % Mild absorption and unit display &quot; 〇K &quot;. Measured at room temperature using the evaluation model of the previously defined .fft file. Three repeated tests were 60 seconds each, and the waiting time between each silica sample was 0. From the raw data curve, the software calculates the particles based on the volume distribution (taking into account Mie theory and the optical model of Fraunhofer). Particle size distribution. Basically, the distribution curves of the two statistical methods found that the A model is between 0 and 1 m (up to about 0.2 m) and the B model is between 1 and 1 0 0 # m (up to about 5 m). μm). According to Figure 1, the wk coefficient can be determined from this. The value shown is the average 値 of 6 measurements. The basic point here is the energy input via ultrasonic waves, which represents the simulation through industrial mixers in the tire industry. The energy input by the mechanical force. This curve shows that the first particle size distribution has a maximum 値 in the range of 1. 0 // m-and another maximum 値 in the range cl.O / zm. Peaks in the range of 1.0-100 # m It is a part of silica particles that have not been pulverized after ultrasonic treatment. These relatively coarse particles are not well dispersed in the rubber mixture. The second peak of a much smaller particle size (&lt; 10 μm) indicates that Sonic Division-22-(19) (19) 200400920 Silica particles that have been crushed during the processing period. These very small particles are well dispersed in the rubber mixture. The wk coefficient is the undisintegrated particles (B) (its largest値 appeared in the peak heights and collapses in the range of 1.0-1000 μm (B '). The ratio between the peak heights of the resolved particles (a) (the largest value of which occurs at &lt; 1 · 0 # m (A)). The modified Sears number of silica (the modified Sears number (hereinafter referred to as The Sears number V2) is an indicator of the number of free hydroxyl groups, which can be determined by titrating stone spar with a potassium hydroxide solution at pH 6 to pH 9. The following chemical reactions form the basis of this assay, where "Si-OH" represents the silanol group: "S i, '-〇 H + N a C 1 &quot; S i &quot;-〇 N a + HC 1 HC1 + KOH KCl + H2〇 Honed 10.000 g of powder, spherical or granular silica (containing 5 ± 1% water vapor) in an IKA M 20 universal honing machine for 60 seconds (550 W; 20,000 rpm). When necessary, it must be dried or even humidified in a drying tank at 105 ° C to adjust the moisture content. 2.50 g of this treated silica is weighed into a 250 ml titration tank at room temperature and tested with 60.0 ml. Pharmaceutical grade methanol is mixed. After the sample is completely dissolved, 40.0 ml of deionized water is added, and all of it is dispensed by Ultra Turrax T 25 (KV-1 8 G stirring shaft, diameter 18 mm) at 18,000 rpm 3 0 seconds. (20) (20) 200400920 1 ο 0 m 1 to remove the water to rinse the sample particles adhering to the edge of the tank and the stirrer and put it in a 2 S ° C constant temperature water bath. PH meter (Knick, model: 766 calimatic PH meter 'with temperature sensor' and p Η electrode (single rod measuring chain, S ch 〇11 'model N 7 6 8 0) was calibrated with buffer solutions (p 溶液 7.0 0 and 9.00) at room temperature. First, determine the initial pH of the suspension at 2 5 r with a pH meter, and then depending on the output 'with a potassium hydroxide solution (〇_ 1 m 〇1 / 1) or a hydrochloric acid solution (0.1 m 0 1Π) Adjust to p Η 値 6. 〇〇. Adjust to ρ Η 6 · 0 0 K Ο Η or HC 1 solution consumption (m 1) is set to V ,,. After that, add 2 0.0 m 1 sodium chloride solution (2 50. 00 g of reagent grade Na C 1 was added to deionized water to 11). Titration with 0.1 m 〇1 η κ Ο Η was continued until ρΗ9 · 00. The consumption of ΚΟΗ to ρΗ9.00 was set to V2. After '°, first normalize V!, Or V 2 to a 1 g theoretical weighing sample and expand it to 5 times to obtain V t and Seas 和 V 2 (m 1/5 g). Repeat this measurement several times. [Embodiment] Examples Examples 1 5 1.5 1 water and 3. 8 1 water glass (density 1. 3 4 6 kg / 1 '27.4% Si02, 8.1% Na20) lead to equipped with a turbine stirring transmission device and double shell heater In a high-grade stainless steel reactor, after 8 minutes of vigorous stirring at 87 ° C for 8 minutes, '8 · 2 1 / h of water glass, 0.3451 / h aluminum sulfate solution (n0g / l Ah〇3) and .6 Ι / h sulfuric acid (21) (21) 200 400 920 (96% Density 1. 8 4 k g / 1). After this addition was completed, the water glass and aluminum sulfate solution was stopped and more sulfuric acid was added until the 20 ° C suspension reached pH 5.0. The resulting suspension was filtered in a general manner 'and washed with water to a sodium sulfate concentration &lt; 4% by weight. This filter cake is liquefied with aqueous sulfuric acid and a shearing unit. This silica slurry containing 16% solids was then spray-dried. The BET surface area of the obtained powder product was 195 m2 / g, the CTAB surface area was 145 m 2 / g, the DBP absorption was 306 g / 100 g, and the wk coefficient was 1.46. The final product has an alumina content of 1.0% and Sears 値 V2 is 2 5.7 m 1/5 g. Example 2 5 1. 5 1 water and 3. 8 1 water glass (density 1.3 3 6 kg / 1, 27.4 ^ 0 ^ 02, 8. 1% Na20) lead to a turbo agitator transmission and double shell heater High-grade stainless steel reactor. After that, while stirring vigorously at 85 ° C for 80 minutes, 8.21 / h of water glass, 0.8 65 1 / h of aluminum sulfate solution (110 g / l Ah〇3) and 0.4 7 5 Ι / h of sulfuric acid (96% 'density) were added. 1.84kg / l). After this addition is complete, stop supplying water glass and aluminum sulfate solution and add more sulfuric acid until 20. (: Suspension reaches ρΗ5.0. The resulting suspension is filtered in a general manner, washed with water to a sodium sulfate concentration &lt; 4% by weight. This filter cake is liquefied with aqueous sulfuric acid and a cutting and shearing unit. After that, the containing 6% solid silica slurry. The BET surface area of the resulting powder product is 200 m2 / g, the C TAB surface area is 150 m2 / g ', the DBP absorption is 285 g / 100 g, and the wk coefficient is 2.78. -25- (22 ) (22) 200400920 The final product has an alumina content of 2.0%, and Se ar s 2V 2 is 2 3.2 m 1/5 g. Example 3 5 1.5 1 water and 3.8 1 water glass (density 1.3 3 4 6 kg / 1, 2 7.4% S i 〇 2 '8.1. 1% N a2 〇) into a high-grade stainless steel reactor equipped with a turbine sample transmission and double shell heater. Afterwards, it was vigorously heated at 8 3 ° C. While stirring for 80 minutes, 8. 2 Ι / h of water glass, 2.170 Ι / h of aluminum sulfate solution (110 g / l Al2O3), and 0.185 Ι / h of sulfuric acid (96% 'density 1.8 4 kg / 1 ). After this addition was completed, the supply of water glass and aluminum sulfate solution was stopped, and more sulfuric acid was added at a rate of 0.475 l / h until the suspension at 20 ° C reached pH 5.0. The resulting suspension was in a general manner It was filtered and washed with water until the sodium sulfate concentration was <4% by weight. The filter cake was liquefied with aqueous sulfuric acid and a cutting and shearing unit. After that, the silica slurry containing 18% solids was spray-dried. The BET surface area of the obtained powder product It is 210m2 / g, CTAB surface area is 149m 2 / g, DBP absorption is 247g / 100g, wk coefficient is 3.11. The alumina content of the final product is 4.5%, and Sears 値 V2 is 25.7ml / 5g. Example 4 The following examples are used The following substances:

Krynol 1712 以乳液聚合反應爲基礎的苯乙烯丁二烯橡膠 X 50 S Si 69(雙（3-三乙氧基甲矽烷基丙基）四硫烷） 和N 330(碳黑，Degussa AG的市售品）的 5 0 : 5 0摻合物 -26- (23) (23)200400920Krynol 1712 Emulsion-based styrene butadiene rubber X 50 S Si 69 (bis (3-triethoxysilylpropyl) tetrasulfane) and N 330 (carbon black, available from Degussa AG) 5): 50 blend (26) (23) (23) 200 400 920

ZnO 氧化鋅 硬脂酸 N aftolene 芳族油ZnO zinc oxide stearic acid N aftolene aromatic oil

Lipoxol 4 0 0 0 聚乙二醇 V u 1 k a η o x N-(l，3 -二甲基丁基）-N’-苯基-對-苯二胺 402 0 DPG 二苯基胍 CBS N-環己基-2-苯噻基次磺醯胺 硫 根據本發明之沉澱矽石以粉末形式混合，標準矽石 U 11 r a s i 1 V N 2 G R ( D e g u s s a A G )則是以純 E - S B R 混合物形 式混合（數據單位是phr): K r y η ο 1 17 12 13 7.5 矽石 5 0 X 50 S 3 ZnO 3 硬脂酸 1 Vulkanox 4020 2 Lipoxol 4000 1.5 DPG 1.5 CBS 1.5 硫 2.2 (24) (24)200400920 使用Werner &amp; Pneiderer i.5N型混合機，所用條件 如下.4 m 1 η -1，1 :.丨i摩擦，捶擊壓力5 · 5巴，無效部 分1 · 6 1，塡充率〇 . 7 3 ’流通溫度9 〇 t。所用混合法是3 步驟法.步驟1 〇 - 1 m 1 η聚合物，1 _ 2 m丨n促進劑和硫以 外的額外構份’淸潔2 m i η ’混合2 - 5 m i η，淸潔（自3 m i η 混合’ 7 0 m i η · 1 )。之後’此混合物於室溫儲存2 4 h。步驟 2 : - 1 m 1 η步驟1批料於7 〇 ni i n - I塑化，塡充量〇 . 7 1，j · 3 m i η以速度變化維持批料溫度1 5 〇艺，3 m i n排料，於 室溫儲存4 h。步驟3 : 0 -2 m i n步驟2批料、混合促進劑 和硫於4 0 m i n _1、5 0 °C流通溫度和塡充率〇 . 6 9 2 m i η之後排 放的條件下，在實驗室用混合滾筒上（直徑2 0 m m，長 4 5 0 ιώ m、流通溫度5 0 °C )形成帶，藉由3 X右和切剪3 X 左’顛動 3x寬（3.5mm)和 3 x窄（1 m m)滾筒前端而均質 化，排出帶狀物。 根據 DIN 5 3 5 2 9/2或ISO 6 5 02於 160°C進行硫化試 驗，根據 DIN 5 3 5 0 4測定電壓模量和破裂時拉伸率，根據 DIN 5 3 5 0 5 於 2 3 °C 測定 S h 〇 r e 硬度，根據 A S 丁 M D 5 3 0 8 測定球回彈率，根據A S T M D 5 6 2 3 A測定積聚熱（0.1 7 5英 吋，stroke，25 mi η)，根據 ASTM D 2231-87(10Hz，事先 拉緊 1 0 %，A m p 1. S w e e p ; 0 . 1 5 · 7 %)測定 Μ T S 數攄，藉表 面起伏測定分散係數[A.Wehmeier，&quot;Filler Dispersion Analysis by Topography Measurements”， Technical Report TR 8 2 0, Degussa AG, Applied Technology AdvancedLipoxol 4 0 0 0 Polyethylene glycol V u 1 ka η ox N- (l, 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine 402 0 DPG diphenylguanidine CBS N- Cyclohexyl-2-phenylthienylsulfenamidinium sulfide The precipitated silica according to the present invention is mixed in powder form, while standard silica U 11 rasi 1 VN 2 GR (D egussa AG) is mixed in the form of a pure E-SBR mixture ( Data unit is phr): K ry η ο 1 17 12 13 7.5 Silica 5 0 X 50 S 3 ZnO 3 Stearic acid 1 Vulkanox 4020 2 Lipoxol 4000 1.5 DPG 1.5 CBS 1.5 Sulfur 2.2 (24) (24) 200 400 920 Use Werner & Pneiderer i.5N mixer, the conditions used are as follows: 4 m 1 η -1, 1:. 丨 i friction, thrashing pressure 5 · 5 bar, invalid part 1 · 6 1, filling rate 0.7 3 'Flow temperature 9 〇t. The mixing method used is a three-step method. Step 1 0- 1 m 1 η polymer, 1 _ 2 m 丨 n promoter and additional components other than sulfur '淸 洁 2 mi η' Mixed 2-5 mi η, 淸(From 3 mi η mixed '7 0 mi η · 1). 'This mixture was then stored at room temperature for 24 h. Step 2:-1 m 1 η Step 1 batch was plasticized at 〇ni in-I, the charge was 0.7. 1, j · 3 mi η maintained the batch temperature at a speed of 1500 ° C, and discharged in 3 minutes. Material, stored at room temperature for 4 h. Step 3: 0-2 min Step 2 batch, mixing accelerator and sulfur at 40 min _1, 50 ° C circulation temperature and filling rate 0.6. 2 mi η in the laboratory under the conditions of discharge after discharge A belt is formed on the mixing drum (diameter 20 mm, length 450 mm, circulation temperature 50 ° C), with 3 X right and cut 3 X left 'tumbling 3x wide (3.5mm) and 3 x narrow (1 mm) Homogenize the front end of the drum and discharge the ribbon. Vulcanization test according to DIN 5 3 5 2 9/2 or ISO 6 5 02 at 160 ° C, voltage modulus and elongation at break measured according to DIN 5 3 5 0 4 and 2 3 according to DIN 5 3 5 0 5 ° C Sh 〇re hardness was measured, ball rebound rate was measured according to AS Ding MD 5 3 0 8, heat of accumulation was measured according to ASTM D 5 6 2 3 A (0.1 7 5 inches, stroke, 25 mi η), according to ASTM D 2231-87 (10 Hz, tightened 10% in advance, A mp 1. S weep; 0.1 5 · 7%) to measure the M TS number and determine the dispersion coefficient by surface fluctuations [A. Wehmeier, &quot; Filler Dispersion Analysis by Topography Measurements ", Technical Report TR 8 2 0, Degussa AG, Applied Technology Advanced

Fillers]。 (25)200400920Fillers]. (25) 200 400920

Ultrasil 根據本發明實 根據本發明實 VN2 GR 例1的矽石 例2的矽石 ML(l+4), 100 °C ；2nd [ME] 51 52 56 MDR:160°C； 0.5° t90% [min] 9.9 9.6 9.8 t80%-t20% [min] 2.7 2.6 2.6 硫化粒數據 模量100% [MPa] 1.1 1.3 1.3 模量300% [MPa] 4.6 5.3 5 破裂時張力 [%] 470 450 450 Shore A硬度 [SH] 52 52 52 球回彈率，o°c [%] 19.3 19.5 20.5 球回彈率，6(TC [%] 65 65.4 67.8 Goodrich Flexometer, 0.225inch, 25min; RT 熱積聚 rc] 79 79 79 永久固定 [%] 1.8 1.7 1.7 MTS, 16Hz, 50N+/-25N E*, 0°C [MPa] 7.7 8.4 8.3 E*, 60°C [MPa] 5.0 5.2 5.2 tan d, 0°C H 0.282 0.277 0.263 tan d, 60°C [-] 0.100 0.102 0.100 分散形態 峰面積 [%] 3.9 1.8 2.6Ultrasil According to the present invention, according to the present invention, the silica ML (l + 4) of the silica of Example 1 and VN2 GR of Example 2 are 100 ° C; 2nd [ME] 51 52 56 MDR: 160 ° C; 0.5 ° t90% [ min] 9.9 9.6 9.8 t80% -t20% [min] 2.7 2.6 2.6 Vulcanized pellet data Modulus 100% [MPa] 1.1 1.3 1.3 Modulus 300% [MPa] 4.6 5.3 5 Tension at break [%] 470 450 450 Shore A Hardness [SH] 52 52 52 Ball rebound rate, o ° c [%] 19.3 19.5 20.5 Ball rebound rate, 6 (TC [%] 65 65.4 67.8 Goodrich Flexometer, 0.225inch, 25min; RT heat accumulation rc] 79 79 79 Permanently fixed [%] 1.8 1.7 1.7 MTS, 16Hz, 50N +/- 25N E *, 0 ° C [MPa] 7.7 8.4 8.3 E *, 60 ° C [MPa] 5.0 5.2 5.2 tan d, 0 ° CH 0.282 0.277 0.263 tan d, 60 ° C [-] 0.100 0.102 0.100 Peak area of dispersion form [%] 3.9 1.8 2.6

-29 (26) (26)200400920 相較於標準矽石 mtrasil VN2 GR，根據本發明的矽 石1和2之模量値高，破裂時拉伸率高，E Μ直較高，分散 性明顯改善（相當於耐磨性較佳）。此外，根據本發明的兩 種矽石的熱積聚均勻，表面積亦高於 U 11 r a s i 1 V Ν 2 G R。 此相當於在動態張力下的加熱行爲良好，自此可使得彈料 混合物於張力下的服務壽命一樣高。 【圖式簡單說明】 附圖1是計算wk係數所須値的圖示。-29 (26) (26) 200400920 Compared with standard silica mtrasil VN2 GR, the modulus of silica 1 and 2 according to the present invention is high, the elongation is high at the time of breaking, the EM is high, and the dispersion is obvious. Improved (equivalent to better wear resistance). In addition, the two silicas according to the present invention have uniform heat accumulation and a surface area higher than that of U 11 r a s i 1 V Ν 2 G R. This is equivalent to good heating behavior under dynamic tension, and since then it can make the service life of the elastomer mixture under tension as high. [Brief Description of the Drawings] FIG. 1 is a diagram showing the necessary calculation of the wk coefficient.

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Claims (1)

(1) 200400920 拾、申請專利範圍 1. 一種沉澱矽石，其特徵在於 B E T 表面積 1 5 0 - 4 0 0 m 2 / g CTAB 表面積 1 4 0 - 3 5 0 m 2 / g A h 〇 3含量〇 . 2 - 5重量％。 2 .如申請專利範圍第]項之沉澱矽石，其中沉澱矽石 的 DBP 吸收是 180 至 320g/100g。 3 .如申請專利範圍第1或2項之沉澱矽石，其中沉澱 矽石的BET/CTAB表面積比是1.0至1.6。 4 ·如申請專利範圍第1或2項之沉澱砂石，其中沉澱 矽石的修飾s e a r s數V 2是5至3 5 m 1 / 5 g。 5 .如申請專利範圍第1或2項之沉澱矽石，其中其表 面經下列式表示的有機矽烷修飾 fR n(R〇)rSi(Alk)m(Ar)p]q[B] ⑴， R 丨“R〇)3-nSi(Alkyl) (II), 或 Rl _“R〇)3-nSi(Alkenyl) (III)， 其中， B : 'SCN、-SH、-SC(0)CH3、-SC(0)(CH2)6CH3、-Ci、-NH2、-〇c(0)CHCH2、-0C(0)C(CH3)CH2(若 q=l ) ' 或-sx-(若 q = 2 ), R和R1 :具2至30C原子的脂族、烯族、芳族或芳 基芳族基團，其可視情況地經下列基團取代：羥基、胺 基、醇基、氰基、硫氰基、鹵素、磺酸、磺酸酯、硫赶、 2556 -31 - (2) 200400920 笨申酸、苯甲酸酯、碳酸、碳酸酯、丙烯酸酯、甲基丙烯 酸酿、有機矽烷基’其中R和R1可具有相同或不同意義 或取代， n : 0 ; 1 或 2， alk:具1至6個碳原子的二價非支鏈或支鏈烴基， m : 〇 或 1， ar:具6至12C原子（以6C原子爲佳）的芳基，其可 威T列基團取代：羥基 '胺基、醇基、氰基 '硫氰基、鹵 素、磺酸、磺酸酯、硫赶 '苯甲酸、苯甲酸酯、碳酸、碳 酉突酿、有機矽烷基’ ρ : 0或1，但Ρ和η不同時爲0， X : 2 至 8， r: 1 ' 2 或 3，但 r + n + m + p = 4， alkyl:具1至20個碳原子（以2至8個碳原子爲佳） 的單價非支鏈或支鏈不飽和烴基， alkenyl:具2至20個碳原子（以2至8個碳原子爲佳） 的單價非支鏈或支鏈不飽和烴基。 6 . —種製造性質如下之沉澱矽石的方法 BET表面積在150-400m2/g範圍內 CTAB表面積在1 40-3 5 0m2/g範圍內 Al2〇3含量在0.2-5重量°/。範圍內’ 其中 a) 水玻璃水溶液充塡至容器+ b) 於5 5 - 9 5。(：攪拌時’水玻璃和酸化劑同時稱入此容 -32 - (3) (3)200400920 器中達30-100分鐘， c) 以酸化劑酸化至ρ Η約5，及 d) 過濾和乾燥 在此條件，鋁化合物於步驟b)和/或c)添加。 7.如申請專利範圍第6項之方法，其中步驟b)和〇所 供應成份濃度相同或不同。 8 .如申請專利範圍第6或7項之方法，其中步驟b)和 c)所供應成份的進料速率相同或不同。 9.如申請專利範圍第8項之方法，其中步驟b)和…中 所供應成份的濃度相同，步驟c )中的進料速率是步驟b ) 中進料速率的1 1 0至200%。 1 〇 .如申請專利範圍第8項之方法，其中步驟b )和c ) 中所供應成份的濃度相同’步驟c)中的進料速率是步驟b ) 中進料速率的50至1 〇〇%。 1 1 .如申請專利範圍第6或7項之方法，其中藉旋轉 閃蒸、噴嘴乾燥器或噴霧乾燥器和/或具/不具滾筒加壓 機的粒化器乾燥。 1 2 .如申g靑專利範圍第6或7項之方法’其中沉殿砂 石經式I至111所示有機矽烷修飾，有機矽烷混合物用量 是0_5至50份/ 1〇〇份沉澱矽石（特別是丨至15份/ 1〇〇 份沉澱矽石）’藉此，沉澱矽石和有機矽烷之間的反應在 製造混合物（原處）期間內或產製期間之外藉噴霧和後續的 混合物回火處理、藉由使有機矽烷與矽石懸浮液混合及後 續乾燥和回火的方式進行。 -33- (4) (4)200400920 1 3 . —種可硫化的橡膠混合物和硫化粒，其含有如申 ^ 請專利範圍第1至6項中任一項之沉澱矽石。 1 4 . 一種輪胎，其含有如申請專利範圍第1項之沉澱 矽石。 1 5 . —種如申請專利範圍第1項之沉澱矽石於電池分 隔器、抗結塊劑、漆、紙塗料或消沫劑中的無光澤劑、密 封劑、電腦鍵盤、傳輸帶和/或窗密封劑上之應用。(1) 200400920 Scope of application and patent application 1. A precipitated silica characterized by a BET surface area of 150-4 0 m 2 / g CTAB surface area of 1 40-3 50 m 2 / g A h 〇3 content 〇. 2-5% by weight. 2. The precipitated silica according to item [Scope of the patent application], wherein the DBP absorption of the precipitated silica is 180 to 320g / 100g. 3. The precipitated silica according to item 1 or 2 of the patent application scope, wherein the BET / CTAB surface area ratio of the precipitated silica is 1.0 to 1.6. 4. The sedimentary sandstone according to item 1 or 2 of the patent application scope, wherein the modification s e a r s number V 2 of the precipitated silica is 5 to 3 5 m 1/5 g. 5. The precipitated silica according to item 1 or 2 of the patent application scope, wherein the surface is modified with an organosilane represented by the following formula: fR n (R〇) rSi (Alk) m (Ar) p] q [B] ⑴, R丨 "R〇) 3-nSi (Alkyl) (II), or Rl_" R〇) 3-nSi (Alkenyl) (III), wherein: B: 'SCN, -SH, -SC (0) CH3,- SC (0) (CH2) 6CH3, -Ci, -NH2, -〇c (0) CHCH2, -0C (0) C (CH3) CH2 (if q = 1) 'or -sx- (if q = 2) , R and R1: aliphatic, olefinic, aromatic or aryl aromatic groups having 2 to 30C atoms, optionally substituted with the following groups: hydroxyl, amine, alcohol, cyano, thiocyanate Base, halogen, sulfonic acid, sulfonate, thiosulfate, 2556 -31-(2) 200400920 Bensonic acid, benzoate, carbonic acid, carbonate, acrylate, methacrylic acid, organosilyl group, where R And R1 may have the same or different meanings or substitutions, n: 0; 1 or 2, alk: a divalent unbranched or branched hydrocarbon group having 1 to 6 carbon atoms, m: 〇 or 1, ar: having 6 to 12C atom (preferably 6C atom) aryl group, which may be substituted by T group: hydroxy'amino group, alcohol group, cyano'thiocyano group, halogen, Acid, sulfonate, sulfonate, 'benzoic acid, benzoate, carbonic acid, carbon monoxide, organic silyl group' ρ: 0 or 1, but P and η are not 0 at the same time, X: 2 to 8, r : 1 '2 or 3, but r + n + m + p = 4, alkyl: a monovalent unbranched or branched unsaturated hydrocarbon group having 1 to 20 carbon atoms (preferably 2 to 8 carbon atoms), alkenyl: a monovalent unbranched or branched unsaturated hydrocarbon group having 2 to 20 carbon atoms (preferably 2 to 8 carbon atoms). 6. A method for producing precipitated silica with the following properties: BET surface area is in the range of 150-400m2 / g; CTAB surface area is in the range of 1-40-3 50m2 / g; Al2O3 content is 0.2-5 wt. Within the range 'where a) the water glass solution is filled to the container + b) at 5 5-95. (: While stirring, 'water glass and acidifying agent are weighed into this container at the same time -32-(3) (3) 200400920 for 30-100 minutes, c) acidified with acidifying agent to ρ Η approximately 5 and d) filtered and Drying Under these conditions, the aluminum compound is added in steps b) and / or c). 7. The method according to item 6 of the patent application, wherein the concentrations of the ingredients supplied in steps b) and 0 are the same or different. 8. The method of claim 6 or 7, wherein the feed rates of the ingredients supplied in steps b) and c) are the same or different. 9. The method of claim 8 in which the concentration of the ingredients supplied in steps b) and ... is the same, and the feed rate in step c) is from 110 to 200% of the feed rate in step b). 10. The method according to item 8 of the scope of patent application, wherein the concentrations of the ingredients supplied in steps b) and c) are the same. The feed rate in step c) is 50 to 100% of the feed rate in step b). %. 1 1. The method according to item 6 or 7 of the scope of patent application, wherein drying is performed by rotary flash, nozzle dryer or spray dryer and / or granulator with / without roller press. 12. The method according to claim 6 or 7 of the patent scope, wherein the Shendian sandstone is modified by the organic silane shown in Formulas I to 111, and the amount of the organic silane mixture is 0-5 to 50 parts per 100 parts of the precipitated silica. (Especially 丨 to 15 parts / 100 parts of precipitated silica) 'Through this, the reaction between the precipitated silica and the organosilane is by spraying and subsequent mixtures during the production of the mixture (in situ) or outside the production period. Tempering is performed by mixing the organosilane with the silica suspension and subsequent drying and tempering. -33- (4) (4) 200400920 1 3. A vulcanizable rubber mixture and vulcanized pellets containing precipitated silica as described in any one of claims 1 to 6 in the patent application. 1 4. A tire comprising the precipitated silica as described in item 1 of the patent application scope. 1 5. A matting agent such as precipitated silica in battery separators, anti-blocking agents, lacquers, paper coatings, or antifoaming agents such as item 1 of the scope of patent application, sealants, computer keyboards, transmission belts and / Or window sealant. -34 --34-