TW424106B - Emulsion styrene-butadiene rubber compositions, styrene-butadiene rubber latex and tire treads and tires comprising the same - Google Patents
Emulsion styrene-butadiene rubber compositions, styrene-butadiene rubber latex and tire treads and tires comprising the same Download PDFInfo
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- TW424106B TW424106B TW088103716A TW88103716A TW424106B TW 424106 B TW424106 B TW 424106B TW 088103716 A TW088103716 A TW 088103716A TW 88103716 A TW88103716 A TW 88103716A TW 424106 B TW424106 B TW 424106B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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06 A7 B7 42 d 五、發明説明 發明背兔_ 種邁眾多I橡膠產物由苯乙烯-丁二烯橡膠（SBR)製造 _ =如，大量S B R經使用於製造汽車、貨車、飛機及其他 頫里車輛所用輪胎。SBR通常用於製造輪胎，因為它一般 會改善聚丁二烯橡膠之牽引特徵。 R可藉使用落液或乳化聚合技術而加以合成。由乳化 聚合所製造之SBR(乳化SBR) 一般在胎面化合物表現較 優之牵引特徵。然而’由溶液聚合（溶液SBR)所製造之 SBR在面方面一般會表現更優良滾動阻力及胎面耐磨特 徵二基於此理由，溶液SBR通常被視為優於乳化sbr， 目前之售價優於乳化S B R。 藉溶液聚合技術合成SBR時，使用能夠溶解單體（1，3_ 丁 一婦及苯乙缔），S B R及聚合觸媒或起始劑之有機溶劑 。當進行聚合時，製成SBR在溶射之落液。有時稱此聚 合物溶液為"聚合物接合劑,，。接著從聚合物接合劑中回收 SBR ，然後可作為所欲應用上之乾燥橡膠；例如用於調配 胎面。 用於合成S B R之典型乳化系統包含水、乳化劑（皂），自 由基產生劑二苯乙烯單體及丨，3_丁二缔單體。例如，在自 由基乳化聚合系統中，過氧化物或過氧二硫化物之分解會 產生自由基β 常用起始劑包含三級丁基過氧化氫，蒎烷過氧化氩，對 萜烷過氧化氫’過氧亞硫酸鉀（K2S2〇s)，苯甲酿過氧化 物’枯烯過氧化氫及偶氮雙異丁腈（AI BN)。這些化合物 本纸張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） (請先閲讀1r面之注*意事項κί r本頁) -裝-06 A7 B7 42 d 5. Description of the invention Invention of the rabbit _ A variety of I rubber products are made of styrene-butadiene rubber (SBR) _ = For example, a large number of SBR is used in the manufacture of cars, trucks, aircraft and other prone Vehicle tires. SBR is commonly used to make tires because it generally improves the traction characteristics of polybutadiene rubber. R can be synthesized by using liquid dropping or emulsion polymerization techniques. SBR (emulsified SBR) produced by emulsion polymerization generally exhibits superior traction characteristics in tread compounds. However, 'SBR made by solution polymerization (solution SBR) generally shows better rolling resistance and tread abrasion resistance. For this reason, solution SBR is generally considered to be superior to emulsified sbr, and the current price is superior. In emulsifying SBR. When synthesizing SBR by solution polymerization technology, an organic solvent capable of dissolving monomers (1,3_ butyl and styrene), S B R and polymerization catalyst or initiator is used. When the polymerization is carried out, the SBR is made to fall into solution. This polymer solution is sometimes referred to as " polymer cement. SBR is then recovered from the polymer cement, which can then be used as a dry rubber for the desired application; for example, for the preparation of treads. A typical emulsification system used to synthesize S B R includes water, an emulsifier (soap), a free radical generator, a stilbene monomer, and a 3-butadiene monomer. For example, in free-radical emulsion polymerization systems, the decomposition of peroxides or peroxodisulfides can generate free radicals. Β Common starters include tertiary butyl hydroperoxide, pinane argon peroxide, and terpene peroxidation. Hydrogen 'potassium peroxysulfite (K2S2Os), benzoyl peroxide' cumene hydrogen peroxide and azobisisobutyronitrile (AI BN). These compounds are sized according to the Chinese National Standard (CNS) A4 (210X297 mm).
、1T 經濟部智慧財產局員工消費合作社印製 五、發明説明（） 屬熱不穩定性’以中等速率分解而釋出自由基。通常使用 過氧亞硫酸钾與硫醇如十二基硫醇之混合來聚合丁二烯及 SBR 。在熱配方中，硫醇具經由與過氧亞硫酸鹽反應而提 供自由基及藉與一成長鏈反應使其終止並起始另—鏈之成 長而限制聚合物分子量之雙重功能。此種使用硫醇作為鏈 轉移劑或改質劑在以乳化製備’s B R具重要商機，因為它允 許控制橡膠靭度，否則會限制在工廠之加工性。 一種適合工業使用之標準聚合配方係習知之”互相"，„ 準’ G R -s "或"熱"配方。此種標準聚合配方包含以下 組份（以重量為基準）：75 〇份丁二烯，25份笨乙烯 ’ 〇 · 5份正-十二基硫醇’ 〇 . 3份過氧亞疏酸鉀，5 〇份皂 片及180.0份水。 當此標準配方與5 0。(：聚合溫度一起使用時，聚合物之 轉化率為每小時5至6百分比。聚合在70至75百分比轉 化率時終止’因為高轉化率會導致聚合物物理性質及加工 性劣化’可能是因為乳膠顆粒交聯而形微膠或高度支鏈結 構。此種終止係添加速止物’’如氫醌（約〇 .丨份重量），其 快速與自由基及氧化劑反應。因此，速止物破壞任何殘留 起始劑’也與聚合基反應而防止形成新鏈。然後除去未反 應單體；首先，先後在大氣壓及減壓下藉急驟蒸餾除去丁 二烯’然後在管柱内藉汽提除去苯乙烯。 典型添加抗氧化劑分散物以保護s B R不氧化。然後藉 添加鹽水，然後以缔硫酸或硫酸鋁完全絮凝而使乳膠部份 * · 絮凝（膏化）。然後沖洗絮凝化粒化生膠，乾燥，包裝供運 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公楚〉 ---------裝-- (請先聞讀t面之注•意事項^ Γ本頁) 訂 線 經濟部智慧財產局員工消f合作社印製 ο Α7 Β7 五、發明説明（ 經濟部智惡財產局8:工消費合作社印製 輸°對基本方法之首要改盖& ^法中，苯乙締，丁二缔4 :用連續方 '法。在此連續方 m速續㈣存料人並智―/^1及活化顚助起始劑 —切, 不列維持在適當溫度之攪拌反 應器’使得在最後反庥器ψ ^ ,,,^ 。D出口達到所要轉化率。然後加入 汽加溫轉，急驟_未反應丁二浠。块 /量冬乙烯’為乳㈣整，通常係與油摻混，乳油 化’絮凝化，乾燥及包裝。 關於SBR及"標準配方"之進—步資料，可參考The VanderbUt Rubb- Handbook, George G. Winspear (Editor) R τ \r 」( 1 96 8)，34 至 57頁\ Vanderbllt Company，Inc美國專利第5,583, 173號揭示—種製備苯乙烯_ 丁二烯 橡膠义礼膠之万法，其包含⑴將水，皂系統，自由基產 生训，1，> 丁二烯單體及苯乙烯單體加入第一聚合區域； (2)使1,J-丁二缔單體及苯乙缔單體於第一聚合區域中共 聚合成為單體轉化範圍約為15百分比至約4〇百分比而製 成低轉化率來合媒介，（3 )將低轉化率聚合媒介加入第二 永S區^ 4 )將額外數量1，3 - 丁二烯單體及額外數量苯 乙烯單體加入第二聚合區域；（5 )使共聚合持績，直到達 到早體轉化至少約5 〇百分比而製成笨乙烯—丁二烯橡膠乳 膠此方法有時被稱為F I Μ (入料_注射-單體）方法。 藉使用美國專利第5，5 8 3，1 7 3號所揭示技術，藉乳化 聚合製成苯乙烯-丁二烯橡膠所需要皂數量可減少3 〇百分 比以上。此係有利的，因為降低成本且對環境上具吸引力 »6 - 本紙張尺度通财關家縣（CNs) α视格（2歐加公楚） (請先閲讀t·面之ίΐ.意事項^{ ?本頁> .裝. 訂. 線 五 發明説明（ Α7 Β7 經濟部智葸財產局員工消費合作社印製 。美國專利第5,5 8 3，173^料其所述方法所製得苯乙 缔-丁二浠橡膠提供殘以含量減少之優點。此係減少最終 產物如輪胎之脂肪酸起霜（bl00m)特徵，並且在製備輪胎 程序使層更容易黏著在一起^ 發明概要 本發明揭示一種用於大幅改善乳化SBR物理#質之技 術。事實上，本發明乳化SBR可用於製備具備類似以溶液 S B R製備之牽引及滾動阻力特徵而不會損失胎面耐磨特徵 之胎面調配物。因此，本發明乳化SBR在用於胎面化合物 4許多方面均優於溶液SBR.及傳統SBR。當然，此係因 為本發明獲待改善之乳化SBR可用於製備表現大幅獲改善 之牽引特徵及滾動阻力而不會損失胎面耐磨特徵之胎面化 合物。換言之，本發明乳化S B R具在胎面橡膠調配物應用 上之改善特徵。 本發明獲改善乳化SBR係製備於摻合高分子量SBR乳 化物及低分子量S B R乳化物及共絮凝此乳膠摻合物。本發 明獲改善乳化S B R較佳係製備於摻合由f I Μ方法所製高 分子量S B R乳化物與由F丨μ方法所製低分子量s B R乳化 物及共絮凝it乳膠摻合物。此高分子量SBR典型之數目平 均分子量範固約200,〇〇〇至约1，〇0〇,〇〇〇 ，重量平均分 子量範圍約300,〇〇〇至2，〇〇〇,000。此低分子量SBR典 型之數目平均分子量範圍約20,000至約150,000，重量 平均分子量範圍約40,000至280,000 。使高分子量 S B R具備結合苯乙烯含量與低分子量s B R之結合苯乙烯 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） ---------i-- t (請先閱讀*背面之ii-意事項^β本頁) 訂 -線 4241U 6 Α7 五、發明説明（ 含量之差距至少為5百分點是很重要的。此高分子量sbr 與型具備與低分子量SBR之結合笨乙缔含量差距至少為 百分點之結合苯乙烯，較佳至少15百分點，最佳至 2 0百分點。 本發明更特定地揭示一種乳化笨乙烯_丁二烯橡膠组合 物，其包含（1)重量平均分子量至少約3〇〇,〇〇〇之高分; 量苯乙烯-丁二烯橡膠及（11)重量平均分子量约小於 23(^000之低分子量苯乙諦_ 丁二烯橡膠；其中高分子量 苯乙缔·丁二烯橡膠對低分子量.苯乙烯-丁二烯橡膠之比例 範圍約S〇:2〇至約25:75 ;其中高分子量苯乙烯_ 丁二缔 橡膠之結合苯乙烯含量與低分子量笨乙晞-丁二埽橡膠之結 合苯乙缔含量之差距至少為5百分點；其中苯乙缔-丁二缔 橡膠组合物係藉共絮凝高分子量苯乙烯-丁二烯橡膠乳修及 低分子量苯乙烯-丁二烯橡膠乳膠之摻合物而製備；及其中 高分子量苯乙烯-丁二烯橡膠及低分子量苯乙稀_丁二婦橡 膠乳膠係之製備方法包含（1 )將水，皂系統，自由基產生 劑’ 1，3 - 丁二烯單體及苯乙烯單體加入第—聚合區域； (2)使1,3 -丁二烯單體及苯乙烯單體於第—聚合區域中共 聚合成為單轉化範圍約為1 5百分比至約4 〇百分比而製 成低轉化率聚合媒介，（j)將低轉化率聚合媒介加入第_ 聚合區域；（4)將额外數量1,3 -丁二歸·單體及额外數量苯 乙烯單體加入第二聚合區域；（5 )使共聚合持續，直到達 到單體轉化至少約5 0百分比而製成苯乙烯-丁二歸橡膠乳 膠。 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） ---------^1 (請先聞讀Irf之汰意事項t ?本頁 訂 線 經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T. 5. Description of the invention () It is thermally unstable and decomposes at a moderate rate to release free radicals. Mixtures of potassium peroxysulfite and mercaptans such as dodecyl mercaptan are commonly used to polymerize butadiene and SBR. In hot formulations, thiols have the dual function of providing free radicals by reacting with peroxysulfite and terminating and initiating another-chain growth by reacting with a growing chain to limit the molecular weight of the polymer. This use of thiol as a chain transfer agent or modifier has important business opportunities in the preparation of 's B R by emulsification, because it allows the control of rubber toughness, which would otherwise limit the processability in the factory. A standard polymerization formula suitable for industrial use is known as the "mutual", "quasi" G R -s " or " hot " formula. This standard polymerization formula contains the following components (based on weight): 7500 parts butadiene, 25 parts stupid ethylene '0.5 parts n-dodecyl mercaptan' 0.3 parts potassium peroxysulfite , 50 parts of soap tablets and 180.0 parts of water. When this standard formula comes with 5 0. (: When used together with polymerization temperature, the polymer conversion rate is 5 to 6 percent per hour. The polymerization is terminated at 70 to 75 percent conversion 'because the high conversion rate will lead to deterioration of polymer physical properties and processability' may be because Latex particles are cross-linked to form a microgel or highly branched structure. This type of termination is the addition of a shortstop `` such as hydroquinone (about 0.1 parts by weight), which quickly reacts with free radicals and oxidants. Therefore, the shortstop Destroy any residual initiator 'and also react with the polymer to prevent the formation of new chains. Then remove unreacted monomers; first, butadiene is removed by rapid distillation under atmospheric pressure and reduced pressure, and then stripped in the column Removal of styrene. Antioxidant dispersion is typically added to protect the s BR from oxidation. Then the latex portion is flocculated by adding brine and then fully flocculated with sulphuric acid or aluminum sulfate * · Flocculation (paste). Then rinse the flocculation to granulate Raw rubber, dry, packaging for transportation This paper is sized for China National Standards (CNS) A4 (210X297). --------- Package-(Please read the notes and notices on t side first ^ (Γ page) The line is printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the cooperative. Α7 Β7 V. Description of the invention (Printed by the Intellectual Property Office of the Ministry of Economic Affairs 8: printed by industrial and consumer cooperatives. The primary overhaul of the basic method & Ethylene Association, Dingzhou Association 4: Continuous method is used. Here the continuous method is used to continuously save the material and make it ^ / ^ 1 and the activation assisting starter-cut, not to mention the stirring reaction maintained at an appropriate temperature. The reactor 'makes the final reactor ψ ^ ,,, ^. D outlet reaches the desired conversion rate. Then add steam to warm up, and quickly _ unreacted succinic acid. Block / amount of winter ethylene' is milking, usually the system Blended with oil, emulsified, 'flocculated, dried and packaged. For further information on SBR and " standard formula ", please refer to The VanderbUt Rubb-Handbook, George G. Winspear (Editor) R τ \ r' ' (196 8), pages 34 to 57 \ Vanderbllt Company, Inc. US Patent No. 5,583, 173 discloses a method for preparing styrene_butadiene rubber gelatin, which includes water, soap system, and free Basic training, 1,> Butadiene monomer and styrene monomer are added to the first polymerization region; (2) Copolymerization of 1, J-butadiene monomer and styrene-ethylenic monomer in the first polymerization zone to a monomer conversion range of about 15% to about 40% to make a low conversion rate, (3) Add a low conversion polymerization medium to the second permanent S zone ^ 4) Add an additional amount of 1,3-butadiene monomer and an additional amount of styrene monomer to the second polymerization zone; (5) Keep the copolymerization performance until This method is sometimes referred to as the FI M (feed_injection-monomer) method to produce stupid ethylene-butadiene rubber latex with at least about 50 percent early body conversion. By using the technology disclosed in US Patent No. 5,5 8 3, 173, the amount of soap required to make styrene-butadiene rubber by emulsion polymerization can be reduced by more than 30%. This is advantageous because it reduces costs and is attractive to the environment »6-This paper scales Tongcai County (CNs) α Sight (2 European and Canadian) (Please read t. 面 之 ίΐ. 意Matters ^ {? This page >. Binding. Order. Thread 5 Invention Description (Α7 Β7 Printed by the Employee Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs. US Patent No. 5,5 8 3,173 The styrene-butadiene rubber provides the advantage of reduced residual content. This is to reduce the fatty acid bloom (bl00m) characteristics of the final product, such as tires, and to make the layers easier to stick together during the tire preparation process ^ SUMMARY OF THE INVENTION A technique for greatly improving the physical properties of emulsified SBR is disclosed. In fact, the emulsified SBR of the present invention can be used to prepare a tread formulation having similar traction and rolling resistance characteristics as those prepared with a solution SBR without losing the tread wear characteristics. Therefore, the emulsified SBR of the present invention is superior to solution SBR and traditional SBR in many aspects for use in tread compound 4. Of course, this is because the emulsified SBR to be improved by the present invention can be used to prepare traction characteristics with significantly improved performance and Rolling resistance Tread compounds without losing the abrasion resistance of the tread. In other words, the emulsified SBR of the present invention has improved characteristics in the application of tread rubber formulations. The improved emulsified SBR is prepared by blending a high molecular weight SBR emulsion and Low molecular weight SBR emulsion and co-flocculate this latex blend. The improved emulsified SBR of the present invention is preferably prepared by blending a high molecular weight SBR emulsion prepared by the f I M method with a low molecular weight s prepared by the F 丨 μ method BR emulsion and co-flocculation latex blend. The typical number of this high molecular weight SBR ranges from about 200,000 to about 10,000, and the weight average molecular weight ranges from about 300,000. 0 to 2,000,000. This typical low molecular weight SBR has an average molecular weight ranging from about 20,000 to about 150,000 and a weight average molecular weight ranging from about 40,000 to 280,000. The high molecular weight SBR has a combination of styrene content and low molecular weight s BR. Combined with the standard of styrene, this paper applies the Chinese National Standard (CNS) A4 specification (210x297 mm) --------- i-- t (please read the ii-intentions on the back * ^ this page) Order -Line 4241U 6 Α7 V. Description of the invention (It is important that the content difference is at least 5 percentage points. This high-molecular-weight sbr and type have a combination with low-molecular-weight SBR. The content of ethylene is at least a percentage of the combined styrene, preferably at least 15%. , Optimum to 20%. The present invention more specifically discloses an emulsified styrene-butadiene rubber composition, which comprises (1) a high weight average molecular weight of at least about 30,000, the amount of styrene; -Butadiene rubber and (11) low molecular weight styrene-butadiene rubber with a weight average molecular weight of less than 23 (^ 000); of which high molecular weight styrene-butadiene rubber has a low molecular weight. Styrene-butadiene The ratio of olefinic rubber ranges from S0: 20 to about 25:75; of which the combined styrene content of high molecular weight styrene_butadiene rubber and the combined styrene content of low molecular weight styrene-butadiene rubber The gap is at least 5 percentage points; the styrene-butadiene rubber composition is prepared by co-flocculating a blend of high molecular weight styrene-butadiene rubber latex and low molecular weight styrene-butadiene rubber latex; Polymer Styrene-butadiene rubber and low-molecular-weight styrene-butadiene rubber latex-based preparation method includes (1) water, soap system, radical generator '1,3-butadiene monomer and benzene Ethylene monomer is added to the first polymerization zone; (2) It is prepared by copolymerizing 1,3-butadiene monomer and styrene monomer in the first polymerization zone to a single conversion range of about 15% to about 40%. Into a low-conversion polymerization medium, (j) adding a low-conversion polymerization medium to the first polymerization zone; (4) adding an additional amount of 1,3-butanediene monomer and an additional amount of styrene monomer to the second polymerization zone (5) The copolymerization is continued until a monomer conversion of at least about 50% is reached to make a styrene-butaneic rubber latex. This paper size applies to Chinese National Standards (CNS > A4 size (210X297 mm) --------- ^ 1 (Please read Irf's considerations first? 本页 本页 线 线 本页) Printed by Employee Consumer Cooperative
本發明亦揭一種乳化苯乙烯-丁二烯橡膠組合物，其包 含U)數目平均分子量約為2〇〇,〇〇〇至約1，〇〇〇,〇〇〇之高 分子量苯乙烯-丁二烯橡膠及（11)數目平均分子量約為 2〇,000至約15〇,000之低分子量苯乙烯_ 丁二烯橡膠； 其中高分子量苯乙烯-丁二烯橡膠對低分子量苯乙烯-丁二 蜂橡膠之比例範圍約8 〇 : 2 〇至約2 5 : 7 5 ;其中高分子量苯 乙締-丁二烯橡膠之結合苯乙烯含量與低分子量苯乙烯-丁 二婦橡膠之結合苯乙缔含量之差距至少為5百分點；其中 笨乙烯-丁二烯橡膠組合物係藉共絮凝高分子量苯乙婦-丁 二烯橡膠乳膠及低分子量苯乙烯-丁二烯橡膠乳膠之摻合物 而製備*及其中高分子量苯乙烯-丁二烯橡膠及低分子量苯 乙烯-丁二烯橡膠乳膠係之製備方法包含（丨）將水，皂系統 ’自由基產生劑，1，3 - 丁二烯單體及苯乙烯單體加入第一 聚合區域；（2 )使1，3 - 丁二烯單體及苯乙烯單體於第一聚 合區域中共聚合成為單體轉化範圍約為1 5百分比至約4 〇 百分比而製成低轉化率聚合媒介；（3)將低轉化率聚合媒 介加入第二聚合區域；（4)將額外數量丨，3_ 丁二烯單體及 額外數量苯乙烯單體加入第二聚合區域；使共聚合持 續，直到達>到單體轉化至少約50百分比而製成苯乙烯-丁 二烯橡跟乳膠。 本發明更關於一種本乙婦-丁二婦樣媵組合物，其包4 衍生自苯乙烯及Ιί3· 丁二烯之重覆單元，其中笨乙婦-丁 二烯橡膠组合物經熱場流分級測定之數目平均分子量範圍 約5 0,0〇〇至^ 5 0,000 ，其中苯乙烯-丁二烯橡膠之光散 ___ -9- 本紙張尺度( CNS ) A—规格（21Gx297公釐) '^-- (請先閲讀f-面之ΪΪ-愈事項k r本頁 -裝· 線 絰濟部智慧財產局員工消費合作社印Μ 五 、發明説明 Α7 Β7 經濟部智惡財產局員工消费合作社印製 射對折射係數比例為1 , S比3 , 9。 本發明更揭露-種苯乙烯_丁二烯㈣组合物，里包各 料自之重„元，其中頻率對數^ 尽乙缔-丁二婦橡膠組合物之倚存模數女 、 — 模歡 < 作圖與頻率對數與 本乙稀-丁二烯橡膠组合物之損失模數夕此函 S㈣數〈作®於頻率對數範 園為〇_〇〇1弧度/秒至100弧度/秒，於 ^ Ι5ί 進灯並在笨 乙烯-丁二烤橡膠之動態振動掃使用平行板幾何學時有交又 a ^本發明更揭露一種苯乙烯-丁二缔橡膠组合物，其包含 何生自苯乙烯及1，3 -丁二缔之重覆單元，其中頻率對數對 苯乙烯-丁二烯橡膠组合物，頻率對數與苯乙烯-丁二烯橡 膠組合物之儲存模數之作圖與頻率對數與苯乙烯_丁二埯橡 膠組合物之損失模數之作圖於頻率對數範圍為〇 〇〇ι弧度 /秒至1 0 0弧度/秒，於1 2 0 ec進行並在苯乙烯_ 丁二烯橡 膠之動態振動掃使用平行板幾何學時有交叉，其中笨乙缔 丁二烯橡膠組合物經熱場流分級測定之數目平均分子量^ 圍約50, 000至150,000 ，其中苯乙烯丁二烯橡膠之光 散射對折射係數比例為1 . 8比3.9。 本發明亦揭示一種乳化苯乙烯-丁二烯橡膠組合物，其 製法包含共絮凝乳膠组合物，其包含（a )水，（b )乳化劑， (c)重量平均分子量至少約300,000之高分子量苯乙缔丁 二晞橡膠及（d)重量平均分子量約小於280, 〇〇〇之低分子 量苯乙烯-丁二烯橡膠；其中高分子量苯乙烯-丁二缔橡膠 對低分子量苯乙烯-丁二烯橡膠之比例範圍約8 0 : 2 0至約 • 10 · 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） (讀先閱讀r面之Vi-意事項^£*本頁} -裝' 訂 A7 B7 五、發明説明（） 25:75 ;其中高分子量苯乙埽_ 丁二烯橡膠之結合苯乙烯含 量與低分子量苯乙烯-丁二烯橡膠之結合苯乙烯含量之差距 至少為5百分點》 本發明更揭示一種苯乙烯-丁二埽橡膠組合物，其包含 衍生自苯乙歸及1,3 -丁二晞之重覆單元，其中苯乙稀-丁 二烯橡膠係藉乳化聚合而合成，其中苯乙烯-丁二烯橡膠組 合物在含70份重量苯乙烯-丁二烯橡膠，3〇份重量高度 順_1，4-聚丁二烯橡膠，7.5份重量高度芳族加工油，7〇 份重量N220碳黑’ 2份重量氧化鋅，0.8份重量石壌， 3份重量微結晶蠟’ 1 . 1 5份重量對-苯二胺抗氧化劑， 1.2份重量N -環己基-2-苯并》塞唆亞項酿胺，份重量 四甲基秋蘭化二硫及1 . 4 5份重量硫之橡膠摻合物中硬化 1 在 〇°C 之 tan delta 範圍為 0_13 至 0.19 ，而在 60°C 之 tan delta 範圍為 0.06 至 0.12。 經濟部智慧財產局員工消費合作社印製 本發明更揭示一種苯乙烯-丁二烯橡膠组合物，其包含 衍生自苯乙烯及1，3 - 丁二烯之重覆單元，其中苯乙埽_丁 二烯橡膠係藉乳化聚合而合成，其中苯乙烯-丁二婦橡膠组. 合物在含70份重量苯乙烯-丁二婦橡膠，30份重量高度 順-1,4 -聚丁二稀·橡膠，7.5份重量高度芳族加工油，70 份重量N 2 2 0碳黑，2份重量氧化鋅，0 · 8份重量石壤， 3份重量微結晶堪，1 1 5份重量W i n g s t a y ® 1 0 0抗氧化 劑，1 . 2份重量N -環己基-2 -苯幷嚙唑亞磺醢胺，〇 · 3份 重量四甲基秋蘭化二硫及1 , 4 5份重量硫之橡膠摻合物中 硬化後，在0 °0之tan delta範園為0.1至0.40 ，而在 -11 * 衣紙張尺度適用中國國家梯準（CNS ) A4规格（210X297公ίΰ ' 五、發明説明（ A7 B7 經濟部智慧財產局員工消費合作社印紫 60 °C 之 tan delta 範圍為 0.09 至 〇i6。 本發明更揭露一種輪胎，其係包含一般為具外層圓周胎 面夂複曲面形狀骨架，兩個隔開之撐輪圈，至少於撐輪圈 延伸之—層，以徑向延伸之側壁並將胎面連接至撐輪圈； 其中胎面經修改成為磨口接觸；其中胎面包含乳化苯乙烯_ 丁二埽橡膠组合物，其係製備於包含共絮凝乳膠組合物之 方法，乳膠組合物包含（a)水，（b)乳化劑 分子量至少約30。，。。。之高分子量苯乙缔象= (d)重量平均分子量約小於28 0,0 0 0之低分子量苯乙埽—丁 一烯橡膠；其中高分子量笨乙烯_ 丁二烯橡膠對低分子量苯 乙烯-丁二烯橡膠之比例範圍約8 〇 : 2 〇至約2 5 : 7 5 ;其中 冋刀子量苯乙烯-丁二烯橡膠之結合苯乙缔含量组 苯乙埽-丁二缔橡膠之結合苯乙烯含量之差距至^為5百分 點= 本發明更揭露一種胎面’其係包含一般為具外層圓周胎 面疋複曲面形狀骨架，兩個隔開之撐輪圏，至少於撐輪圏 延伸之一層，以徑向延伸之側壁並將胎面連接至撐輪 其中胎面經修改成為磨口接觸；其中胎面包含乳化苯乙烯· 丁二烯橡膠组合物，其包含衍生自苯乙烯及1，3•丁二烯之 重覆單元，其中頻率對數對苯乙婦丁二缔橡膠组合：^ =對數與苯乙m烯橡膠组合物切存模數之作圖與 二：苯乙缔·丁二浠橡膠组合物之損失模數之作圖於 率對數|&園4 0.001弧度/秒至弧度/秒，於12〇t; 進行並在苯乙n烯«之㈣振動掃使用平行板幾何 -12· (請先閱讀_背面之ii-t事項人 r本買) .裝. 訂 • — I —^n ^n— 本紙張尺糾财@g?T^T^721()x297公整） 經濟部智慧財產局員工消費合作社印製 4^4106 Μ A7_____B7五、發明説明（1 學時有交叉，其中苯乙烯-丁二烯橡膠組合物經熱場流分級4 A之數目平均分子量範圍約50，〇〇〇至150,000 ，其中 苯乙烯-丁二烯橡膠之光散射對折射係數比例為18比3 9 0 本發明更揭露一種胎面，其係包含一般為具外層圓周胎 面之複曲面形狀骨架，兩個隔開之撐輪圈，至少於撐輪圏 延伸之一層’以控向延伸之侧壁並將胎面連接至撐輪圈； 其中胎面經修改成為磨口接觸；其中胎面包含乳化苯乙烯· 丁二烯橡膠組合物，其包含衍生自苯乙烯及丨，3 丁丄烯之 重覆單元’其中頻率對數對苯乙烯-丁二婦橡膠组合物’ 頻率對數與笨乙烯-丁二烯橡膠組合物之儲存模數之作圖與 頻率對數與苯乙烯-丁二烯橡膠组合物之損失模數之作圖於 頻率對數範圍為0.0 0 1弧度/秒至1 0 0弧度/秒，於1 2 〇。〇 進行並在苯乙烯-丁二婦橡膠之動態振動掃使用平行板幾何 學時有交叉。 本發明更揭露一種輪胎，其係包含一般為具外層圓周胎 面之複曲面形狀骨架，兩個隔開之撐輪圏，至少於撐輪圈 延伸之一層’以徑向延伸之侧壁並將胎面連接至撐輪圈； .**· 其中胎面經修改成為磨口接觸；其中胎面包含乳化苯乙烯-丁二烯橡膠組合物，其係製備於包含共絮凝乳膠組合物之 方法，乳膠组合物包含（a )水，（b )乳化劑，（c )重量平均 分子量至少約3 0 0,0 0 0之高分子量苯乙埽-丁二烯橡膠及 (d)重量平均分子量约小於28〇,〇〇〇之低分子量苯乙烯-丁一婦橡膠；其中高分子量苯乙埽-丁二缔橡膝對低分子量 (請先閲讀^:面之毛愈事項^β本買) •裝' -:¾. 線· -13 - 本紙張尺度適用中國國家榇準（CNS ) A4規格（210X297公釐） Α7 _____Β7 _ 五、發明説明（13 各乙缔丁二缔橡膠之比例範圍約8 0 : 2 0至約2 5 . 7 5 甘 中高分子量苯乙烯-丁二烯橡膠之結合苯乙烯含量至少為 1 〇重量百分點。 本發明更揭露一種輪胎，其係包含一般為具外層圓周胎 面之複曲面形狀骨架，兩個隔開之撐輪圏，至少於撐輪圏 延伸之一層，以徑向延伸之侧壁並將胎面連接至撐輪圈； 其中胎面經修改成為慶口接觸；其中胎面包含乳化苯乙烯· _ 丁二烯橡膠组合物’其係製備於包含共絮凝乳膠组合物之 方法’乳膠組合物包含（a)水，（b )乳化劑，（c )重量平均 分子量至少約300,000之高分子量笨乙烯-丁二烯橡膠荩 (d)重量平均分子量約小於280,000之低分子量苯匕烯-丁二烯橡膠；其中高分子量苯乙婦-丁二烯橡膠對低分子責 苯乙婦-丁二烯橡膠之比例範圍約8 0 : 2 0至約2 5 : 7 5 其 中低分子量苯乙烯-丁二烯橡膠之結合苯乙烯含量至少為 1 0重量百分點。 本發明更揭露一種乳化苯乙烯-丁二烯橡膠组合物，其 係製備於包含共絮凝乳膠組合物之方法，乳膠組合物包含 (a)水，（b )乳化劑，（C )重量乎均分子量至少约3 0 0，〇 0 0 ...* * 之高分子量苯乙烯-丁二烯橡膠及（d )重量平均分子量约小 於280,000之低分子量苯乙烯-丁二烯橡膠；其中高分予 量苯乙烯-丁二烯橡膠對低分子量苯乙烯-丁二烯橡膠之此 例範圍約8 0 : 2 0至約2 5 : 7 5 ;其中高分子量笨乙烯-丁 > 婦橡膠之結合笨乙烯含量至少為1 0重量百分點。 本發明更揭露一種乳化苯乙烯-丁二烯橡膠組合物，其 __-_±_ 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公酱） 請先閱讀t面之t倉事項k t本真) 装- ir 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明説明（13) ---------穿I 請先閲讀_背面之fi.意事項I 巧本頁 係製備於包含共絮凝乳膠组合物之方法，乳膠組合物包含 (a)水，（b)乳化劑，（c)重量平均分子量至少約3〇〇,〇〇〇 之高分子量苯乙烯-丁二烯橡膠及（d)重量平均分子量約小 於280,000之低分子量苯乙烯· 丁二烯橡膠；其中高分子 量苯乙烯-丁二烯橡膠對低分子量苯乙烯-丁二烯橡膠之比 例範圍約8 0:20至約25:75 ;其中低分子量苯乙烯-丁二 婦橡膠之結合苯乙梯含量至少為1 〇重量百分點β 發明詳述 本發明之表乙烯-丁 —歸橡膠係藉自由基乳化聚合方法 製,備於合成向分子量SBR及低分子量SBR. °本發明之苯 乙缔-丁二缔橡膠較佳係使用美國專利第5，5 8 3，1 7 3所述 一般自由基乳化聚合方法合成高分子量SBR及低分子量 S B R »聚合方法技術係習知之F丨μ方法（入料·注射-單體 )。然後摻合高分子量SBR之乳膠及低分子量SBR之乳膠 ，再進行絮凝=The present invention also discloses an emulsified styrene-butadiene rubber composition, which comprises a high molecular weight styrene-butadiene having a number average molecular weight of about 20,000 to about 1,000,000. Diene rubber and (11) low-molecular-weight styrene-butadiene rubber having an average molecular weight of about 20,000 to about 150,000; wherein high-molecular-weight styrene-butadiene rubber versus low-molecular-weight styrene-butadiene rubber The ratio of dibee rubber ranges from about 80:20 to about 25:75; of which the combined styrene content of high molecular weight styrene-butadiene rubber and the low molecular weight styrene-butadiene rubber combined styrene The difference in the content should be at least 5 percentage points; the stupid ethylene-butadiene rubber composition is obtained by co-flocculating a blend of high molecular weight styrene-butadiene rubber latex and low molecular weight styrene-butadiene rubber latex. Preparation * and its medium and high molecular weight styrene-butadiene rubber and low molecular weight styrene-butadiene rubber latex preparation method include (丨) water, soap system 'radical generator, 1,3-butadiene Monomers and styrene monomers are added to the first polymerization zone; 2) Copolymerize the 1,3-butadiene monomer and styrene monomer in the first polymerization zone into a monomer conversion range of about 15% to about 40% to make a low-conversion polymerization medium; (3) ) Add a low conversion polymerization medium to the second polymerization zone; (4) Add an additional amount of 丨, 3_ butadiene monomer and an additional amount of styrene monomer to the second polymerization zone; continue the copolymerization until > The monomer is converted to at least about 50% to make a styrene-butadiene rubber and latex. The present invention further relates to a present ethyl-butadiene-like tincture composition comprising a repeating unit derived from styrene and Ι 3 · butadiene, wherein the ethyl ethyl-butadiene rubber composition flows through a thermal field. The average molecular weight range of the number of classification determination is about 50,000 to ^ 50,000, among which the light dispersion of styrene-butadiene rubber ___ -9- Paper Size (CNS) A—Specification (21Gx297 mm) '' ^-(Please read f- 面 之 ΪΪ-ΪΪ 事 kr this page-installation · line print by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Ⅴ. Description of invention Α7 Β7 printed by the Consumer ’s Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs The ratio of the radiation to the refractive index is 1, and the ratio of S to 3, 9. The present invention further discloses a styrene-butadiene fluorene composition. Residual modulus of women's rubber compositions, — Modulus < Plotting and logarithmic frequency vs. loss modulus of the ethylene-butadiene rubber composition 〇_〇〇1 radian / second to 100 radians / second, enter the light at ^ Ι5ί and scan the dynamic vibration of the stiff vinyl-butadiene rubber When parallel plate geometry is used, the present invention also discloses a styrene-butadiene rubber composition, which includes He Shengzi styrene and 1,3-butadiene repeating units. Plot of styrene-butadiene rubber composition, logarithm of frequency and storage modulus of styrene-butadiene rubber composition, plot of logarithm of frequency, and loss modulus of styrene_butadiene rubber composition at The logarithm of the frequency ranges from 100,000 radians / second to 100 radians / second. It is performed at 12 ec and the dynamic vibration sweep of styrene butadiene rubber is crossed when using parallel plate geometry. The number-average molecular weight of the butadiene rubber composition determined by thermal field flow classification is around 50,000 to 150,000, in which the ratio of the light scattering to the refractive index of the styrene butadiene rubber is 1.8 to 3.9. The present invention also An emulsified styrene-butadiene rubber composition is disclosed. The method comprises a co-flocculating latex composition, which comprises (a) water, (b) an emulsifier, and (c) a high molecular weight styrene ethyl alcohol having a weight average molecular weight of at least about 300,000. Butadiene rubber and (d) weight average Low-molecular-weight styrene-butadiene rubber having a molecular weight of less than 280,000; wherein the ratio of high-molecular-weight styrene-butadiene rubber to low-molecular-weight styrene-butadiene rubber ranges from about 80 to 20 Approx. 10 · This paper uses the Chinese National Standard (CNS) A4 specification (210X297 mm) (Read the Vi-Notes on the r side first ^ £ * this page}-binding 'Order A7 B7 V. Description of the invention ( 25:75; where the difference between the content of styrene in high molecular weight styrene-butadiene rubber and the content of styrene in low molecular weight styrene-butadiene rubber is at least 5 percentage points "The present invention further discloses a styrene -Butadiene rubber composition comprising repeating units derived from styrene and 1,3-butadiene, wherein styrene-butadiene rubber is synthesized by emulsion polymerization, of which styrene-butadiene rubber The composition contains 70 parts by weight of styrene-butadiene rubber, 30 parts by weight of highly cis-1,4-polybutadiene rubber, 7.5 parts by weight of highly aromatic processing oil, and 70 parts by weight of N220 carbon black '2 Parts by weight of zinc oxide, 0.8 parts by weight of stone ballast, 3 parts by weight of microcrystalline wax '1.1 5 parts by weight of p-phenylenediamine antioxidant, 1.2 parts by weight of N-cyclohexyl-2-benzo "saidine sub-fermented amine, parts by weight of tetramethylthiulan disulfide and 1.5 parts by weight of sulfur The tan delta range of hardened 1 in rubber blends is 0-13 to 0.19 at 0 ° C and the tan delta range is 0.06 to 0.12 at 60 ° C. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention further discloses a styrene-butadiene rubber composition comprising repeating units derived from styrene and 1,3-butadiene, of which acetofluorene-butadiene Diene rubber is synthesized by emulsion polymerization. The styrene-butadiene rubber group contains 70 parts by weight of styrene-butadiene rubber and 30 parts by weight of cis-1,4-polybutadiene. Rubber, 7.5 parts by weight of highly aromatic processing oil, 70 parts by weight of N 2 2 0 carbon black, 2 parts by weight of zinc oxide, 0 by 8 parts by weight of stone soil, 3 parts by weight of microcrystalline, 1 15 parts by weight of Wingstay ® 1 0 0 Antioxidants, 1.2 parts by weight of N-cyclohexyl-2 -benzopyridazolium sulfenamide, 0.3 parts by weight of tetramethylthiulan disulfide, and 1.5 parts by weight of sulfur rubber After hardening in the blend, the tan delta range at 0 ° 0 is 0.1 to 0.40, and at -11 * the size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297) 五 5. Description of the invention (A7 B7 The tan delta range of Yinzi 60 ° C in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is 0.09 to 0. This invention is further disclosed A tire is disclosed, which generally comprises a torus-shaped skeleton with an outer circumferential tread, two spaced-apart rims, at least one layer extending from the rims, with radially extending side walls and connecting the treads. To the rim; where the tread is modified to be ground contact; where the tread contains an emulsified styrene butadiene rubber composition, which is prepared by a method comprising a co-flocculating latex composition, the latex composition comprising (a) Water, (b) an emulsifier with a molecular weight of at least about 30 ... high molecular weight phenethyl association = (d) a low molecular weight styrene-butadiene rubber having a weight-average molecular weight of less than 280,000; Among them, the ratio of high molecular weight stupid ethylene butadiene rubber to low molecular weight styrene-butadiene rubber ranges from about 80:20 to about 25:75; among which the combination of trowel amount of styrene-butadiene rubber The difference between the styrene content of styrene-acetylene-butadiene rubber and the combined styrene content is 5% = ^ = The present invention further discloses a tread, which includes a torus-shaped skeleton generally having an outer circumferential tread, Two spaced-apart wheels 至少, less than the wheels圏 Extends a layer with radially extending sidewalls and connects the tread to the support wheel where the tread is modified to be ground contact; where the tread contains an emulsified styrene-butadiene rubber composition containing styrene-derived And 1,3 • butadiene repeating unit, in which the frequency logarithm of styrene-butadiene rubber is combined: ^ = plot of the logarithm and the modulus of cut of the styrene-methylene rubber composition and two: styrene · The plot of the loss modulus of the butadiene rubber composition is plotted on the logarithm of the log | & yuan 4 0.001 radians / second to radians / second, performed at 12 〇; Board Geometry-12 · (Please read the ii-t items on the back side and buy it by yourself). Install. Order • — I — ^ n ^ n— This paper ruler corrects money @g? T ^ T ^ 721 () x297 Printing) 4 ^ 4106 Μ A7_____B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1 hour, there are crossovers, in which the styrene-butadiene rubber composition is classified by thermal field flow 4 A number average molecular weight The range is about 50,000 to 150,000, of which the ratio of light scattering to refractive index of styrene-butadiene rubber is 18 to 390 The invention further discloses a tread, which comprises a toric skeleton with an outer circumferential tread, two spaced-apart rims extending at least one layer from the rim to control the extending side wall and The tread is connected to the support rim; where the tread is modified to be ground contact; where the tread contains an emulsified styrene-butadiene rubber composition that includes repeating units derived from styrene and 3,3-butadiene 'The logarithm of frequency vs. styrene-butadiene rubber composition' Plot of the logarithm of frequency vs. storage modulus of stupid ethylene-butadiene rubber composition and the logarithm of frequency vs. loss mode of styrene-butadiene rubber composition The plotting of the numbers is in the logarithmic frequency range from 0.01 radians / second to 100 radians / second, at 120. 〇 Performed and crossed in the dynamic vibration sweep of styrene-butadiene rubber using parallel plate geometry. The present invention further discloses a tire, which comprises a toric skeleton with a generally outer circumferential tread, two spaced-apart support wheels, at least one layer extending from the support wheels, and a side wall extending radially and The tread is connected to the support rim;... Where the tread is modified to be ground contact; where the tread contains an emulsified styrene-butadiene rubber composition prepared by a method comprising a co-flocculating latex composition, The latex composition comprises (a) water, (b) an emulsifier, (c) a high molecular weight styrene-butadiene rubber having a weight average molecular weight of at least about 3 0,0 0, and (d) a weight average molecular weight of less than about 28,00,00 low molecular weight styrene-butadiene rubber; of which high molecular weight acetophenone-butadiene rubber knee pair low molecular weight (please read ^: surface hair healing matters ^ β buy) '-: ¾. Line · -13-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) A7 _____ Β7 _ V. Description of the invention (13 The proportion of each ethylene butadiene rubber is about 80 0 : 20 to about 2 5. 7 5 high-molecular-weight styrene-butadiene rubber combined with styrene The amount is at least 10% by weight. The present invention further discloses a tire comprising a toric skeleton generally having an outer circumferential tread, two spaced apart support wheels 圏 extending at least one layer from the support wheels 以, and Radially extending sidewalls and connecting the tread to the supporting rim; where the tread is modified to make contact with the mouth; where the tread contains an emulsified styrene · butadiene rubber composition 'which is prepared from a coflocculating latex Method of Composition 'The latex composition comprises (a) water, (b) an emulsifier, (c) a high molecular weight stupid ethylene-butadiene rubber having a weight average molecular weight of at least about 300,000 (d) a weight average molecular weight of less than about 280,000. Low-molecular-weight styrene-butadiene rubber; the ratio of high-molecular-weight styrene-butadiene rubber to low-molecular-weight styrene-butadiene rubber ranges from about 8 0: 2 0 to about 2 5: 7 5 The combined styrene content of the low-molecular-weight styrene-butadiene rubber is at least 10 weight percent. The invention further discloses an emulsified styrene-butadiene rubber composition, which is prepared by a method comprising a co-flocculating latex composition. The latex composition comprises (a) water, (b) an emulsifier, (C) a high-molecular-weight styrene-butadiene rubber having a weight average molecular weight of at least about 3,000,000, ... * *, and (d) Low-molecular-weight styrene-butadiene rubber having a weight-average molecular weight of less than about 280,000; among which, a high amount of styrene-butadiene rubber versus low-molecular-weight styrene-butadiene rubber ranges from about 80 to 20 in this example. About 25:75; wherein the high molecular weight stupid ethylene-butadiene> combined stupid ethylene content is at least 10 weight percent. The present invention further discloses an emulsified styrene-butadiene rubber composition, which __- _ ± _ This paper size is in accordance with Chinese national standard (CNS > A4 size (210X297 male sauce) Please read the t warehouse item kt authentic first) Packing-ir Printed by Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Α7 Β7 5 、 Explanation of the invention (13) --------- Wear I, please read _fi on the back side. I This page is prepared by a method containing a co-flocculating latex composition. The latex composition contains (a) Water, (b) emulsifier, (c) high molecular weight styrene having a weight average molecular weight of at least about 30,000 -Butadiene rubber and (d) low molecular weight styrene · butadiene rubber with a weight average molecular weight of less than 280,000; the ratio of high molecular weight styrene-butadiene rubber to low molecular weight styrene-butadiene rubber ranges 8 0:20 to about 25:75; of which the combined styrene content of the low molecular weight styrene-butadiene rubber is at least 10% by weight β Manufactured by emulsion polymerization method and prepared for synthesis of low molecular weight SBR and low molecular weight SBR. ° The styrene-butadiene rubber of the present invention is preferably a general free-radical emulsification described in US Patent Nos. 5,5 8 3, 1 7 Polymerization method to synthesize high molecular weight SBR and low molecular weight SBR »Polymerization method technology is the familiar F 丨 μ method (feed · injection-monomer). Then blend the high molecular weight SBR latex and low molecular weight SBR latex, and then flocculate =
I 經濟部智慧財產局8工消費合作社印製 F I Μ方法係藉添加苯乙歸單體，丨，3 _ 丁二烯單體，水 ’自由基產生劑及皂系統至第一聚合區域以形成水性聚合. 媒介而進行的。第一聚合區域一般為反應器或—系列二或 多個反應器。單體共聚合係以自由基產生劑予以引發。此 共聚合反應形成低轉化率聚合媒介。 在低轉化率聚合媒介達到約1 5百分比至約4 0百分比之 單體轉化率之點，將低轉化率聚合媒介加入第二聚合區域 。第二聚合區域可為反應器或二或多個反應器系列。在任 何情況下，第二聚合區域係在第一聚合區域之後β低轉化 15- 本紙張尺度適用中國國家標準（CNS ) 210X297.^ ) ^ f Λ π q - f A7 _____B7 五、發明説明（13) 率聚合媒介一般係在單體轉化率水平為約丨7百分比至約 j 5百刀比時加入第二聚合區域。更佳係在單體轉化率水平 為約20百分比至約30百分比時加入第二聚合區域。 額外苯乙烯單體及丁二烯單體被加入第二聚合區域，一 般情況下，苯乙烯單體及1，3 - 丁二缔總數量之約2 〇百分 比至約50百分比被加入第二聚合區域（所有單體之5〇百 分比至8 0百分比被加入第一聚合區域）β _般較佳將總數 量單體‘約3 0 f量百彳比至，約4 5 f量百》比加a第二聚合 區域（所有單體之5 5百分比至7 0百分比被加入第一聚合. 區域）。一般最佳將總數量單體約35重量百分比至钓42 重量百分比加入第二聚合區域（所有單體之5S百分比至65 百分比被加入第一聚合區域）^藉分散單體入料於第一聚合 區域及第二聚合區域，提供穩定乳膠所需要皂之總量被減 少至少約3 0百分比。 弟一水合區域内之共聚合可持續至單體轉化率至少達到 5 0百分比9共聚合較佳可持續至所有單體轉化率達到5 〇 至68百分比《更佳者，第二反應區域内之共聚合可持續 至所有單體轉化率達到5 8至6 5百分比， 經濟部智慧財產局員工消費合作社印製 在合成S B R乳膠時，一般係共聚合約1重量百分比至約 5 0重量百分比苯乙烯及約5 〇重量百分比至約9 9重量百分 比1，：> - 丁一烯。然而，咸認為各種其他乙烯基芳族單體可 用於取代SBR中之苯乙烯。例如，本發明中可取代苯乙烯 或與苯乙稀遇合並與1，3 -丁二浠共聚合之乙晞芳族單體之 一些代表性λ例包括1-乙婦基各3 -甲基苯乙歸，4_甲 _ -16 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐} 424106 A7 B7 五、發明説明（1 基苯乙烯，3,5-二乙基苯乙烯，4 -丙基苯乙歸·，4-三級 丁基表乙錦·， 2,4,6 -三甲基苯乙缔，4 -十二基苯乙埽， ---------壯衣-- (碕先閲讀^:面之>1-#-事項表 Γ本頁) 3 -甲基-5-正已基苯乙締’ 4 -苯基苯乙烯，2 -乙基-4-苯 甲基苯乙烯，3,5 -二苯基苯乙烯，2,3，4,5_四乙基苯乙 烯，3 -乙基-1-乙烯基葚’ 6 -異丙基_i -乙烯基苯，6_環 己基-1-乙浠基苯，7 -十二基-2-乙婦基莕，α-甲基苯乙 烯’及類似物。高分子量S B R典型含約5重量百分至約 5 0重量百分比結合苯乙缔及約5 〇重量百分比至約9 5重量 百分比結合丁二烯。較佳者’高分子量SBr典型含約20 重量百分至約3 0重量百分比苯乙烯及約7 〇重量百分比至 約80重量百分比ι，3 -丁二埽。最佳者，高分子量SBR典 型含約22重量百分至約28重量百分比苯乙烯及约72重 量百分比至約7 8重量百分比I，3 - 丁二缔^類似之苯乙烯 早體及丁二烯單體比例也可據上所述加入第一聚合區域及 第二聚合區域。 經濟部智慧財產局員工消費合作社印製 低分子量SBR —般含約1重量百分比至約5〇重量百分 比苯乙晞及約5 0重量百分比至約9 9重量百分比1，3 - 丁二. 埽。在斤些情況下，例如當希望要低滾動阻力及優良胎面 耐磨特徵，分子量S B R含相當少量苯乙婦，其係約3重 量百分比至約1 0重量百分比，而S B R中i，3 - 丁二烯數量 約9 0重量百分比至約9 7重量百分比《低分子量聚合物可 含更少量結合苯乙烯》例如，低分子量橡膠聚合物可含〇 重量百分比至3重量百分比結合苯乙烯及97重量百分比 至100重量百分比結合丁二諦。因此，在最極端例子中， -17- 本紙張尺度適用中國國家標準（CNS ) Ad規格（210 X 297公楚） 五、發明説明（ 15 Α7 Β7 經濟部智慧財產局8工消費合作社印製 f希可作為摻合物聚合成份…在其他情況中，例如 "希望高牵引特徵時，可將更水平苯乙烯併入低分子量 SBR。在此類情況下’較佳使低分子量含約々ο重量 百刀比至’.勺：>〇重量百分比苯乙烯及約5〇重量百分比至约 6〇重量百分比r’3-丁二烯。類似之苯乙烯單體及丁二烯 早體比例也可據上所述加入第―聚合區域及第二聚合區域 〇 使分子量SBR具備結合苯乙埽含量與低分子量 ^結合苯乙缔含量之差距至少為，5百分點是很重要的。此 η刀子量SBR -般具備結合苯乙埽含量與低分子量 之結合苯乙烯含量差距為5至4〇百分點。此高分子量 SBR典型具備結合苯乙烯含量與低分子量之結合苯 乙烯含量差距至少A 10百分點。大部份情況下，此高分 子量SBR具備結合苯乙烯含量與低分子量sbr之結合苯 乙烯含I差距為1 0至3 〇百分點”乂】5至2 5百分點之差 距最佳…般較佳係使此高分子量SBR之結合苯乙缔含量 與低分子量SBR之結合苯乙烯含量差距至少為15百分母 ’以至少2 0百分點之差距最佳。 應理^的是，高分子量或低分子量s B R可1較高站合 苯乙烯含量m ’具較高結合苯乙缔含量：摻合：； (SBR在接合物中可為低或高分子量聚合物。亦應理解的 是含0百分比結合苯乙諦）可作為換合物中之 聚合物。在此類情況下，聚丁二缔可為高或低分子量聚合 物。在聚丁二烯作為摻合物中橡膠聚合物之一時，摻合物 -18- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公着 --------—裳-- (請先閲讀r®-之νί,-t事項Γ本頁) 訂 線 4 2 4 10 6 ^ A7 B7 經濟部智慧財產局資工消費合作社印製 16 -----五、發明説明（) 中之SBR典型具備至少約1〇重量百分比之結合苯乙烯含 量。在此類情況下，摻合物中之S B R更典型具至少約1 5 重量百分比之結合苯乙烯含量，更佳具至少約2〇重量百 分比之結合本乙婦含量β 基本上’任何型態自由基產生劑可用於引發此類自由基 乳化聚合反應。例如，照可.使用產生自由基之化學化合物 ，紫外線或光。為了確保令人滿意之聚合速率，一般使用 一致性及可控制聚合，.在聚合條件下為水溶性或油溶性之 產生自由基之化學劑，並獲得優良結果。 .常用之自由基起始劑之一些代表性實例包括各種過氧化 合物’例如蒎燒氫過氧化物，過硫酸鉀，過硫酸銨，苯醯 過氧化物，過氧化氫，二-三級丁基過氧化物，二祜基過氧 化物’ 2,4 -二氯苯醯過氧化物，癸醯過氧化物，月桂過氧 化物，枯烯氫過氧化物，萜烷氫過氧化物，三級丁基氫過 氧化物’乙醯基丙酮過氧化物’二鯨蠟過氧二碳酸鹽，三 級丁基過氧醋酸鹽’三級丁基過氧順丁烯二酸，三級丁基 過氧私甲叙鹽’乙醯基環己基績酿基過氧化物，及類似物 _ :各種f氮化合物，例如2 -三級丁基偶氮_ 2 氰基丙烷， 二甲基偶氮一異丁酸鹽，偶氮二異丁腈，2 -三級丁基偶氮 -I -氰基環己燒及類似物；各種垸基過氧縮酮，例如2，2 -雙（三級丁基過氧）丁烷，3 ,3 -雙（三級丁基過氧）丁酸乙酯 ’ 1，1 _二三級丁基過氧）環己烷及類似物。過硫酸鹽起 始劑如過硫酸鉀及過硫酸銨特別有用於此類水性乳化聚合 -19- 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） (锖先閱讀f-面之注意事項甚^本頁) 裝- 線 424I The method of printing FIM by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economics is to add the styrene ethyl monomer, 丨 butadiene monomer, water 'radical generator and soap system to the first polymerization area to form Water-based polymerization. The first polymerization zone is generally a reactor or a series of two or more reactors. The monomer copolymerization is initiated with a radical generator. This copolymerization reaction forms a low conversion polymerization medium. At the point where the low conversion polymerization medium reaches a monomer conversion of about 15% to about 40%, the low conversion polymerization medium is added to the second polymerization zone. The second polymerization zone may be a reactor or a series of two or more reactors. In any case, the second aggregation area is a low β conversion after the first aggregation area. 15- This paper size applies the Chinese National Standard (CNS) 210X297. ^) ^ F Λ π q-f A7 _____B7 V. Description of the invention (13 The rate polymerization medium is generally added to the second polymerization zone when the monomer conversion level is from about 7 percent to about 5 hundred knife ratio. More preferably, the second polymerization zone is added at a monomer conversion level of about 20% to about 30%. Additional styrene monomer and butadiene monomer are added to the second polymerization zone. Generally, about 20% to about 50% of the total amount of styrene monomer and 1,3-butadiene are added to the second polymerization. Zone (50% to 80% of all monomers are added to the first polymerization zone) β _ is generally better to add the total number of monomers' from about 30 f to 100%, and to about 4 5 f to 100% a Second polymerization zone (55 to 70 percent of all monomers are added to the first polymerization zone). It is generally best to add the total amount of monomers from about 35 weight percent to 42 weight percent to the second polymerization zone (5S percent to 65 percent of all monomers are added to the first polymerization zone) ^ The dispersed monomer is fed to the first polymerization In the zone and the second polymerization zone, the total amount of soap required to provide a stable latex is reduced by at least about 30 percent. The copolymerization in the first hydration zone can continue until the monomer conversion reaches at least 50%. 9 The copolymerization is preferably sustainable until the conversion of all monomers reaches 50 to 68%. The copolymerization can last until the conversion rate of all monomers reaches 5 8 to 6 5 percent. When printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs when synthesizing SBR latex, it is generally copolymerized from about 1 weight percent to about 50 weight percent styrene and From about 50% by weight to about 99% by weight 1, >-butadiene. However, Xian believes that various other vinyl aromatic monomers can be used to replace styrene in SBR. For example, in the present invention, some representative lambda examples of acetamidine aromatic monomers that can be substituted for styrene or combined with styrene and copolymerized with 1,3-butanefluorene include 1-ethynyl 3-methyl. Acetophenone, 4_ 甲 _ -16-This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 424106 A7 B7 V. Description of the invention (1-based styrene, 3,5-diethylstyrene , 4-propylacetophenone, 4-tert-butyl epiethyl bromide, 2,4,6-trimethylphenylethylidene, 4-dodecylphenethylhydrazone, ------- --Zhuang Yi-(碕 Read first ^: Face of >1-#-Matters Table Γ page) 3-Methyl-5-n-hexylphenylethyl '4-phenylstyrene, 2-ethyl 4-benzylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene, 3-ethyl-1-vinylfluorene '6-isopropyl _i -vinylbenzene, 6_cyclohexyl-1-ethylfluorenylbenzene, 7-dodecyl-2-ethynylhydrazone, α-methylstyrene 'and the like. High molecular weight SBR typically contains about 5 Weight percent to about 50 weight percent combined with styrene and about 50 weight percent to about 95 weight percent combined with butadiene. The preferred is the 'high molecular weight SBr code The type contains about 20% by weight to about 30% by weight of styrene and about 70% by weight to about 80% by weight ι, 3-butadiene. The best, high molecular weight SBR typically contains about 22% by weight to about 28% by weight of styrene and about 72% by weight to about 78% by weight of I, 3-butadiene ^ Similar styrene precursor and butadiene monomer ratios can also be added to the first polymerization zone and the first Dimerization area. Low-molecular weight SBR printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics-generally contains about 1% by weight to about 50% by weight phenylethylhydrazone and about 50% by weight to about 9 9% by weight 1, 3-D 2. In some cases, for example, when low rolling resistance and excellent tread wear characteristics are desired, the molecular weight SBR contains a relatively small amount of acetophenone, which is about 3 weight percent to about 10 weight percent, and SBR i, 3-butadiene amount from about 90 weight percent to about 97 weight percent "low molecular weight polymer may contain a smaller amount of bound styrene" For example, low molecular weight rubber polymers may contain from 0 weight percent to 3 weight percent bound Styrene and 97% by weight to 100% by weight combined with dioxin. Therefore, in the most extreme example, -17- this paper size applies the Chinese National Standard (CNS) Ad specifications (210 X 297). 5. Description of the invention ( 15 Α7 Β7 Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs may be used as the polymerized component of the blend ... In other cases, such as " when high traction characteristics are desired, higher levels of styrene may be incorporated into the low molecular weight SBR. In such cases, it is preferred to have a low molecular weight of about 100% by weight to about 100% by weight. Spoon: > 0 weight percent styrene and about 50 weight percent to about 60 weight percent r'3-butadiene . Similar ratios of styrene monomer and butadiene early body can also be added to the first polymerization zone and the second polymerization zone as described above, so that the molecular weight SBR has the difference between the content of combined styrene and low molecular weight ^ combined with styrene. At least 5 percent is important. This η knife amount SBR-generally has a bound styrene content of styrene and low molecular weight bound styrene content of 5 to 40 percent. This high-molecular-weight SBR typically has a difference of at least A 10 percent between the combined styrene content and the combined low-molecular-weight styrene content. In most cases, this high-molecular-weight SBR has a combined styrene content of low-molecular-weight sbr and a low-molecular-weight sbr. The difference in I content is 10 to 30 percent. It is best to make the difference between the combined styrene content of the high molecular weight SBR and the combined styrene content of the low molecular weight SBR to be at least 15 denominators, and at least 20 percentage points. It should be noted that the high molecular weight or low molecular weight s BR May 1 higher standing styrene content m 'with higher bound styrene content: blended :; (SBR may be a low or high molecular weight polymer in the joint. It should also be understood that it contains 0% bound styrene Ii) Can be used as a polymer in a blend. In such cases, polybutadiene can be a high or low molecular weight polymer. When polybutadiene is used as one of the rubber polymers in the blend, the blend -18- This paper size is in accordance with Chinese National Standard (CNS) Α4 specification (210 × 297) -------- Shang-- (Please read r®- 之 νί, -t matter Γ page) 4 2 4 10 6 ^ A7 B7 Printed by the Intellectual Property Bureau Consumers' Cooperatives of the Ministry of Economic Affairs 16 ----- It is stated that the SBR in () typically has a bound styrene content of at least about 10 weight percent. In such cases, the SBR in the blend is more typically with a bound styrene content of at least about 15 weight percent, and more preferably With a content of at least about 20% by weight of the bound beta, substantially any type of free radical generator can be used to initiate such free-radical emulsion polymerization. For example, according to the use of free-radical-generating chemical compounds, ultraviolet or Light. In order to ensure a satisfactory polymerization rate, uniformity and controllable polymerization are generally used. Under polymerization conditions, water-soluble or oil-soluble free-radical-generating chemicals are used and excellent results are obtained. Some representative examples of initiators include various peroxy compounds such as tritium hydroperoxide, potassium persulfate, ammonium persulfate, phenylhydrazone peroxide, hydrogen peroxide, di-tertiary butyl peroxide, di Fluorenyl peroxide '2,4-dichlorophenylhydrazone peroxide, decanonium peroxide, lauryl peroxide, cumene hydroperoxide, terpane hydroperoxide, tertiary butyl hydroperoxide Oxide 'Ethylacetone peroxide' Dicetyl peroxydicarbonate, Tertiary butyl peroxyacetate 'Tertiary butyl peroxymaleic acid, Tertiary butyl peroxymonomethyl Salts' ethynylcyclohexyl aryl peroxides, and the like: various nitrogen compounds, such as 2-tertiary butyl azo-2 cyanopropane, dimethyl azo-isobutyrate, Azobisisobutyronitrile, 2-tert-butylazo-I-cyanocyclohexane and the like; various fluorenyl peroxyketals, such as 2,2-bis (tert-butylperoxy) butane Alkane, 3,3-bis (tertiary-butylperoxy) butyrate ethyl '1,1_di-tertiary-butylperoxy) cyclohexane and the like. Persulfate initiators such as potassium persulfate and Ammonium persulfate is particularly useful for this type of water-borne emulsion polymerization. 19- This paper is sized to the Chinese national standard (CNS > A4 size (210X297 mm) (锖 read the precautions on f-side first, even ^ this page). 424
D 經濟部智慧財產局sc工消費合作社印製 A7 -------------Β7 五、發明説明（^ ' —--- /〔用f始隸量依被合成SBR之所要分子量而定。較 高分=量係藉較少量起始劑達成，較低分子量係藉較大量 起始劑達成、然而，~般規則中，反應混合物含〇‘〇05至 P (每ι〇0 6重量單體之份重量）起始劑。若為金屬過 .硫酸鹽起始劑，典型使用O.lphm至0.5phm起始劑於聚 。媒^ s然’所製得s B R分子量亦依聚合期間之鏈轉移 劑如三級十二基硫醇之數量而定。例如，低分子量sbr可 藉簡單提高鏈轉移劑之水平而合成。一特定實例中，在合 成南分子量S B R時.，.所用三級十二基硫醇數量範園約 0_125phm至約〇.i5〇phm。低分子量SBR可藉簡單提 高聚合期間三級十二基硫蒔之水平而製成。例如， 0‘38plim至0.40phm三級十二基硫醇典型會合成低分子 量 S B R。 除非另外指明，分子量係藉膠滲透層析（G p c )加以測定 。使用傳統G P C系統以光散射（w y a U技術公司^ μ i n i D A W N型號）及微分折射係數進行測試。樣品經丨· 〇微米 孔徑注射過濾器過濾。在某些情況下，數目平均分子量係 由熱場動-分級測定。由熱場流動分級測定之數目平均分 子量有時縮寫為MnSF。測定Mn3F時，係使用配備τ-〇〇5 管路分隔器之FFFractionation，LLC(鹽湖城，猶它）τ_ 100 聚合物分級器型號 ’ Hewlett Packard(Palo Alto 加州）1 0 4 7 A型號折射係數檢測器及W y a 11技術公司 (S a n t a B a τ: b a r a，加州）D A W N D S P型號雷射光度計檢 測器。試驗程序中，使用脫泡四氫呋喃作為載體溶劑，其 -20 - 本紙張&度適财關家標率（CNS ) A4規格（21GXW公釐)~ -- (請先閲讀t:面之·ίΛ-t-事項k β本頁 裝- 訂 -線 424106 A7 B7 五、發明説明（” 經濟部智辏財產局員工消費合作社印製 以〇, 6毫升/分鐘之速率被系入系蘇。熱場流動分級中之冷 壁溫度經F T S系統R C 1 5 0型號再循環冷卻器控制。 聚合物分級伴隨著使用FFFractl〇riati〇n，LLC之動力 程式方法之軟體程式TEMP。程式條件如下：起始DeUa T為60C，平衡時間為0.5分鐘，tlA5 〇分鐘，“為 -6.0 ’固時時間為30分鐘及最終DeIta 丁；為〇 。冷壁 冷卻器之設定點溫度為25 C。然而，起始Delta T為60 °C時’冷壁溫度典型為40 t左右。聚合物樣品溶於溶劑 ’然後在未過滤下注射入熱場流動分級系統。被注射之樣 品.團塊典型約0 . 1 2毫克。 收集原始數據，以Wyatt技術公司軟體程式astra處 理。數據收集期間為2 5分鐘。對光散射檢測器而言，尖 拳基線典型設定於丨.5分鐘至2 5分鐘，而折射係數檢測 器則設定於1.5分鐘至2 0分鐘。對數據處理而言，所使 用DAWN光散射檢測器包含5至16(代表角度從39。至 139。（THF中））。使用Zimm形式之一級方程式適合角 度與光散射之關係。所有乳化聚合物樣品均使用折射係數 增量（d n ,/ d c )為0 . 1 5 4者’溶液聚合物樣品則使用〇 . 1 4 0 。折射係數檢測器（Aux 1常數）之敏度係根據Wyatt技術 程序並使用單分散3 0，0 0 0分子量聚苯乙烯標準加以測定 〇 樣品之平均分子量係使用適合一級多片數據。光散射對 折射係數比例（LS · RI)係使用校正基線，DAWN 90。檢 測器（dll)之正常化電壓及Hewlett Packard 1 047A型 請 先 閱_ 讀背: 面- 之 注 意· 事_ 項 頁 裝 訂 .線 -21 - 本紙張尺度通用中國固家標準（CNS )六4規格（21〇χ 297公釐 Λ24.1 06 Α7 Β7 - "" * —~ 五、發明説明（） 號折射係數檢測器。每一個尖辜底下之面積係依2.5分鐘 至21分鐘之界定整合限度範圍之總電壓加以預估^ 高分子量SBR典型之數目平均分子量（gpc)範園约 200，000至1,000,000 ，重量平均分子量（GPC)範圍約 30 ’ 000 至 2,000, 〇〇〇 ，Mooney ML 1+4 黏度範圍約 80至約160。較佳者’高分_子量SBR典型之數目平均分 予量（GPC)範圍約30,000至970,000，重量平均分子量D Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Consumer Cooperative A7 ------------- B7 V. Description of the invention (^ '----- / [starting with f according to the amount of SBR being synthesized The higher molecular weight = amount is achieved by a smaller amount of initiator, and the lower molecular weight is achieved by a larger amount of initiator. However, in the general rule, the reaction mixture contains 0'05 to P (each ι0 6 parts by weight of monomer) initiator. If it is a metal persulfate initiator, typically 0.1 to 0.5 phm initiator is used in the polymerization. Br The molecular weight also depends on the amount of chain transfer agent such as tertiary dodecyl mercaptan during the polymerization. For example, low molecular weight sbr can be synthesized by simply increasing the level of the chain transfer agent. In a specific example, when synthesizing a South Molecular Weight SBR The amount of tertiary dodecyl mercaptan used ranges from about 0 to 125 phm to about 0.150 phm. Low molecular weight SBR can be made by simply increasing the level of tertiary dodecyl mercaptan during polymerization. For example, 0 ' 38plim to 0.40phm tertiary dodecyl mercaptan typically synthesizes low molecular weight SBR. Unless otherwise indicated, molecular weights are by gel permeation chromatography G pc). Using a traditional GPC system, the light scattering (wya U technology ^ μ ini DAWN model) and the differential refractive index were used for testing. The sample was filtered through a Ø · 0 micron pore size injection filter. In some cases, the number The average molecular weight is determined by thermal field dynamic-classification. The number measured by thermal field flow classification is sometimes abbreviated as MnSF. When Mn3F is measured, FFFractionation, LLC (Salt Lake City) equipped with a τ-005 tube separator is used. , Utah) τ_ 100 polymer classifier model 'Hewlett Packard (Palo Alto, California) 1 0 4 7 A model refractive index detector and W ya 11 Technologies (Santa B a τ: bara, California) DAWNDSP model laser light Detector for the meter. In the test procedure, defoamed tetrahydrofuran is used as the carrier solvent, which is -20-this paper & degree of financial standard (CNS) A4 specification (21GXW mm) ~-(Please read t: surface first Zhi · ίΛ-t-item k β This page is installed-Order-line 424106 A7 B7 V. Description of the invention ("Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at the rate of 0.6 ml / min. Into the Soviet Union. The temperature of the cold wall in the thermal field flow classification is controlled by the FTS system RC 150 model recirculating cooler. The polymer classification is accompanied by the software program TEMP using the power program method of FFFractioriati, LLC. Program The conditions are as follows: the initial DeUa T is 60C, the equilibration time is 0.5 minutes, t1A50 minutes, "is -6.0 'fixed time is 30 minutes and the final DeIta Ding; is 0. The setpoint temperature of the cold wall cooler is 25 ° C. However, when the initial Delta T is 60 ° C, the cold wall temperature is typically around 40 t. The polymer sample was dissolved in a solvent ' and then injected into a thermal field flow classification system without filtration. Samples to be injected. Pellets are typically about 0.12 mg. The raw data was collected and processed by Wyatt Technology's software program astra. The data collection period was 25 minutes. For light scattering detectors, the baseline of the fist boxer is typically set at 1.5 minutes to 25 minutes, while the refractive index detector is set at 1.5 minutes to 20 minutes. For data processing, the DAWN light scattering detector used contains 5 to 16 (representing angles from 39 ° to 139 ° (in THF)). The first-order equation using the Zimm form fits the relationship between angle and light scattering. All emulsified polymer samples use a refractive index increment (d n, / d c) of 0.154, and solution polymer samples use 0.140. The sensitivity of the refractive index detector (Aux 1 constant) is determined according to the Wyatt technical procedure using a monodisperse 3,0 0 0 molecular weight polystyrene standard. 0 The average molecular weight of the sample is suitable for multi-level data. The ratio of light scattering to refractive index (LS · RI) uses a corrected baseline, DAWN 90. Detector (dll) normalization voltage and Hewlett Packard 1 047A type, please read _ Read Back: Side-Attention · Things _ Item Binding. Line-21-This paper is in accordance with the Chinese Standards (CNS) 6-4 Specifications (21〇χ 297 mm Λ24.1 06 Α7 Β7-" " * — ~ V. Description of the invention () Refractive index detector. The area under each sharp object is defined according to 2.5 minutes to 21 minutes The total voltage of the integration limit range is estimated ^ Typical number of high molecular weight SBR Average molecular weight (gpc) Fan Yuan is about 200,000 to 1,000,000, weight average molecular weight (GPC) range is about 30'000 to 2,000,000, Mooney ML 1 + 4 viscosity range of about 80 to about 160. The best is' high score_sub-quantity SBR typical number average fraction dose (GPC) range of about 30,000 to 970,000, weight average molecular weight
(GPC)範圍約 40,000 至 1，750,000 ， Mooney ML 1+4黏度範圍約9.0至約.150。最佳者··高分子量sbr典 型之數目平均分子量（GPC)範圍約65,000至930,000， 重量平均分子量（GPC)範圍約1,000,000至1,500,000 ，Mooney ML 1 + 4黏度範圍約95至約130 » 低分子量SBR典型之數目平均分子量（gpC)範園約 20,000至150,000 ，重量平均分子量（Gp〇範圍約 40，000 至 280,000 ，Mooney ML 1+4 黏度範圍約 2 至約40 。較佳者，高分子量SBR典型之數目平均分子量 (GPC)範圍約50,000至120,000 ，重量平均分子量 (GPC)範園約 70,000 至 270,000 ，Mo〇ney ML 1+4 黏度範圍約、至約1 3 0 。最佳者，高分子量s B R典盤之 數目平均分子量（G P C )範圍約5 5，0 0 0至1 1 〇，〇 〇 〇，重量 平均分子量（GPC)範圍約120,000至260,000 ，(GPC) range is about 40,000 to 1,750,000, Mooney ML 1 + 4 viscosity range is about 9.0 to about .150. Best ... High molecular weight sbr Typical number Average molecular weight (GPC) range of about 65,000 to 930,000, Weight average molecular weight (GPC) range of about 1,000,000 to 1,500,000, Mooney ML 1 + 4 viscosity range of about 95 to about 130 »Low molecular weight SBR Typical number average molecular weight (gpC) Fan Yuan is about 20,000 to 150,000, weight average molecular weight (Gp0 range is about 40,000 to 280,000, Mooney ML 1 + 4 viscosity range is about 2 to about 40. Preferably, high molecular weight SBR is typical The number average molecular weight (GPC) ranges from about 50,000 to 120,000, the weight average molecular weight (GPC) ranges from about 70,000 to 270,000, and the Money ML 1 + 4 viscosity ranges from about 1 to about 3 0. The best, high molecular weight s The number of BR code plates has an average molecular weight (GPC) range of approximately 55,000 to 110,000, and a weight average molecular weight (GPC) range of approximately 120,000 to 260,000.
Mooney ML 1+4黏度範圍約5至約20。低分子量sBR 通常之Mooney ML 1+4黏度範園為10至18 β 低分子量SBR之Mooney ML 1+4黏度與高分子量 -22- 本紙張尺度適用中國國家標準（CNS >A4規格（210X297公楚） ---------^-- (請先閲讀'r面之：^-^-事項^约本頁)Mooney ML 1 + 4 has a viscosity ranging from about 5 to about 20. Low molecular weight sBR usually Mooney ML 1 + 4 viscosity range is 10 to 18 β Low molecular weight SBR Mooney ML 1 + 4 viscosity and high molecular weight-22 (Chu) --------- ^-(Please read 'r Face: ^-^-Matters ^ About this page)
iT 經濟部智慧財產局§(工消費合作社印製 06 A7 B7 on ------------一 五、發明説明（） SBR之Mooney ML 1+4黏度之差距至少為50M〇〇ney 點。南分子量SBR之Mooney ML 1+4黏度一般至少比 低分子量SBR之M00ney ML i + 4.黏度高7〇M〇〇ney點 。问分子量SBR之Mooney ML .1 + 4黏度較佳至少比低 分子量SBR之Mo〇ney ML 1 + 4黏度高8〇M;〇〇ney點。 用於乳化聚合方法之皂系統含松香酸與脂肪酸乳化劑之 组合》脂肪酸含對松香酸皂之重量比例範圍約5 〇 : 5 〇至 9 〇 . 1 〇 。脂防酸皂對松香酸皂之重量比例範圍—般較佳約 6 0 : 4 0至8 5 : 1 5 »脂肪酸皂對松香酸皂之重量比例範圍一 般更佳約75:25至82:18 所有皂均被加入第一聚合區域 °所用皂總量小於3 . 5 p h m 。所用皂總量範圍一般約 2.5 p h m至3.2 p h m 。所用皂水平範圍典型較佳約 2.6phm至3,0phm 。在大部份情況下，所用皂系統數量 範園最佳約2.7phm至2.9phm 。當然，達到最適結果所 需要琶系統之精確數量將依所用特定皂系統而定。然而， 熟習此項技藝人士將能夠輕易知悉為了達到最適結果所需 要特定數量皂。 自由基乳化聚合典型將在約3 5。F ( 2 °C )至約6 5。F ( 1 8 •一 ） °C )溫度範圍進行。聚合—般較佳在約4 〇。F ( 4。(3 )至約 6 0 ° F ( 1 6 °C )溫度範圍進行。聚合典型較佳使約4 5。F ( 7 °C )至約5 5。F ( 1 3 °C )溫度範圍。為了提高轉化水平，邛以 有利地隨著聚合進行而提高溫度。 在第二聚合區域達到所欲單體轉化率時，由第二聚合區 域取出所製S B R乳膠，加入速止物以終止共聚合反應。挣 -23 - 本纸浪尺度適別中國國家標準（CNS ) Λ4規格（2ΐ〇χ297公着) ---------^— (請先閱讀'背面之>1.-愈事項.^4内本頁) -訂 線 經濟部智慧財產局員工消f合作社印製 424106;^ A7 _________________ B7五、發明説明（2、 經濟部智慧財產局員工消費合作社印製 〇门刀子I S B R乳化物與低分子量S㈣乳化物是方便之 舉摻》物中向分子量SBR對低分子量sbr之重量比例 二為8 〇 : 2 〇至約2 5 : 7 5。在大部情沉下，摻合物 中问刀子量S B R對低分子量s B r之重量比例範園約為 7〇 ‘ 3〇至約30:70 。摻合物中高分子量SBR對低分子量 SBR之重量比例範圍典型較佳約為6〇:4〇至約4〇 6〇 。 ”二後本發明乳化S B R摻合物可藉使用標準共絮凝及乾燥 技術自乳_膠回收。 摻合一札膠所製得本發明苯乙烯-丁二婦橡膠組合物之 範圍為50, 〇〇〇至15〇, 〇〇〇 。笨乙烯-丁二烯橡膠组 合物典型具備Mn3F範圍為60, 〇〇〇至145,000 ，更典型 之Mn3F範圍為75,000至14〇,〇()()。苯乙缔-丁二烯橡膠 組合物較佳具備Mn3F範圍為90,000至135,000 。苯乙 烯-丁二烯橡膠組合物也具備光散射對折射係數比例 (L S / R I)範圍為1 . 8至3 . 9。苯乙烯丁二烯橡膠组合物典 型光散射對折射係數比例範圍為2 _ 0至3 · 8 ，更典型之光 散射對折射係數比例範圍為2 . 1至3.7。較佳者，苯乙烯_ 丁二烯橡膠組合物典型光散射對折射係數比例範圍為2 2 至 3.0。、 若動態振動掃頻對儲存模數（G ’）作圖且頻率對損失模數 (G ")作圖，本發明苯乙烯-丁二烯橡膠組合物在頻率範圍 為〇 _ 0 0 1弧度/秒至1 0 0弧度/秒，於9 0 SC至1 2 0 t進行 並使用平行板幾何學時有交叉。換言之，120 °C於低頻率 如〇 . 1弧度/秒，G 1低於G ”》然而，G 4隨著頻率增加而 -24 - 冬紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀t.面之iit'事項蟲衿本頁) -裝 -*·ιτ 線 424106 Α7 Β7 五、發明説明（, 増加，直到G，等於G，，且最終於高頻率如1〇策度/秒時大 於G，，。交叉點典型頻率範圍為〇 〇〇ι弧度/秒至ι〇〇弧度 /秒，更典型頻率範園為〇 〇1弧度/秒至5弧度/秒。在大 2份情況下，120。(：時，交又點頻率範園為〇〇5弧度/秒 至^狐度/秒。所用試驗程序中，橡膠樣品經預成形為直徑 毫米、厚度2毫米之樣品。然後將樣品置於介於相距給 予間隙距離之平行板間之控制應力流變計。然後在一些施 用應力強度（如1 0,0 0 0 1^至2〇,〇〇〇Pa)下使樣品在掃頻（ 如〇 . 0 1 Η z至1 〇 〇 Η z)操作此程序係在丨2 〇下進行.。 為儲存模數五代表聚合物之彈性部份’對膠和分子量之 改變十分敏感。G η為損失模數，代表樣品之黏性部份。 由此方法製備之SBR可用於製備輪胎及範圍廣泛之其 他具改善性能特徵之橡膠物件。使用本發明乳化s B R於製 備輪胎面化合物有許多相關聯之優點。更特定的，牽引特 徵可顯著獲得改善而不會損失胎面耐磨或滾動阻。在許多 情況下，摻合本發明乳化S B R組合物與其他橡膠聚合物而 達到所要特徵係有利的。當然，此類輪胎面化合物含可與 本發明$化^ BR組合物共同硬化之其他橡膠。可與本發明 乳化S B R ^同硬化之其他橡膠之—些代表性實例包含天然 橡膠，南度順-1，4 -聚丁二烯橡膠，高乙烯基聚丁二烯橡 膠，中等乙烯基聚丁二缔橡膠，高度反聚丁二烯橡 膠，溶液苯乙烯-丁二烯橡膠，苯乙烯-異戊間二烯_丁二烯 橡膠，苯乙烯-異戊間二歸橡膠，異戊間二烯_ 丁二烯橡膠 及3，4 -聚異戊間二烯橡膠。本發明乳化s B R與天然橡膠 -25- 冬紙浪尺度適用中國國家標準（CNS ) A4規格（210χη7公釐 —^-------装— (諳先閲讀’f.面之ii>意事項朽本頁) 訂 線 經濟部智態財產局員工消費合作社印製 4 2 4 1 〇 6 " *4 * AI B7 經濟部智慧財產局員工消費合作社印製 23 - ---- 五、發明説明（） 或合成聚異戊間二烯之摻合物在用於輪胎面調配物方面高 度有利。例如，3 0 p h r至7 0 p h r之S B R可與天然橡膠或 合成聚異戊間二缔橡膠挣合。40phr至60pl!r之SBR與 4 0phr至6 0phr天然橡膠及/或合成聚異戊間二烯橡膠之 摻合物為典型》此類摻合物一般含30phr至70phr之 SBR與30phr至70phr夭然橡膠及/或順-1，4-聚丁二歸 橡膠。40phr至60phr之SBR與40phr至6〇phr天然橡 膠及/或順式-1,4 -聚丁二烯橡膠之摻合物為最典型。此類 摻合物所用順-1，4 -聚丁.二烯橡膠之順· 1，4 -聚丁二烯橡膠 含里至少約9 5百分比。適用於此類摻合物之高度順_ 1 4· 聚1二稀橡膠典型之順-異構物含量大於90百分比且可藉 加拿大專利第1，2 3 6，6 4 8所述方法加以製備•適合用於此 類#合物中之高度順-ls4_聚丁二婦橡膠也由G〇〇dyear Tire & Rubber公司以Bude n e® 1 2 0 7聚丁二烯據膠及 Budene®1208聚丁二烯橡膠販售。 具十分有用特徵之輪胎面化合物也可藉3,4 -聚異戊間二 烯於摻合物而製備。一般規則中，約5 p h r (每1 〇 〇份橡膠 之份數）至約40p hr高Tg之3,4-聚異戊問二埽與約 60Phr至約’95phr之本發明SBR组合物包含於輪胎面化 合物。一般情況下’此類輪胎面化合物會含約l〇phr至 25?111"之3>4-聚異戊間二浠及約751)11]>至9〇13111：之3311 组合物。此類輪胎面化合物典型更佳含高T g之3，4 -聚異 戊間二烯橡膠。當然，除了 S B R組合物以外，此類輪胎面 化合物也可含其他橡膠。然而，此類橡膠可與s B R組合物 _ -26- _ 本紙張尺度適财家轉（CNS )織格（210X297公釐} '----- (請先閱^.1¾之；kt-事項..^.¾本 K) •裝- 訂 -線 0 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（ 及4 -聚兴戊問二烯橡勝共同硬化之其他橡膠之一些代表 性實例包含天然橡膠，高度順-丨，4 _聚丁二烯橡膠，高度 乙烯基聚丁二烯橡膠，中等乙烯基聚丁二烯橡膠，高度反_ 1，4 -聚丁二烯橡膠’苯乙埽-異戊間二烯-丁二烯橡膠，苯 乙烯-开戊間二烯橡膠，異戊間二烯_ 丁二烯橡膠。 用於高性能汽車.輪胎之較佳摻合物包含，以1 〇 〇份重量 橡膠為基準，（1 )約2 0至約6 〇份天然橡膠，（2 )約5至約 30份高度順·Ι，4-聚丁二烯橡膠，（3)約10份至約50份 SBR组合物及（4).約5至約3〇份3,4_聚異戊間二烯橡膠 。較佳使此類摻合物含（1)约3〇至約5〇份天然橡膠，（2) 约1 0至約2 0份高度順-1 s 4 _聚丁二烯橡膠，（3 )约2 〇份 至約4 0份S B R組合物及（4 )約1 〇至約2 0份3，4 -聚異戌 間二烯橡膠。更佳使此類輪胎面橡膠調配物含（丨）約3 5至 約4 5份天然橡膠’（2 )約1 〇至約2 〇份高度順-1，4 -聚丁 二烯橡膠，（3 )約2 5份至約3 5份S B R組合物及（4 )約1 〇 至約2 0份3，4 -聚異戊間二缔橡膠。 為了使輪胎性能特徵達到最大效果，高T g 3，4 -聚異戊 間二烯，低T g 3,4 -聚異戊間二烯及本發明s B R組合物可 用於輪胎面化合物。低T g 3，4 -聚異戊間二烯的T g約小於 -5 eC。低T g之3，4 -聚異戊間二烯的τ g典槊範圍約_ 5 5 eC至約-5 °C。低T g之3，4 -聚異戊間二烯的T g較佳範圍 約-30。〇至約-10 °C。低Tg之3,4-聚異戊間二埽的Tg最 佳範圍約-2〇 °C至約-10。(：。低Tg之3,4-聚異戊間二埽 典型具備大於約200,000之數目平均分子量。低Tg之 -27 « " 本紙張尺歧财關“率（CNS ) ( 21GX297公釐) 一~ "' <請先閱讀免面之注.^-事項函巧本頁) -¾衣 -訂 線 424106^ A7 B7 五、發明説明（ 經濟部智块？財產局員工消費合作杜印製 3，4-聚異戊間二烯一般具備數目平均分子量範圍約 20〇,〇〇0至約5 0 0,0 0 0 ，較佳具備數目平均分子量範圍 約25 0,0 00至約4〇〇,〇〇〇 。高Tg之3 4_聚異戊間二烯 的Tg典型範圍為〇 C至約25 C 數目平均分子量範圍約 30’〇〇〇至約18〇,000。高Tg<3,4·聚異戊間二烯的丁^ .較佳ia圍約為5 °C至約2 0。〇。高T g之3，4 -聚異戊間二烯 典型3,4 -異構物含量範圍約75百分比至約95百分比， 1，2 -異構物含量範圍約5百分比至约2 5百分比= 在此類輪胎面化合物中’高T g之3 ^ 4 -聚異戊間二婦對 低T g之3,4 -聚異戊間二烯之重量比例之典型.範圍約 0，1:1至約1〇:ϊ。高Tg之3,4-聚異戊間二埽對低Tg之 3，4 -聚異戊間二烯之重量比例之一般較佳範圍約〇 5 :丨至 約2 : 1 。高T g之3，4 -聚異戊間二缔對低τ g之3 ^ 4 -聚異 戊間二烯之重量比例之一般最佳範圍約〇 . 8 :丨至約丨2 : i 。一般使用等量之高Tg3,4 -聚異戊間二烯與低Tg之 3，4 -聚異戊間二烯以達到最適結果。 高性能汽車輪胎之高度較佳摻合物包含，以1 〇 〇份重量 橡膠為基準，（1 )约2 0·至約6 0份天然橡膠，（2 )约5至約 3 〇份高度】A - 1，4 -聚異戊間二烯橡膠，（3 )約1 0至約5 0 份本發明S B R組合物，（4 )約2 · 5份至約15份高T g之 3，4 -聚異戊間二烯橡膠及（5 )約2.5份至約1 5份低T g之 3，4 -聚異戊間二烯橡膠。此摻合物較佳包含（1 )約3 0至约 5 0份天然橡膠，（2 )約1 0至約2 0份高度順-1，4 -聚異戊 間二烯橡膠，（3 )約2 0至約4 0份本發明S B R组合物， .28 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4 +JT本頁) •裝· 訂 -線 Α7 Β7 五、發明説明（” (4) 約5份至約1〇份高Tg之3,4_聚異戊間二烯橡膠及 (5) 約5份至約1〇份低丁g之3 s4-聚異戊間二烯橡膠。此 輪胎面橡膠調配物更佳包含（丨广約3 5至約4 5份天然橡膠 ’（2)約10至約20份高度順-1，4·聚異戊間二烯橡膠， (3 )約2 5至約3 5份本發明s B R組合物，（4 )約5份至約 1 0份高T g 3，4 -聚異戊間二烯橡膠及（5 )約5份至約1 〇份 低Tg3,4 -聚異戊間二烯橡膠。 若希望使輪胎牵.引特徵達到最大效果，由挣合物除去高 度順-1 ’ 4 -聚異戊間二烯橡膠。然而’應該理解在此情況 下爿β面耐磨可作某種程度之妥協。在任何情況下，高性 能輪胎之突出輪胎面化合物可製備於摻合，以份重量 橡膠為基準，（1)約20至約60份天然橡膠，（2)約1()至 約5 0份本發明s β R組合物及（3 )約1 〇份至約3 〇份高 Tg3,4·聚異戊間二缔橡勝。另一内容中，此摻合物包含， 以1 0 0份重量橡膠為基準’（丨）約2 〇至約6 〇份天然橡膠 ，（2 )约1 〇至約5 〇份本發明5 b r组合物，（3 )約5份至 约1 5份鬲丁 g 3，4 -聚異戊間二烯橡膠及（4 )約5扮至約1 5 份低T g 3,4 -聚異戊間二烯橡膠。 經濟部智葸財產局員工消費合作社印製 (請先閱讀f;面之·ii-t-事項b JT本頁) 含本發明橡膠摻合物之乳化S B R可經傳統组份及標準 技術加以混鍊。例如，此類橡膠摻合物典型與碳黑及/或矽 ^ 填料，促進货】，油，螺過早疏化抑制劑，及加工 助劑a在大部份情況下，乳化S β R摻合物與硫及/或含硫 化合物，至少一種填料，至少一種促進劑，至少一種抗降 解劑，至少一種加工油，氧化鋅，選用增稠樹脂，選用補 -29- 卜纸掁尺度適用中國國家榇準（〇«)八4規格（21〇父297公釐） 24 4 10 6 A7 B7 經濟部智.¾財產局員H消費合作社印製 五、發明説明（ 強樹月H ’ it用-或多種脂肪酸，選用膠溶劑及選用一或多 種杬過早&化劑。此類摻合物一般含約0 · 5至5 p h r (每 1.00份重量橡膠之份數）硫及/或含硫化合物，以ip。至 -.3 p h r軼佳。當發生起霜問題時，希望使用不會溶解之硫 〇 一般情況下，摻合物中使用〇至15〇phr之至少一種填 料，以30至80phr較佳。在大部份情況下，至少—些碳 黑可用於填料中。當然，填料可以全部為碳黑。矽可含於 填料中以改善抗撕裂及熱累積。黏土及/或滑石可包含於填 料中以降低成本。摻合物一般亦含〇1至2 5phr之至少 一種促進劑’以0.2至15phr較佳。抗降解劑如抗氧化 劑及抗臭氧劑在胎面化合物摻合物中之數量一般為〇 2 5 至lOphr，以1至5phr較佳。摻合物中之加工油數量— 般為2至1 〇 〇 p h r，以5至5 0 p h r較佳。本發明乳化s b r 橡膠摻合物一般亦含0.5至l〇phr氧化鋅，以1 , p h r 較佳。這些摻合物選用含0至1〇1)111_增稠劑，〇 ^ 王丄◦ p h r 補強樹脂’ 1至lOphr脂肪酸，0至2‘5phr膠溶劑及〇 至2 p h r過早硫化抑制劑。iT Intellectual Property Bureau of the Ministry of Economic Affairs § (Printed by the Industrial and Consumer Cooperatives 06 A7 B7 on ------------ V. Invention Description) The Mooney ML 1 + 4 viscosity difference of SBR is at least 50M. 〇ney point. The viscosity of Mooney ML 1 + 4 of South molecular weight SBR is generally at least 70% higher than the viscosity of M00ney ML i + 4 of low molecular weight SBR. Ask Mooney ML .1 + 4 with better viscosity The viscosity is at least 800M; 00ney point higher than the low molecular weight SBR Mooney ML 1 + 4. The soap system used in the emulsification polymerization method contains a combination of rosin acid and fatty acid emulsifiers. The weight of fatty acid contains rosin acid soap. The ratio range is about 50: 50 to 9 0.1. The weight ratio range of fat-proof acid soap to rosin acid soap-generally preferred is about 60:40 to 8 5: 1 5 »fatty acid soap to rosin acid soap The weight ratio range is generally better about 75:25 to 82:18. All soaps are added to the first polymerization zone. The total amount of soap used is less than 3.5 phm. The total amount of soap used is generally about 2.5 phm to 3.2 phm. Soap used The horizontal range is typically about 2.6 phm to 3,0 phm. In most cases, the number of soap systems used is about 2.7 phm. 2.9phm. Of course, the exact number of cymbal systems required to achieve the optimal result will depend on the particular soap system used. However, those skilled in the art will be able to easily understand the specific amount of soap required to achieve the optimal result. Typical examples of free radical emulsion polymerization It will be performed at a temperature range of about 3 5. F (2 ° C) to about 6 5. F (1 8 • 1) ° C). Polymerization-generally preferred at about 40. F (4. (3)) to about 60 ° F (16 ° C) temperature range. The polymerization is typically preferably about 4 5. F (7 ° C) to about 5 5. F (1 3 ° C) Temperature range. In order to increase the conversion level, it is advantageous to increase the temperature as the polymerization proceeds. When the second polymerization zone reaches the desired monomer conversion rate, the prepared SBR latex is taken out from the second polymerization zone, and a quick stop is added to Terminate the copolymerization reaction. Earn -23-The size of this paper conforms to the Chinese National Standard (CNS) Λ4 specification (2ΐ〇χ297)---------- ^ — (Please read 'Back of the > first> 1.-Healing matters. ^ 4 in this page)-Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the cooperative 424106; ^ A7 _________________ B7 V. Invention description (2, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The door knife ISBR emulsion and low-molecular-weight Sr emulsion are convenient to blend. The weight ratio of the molecular weight SBR to the low-molecular-weight sbr in the second is 80:20 to about 2 5: 7 5. In most cases, it sinks. In the blend, the weight ratio of the amount of the knife SBR to the low molecular weight s B r ranges from about 70 ′ 30 to about 30:70. The weight ratio range of molecular weight SBR to low molecular weight SBR is typically preferably about 60:40 to about 4600. "Secondly, the emulsified SBR blend of the present invention can be prepared from latex by using standard coflocculation and drying techniques. Recovery. The range of the styrene-butadiene rubber composition of the present invention prepared by blending a gum is in the range of 50,000 to 150,000. The styrene-butadiene rubber composition typically has a Mn3F range. It is 60,000 to 145,000, and a more typical Mn3F range is 75,000 to 140,000 () (). The styrene-butadiene rubber composition preferably has a Mn3F range of 90,000 to 135,000. Styrene-butadiene The diene rubber composition also has a light scattering to refractive index ratio (LS / RI) ranging from 1.8 to 3.9. A typical light scattering to refractive index ratio of a styrene butadiene rubber composition ranges from 2 to 0 to 3. · 8, more typical light scattering to refractive index ratio ranges from 2.1 to 3.7. Preferably, the typical light scattering to refractive index ratio of styrene butadiene rubber composition ranges from 2 2 to 3.0. If dynamic Vibration sweep vs. storage modulus (G ') and frequency vs. loss modulus (G ") Mapping, the styrene-butadiene rubber composition of the present invention is performed in the frequency range of 0_ 0 01 radians / second to 100 radians / second at 90 ° SC to 1 2 0 t and using parallel There is a crossover in plate geometry. In other words, at 120 ° C at low frequencies such as 0.1 radians / second, G 1 is lower than G "" However, as the frequency increases, -24-winter paper scale applies Chinese national standards ( CNS) A4 specification (210X297 mm) (please read t. Face of the iit 'matters on this page)-Install-* · ιτ line 424106 Α7 Β7 V. Description of the invention (, Add until G, equal to G ,, And finally, it is larger than G at high frequency such as 10 strategies / second. The typical frequency of the intersection is in the range of 100,000 radians / second to 500,000 radians / second, and the more typical frequency range is 0.001 radians / second to 5 radians / second. In the case of 2 servings, 120. (: Hour, cross point frequency range is from 0.05 radians / second to ^ fox degrees / second. In the test procedure used, the rubber sample was preformed into a diameter of 2 mm and a thickness of 2 mm. The sample was then placed in the media A controlled stress rheometer between parallel plates that are given a gap distance from each other. Then the sample is swept at a frequency (such as 〇) at some applied stress intensity (such as 10,000 to 20,000 Pa). 0 1 Η z to 100 Η z) operation This procedure is performed under 丨 2 0. To store the modulus five represents the elastic part of the polymer 'is very sensitive to changes in gum and molecular weight. G η is the loss The modulus represents the viscous part of the sample. The SBR prepared by this method can be used to prepare tires and a wide range of other rubber objects with improved performance characteristics. The use of the emulsified s BR of the present invention in the preparation of tire tread compounds has many related Advantages. More specifically, traction characteristics can be significantly improved without loss of tread abrasion or rolling resistance. In many cases, it is advantageous to blend the emulsified SBR composition of the present invention with other rubber polymers to achieve the desired characteristics. Of course, such tires The surface compound contains other rubbers that can be co-cured with the BR composition of the present invention. Other rubbers that can be hardened with the emulsified SBR of the present invention. Some representative examples include natural rubber, Nandushun-1, 4-poly Butadiene rubber, high vinyl polybutadiene rubber, medium vinyl polybutadiene rubber, highly reverse polybutadiene rubber, solution styrene-butadiene rubber, styrene-isoprene_butene Diene rubber, styrene-isoprene dimer rubber, isoprene_butadiene rubber and 3,4-polyisoprene rubber. The emulsified s BR and natural rubber of the present invention-25- winter paper The wave scale applies the Chinese National Standard (CNS) A4 specification (210χη7 mm — ^ ------- installation— (read the 'f. Face of ii > matters of interest on this page first) the intellectual property of the Ministry of Economics Printed by the employee consumer cooperative of the Bureau 4 2 4 1 〇6 " * 4 * AI B7 Printed by the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 23----- V. Description of the invention () or synthetic polyisoprene Blends are highly advantageous for use in tire tread formulations. For example, 30 phr to 70 phr of SBR is compatible with natural Rubber or synthetic polyisoprene rubber. The blend of SBR from 40phr to 60pl! R with 40phr to 60phr natural rubber and / or synthetic polyisoprene rubber is typical. It usually contains 30 to 70 phr of SBR and 30 to 70 phr of natural rubber and / or cis-1,4-polybutadiene rubber. 40 to 60 phr of SBR and 40 to 60 phr of natural rubber and / or cis-1 Blends of 4,4-butadiene rubber are the most typical. The cis-1,4-polybutadiene rubber used in such blends has a cis-1,4-polybutadiene rubber content of at least about 95%. High cis__ suitable for such blends_ 1 4 · Poly 1 dilute rubber typical cis-isomer content is greater than 90% and can be prepared by the method described in Canadian Patent Nos. 1, 2 3 6, 6 4 8 • Highly cis-ls4_polybutadiene rubber suitable for this type of compound is also manufactured by Godyear Tire & Rubber Company as Bude ne® 1 2 0 7 polybutadiene rubber and Budene® 1208 Polybutadiene rubber is sold. Very useful tire tread compounds can also be prepared by blending 3,4-polyisoprene with a blend. As a general rule, about 5 phr (parts per 1,000 parts of rubber) to about 40 p hr of high Tg 3,4-polyisoprene, and about 60 Phr to about '95 phr of the present SBR composition are included in Tire tread compounds. In general, such a tire tread compound will contain about 10 phr to 25? 111 " 3 > 4-polyisoprene dioxin and about 751) 11] > to 903111: 3311 composition. Such tire tread compounds typically have a higher T g of 3,4-polyisoprene rubber. Of course, such tire tread compounds may contain other rubbers in addition to the S B R composition. However, this kind of rubber can be combined with s BR composition _ -26- _ This paper size is suitable for wealth transfer (CNS) weaving grid (210X297 mm) '----- (please read ^ .1¾ of it first; kt- Matters: ^ .¾ this K) • Packing-ordering-thread 0 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (and 4-Poly-pentadiene rubber win-hardened other rubbers. Some representative examples include natural rubber, highly cis- 丨, 4-polybutadiene rubber, highly vinyl polybutadiene rubber, medium vinyl polybutadiene rubber, highly trans- 1,4-polybutadiene Rubber 'Styrene-isoprene-butadiene rubber, styrene-openprene rubber, isoprene_butadiene rubber. Used in high-performance automobiles. The best blend of tires The product includes, based on 100 parts by weight of rubber, (1) about 20 to about 60 parts of natural rubber, (2) about 5 to about 30 parts of highly cis. 1,4-polybutadiene rubber, ( 3) about 10 to about 50 parts of the SBR composition and (4) about 5 to about 30 parts of 3,4-polyisoprene rubber. It is preferred that such blends contain (1) about 3 〇 to about 50 parts of natural rubber, (2) about 1 0 to about 20 parts of highly cis-1 s 4-polybutadiene rubber, (3) about 20 to about 40 parts of the SBR composition and (4) about 10 to about 20 parts of 3, 4- Polyisoprene diene rubber. It is more preferred that such tire tread rubber formulations contain (35) about 35 to about 45 parts of natural rubber '(2) about 10 to about 20 parts highly cis-1,4 -Polybutadiene rubber, (3) about 25 parts to about 35 parts of SBR composition and (4) about 10 to about 20 parts of 3,4-polyisoprene rubber. In order to make tire performance Features achieve maximum effect, high T g 3,4-polyisoprene, low T g 3,4-polyisoprene and the s BR composition of the present invention can be used for tire tread compounds. Low T g 3, The T g of 4-polyisoprene is less than about -5 eC. The τ g range of 3,4-polyisoprene of low T g is about _ 5 5 eC to about -5 ° C. Low The T g of 3,4-polyisoprene is preferably in the range of about -30 ° to about -10 ° C. The optimal range of Tg of 3,4-polyisoprene in low Tg is about -2 ° C to about -10. (:. Low Tg of 3,4-polyisoprene difluorene typically has a number average molecular weight greater than about 200,000. Low Tg of -27 «" Ruler of wealth (CNS) (21GX297mm) 1 " '< Please read the note of face-free first. ^ -Matters on this page) -¾¾- 定 线 424106 ^ A7 B7 V. Invention Explanation (Ministry of Economics? Property Bureau employee consumer cooperation Du printed 3,4-polyisoprene generally has a number average molecular weight range of about 20,000 to about 50,000, preferably a number average molecular weight range of about 25 0.00 to about 40,000. The high Tg of 3 4-polyisoprene typically has a Tg in the range of 0 C to about 25 C. The number average molecular weight range is about 30'000 to about 18,000. High Tg < 3,4 · butane of polyisoprene. The preferred ia range is from about 5 ° C to about 20 °. 〇. High T g 3,4-polyisoprene typical 3,4-isomer content range from about 75% to about 95%, and 1,2-isomer content range from about 5% to about 25% = Typical of the weight ratio of 3 ^ 4-polyisoprene to 3,4-polyisoprene of low Tg in such tire tread compounds. The range is about 0, 1: 1 To about 10: ϊ. A generally preferred range of the weight ratio of 3,4-polyisoprene of high Tg to 3,4-polyisoprene of low Tg is about 0.5: 1 to about 2: 1. The generally optimal range of the weight ratio of 3,4-polyisoprene with high T g to 3 ^ 4-polyisoprene with low τ g is about 0.8: 1 to about 2: i. The same amount of high Tg3,4-polyisoprene and low Tg 3,4-polyisoprene are generally used to achieve the best results. A highly preferred blend of high performance automotive tires includes, based on 100 parts by weight of rubber, (1) about 20 · to about 60 parts of natural rubber, and (2) about 5 to about 30 parts in height] A-1,4-polyisoprene rubber, (3) about 10 to about 50 parts of the SBR composition of the present invention, (4) about 2.5 to about 15 parts of high Tg 3,4 -Polyisoprene rubber and (5) about 2.5 parts to about 15 parts of low Tg 3,4-polyisoprene rubber. This blend preferably comprises (1) about 30 to about 50 parts of natural rubber, (2) about 10 to about 20 parts of highly cis-1,4-polyisoprene rubber, (3) About 20 to about 40 parts of the SBR composition of the present invention, .28 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-(Please read the note on the back 4 + JT page first) • Binding and binding-thread A7 B7 V. Description of the invention ("(4) about 5 parts to about 10 parts of high Tg 3,4-polyisoprene rubber and (5) about 5 parts to about 10 parts Low butyl g 3 s4-polyisoprene rubber. This tire tread rubber formulation preferably contains (丨 about 35 to about 4 5 parts of natural rubber '(2) about 10 to about 20 parts highly cis- 1,4 · polyisoprene rubber, (3) about 25 to about 35 parts of the s BR composition of the present invention, (4) about 5 to about 10 parts high T g 3,4-polyisoprene Intermediate rubber and (5) about 5 parts to about 10 parts of low Tg3,4-polyisoprene rubber. If it is desired to maximize tire pull characteristics, remove highly cis- 1 '4 -polyisoprene rubber. However, it should be understood that in this case, the β-side abrasion resistance can be used as A degree of compromise. In any case, the outstanding tread compound of a high-performance tire can be prepared by blending, based on parts by weight of rubber, (1) about 20 to about 60 parts of natural rubber, (2) about 1 () To about 50 parts of the sβR composition of the present invention and (3) about 10 parts to about 30 parts of high Tg3,4 · polyisoprene diene rubber. In another aspect, the blend comprises, Based on 100 parts by weight of rubber, '(丨) about 20 to about 60 parts of natural rubber, (2) about 10 to about 50 parts of the 5 br composition of the present invention, and (3) about 5 parts to about 15 parts of gadolinium g 3,4-polyisoprene rubber and (4) about 5 parts to about 15 parts of low T g 3,4-polyisoprene rubber. Ministry of Economic Affairs, Intellectual Property Office Printed by employee consumer cooperatives (please read f; face-ii-t-item b JT page) Emulsified SBR containing the rubber blend of the present invention can be mixed with traditional components and standard technology. For example, this type Rubber blends are typically mixed with carbon black and / or silica ^ fillers], oil, snail premature dredging inhibitors, and processing aids a. In most cases, emulsify S β R blends with sulfur And / or sulfur compounds , At least one filler, at least one accelerator, at least one anti-degradation agent, at least one processing oil, zinc oxide, thickening resin is selected, and the supplementary -29- Pu paper standard is applicable to China National Standard (〇 «) 8-4 specifications (21〇 Father 297 mm) 24 4 10 6 A7 B7 Ministry of Economic Affairs. ¾ Printed by the property bureau member H Consumer Cooperative. V. Description of the invention (Strong tree moon H'it-or multiple fatty acids, select peptizer and select one or A variety of premature & chemical agents. Such blends generally contain about 0.5 to 5 p h r (parts per 1.00 parts by weight of rubber) of sulfur and / or sulfur-containing compounds, based on ip. To -.3 p h r Yi Jia. When blooming problems occur, it is desirable to use sulfur that does not dissolve. In general, at least one filler of 0 to 150 phr is used in the blend, preferably 30 to 80 phr. In most cases, at least some carbon black can be used in the filler. Of course, the filler can be all carbon black. Silicon can be included in the filler to improve tear resistance and heat build-up. Clay and / or talc may be included in the filler to reduce costs. Blends also generally contain at least one accelerator ' from 0 to 25 phr, preferably from 0.2 to 15 phr. The amount of the antidegradant such as an antioxidant and an antiozonant in the compound of the tread compound is generally 0 2 to 10 phr, preferably 1 to 5 phr. The amount of processing oil in the blend is generally 2 to 100 p h r, and preferably 5 to 50 p h r. The emulsified s b r rubber blend of the present invention generally also contains 0.5 to 10 phr of zinc oxide, with 1, p h r being preferred. These blends are selected to contain 0 to 10) 111_ thickener, ^ Wang 丄 ◦ p h r reinforcing resin '1 to 10 phr fatty acids, 0 to 2 ′ 5 phr peptizer and 0 to 2 p h r premature vulcanization inhibitor.
.-V 在許多情況下，本發明胎面橡膠調配物包含矽在士 D ^诔有利的 。含乳化S B R之摻合物之加工一般係在含硫有機砂化入物 (矽偶合劑）存在下進行以達到最大效益，合適之*1 δ碌有機 矽化合物之實例為下式： Ζ-Alk-Sn-Alk-Z (I) 其中Z係選自以下所組成者 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） I I I n 1 ϋ n n HI ^ l> I n I— n n ^ I— If n I I* I ^ (^F^-Mlt.f.fiiiA-Jfw-SMi¾本頁} ( 424 1υ b Α7 Β7 五、發明説明（1 R1 *Si — R2 R1 Si—R2 R2 及 R2 —Si —R： R2 讀 先 聞.-V In many cases, it is advantageous for the tread rubber formulations of the present invention to contain silicone. Processing of blends containing emulsified SBR is generally performed in the presence of sulfur-containing organic sanding compounds (silicon coupling agents) to achieve maximum benefits. An example of a suitable * 1 δ organic silicon compound is the following formula: AZ-Alk -Sn-Alk-Z (I) where Z is selected from the following. The paper size is applicable to Chinese national standards (CNS > A4 size (210X297 mm) III n 1 ϋ nn HI ^ l > I n I— nn ^ I— If n II * I ^ (^ F ^ -Mlt.f.fiiiA-Jfw-SMi¾ this page} (424 1υ b Α7 Β7 V. Description of the invention (1 R1 * Si — R2 R1 Si—R2 R2 and R2 —Si —R: Read R2
I 其中R1為1至4個碳原子之烷基’環己基或苯基；其中 R2為含1至8個碳原子之烷氧基或含5至8個碳原子之環 烷氧基；及其中Aik為1至18個碳原子之二價烴及η為2 至8之整數。 可供本發明使用之含硫有機矽化合物之特定實例包含： 3，3，-雙（三甲氧基甲矽烷丙基）二硫化物，3,3、雙（三乙 氧基甲秒燒丙基）四破·化物，3,3·-雙（三乙氧基甲矽燒丙 基）八硫化物，3，3 '-雙（三甲氧基甲矽烷丙基）四硫化物，. 2,2，-雙（三乙氧基甲矽烷乙基）四硫化物，3，3’-雙（三甲 · * * 氧基甲矽烷"丙基）三硫化物，3 , 3 _ -雙（三乙氧基甲矽烷丙 基）三硫化物，3 , 3 ’ -雙（三丁氧基甲矽烷丙基）二硫化物， 3，3 ·-雙（三甲氧基甲矽烷丙基）六硫化物，3 , 3 1 -雙（三甲 氧基甲矽烷丙基）八硫化物’ 3，3、雙（三辛氧基甲矽烷丙 基）四硫化物，3,3、雙（三己氧基甲矽烷丙基）二硫化物， 3，3 1 -雙（三-2 "-乙己氧基甲矽烷丙基）三硫化物，3，3 ·-雙 -31 - 本紙張尺度適用中國國家標隼（CNS ) Α4規格（2i〇X297公釐） 頁 訂 線 經濟部智慧財產局員工消費合作社印製 A7 B7 五 經濟部智慧財產局員工消費合作社印製 4 2 411 0 6 '舞明説明 (三異辛氧基甲矽烷丙基）四硫化物，3,3、雙（三·三級丁 氧基甲矽烷丙基）二硫化物’ 2,2'-雙（甲氧二乙氧甲矽烷 乙基）四硫化物，2，2，-雙（三丙氧甲矽烷乙基）五硫化物， 3，3 雙（三環己氧甲矽烷丙墓）四硫化物’ 3，3 · ·雙（三環 戊氧甲矽烷丙基）三硫化物，2,2、雙（三-2、甲基環己氧 甲矽烷乙基）四硫化物，雙（三甲基甲矽烷甲基）四硫化物， 3 -甲乳基乙氧基丙氧甲甲麥規•基·5- —乙氧丁氧甲梦虎丙 基四硫化物，2，2 1 -雙（二甲基甲氧甲矽烷乙基）二硫化物 ’ 2，2 ’ -雙（二甲基二級丁氧甲石夕燒乙基）三繞化物，3，3，- 雙（甲基丁基乙氧曱矽烷丙基）四硫化物，3,3，-雙（二-三 級丁基甲氧甲矽烷丙基）四硫化物，2,2’-雙（苯基甲基甲 氧甲碎燒乙基）三硫化物j，3 -雙（—本基異丙氧甲梦披 丙基）四硫化物，3，3 1 -雙（二苯基環己氧甲矽烷丙基）二硫 化物，3，3，-雙（二甲基乙基氫硫基甲矽烷丙基）四硫化物 ’ 雙（甲基二甲氧甲矽烷乙基）三硫化物，2,2t_雙（ 甲基乙氧基丙氧甲矽烷乙基）四硫化物’ 雙（二乙基 甲氧基甲矽烷丙基）四硫化物，3，3、雙（乙基二，二級丁氧 曱5夕規丙基）二硫化物’ 3，3 ·-雙（丙基二乙氧甲矽虎丙基） 二硫化物，> 3，3 ·-雙（丁基二甲氧甲矽烷丙基）三硫化物， 3，3，-雙（苯基二甲氧甲矽烷丙基）四硫化物，3 _苯基乙氧 基丁氧甲矽烷3，-三甲氧甲矽烷丙基四硫化物，4，4，_雙（ 三甲氧甲矽烷丁基）四硫化物，6，6匕雙（三乙氧甲妙燒己 基）四硫化物，1 2，1 2，-雙（三異丙氧甲矽烷十二基）二硫化 物，1 8，1 S 1 -雙（三甲氧甲矽烷十八基）四硫化物， -32- 本紙張尺度通用中國國家標準（CNS ) A4規格（21 〇 X 297公釐） ---------裝-- 請A-閲Af.面之·ii-t-事項'4¾本頁) -# 線 4 2 4 10 6 : 經濟部智慧財產局員工消費合作社印製 A7 B7_五、發明説明（I 18, 18· -雙（三丙氧甲矽烷十八烯基）四硫化物，4,4·-雙（ 三甲氧甲矽烷基-丁烯-2-基）四硫化物，4,4‘-雙（三甲氧 甲矽烷基環伸己基）四硫化物，5，5 ·-雙（二甲氧基甲基甲 矽烷基戊基）三硫化物，3，3 1 -雙（三甲氧基甲矽烷基-2 -甲 丙基）四硫化物及3,3'-雙（二曱氧基苯基甲矽烷基-2 -甲丙 基）二硫化物。 較佳含硫有機矽化合物為3,3· -雙（三曱氧基或三乙氧基 甲矽烷丙基）硫化物。最佳化合物為3,3，·雙（三乙氧基甲 矽烷丙基）四硫化物。因此，至於式I，較佳Ζ為 R2 —Si—R2 R2 其中R2為含2至4個碳原子之烷氧基，以2個碳原子特佳 ;Aik為2至4個碳原子之二價烴，以3個碳原子特佳； 及η為3至5之整數，以4為特佳。 橡膠组合物中之式I含硫有機矽化合物之數量將依所用 矽石水平而改變。一般而言，式I化合物之數量範圍约 0.0 1至約1，0份重量/份重量矽石。較佳者，數量範圍約 0 · 0 2至約0 4份重量/份重量矽石。最佳者，式I化合物 之數量範圍約0.0 5至約0 2 5份重量/份重量矽石。 除了含硫有機矽以外，橡膠組合物含充分數量矽石及碳 黑（若使用）以貢獻高模數及高抗撕裂。矽石填料可添加之 數量範圍约1 0 p h Γ至約2 5 0 p h r，較佳者，矽石數量範園 ___— ______^33 · 本^*張^^^用中關家標準（^>^)人4規格（2丨0^97公釐) ---------裝I {請it·閱i^.t.面之ii·^·事項‘巧本！ 訂 線 4 24 1 Ο β ； Α7 ______Β7 五、發明説明（3]) ' -- 约i5phr至约s〇phr。若也有碳黑，碳黑數量(若使用）可 以改變…般而言，碳黑數量變化為5phr至約sGphr。 較佳者，碳黑數量範圍约；l 〇 h P « Γ主約4 0 p h r 。應理解矽 偶合劑可與碳黑-起使用；也就是在添加至橡膠組合物之 前先與碳黑預混，此碳黑被含於上述數量碳黑供橡膠组合 物調配物使用。在任何情沉下，矽石及碳黑之總量至少約 3 〇phr »同前所述，矽石及碳黑之混合重量可低至約 3 °Phr，但是較佳約45至約i 3 0phr。 橡膠混鍊應用上常用含矽顏料.可為本發明中之矽石，包 含熱解及沈積含矽顏料（矽石），雖然以沈積矽石較佳β較 佳供本發明使用之含矽顏料為沈積矽石，例如那些得自於 可溶矽酸鹽之酸化者；例如矽酸鈉。 此類矽石之特徵可能為Β Ε Τ表面積’如使用氮氣測量 ，較佳範圍約4 0至約6 0 0，更常見範圍约5 〇至約3 〇 〇平 方米/克。測定表面積之Β Ε Τ方法記載於lournal nf 11, Q Am e r j c a C_hemi c_al Society.第 60 冊，304 頁（193。） ο 矽石典型特徵也可為gi;酸二丁酯（D Β P )吸收值範固約為 1 〇 0至約4 (To ’更常見範圍約為1 5 0至約3 〇 〇。預期秒石 之平均最終粒徑範圍例如為0 · 0 1至0 . 〇 5微米（如電子顯 微鏡所測），雖然碎石粒子尺寸甚至更小，或者可能更大β 各種商業販焦矽石可視為供本發明使用，例如僅為舉例 而不為限制，PPG Industries以Hi-Sil商標及21〇 ， 24j等編號販售之麥石商品，Rl\〇ne_P〇ulenc·所販隹之 -34- 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297^釐j I--I----—裝-- * 铕λ·閲tf.面之：k*·事項4¾本頁) 訂. 線 經濟部智慈財產局員工消費合作社印製 A7 B7 4 2 4 10 6 五、發明説明（3今 編號為Z1165MP及Z165GR之矽石及Degussa AG所 販售以VN2及VN3編號之矽石。 包含矽石及有機矽化合物之輪胎面調配物典型以熱機械 混合技術加以混合。輪胎面橡膠調配物之混合可藉橡膠混 合技藝人所習知方法完成。例如，組份典型以至少二階段 進行混合；即至少一個非生產階段，接著為生產混合階段 。包含硫-硫化劑之最終硬化劑典型於最終階段混合，該階 段傳統上被稱為”生產”混合階段’其中混合典型在低於前 一非生產混合階段所用混合溫度之溫度或最終溫度下發生 °橡膠，碎石及含稅有機碎’以及碳黑（若有使用）於一或 多個非生產混合階段中混合。"非生產”及”生產"混合階段 之用詞為熟悉橡膠·混合技藝人士所習知。若矽石填料被使 用於化合物，包含含硫有機矽化合物，可硫化橡膠及„般 至少部份矽石之硫-可硫化橡膠組合物應該進行熱機械混合 步驟°熱機械混合步騾一般包含在混合機或擠出機中機械 作業一段適合生產橡膠之時間，溫度為140 t及190。〇之 間《合適熱機械作業期間隨著作業條件及成份體積及特性 而改變。.例如，熱機械作業可進行约2分鐘至約2 〇分鐘 。橡膠一般較佳達到约1 4 5 °C至約1 8 0 °C之溫度，並維持 在该溫度達約4分鐘至約1 2分鐘°橡膠一般更佳達到約 1 5 5 ec至約i 7 0 °c之溫度，並維持在該溫度達約5分鐘至 約1 〇分鐘。 含本發明輪胎面化合物之乳化S B R可與一般輪胎製造 技術一起使用。輪胎之製造係使用標準程序，以本發明乳 -35 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） ----------赛-- *' (請it·閲讀ΐ;面之、&意事項Μ本買). 訂 經濟部智慧財產局S工消費合作社印製 經濟部智慧財產局員工消費合作杜印製 4 2 4 10 6- A7 ---—_________B7 五、發明説明（巧 化s B R取代典型作為胎面橡膠之橡膠化合物。輪胎經含乳 化S B R之摻合物製成後，使用正常輪胎硬化循環予以硫化 。依本發明製成之輪胎可範圍廣泛之溫度硬化。然而，本 發明之輪胎一般較佳之硬化溫度约丨3 2 (2 7 0。ρ)至约 166 C( 3 3 0°F)。本發明之輪胎更典型之硬化溫度约U3 C(2 9 0 〇F)至約154 t(3l〇°F)。一般較佳用於硫化本發 明輪胎之硬化循環約]0至2 〇分鐘，以硬化循環约為j 2 至約1 8分鐘最佳。 本發明由以下實例所例示，其目的僅為例示而不被梘為 限J本發明範圍或可實施之方式。除非特定指明，所有份 數及百分比均以重量計。 1例U斟照1 在此實驗中，S B R乳膠藉標準連續方法共聚合丨，3 -丁 一浠單體及苯乙烯單體而合成。此程序係於由5個聚合反 應益_連所组成之先導廠中進行。所用此程序中所用反應 器為3〇加錢拌反應器，其以串連方式連接操作（反應器 鏈之總鏈體積為1 5 〇加侖）^反應器鏈以丨8 . 5 3加侖/小時 之實際释作，率連續操作，所提供實際反應時間為81小 時。 單體以4 S . 9磅/小時之速率經入料至第一反應器。所用 單把入料含69重量百分比丨，3_丁二烯及η重量百分比苯 乙缔。活化劑溶液，息溶液，淨化劑溶液，改質劑及起始 劑亦被連接加入第一反應器α 涪化劑洛液為含〇 . 6 7百分比亞鐵伸乙基二胺四乙酸鈉 本紙乐尺度適财關家操CNS ) Μ規格（ (請先閱讀背面之注.意事頊|4 .¾本頁) -裝_ -訂' 36 4 24 1〇 6 -- 五、發明説明（ 之水溶液°其以足以維持0 . 〇 2 6 p h m水平亞鐵仲乙基二胺 四乙酸鈉以速率被加入第一反應器。 皂溶液含9 6.7 9 ·百分比水，0 . i 9百分比氫氧化鈉， 0.2 0百分比氳氧化鉀，0.5 9百分比歧化木材松香之鉀皂 ’ 1 . 1 0百分比氫化混合牛脂脂肪酸，〇 . 8 9百分比歧化妥 -爾油松香之鉀皂* 〇 . 1 8百分比縮合莕磺酸之鈉鹽，〇 . 〇 3 百分比焦磷酸四鉀，0.02百分比甲醛次硫酸鈉及o.oi百 分比亞硫酸氩鈉。皂系統溶液以足以維持〇 · 3 4 1 p h m水平 氫氧化钟’ 1，0 8 8 p h m水.平歧化.木材松香之抑乾， 2.0 2 2 p h m水平氫化之混合牛脂脂肪酸’ 1 . 6 3 1 p h m水平 歧化妥爾油松香之鉀皂，0 · 3 3 5 p h m水平縮合苯磺酸之納 鹽，0.057phin水平焦磷酸四鉀，〇.〇34phm水平甲醛次 硫酸鈉及0.0 1 9 p h m水平亞硫酸氫鈉之速率被加入第一反 應器。 淨化劑溶液含9 9 · 3 1百分比水，0 · 0 9 6百分比氫氧化納 ’ 0 · 6 0百分比亞硫酸氫鈉°淨化劑溶液以足以維持 0 0 0 4 p h m水平氫氧化鈉及0 . 〇 2 6 p h m亞硫酸氫鈉（亞硫 酸氫鋼等.水平。為0.045phm)之速率被加入第一反應器 0 經濟部智慧財產局員K消費合作社印製 被加入第一反應器之改質劑為三級-十二基硫醇。其係 以0.137phm之速率被加入反應器。被加入第一反應器之 起始劑為蒎烷過氧化氫 > 其加入速率為〇 . 〇 8 7 p h m。 在此程序中，聚合反應係在乳膠自第5反應器輸出時藉 添加二乙每胺及二甲二疏胺基甲酸制之混合物至乳膠以作 __ — 拜37- 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公:t ) —-- 經濟部晳慈財產局員工消費合作社印製 06， 7、發明説明（ 為速止物而終止°由此程序製備之乳膠為穩定的。然而， 若添加至第—反應器之息水乎減少’則無法製備穩定乳膠 〇 實例2 在此在試驗中，係藉FIM方法製備高分子量乳化sbr 。在所用程序中，重覆實例1所述設備及程序’唯一不同 的是單體入科被分離，一部份單體被加入第三反應器。在 此程序中，2 9.6磅/小時之單體被連績加入第一反應器， Ι9·ι碎/ +時之單體被連續加入第三反應器。此作法使惠 總水平降低約4 〇 %。 此實驗中，被加入第一反應器之皂溶液含9 8 〇百分比 水，〇 . 2 5百分比氫氧化鈉，〇 . 1 3百分比氣化鉀，〇 〇百 分比歧化木材松香之鉀惠，ί，）8百分比氫化混合牛脂脂 肪I , 0.2 8百分比歧化妥爾油松香之針皂，〇 . 1 2百分比 縮合萘磺酸之鈉鹽，〇 . 〇 2百分比焦磷酸四鉀，〇 〇 2百分 比甲兹次硫酸鈉及〇 〇〗百分比亞硫酸氬鈉。皂系統溶液 以足以維持〇.435hm水平氫氧化鉀，〇.230phm水平氣 化鉀’ 0,: 0 p h m水平歧化木材松香之鉀皂，2 . 〇 7 6 p h m水 平風化之混^^丰脂脂肪酸’ 〇 4 9 2 p h m水平歧化妥爾油松 香之_惠’ 〇206ph水平縮合莕磺酸之鈉鹽，03〇5phm 水平焦磷酸四钾，〇 . 〇 3 5 p h m水平甲搭次疏酸鈉及 0.019phm水平亞硫酸氫鈉之速率被加入第一反應器。 此程序中’也將〇 5〇3phmWitconate® 1223L水溶 液（Witco化學公司之直鏈烷基苯磺酸之鈉鹽）加入第一反 -38 - 本紙張尺度適用t國國家標準（CNS ) Α4規格（210X297公釐） (請λ·閲^背.面之;±-"-事項^:馬本1) -裝' 線1 424I wherein R1 is an alkyl'cyclohexyl or phenyl group having 1 to 4 carbon atoms; wherein R2 is an alkoxy group having 1 to 8 carbon atoms or a cycloalkoxy group having 5 to 8 carbon atoms; and wherein Aik is a divalent hydrocarbon of 1 to 18 carbon atoms and η is an integer of 2 to 8. Specific examples of sulfur-containing organosilicon compounds that can be used in the present invention include: 3,3, -bis (trimethoxysilylpropyl) disulfide, 3,3, bis (triethoxymethylsulfanyl) propyl ) Tetrahydro ·, 3,3 · -bis (triethoxysilylpropyl) octasulfide, 3,3′-bis (trimethoxysilylpropyl) tetrasulfide, 2,2 , -Bis (triethoxysilylethyl) tetrasulfide, 3,3'-bis (trimethyl · * * oxysilane " propyl) trisulfide, 3, 3 _ -bis (triethyl Oxysilylpropyl) trisulfide, 3, 3'-bis (tributoxysilylpropyl) disulfide, 3,3 · -bis (trimethoxysilylpropyl) hexasulfide, 3, 3 1 -bis (trimethoxysilylpropyl) octasulfide '3,3, bis (trioctyloxysilylpropyl) tetrasulfide, 3,3, bis (trihexyloxysilyl) Propyl) disulfide, 3,3 1 -bis (tri-2 " -ethhexyloxysilylpropyl) trisulfide, 3,3 · -bis-31-This paper is applicable to Chinese national standard ( CNS) Α4 size (2i × 297mm) economy Printed by the Intellectual Property Bureau employee consumer cooperative A7 B7 Five printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs 4 2 411 0 6 'Wu Ming description (triisooctyloxysilylpropyl) tetrasulfide, 3, 3, double (Tri-tertiary butoxysilylpropyl) disulfide '2,2'-bis (methoxydiethoxysilylethyl) tetrasulfide, 2,2, -bis (tripropoxysilyl) Ethyl) pentasulfide, 3,3 bis (tricyclohexyloxysilylpropane) tetrasulfide '3,3 ·· bis (tricyclopentyloxysilylpropyl) trisulfide, 2,2,2 (Tri-2, methylcyclohexyloxysilylethyl) tetrasulfide, bis (trimethylsilylmethyl) tetrasulfide, 3-methyllactylethoxypropoxymethylmethanine • yl · 5- —Ethoxybutoxymethyl dream tiger propyl tetrasulfide, 2,2 1 -bis (dimethylmethoxysilylethyl) disulfide '2,2' -bis (dimethyl secondary butyl Oxymethanthyl ethyl) trifluoride, 3,3, -bis (methylbutylethoxysilylpropyl) tetrasulfide, 3,3, -bis (di-tert-butylmethoxysilylpropane) ) Tetrasulfide, 2,2'-bis (phenylmethyl Methoxymethane, ethyl) trisulfide j, 3-bis (-benzylisopropoxymethyl dreampropyl) tetrasulfide, 3,3 1-bis (diphenylcyclohexyloxysilylpropyl) ) Disulfide, 3,3, -bis (dimethylethylhydrothiosilylpropyl) tetrasulfide 'bis (methyldimethoxysilylethyl) trisulfide, 2,2t_bis (Methylethoxypropoxysilylethyl) tetrasulfide 'bis (diethylmethoxysilylpropyl) tetrasulfide, 3,3, bis (ethyldi, secondary butoxyfluorene 5 Xiqi propyl) disulfide '3,3 · -bis (propyldiethoxysilazolyl) disulfide, > 3,3 · -bis (butyldimethoxysilylpropyl) Trisulfide, 3,3, -bis (phenyldimethoxysilylpropyl) tetrasulfide, 3_phenylethoxybutoxysilane 3, -trimethoxysilylpropyltetrasulfide, 4 , 4, _bis (trimethoxysilylbutyl) tetrasulfide, 6,6 bis (triethoxymethylhexyl) tetrasulfide, 1 2,1,2, -bis (triisopropoxysilyl) Dodecyl) disulfide, 1 8,1 S 1 -bis (trimethoxysilyloctadecyl) ) Tetrasulfide, -32- The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (21 × 297 mm) --------- Installation-Please read A-. -t-Matter '4¾ This page)-# Line 4 2 4 10 6: Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_V. Description of the invention (I 18, 18 · -bis (tripropoxysilyl 10) Octenyl) tetrasulfide, 4,4 · -bis (trimethoxysilyl-buten-2-yl) tetrasulfide, 4,4'-bis (trimethoxysilylcyclohexyl) tetrasulfide Compounds, 5,5 · -bis (dimethoxymethylsilylpentyl) trisulfide, 3,3 1-bis (trimethoxysilyl-2-methylpropyl) tetrasulfide and 3 3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide. A preferred sulfur-containing organosilicon compound is 3,3 · -bis (trimethoxy or triethoxysilylpropyl) sulfide. The most preferred compound is 3,3, · bis (triethoxysilylpropyl) tetrasulfide. Therefore, as for formula I, it is preferable that Z is R2—Si—R2 R2, wherein R2 is an alkoxy group having 2 to 4 carbon atoms, and 2 carbon atoms are particularly preferred; Aik is a bivalent of 2 to 4 carbon atoms. A hydrocarbon is particularly preferably 3 carbon atoms; and η is an integer of 3 to 5, particularly preferably 4; The amount of the sulfur-containing organosilicon compound of formula I in the rubber composition will vary depending on the level of silica used. Generally, the amount of the compound of formula I ranges from about 0.01 to about 1.0 part weight per part weight silica. Preferably, the amount ranges from about 0.2 to about 0.2 parts by weight per part by weight of silica. Most preferably, the amount of the compound of formula I ranges from about 0.05 to about 0 2 5 parts by weight per part by weight of silica. In addition to sulfur-containing silicones, the rubber composition contains sufficient quantities of silica and carbon black (if used) to contribute high modulus and high tear resistance. The amount of silica filler that can be added ranges from about 10 ph Γ to about 250 phr, preferably, the amount of silica Fan Yuan ___ — ______ ^ 33 · This ^ * 张 ^^^ uses Zhongguanjia standards (^ > ^) People 4 specifications (2 丨 0 ^ 97mm) --------- install I {please it · read i ^ .t. face ii · ^ · events' smart book! Order line 4 24 1 〇 β; Α7 ______ Β7 V. Description of the invention (3)) '-about i5phr to about sophr. If carbon black is also present, the amount of carbon black (if used) can be changed ... Generally, the amount of carbon black varies from 5 phr to about sGphr. Preferably, the amount of carbon black ranges from about 10 h P «Γ to about 40 p h r. It should be understood that the silicon coupling agent can be used together with carbon black; that is, it is premixed with carbon black before being added to the rubber composition, and this carbon black is contained in the above amount of carbon black for use in the rubber composition formulation. In any case, the total amount of silica and carbon black is at least about 30 phr. »As mentioned before, the mixed weight of silica and carbon black can be as low as about 3 ° Phr, but preferably about 45 to about i 3 0phr. Silicon-containing pigments are commonly used in rubber mixed-chain applications. They can be the silica in the present invention, including pyrolytic and sedimentary silicon-containing pigments (silica), although the silica-deposited silica is preferred, and the silicon-containing pigment is preferably used in the present invention. Sedimentary silica, such as those obtained from acidification of soluble silicates; such as sodium silicate. This type of silica may be characterized by a β ET surface area, as measured using nitrogen, preferably in the range of about 40 to about 600, and more commonly in the range of about 50 to about 300 square meters per gram. The Beta ET method for measuring surface area is described in the journal nf 11, Q Am erjca C_hemi c_al Society. Volume 60, page 304 (193.) ο The typical characteristic of silica can also be gi; dibutyl acid (D Β P) absorption The value range is from about 10,000 to about 4 (To 'a more common range is from about 150 to about 3,000. The average final particle size range of the second stone is expected to be, for example, from .01 to .05 microns ( As measured by an electron microscope), although the size of the crushed stone particles is even smaller, or may be larger β, various commercial coke silica can be considered for use in the present invention, for example, but not for limitation, PPG Industries under the Hi-Sil trademark And 21/10, 24j and other maisite products sold under the serial number, Rl \ 〇ne_P〇ulenc-sold -34- This paper size applies the Chinese National Standard (CMS) A4 specification (210X297 ^^ j I--I- ----- Installation-* 铕 λ · read tf. Face: k * · Item 4¾ page) Order. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Online Economics A7 B7 4 2 4 10 6 V. Description of the invention (3 The silicas currently numbered Z1165MP and Z165GR and the silicas numbered VN2 and VN3 sold by Degussa AG. Including silica and organosilicon compounds The compound of the tire tread is typically mixed by thermo-mechanical mixing technology. The mixing of the rubber compound of the tire tread can be accomplished by methods known to rubber mixing artisans. For example, the components are typically mixed in at least two stages; that is, at least one non- The production stage, followed by the production mixing stage. The final hardener containing the sulfur-vulcanizing agent is typically mixed in the final stage, which is traditionally referred to as the "production" mixing stage 'where the mixing is typically performed below the previous non-production mixing stage The temperature of the mixing temperature or the final temperature ° rubber, crushed stone and tax-containing organic crushing 'and carbon black (if used) are mixed in one or more non-production mixing stages. &Quot; non-production " and " production " The term used in the mixing stage is familiar to those familiar with rubber and mixing techniques. If silica fillers are used in compounds, including sulfur-containing organosilicon compounds, vulcanizable rubbers, and sulfur-vulcanizable rubber compositions that are at least partially silica-like, should Perform a thermo-mechanical mixing step ° The thermo-mechanical mixing step generally includes mechanical operation in a mixer or extruder for a period of time suitable for production The temperature of the glue is between 140 t and 190 °. The period of suitable thermomechanical operation varies with the conditions of the work and the volume and characteristics of the ingredients. For example, the thermomechanical operation can be performed for about 2 minutes to about 20 minutes. Rubber It is generally preferred to reach a temperature of about 145 ° C to about 180 ° C, and to maintain the temperature for about 4 minutes to about 12 minutes. The rubber is generally more preferably about 1 5 5 ec to about i 7 0 ° C and maintained at that temperature for about 5 minutes to about 10 minutes. The emulsified S B R containing the compounds of the tire tread of the present invention can be used with general tire manufacturing techniques. The manufacture of tires uses standard procedures, with the milk of the present invention -35-this paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) ---------- Sai-* '( Please it · read 面; face, & Italian purchase). Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs, S Industrial Consumer Cooperative, printed by the Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperation, printed by Du 2 4 4 10 6- A7- ---_________ B7 V. Description of the Invention (Ingenious s BR replaces rubber compounds typically used as tread rubber. After tires are made from blends containing emulsified SBR, they are vulcanized using normal tire hardening cycles. Tires made according to the invention It can be hardened at a wide range of temperatures. However, the tires of the present invention generally have a preferred hardening temperature of about 3 2 (2 7 0.ρ) to about 166 C (3 3 0 ° F). The tires of the present invention have a more typical hardening temperature. About U3 C (2900 ° F) to about 154 t (310 ° F). Generally preferred for curing cycle of the tire of the present invention is about 0 to 20 minutes, with a hardening cycle of about j 2 to about 18 minutes is best. The present invention is illustrated by the following examples, the purpose of which is for illustration only and is not limited. The scope of the present invention may be Unless otherwise specified, all parts and percentages are based on weight. 1 case U consider 1 In this experiment, SBR latex was copolymerized by standard continuous method. 3-Butadiene monomer and styrene monomer This process is carried out in a pilot plant consisting of 5 polymerization reactors. The reactor used in this procedure is a 30 plus reactor, which is connected in series (reactors) The total chain volume of the chain is 150 gallons) ^ The reactor chain is continuously operated at a rate of 8.53 gallons / hour, and the actual reaction time provided is 81 hours. The monomer is 4 S. 9 pounds The rate per hour is fed to the first reactor. The single feed used contains 69% by weight 丨 3-butadiene and η% by weight styrene. Activator solution, interest solution, detergent solution, modification Agent and starter are also connected to the first reactor α ammonium chloride solution containing 0.67% ferrous ethylene diamine tetraacetic acid sodium paper, paper scales, scales, wealth management, CNS) M specifications ((please first Read the note on the back. 顼 事 顼 | 4.¾ This page)-装 _ -Order '36 4 24 1〇 6-V. Description of the invention (aqueous solution ° It is added to the first reactor at a rate sufficient to maintain a level of 0.02 6 phm sodium ferrous sec-ethyl diamine tetraacetate. The soap solution contains 9 6.7 9 percent water , 0. 9% sodium hydroxide, 0.20% rubidium potassium oxide, 0.59% disproportionated potassium rosin potassium soap '1.10% hydrogenated mixed tallow fatty acid, 0.89% disproportionated potassium rosin potassium Soap * 0.18% sodium salt of condensed sulfonic acid, 0.03% tetrapotassium pyrophosphate, 0.02% sodium formaldehyde sulfoxylate and o.oi% sodium sulfite. The soap system solution is sufficient to maintain a level of 0.34 1 phm of hydroxide hydroxide '1, 0 8 8 phm of water. Level disproportionation. Wood rosin inhibits drying, 2.0 2 2 phm level of hydrogenated mixed tallow fatty acid' 1. 6 3 1 Potassium soap with disproportionated tall oil rosin at phm level, sodium salt of condensed benzenesulfonic acid at 0.35 phm level, tetrapotassium pyrophosphate at 0.057 phin level, sodium formaldehyde hypophosphite at 0.034 phm level and 0.0 1 9 phm level The rate of sodium bisulfate was added to the first reactor. The scavenger solution contains 9 9 · 3 1% water, 0 · 0 9 6% sodium hydroxide '0 · 60% sodium bisulfite ° The scavenger solution is sufficient to maintain 0 4 0 4 phm levels of sodium hydroxide and 0. 〇2 6 phm sodium bisulfite (bisulfite steel, etc. level. 0.045phm) was added to the first reactor. 0 Printed by K Consumer Cooperative, a member of the Intellectual Property Bureau of the Ministry of Economic Affairs, was added to the first reactor. It is tertiary-dodecyl mercaptan. It was added to the reactor at a rate of 0.137 phm. The starter added to the first reactor was oxane hydrogen peroxide > and its addition rate was 0.087 p h m. In this procedure, the polymerization reaction is to add a mixture of diethylamine and dimethylbisaminosulfonic acid to the latex when the latex is output from the fifth reactor to make latex. — Bye 37- This paper size applies to China Standard (CNS) 8-4 specification (210X297 male: t) --- Printed by Employee Consumer Cooperative of Xici Property Bureau of the Ministry of Economic Affairs 06, 7, Description of the invention (terminated for quick-stops) The latex prepared by this procedure is stable However, if the amount of water added to the first reactor is reduced, the stable latex cannot be prepared. Example 2 In this experiment, the high molecular weight emulsified sbr was prepared by the FIM method. In the procedure used, the example 1 was repeated. The only difference between the described equipment and procedures is that the monomers are separated and some monomers are added to the third reactor. In this procedure, 2 9.6 lbs / hour of monomers are added to the first reactor in succession. The monomer at the time of I9 · ι crushing / + was continuously added to the third reactor. This method reduced the total benefit level by about 40%. In this experiment, the soap solution added to the first reactor contained 9800% water, 0.25 percent sodium hydroxide, 0.13 percent Gasified potassium, 0.00% disproportionated potassium rosin potassium benefit, ί,) 8% hydrogenated mixed tallow fat I, 0.28% disproportionated tall oil rosin needle soap, 0.12% condensed sodium naphthalenesulfonate Salt, 0.02% tetrapotassium pyrophosphate, 002% sodium formate sodium sulfate, and 〇% sodium sulfite. The soap system solution is sufficient to maintain potassium hydroxide at a level of 0.435hm, potassium gasification at a level of 0.230phm, potassium soap of disproportionated wood rosin at a level of 0 ,: 0 phm, and a weathering mixture of 2.070.7 phm level. '〇4 9 2 phm level disproportionation of tall oil rosin of _Hui' 〇206ph level condensed sodium salt of sulfonic acid, 0305phm level potassium potassium pyrophosphate, 0.03 phm level sodium hypophosphite and A rate of 0.019 phm level of sodium bisulfite was added to the first reactor. In this procedure, '0503phmWitconate® 1223L aqueous solution (sodium salt of linear alkylbenzene sulfonic acid of Witco Chemical Co., Ltd.) is also added to the first trans-38-This paper standard is applicable to National Standard (CNS) A4 specifications 210X297 mm) (please read λ. ^ Back. ±-"-matters ^: Maben 1)-installed 'line 1 424
五、發明説明（ 應、益作為第二界面活性劑5蒎烷過氧化氩起始劑水平亦增 加至 〇. 1 lOphm。，利用此程序製備之s B R乳膠經證實係穩定的。利用此 技術會製待數目平均分子量约〖3〇,〇〇〇及重量平均分子量 •々 490,000之乳化SBR。自乳膠回收之sbr之殘留皂水 平亦降低。 ^ f例3 低分子量乳化S B R可藉實例2所述技術僅提高三級十二 基&醇水平至〇 · 3 9 p h m而製備。在此情況，所製得乳化SBR之重量平均分子量约6〇,〇〇〇 ，其重量平均分子量约 185,〇〇〇。 實例4 $ 6此實驗中，製備由FIM方法所製得高分子量乳化SBR 及由fim方法所製得低分子量乳化SBR之摻合物，經混 鍊成為標準輪胎面橡膠^此橡膠經硬化， 準乳化⑽及標準溶液SBR所製得類似橡膠化合:作^ 幸乂。接合物中高分子量SBR含23 5百分比結合苯乙婦， 數目平均分子量為1 3 0,000 ，重量平均分子量為 4 90,0 0 0 ，玻璃轉移溫度K_55t。摻合物中低分子量SBR含5百分比結合苯乙缔，數目平均分子量為”, ，重T平均分子量為251，0〇〇 , M〇〇ney ML ]+4黏度 為20,7 ^摻合物中高分子量SBR對低分子量之重 量比例為5 0 : 5 0 » 橡膠化合物係製備於混合70份三種不同SBR橡膠與 ____-39* ^紙^^適用情國^標準（CNS 規格（21GX297公釐） (請:马本頁) 裝- 訂 線. -«^1 II >V. Description of the invention (Ying and Yi as the second surfactant, the 5 oxane argon peroxide initiator level has also increased to 0.1 lOphm. The s BR latex prepared using this procedure has been proven to be stable. Using this technology Emulsified SBR with a number average molecular weight of about 30,000 and weight average molecular weight of 々490,000 will be prepared. The residual soap level of sbr recovered from latex is also reduced. ^ Example 3 Low molecular weight emulsified SBR can be borrowed from Example 2 The technology is prepared by only raising the level of tertiary dodecyl alcohol to 0.39 phm. In this case, the weight average molecular weight of the emulsified SBR obtained is about 60,000, and its weight average molecular weight is about 185, 〇〇〇。 Example 4 $ 6 In this experiment, a blend of high molecular weight emulsified SBR prepared by the FIM method and a low molecular weight emulsified SBR prepared by the fim method was prepared, and then mixed into a standard tire surface rubber. This rubber After hardening, quasi-emulsified hydrazone and standard solution SBR are similar rubber compounds: ^ Fortunately, the high molecular weight SBR in the joint contains 23 5 percent bound acetophenone, the number average molecular weight is 1 3,000, the weight average molecular weight is 4 90 , 0 0 0, glass transition temperature K_55t. The low molecular weight SBR in the blend contains 5% bound styrene, the number average molecular weight is "," and the weight T average molecular weight is 251,000, 〇ney ML] + 4 The viscosity is 20,7 ^ The weight ratio of high molecular weight SBR to low molecular weight in the blend is 5 0: 5 0 »The rubber compound is prepared by mixing 70 parts of three different SBR rubbers with ____- 39 * ^ paper ^^ National ^ standard (CNS specification (21GX297 mm) (please: page)) Binding-Threading.-«^ 1 II >
m HV n n f— A7 B7 37.5份高度順-1，4-聚丁二烯橡膠，7〇份碳黑，2 化鋅’ 0.8份石蠟，3份微結晶蠟，115份 1 0 0對-苯二胺抗氧化劑，；! . 2份N •環己基_ 2 _苯并嘍 磺醯胺，0.3份四甲基秋蘭化二硫.及145份硫。然L 橡膠調配物硬化’經評估以測定物理性質。經硬化橡^ 合物在0 °C及60 t之tan delta記載於表t。tan “ 係使用動，邊機械試驗機以抗張模式於丨丨赫及〇 · 〇 1至】 分比之應變範圍測定的。 a 1 表I 實例 tan delta -----—--- taQ delta @〇 °c β, 6〇 °r 4 -新乳化S B R摻合物 0.15 ------ 〇 in 5 -標準溶液S B R 0.12 ------— 〇 i〇 6 - F I Μ 乳化 S B R 0.16 ~~--— 0.13 摻 百 一 - * - , » ( 碕先聞讀背面之注·意事項I 趑本頁} -裝』 -訂 在60 °C之低tan delta值為低滯後現象之象徵，因此 以此橡曼製j寻輪胎面比以具備在6 〇。(：較高t a n d e 11 a值 橡膠製仔輪胎表現較低故動阻力。另一方面，在〇 tan delta值之橡膠可用於製造相較於在〇 t具較低tan d e 11 a值之胎面橡膠组合物製得輪胎表現較佳牽引特徵之 輪胎面。胎面橡勝組合物一般較佳具備在〇它時最高可能 tan delta值’以實現優於所有驅動狀況及在所有驅動速 度之最佳可能牽引特徵。輪胎橡膠組合物亦較佳具在6 〇 -40· 本紙張尺度通用中國國家標準（CNS ) M規格（2丨〇、χ297公釐） 線 經濟部智慧財產局員工消費合作社印製 424 1 0 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（ c時最低可能tan delta值，以提供低滾動阻力及優良胎 面耐磨特徵β 使用本發明乳化s B R摻合物於混鍊橡膠會在〇 t：得到高 t a π d e It a值及在6 0 °C得到低t a η ' d e 11 a值。此係象徵優 良牽引特徵，滾動阻力及胎面耐磨。事實上，以本發明乳 化橡膠製得之硬化橡膠摻合物在〇 〇c之t a n d e 11 a值幾乎 與傳統乳化S B R製得硬化橡膠一樣高。顯著的是，以本發 明乳化SBR製得之硬化橡膠摻合物在6〇它之tan delta 值幾乎與標準溶液s B R製得硬化橡膠一樣高。因此，藉利 用本發明技術’乳化SBR可被製成具備溶液SBR及乳化 •SBR之最佳特徵者。 本發明本乙烯-丁二錦橡膠一般在含7〇偷重量苯乙烯_ 丁二燁橡膠，3 0份重量高度順· I，4 ·聚丁二浠橡膠，7.5 份重量高度芳族加工油’ 7 0份重量N 2 2 0碳黑，2份重量 氧化鋅，0 . 8份重量石蠟，3份重量微結晶蠟，丨丨5份 重里對-苯二胺抗氧化劑，丨^ 2份重量N _環己基_ 2 _苯幷噻 唑亞磺醯胺，0.3份重量四甲基秋蘭化二硫及145份重 :硫乏，膠^合物中硬化後，在〇 t之t a n d e H a範圍為 0.13 至 0.ί9 ，而在 60 °c 之 tan delta 範圍為 〇·〇6 至 〇·12 。大部份情況下，本發明苯乙烯·丁二烯橡膠組合物 在此橡膠摻合物中硬化後，在〇它之tan delta範園為 0.14至0.18 ’而在60 1之tan delta範園為〇 至 0 · 1 1 。本發明苯乙埽_ 丁二埽橡膠組合物在此橡膠接合物 中硬化後，一般較佳在〇。(：之tan delta範圍為〇 ^至 _________-41- 本紙張尺度適用中國國ΐ標率（CNS ) Α4規格（210X297^~y --------餐-- 1 ^ - ---1-一 (請先閱讀背面之.ίϊ.意事項4¾本頁) 訂 線 424106 A7 B7 五、發明説明（1 0.17 ’ 而在 60 °C 之 tan delta 範圍為 0.09 至 0.10。 實例7至9 --------1$-- , · -. - -. / 請先閱讀背面之注意事項4. .¾本頁) 此實驗中，製備由FI Μ方法所製得高分子量乳化sBR 及由F I Μ方法所製得低分子量乳化5 b R之摻合物，經混 鍊成為標準輪胎面橡膠β此橡膠經硬化，其物理性質與標 準乳化S B R及標準溶液s B R所製得類似橡膠化合物作比 較。摻合物中高分子量SBR含23.5百分比結合苯乙烯， 數目平均分子量為130,000 ，重量平均分子量為 4 9 0，0 0 0 ’玻璃轉移溫度約_ 5 5。匸。掺合物中低分子量 SBR含48百分比結合苯乙缔，數目平均分子量為56,〇〇〇 ’重量平均分子量為137,〇〇〇 ’ Mooney ML 1+4黏度 為11.4 。摻合物中咼分子量對低分子量之童 量比例為5 〇 : 5 0。 橡膠化合物係製備於混合7 〇份三種不同$ B R橡膠與 37.5份高度順-〗，4-聚丁二烯橡膠，7〇份碳黑，2份氧 化鋅，0‘8份石蠟，3份微結晶蠟，份wingstay@ 1〇〇抗氧化劑’ 1.2份N-環己基冬苯并„塞吐亞橫縫胺， 經濟部智慧財產局員工消費合作社印製 〇.3份四甲f秋蘭化二硫及丨.45份硫，然後，橡膠調配物 硬化，經評估以測定物理性質。經硬化橡膠接合物在〇 t 及60t之tan deUa記載於表π。tan deifa係使用動 態機械試驗機以抗張模式於I 1赫及〇 . 〇 1至丨百分比之應 變範圍測定的。 _______-42- 本紙張尺度適用中國國家榇準（CNS ) A4規格(2Ι0Χ29Τ^Ϊ7 經濟部智慧財產局員工消費合作社印製 * Α7 Β7 發明説明（4() 表II 實例 tan delta tan delta @0 °C ⑬6 0 V 7 -新乳化S B R摻合物 0.25 〇 12 _8 -標準溶液S B R 0.13 0.11 9 - F I Μ 乳化 S B R ----------—1 _ 0.12_ __ 0 . 1 _ -43 - 如先前所解釋，在60 t之低tan delta值為低滯後現 象之象徵，因此以此橡膠製得輪胎面比以具備在6〇它較 阿tan delta值橡膠製得輪胎表現較低滾動阻力。另一方 面，在0 C具高tan delta值之橡膠可用於製造之輪胎面 相較於在0 C具較低ta n d e 11 a值之胎面橡膠組合物所製 得輪胎表現較佳牵引特徵。胎面橡膠组合物一般較佳具備 在〇 C時最高可能tan delta值，以實現優於所有驅動狀 況及在所有驅動速度之最佳可能牽引特徵。輪胎橡膠組合 物亦較佳具在60。(：時最低可能tan delta值，以提供低 滾動阻力及優良胎面耐磨特徵。 使用.本.發 >明乳化S B R摻合物於混鍊橡膠會在〇 t得到高 Un de.lta值及在60t得到低tan以丨^值。此係象徵優 艮牽引特徵，滾動阻力及胎面耐磨。以本發明乳化橡膠製 得之硬化橡勝摻合物在0 t之tan delta值幾乎與傳統乳 化SBR製得硬化橡膠—樣高。顯著的是，以本發明乳化 製得之硬化橡膠摻合物在60 t之tan delta值幾乎 與標準溶液SBR製得硬化橡膠一樣高。因此，藉著利用本 表紙張尺度適用中國國家標準（CNS ) A4規格（2丨0 X 2奵公釐） ---------装-- . ·--··《 (請先聞讀背面之注意事項.>:¾本 -:¾ 線 2 4 1 Ο 6 ; Α7 ___Β7 五、發明説明（4¾ 發明技術，乳化SBR可被製成具備溶液SBR及乳化SBR 之最佳特徵者。 本發明本乙稀-丁二’歸橡膠一般在含70份重量苯乙豨-丁二婦橡勝，3 0份重量高度順· 1，.4 -聚丁二烯橡膠，7 · 5 份重量高度芳族加工油’ 70份重量N220碳黑，2份重量 氧化鋅’ 0.8份重量石蠟’ 3份重量微結晶蠟，1_ 15份 重量對-苯二胺抗氧化劑，1 . 2份重量N -環己基-2 -苯并喳 .唑亞磺醯胺，0.3份重量四甲基秋蘭化二硫及1 . 4 5份重 量破之橡膠摻合物中硬化後，在〇。〇之t a n d e 11 a範圍為 0-18 至 0.40 ，而在 60 °C 之 tan delta 範圍為 0.09 至 0 ‘ 1 6 。大部份情沉下，本發明苯乙烯·丁二烯橡膠組合物 在此橡膠摻合物中硬化後，在〇之t a n d e 11 a範圍為 0.20 至 0.30 ，而在 60 t：之 tan delta 範圍為 0.10 至 0.14 。本發明苯乙烯·丁二烯橡膠组合物在此橡膠摻合物 中硬化後，一般較佳在〇 之tan delta範圍為0.23至 0.27，而在 60°C 之 tan delta 範圍為 〇·10 至 〇.13。 實例1〇 此實，中以連續方式藉共聚合13•丁二烯單體及苯乙 烯單體合成兩種苯乙晞-丁二烯（SBR)乳膠。聚合後，以 特定比例摻合乳膠，然後經絮凝及乾燥。在G〇〇dyear‘s尸 Houston production facility 進行此實驗。 具高Mooney ML 1+4黏度及中等結合苯乙烯含量之 乳膠係於一系列13個連績攪動槽反應器（CSTRs)中合成 。在被分開並入料至聚合反應器之前，苯乙烯物流， — - -_- _________~ 44 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（2lGY97公釐） . --.--. / 請先閣讀背面之注-意事項反¾本頁 -裝 -訂 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局S工消費合作社印製 4^4 1 〇6 ° A7 ----- —_ B7 ______ 五、發明説明（ 丁二缔物流及改質劑物流經混合並入料至直徑約3叶（7 · 6 公分）及長度3約30吋（76公分）之Ligtnin靜態混合器。 约6 0百分比此單體/改質劑物流與軟水混合，在熱交換器 中經冷卻至約5 2。F ( 1 1 t：)之溫度。活化劑溶浪’ 4溶液 ’氧淨化劑溶液及起始劑在離開熱交換器後、進入長度 '约 36吋（91公分）及直徑約4吋（10.2公分）之第二LlgtlUfl 靜態混合器前加入物流。靜態混合機之後’混合物流在進 入第一 C S T R前之管式反應器内之停留時間約4 0秒。刺 下4 〇百分比之單體/改質劑物流被速續入料至連鎖第5反 應器。反應器連鎖組態如下表.所述：m HV nnf— A7 B7 37.5 parts of highly cis-1,4-polybutadiene rubber, 70 parts of carbon black, 2 zinc '0.8 parts of paraffin wax, 3 parts of microcrystalline wax, 115 parts of 100 p-benzenediene Amine antioxidants;!. 2 parts of N • cyclohexyl — 2 —benzopyrenesulfonamide, 0.3 parts of tetramethylthiulan disulfide, and 145 parts of sulfur. However, the L rubber formulation is hardened 'and evaluated to determine physical properties. The tan delta of the hardened rubber at 0 ° C and 60 t is reported in Table t. tan "is determined by using a dynamic and edge mechanical testing machine in tensile mode at the strain range of 丨 丨 Hz and 〇 · 〇1 ～] ratio. a 1 Table I Example tan delta ------------- taQ delta @ 〇 ° c β, 6〇 ° r 4-new emulsified SBR blend 0.15 ------ 〇in 5-standard solution SBR 0.12 -------〇i〇6-FI Μ emulsified SBR 0.16 ~~ --— 0.13 doped with one hundred-*-, »(碕 First read the notes on the back · Identifications I 趑 This page} -Installation" -The low tan delta value set at 60 ° C is the value of low hysteresis Symbol, therefore, this rubber-manufactured tire-to-tire ratio has a value of 60. (: High tande 11 a rubber tires have lower dynamic resistance. On the other hand, rubber with a tan delta value is available. A tire tread having a better traction characteristic is obtained when a tread rubber composition having a lower tan de 11 a value than that at 0 t is manufactured. The tread rubber victory composition is generally preferably provided with the highest possible tan delta value 'to achieve the best possible traction characteristics better than all driving conditions and at all driving speeds. The tire rubber composition is also preferably between 60 and 40 · Paper standard General Chinese National Standard (CNS) M specification (2 丨 〇, χ297 mm) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 424 1 0 Printed by the Consumer ’s Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (The lowest possible tan delta value at c, in order to provide low rolling resistance and excellent tread wear characteristics β. Using the emulsified s BR blend of the present invention in a hybrid rubber will obtain a high ta π de It a value and A low value of ta η 'de 11 a is obtained at 60 ° C. This symbolizes excellent traction characteristics, rolling resistance and tread wear resistance. In fact, the hardened rubber blend made from the emulsified rubber of the present invention is in the range of 0 ° C. The tande 11 a value is almost as high as that of the hardened rubber produced by the conventional emulsified SBR. It is remarkable that the tan delta value of the hardened rubber blend produced by the emulsified SBR of the present invention is almost hardened by the standard solution s BR. The rubber is as high. Therefore, by using the technology of the present invention, 'emulsified SBR can be made with the best characteristics of solution SBR and emulsification • SBR. The ethylene-butadiene rubber of the present invention generally contains 70 stolen weight styrene_ Ding Nitrogen rubber, 30 parts by weight highly cis I, 4, Polybutadiene rubber, 7.5 parts by weight highly aromatic processing oil '70 parts by weight N 2 2 0 carbon black, 2 parts by weight zinc oxide, 0.8 Parts by weight of paraffin wax, 3 parts by weight of microcrystalline wax, 5 parts by weight of p-phenylenediamine antioxidant, ^^ 2 parts by weight of N_cyclohexyl_ 2 _ benzothiazolium sulfenamide, 0.3 parts by weight of tetramethyl Thiulan disulfide and 145 parts by weight: sulfur depleted. After hardening in the gel compound, the tande H a range is 0.13 to 0.16 at 0 °, and the tan delta range is 60 ° C at 60 ° C. To 〇12. In most cases, after the styrene-butadiene rubber composition of the present invention is hardened in this rubber blend, it has a tan delta range of 0.14 to 0.18 ′ and a tan delta range of 60 1 is 〇 to 0 · 1 1. After the styrene-butadiene rubber composition of the present invention is hardened in this rubber joint, it is generally preferably 0. (: The tan delta range is 0 ^ to _________- 41- This paper size is applicable to China National Standard Rate (CNS) Α4 specification (210X297 ^ ~ y -------- meal-1 ^-- -1- 一 (Please read the first. Ϊ ϊ. Note 4¾ this page) 424106 A7 B7 5. Description of the invention (1 0.17 'and the tan delta range at 60 ° C is 0.09 to 0.10. Examples 7 to 9 -------- 1 $-, ·-.--. / Please read the note on the back 4 .. ¾ page) In this experiment, the high molecular weight emulsified sBR prepared by the FI M method was prepared. And a blend of low molecular weight emulsified 5 b R prepared by the FI M method, and mixed into a standard tire tread rubber β. This rubber is hardened, and its physical properties are similar to those of the standard emulsified SBR and the standard solution s BR. The compounds are compared. The high molecular weight SBR in the blend contains 23.5 percent bound styrene, the number average molecular weight is 130,000, and the weight average molecular weight is 49,0 0 0 'glass transition temperature is about _ 5 5. 匸. Low in the blend Molecular weight SBR contains 48% bound styrene, with a number average molecular weight of 56,000 'and a weight average molecular weight of 137,000' Moon ey ML 1 + 4 has a viscosity of 11.4. The ratio of the molecular weight to the low molecular weight of the blend in the blend is 50: 50. The rubber compound is prepared by mixing 70 parts of three different $ BR rubbers with 37.5 parts of highly cis-〗 , 4-polybutadiene rubber, 70 parts of carbon black, 2 parts of zinc oxide, 0'8 parts of paraffin wax, 3 parts of microcrystalline wax, parts of wingstay @ 1〇〇Antioxidant '1.2 parts of N-cyclohexyl winter benzo „Cetulamide, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 0.3 parts of tetramethyl fiulanized disulfide and 丨 45 parts of sulfur, and then the rubber compound is hardened and evaluated to determine physical properties The tan deUa of the hardened rubber joints at 0t and 60t is described in Table π. The tan deifa is measured using a dynamic mechanical testing machine in a tensile mode at a strain range of 1 Hz and 0.001 to 丨 percentage. _______ -42- This paper size is applicable to China National Standard for Standards (CNS) A4 (2Ι0 × 29Τ ^ Ϊ7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * Α7 Β7 Description of Invention (4 () Table II Example tan delta tan delta @ 0 ° C ⑬6 0 V 7 -New emulsified SBR blend 0.25 〇12 _8 -Standard solvent Liquid SBR 0.13 0.11 9-FI Μ Emulsified SBR ----------— 1 _ 0.12_ __ 0. 1 _ -43-As explained earlier, low tan delta values at low values of 60 t have low hysteresis As a symbol, the tire made of this rubber has a lower rolling resistance than a tire made of rubber with a delta value of 60. On the other hand, a rubber having a high tan delta value at 0 C can be used to make a tire tread that has better traction characteristics than a tire rubber composition having a lower ta n d e 11 a value at 0 C. The tread rubber composition generally preferably has the highest possible tan delta value at 0 C to achieve the best possible traction characteristics superior to all driving conditions and at all driving speeds. The tire rubber composition is also preferably 60. (: The lowest possible tan delta value, to provide low rolling resistance and excellent tread wear characteristics. Use. Ben. Fat> Ming emulsified SBR blends in the chain rubber will get a high Un de.lta value At 60t, a low tan value is obtained. This is a symbol of traction characteristics, rolling resistance and tread abrasion resistance. The hardened rubber-vintage blend made with the emulsified rubber of the present invention has a tan delta value of almost 0 t. The conventional emulsified SBR produces a hardened rubber—all the same. It is remarkable that the tan delta value of the hardened rubber blend prepared by the emulsification of the present invention at 60 t is almost as high as the hardened rubber prepared by the standard solution SBR. Therefore, by Use the paper size of this table to apply the Chinese National Standard (CNS) A4 specification (2 丨 0 X 2 奵 mm) --------- Installation-. ·-·· (Please read the back Matters needing attention. ≫: ¾ 本-: ¾ 线 2 4 1 Ο 6; Α7 ___ Β7 V. Description of the invention (4¾ Inventive technology, emulsified SBR can be made with the best features of solution SBR and emulsified SBR. The present invention Ethylene-butadiene rubber is generally contained in 70 parts by weight of acetophenone-butadiene rubber, and 30 parts by weight is highly cis. Diene rubber, 7.5 parts by weight of highly aromatic processing oil '70 parts by weight of N220 carbon black, 2 parts by weight of zinc oxide' 0.8 parts by weight of paraffin '3 parts by weight of microcrystalline wax, 1-15 parts by weight of p-phenylenediamine resistance Oxidizing agent, 1.2 parts by weight of N-cyclohexyl-2 -benzopyrene. Sulfenimidine, 0.3 parts by weight of tetramethylthiulan disulfide, and 1.5 parts by weight of broken rubber blend. Then, the range of tande 11 a at 0.0 is 0-18 to 0.40, and the range of tan delta at 60 ° C is 0.09 to 0 '16. Most of the sags, the styrene butadiene of the present invention After the rubber composition is hardened in this rubber blend, the tande 11 a range of 0 is 0.20 to 0.30, and the tan delta range of 60 t: 0.10 to 0.14. The styrene-butadiene rubber composition of the present invention After hardening in this rubber blend, it is generally preferred that the tan delta range at 0 is 0.23 to 0.27, and the tan delta range at 60 ° C is 0.10 to 0.13. Example 10 This is true. Two kinds of styrene-butadiene-butadiene (SBR) latex were synthesized by continuous polymerization of 13 • butadiene monomer and styrene monomer. After polymerization, the latex was blended in a specific ratio, and then flocculated and dried. This experiment was performed at Godyear's Houston production facility. The latex with high Mooney ML 1 + 4 viscosity and medium bound styrene content was synthesized in a series of 13 successive agitation tank reactors (CSTRs). Before being separated and fed into the polymerization reactor, the styrene stream, —--__ _________ ~ 44-This paper size is applicable to the Chinese National Standard (CNS) Α4 specification (2lGY97 mm). -----. / Please read the note on the back-Issue ¾ This page- Binding-booking Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed by the Intellectual Property Bureau of the Ministry of Economics Printed by S Industrial Consumer Cooperatives 4 ^ 4 1 〇6 ° A7 --- -—_ B7 ______ V. Description of the invention (Dinger Dian logistics and modifier stream are mixed and fed to a static mixing of Ligtnin with a diameter of about 3 leaves (7.6 cm) and a length of about 30 inches (76 cm) About 60% of this monomer / modifier stream is mixed with soft water and cooled in a heat exchanger to a temperature of about 5 2 F (1 1 t :). Activator dissolved waves '4 solution' oxygen purification After leaving the heat exchanger, the solvent solution and starter enter the stream before the second LlgtlUfl static mixer with a length of about 36 inches (91 cm) and a diameter of about 4 inches (10.2 cm). After the static mixer, the mixture flows The residence time in the tubular reactor before entering the first CSTR is about 40 seconds. Division ratio of the monomer / modifier stream was continuously feeding speed of the chain 5 to the reaction reactor chain configuration in the following table.:
本紙張尺度通用中國囷家標準（CNS>A4说格（210X297公釐） 424 彳 06 五、發明説明（巧 A7 B7 經濟部智慧財凌局員工消費合作社印製 RV 型態 體積 (加侖） Pzm -&^CF) 1 r 攬拌· 攪拌機型S1' 速度(rpm) 0 管式- 100 63 1 CSTR 5700 so 布魯門金攪拌機 71 2 CSTR 5700 50 布魯門金_挽拌機 71 3 CSTR 5700 50 布魯門金攪拌機 * 71 4 CSTR 5700 50 布魯Π金f拌機 71 5 CSTR S700 50 布魯門金承拌機 71 6 CSTR 5700 50 布魯門金|党拌機 71 7 CSTR 5700 50 布魯門金®拌機 71 8 CSTR 5700 50 布魯門金i®拌機 71 9 CSTR 5700 50 抽流滿輪 71 10 CSTR 5700 50 軸流渴輪 71 11 CSTR 5700 50 軸流渴輪 71 12 • CSTR .> 5700 50 柏流滿輪 71 13 CSTR 5700 50 抽流滿輪 71 -46- 請 先- 閱 ♦-背κ έ ' 之 注/ 項 |裝 頁 訂 本紙張尺度適用中國國家標孪（CNS ) Α4规格（210 X 297公釐} 424106 A7The paper size is in accordance with the Chinese standard (CNS > A4 scale (210X297 mm) 424 彳 06. V. Description of the invention (Qiao A7 B7) The RV type volume (Gallon) printed by the Consumer Cooperatives of the Ministry of Economic Affairs and Intelligent Finance Bureau Pzm- & ^ CF) 1 r Mixing and mixing machine S1 'Speed (rpm) 0 Tube-100 63 1 CSTR 5700 so Blumenkin mixer 71 2 CSTR 5700 50 Blumenkin_Blender 71 3 CSTR 5700 50 Blumenkin Mixer * 71 4 CSTR 5700 50 Blumen Gold Mixer 71 5 CSTR S700 50 Blumenkin Mixer 71 6 CSTR 5700 50 Blumenkin | Party Mixer 71 7 CSTR 5700 50 Cloth Lumkin® mixer 71 8 CSTR 5700 50 Blumenkin i® mixer 71 9 CSTR 5700 50 Full pumping wheel 71 10 CSTR 5700 50 Axial thirst wheel 71 11 CSTR 5700 50 Axial thirst wheel 71 12 • CSTR . > 5700 50 Cypress full wheel 71 13 CSTR 5700 50 Pump full wheel 71 -46- Please first-read ♦ -back ) Α4 size (210 X 297 mm) 424106 A7
7 B 五、發明説明（” 經濟部智慧財產局員工消費合作社印製 以連績方式將以下物流被加入此反應器组態。 ' 質量流量率 (靖/分鐘） 物流组合 (%) 笫一味段：添加入管式反應器之物流 丁二烯單體： 2 0 9.6 5 1 , 3 - 丁二烯 :90.00 雜質（混合丁烯，異丁烯，異伸 丁基，4 -乙烯基環己烯等） 10,00 苯乙烯單體： 8 5.93 苯乙烯 9 1.00 雜質（4 -乙烯基環己烯，乙基苯 ，混合二甲苯等） 9.00 皂溶液： 124.25 軟水 7 9.33 4 5 %氫氧化鉀水溶液 2.04 4 0 %磷酸三鉀水溶液 2.06 2 0 %氫氧化鉀水溶液 1.71 混合之氫e牛脂脂肪酸 8.21 4 7 %茶續酸納水溶液 1.70 歧化妥爾油松香之鉀皂（8 0 %活 性） 1.95 2 3 %十二基苯績酸納水溶液 3.00 敕水 702.64 100.00 起始劑： 0.68 -47 - 本紙張尺度適用中國國家標率（CNS > A4規格（210X297公釐） ---------择------ir------^ (^£-Β3#?®·ν/ίΐ·*-ΐ^4 β 本 V=0 ( A7 4241067 B V. Invention Description ("Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the following logistics has been added to this reactor configuration in a continuous manner. 'Mass flow rate (jing / min) Logistics combination (%) : Butadiene monomer added to the tube reactor: 2 0 9.6 5 1, 3-Butadiene: 90.00 impurities (mixed butene, isobutylene, isobutylene, 4-vinylcyclohexene, etc.) 10,00 Styrene monomer: 8 5.93 Styrene 9 1.00 Impurities (4-vinylcyclohexene, ethylbenzene, mixed xylene, etc.) 9.00 Soap solution: 124.25 Soft water 7 9.33 4 5% potassium hydroxide aqueous solution 2.04 4 0% Tripotassium Phosphate Aqueous Solution 2.06 2 0% Potassium Hydroxide Aqueous Solution 1.71 Mixed Hydrogen e Tallow Fatty Acid 8.21 4 7% Tea Sodium Sodium Aqueous Solution 1.70 Disproportionated Tall Oil Rosin Potassium Soap (80% Active) 1.95 2 3% Ten Sodium diphenylbenzoate aqueous solution 3.00 Sodium water 702.64 100.00 Starter: 0.68 -47-This paper size is applicable to China National Standard (CNS > A4 specification (210X297 mm) --------- select- ----- ir ------ ^ (^ £ -Β3 #? ® · ν / ίΐ · *- ΐ ^ 4 β this V = 0 (A7 424106
B 五、發明説明（45) 經濟部智葸財產局員工消費合作社印製 蒎烷過氧化氫（44%活性） 100.00 活性劑溶液： 6 5.59 软水 9 8.69 2 0 %硫酸亞鐵水溶液 0.4 1 4 0 %乙烯二胺四乙酸四鈉 0.56 甲醛次硫酸鈉 0.34 改質劑（鏈轉移劑）： 0.29 三級十二基硫醇 100,00 氧淨化劑溶液； 2.46 軟水 9 7.00 亞硫酸氫納 3.00 第二階段：添加至第5個C S T R之物流 丁二烯單體： 13 9.76 1，3 - 丁二烯 90.00 雜質（混合丁烯，異丁烯，異伸 丁基，4 -乙烯基環己烯等） 10.00 苯乙烯單體： 5 7.28 苯乙烯-. 9 1.00 雜質（4 -乙烯基環己烯，乙基苯 ，混合二甲苯等） 9.00 改質劑（鏈轉移劑） 0.20 三級十二基硫醇 100.00 速止劑：第门個C S T R後添加， 轉化率為6 2 % (或2 2 . 6 %固體） 4 2.56 ----------¢------1T------1 (請-先 M#t.©*之>!'意事項〈：寫本 ( -4S " 本紙浪尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 424106 A7 B7 五 '發明説明 軟水 ·*" ' II —t— 二乙羥基胺永汝汸__ 4 0 %二甲二硫胺基甲酸鈉水溶 液 12 %葚磺酸鉀水溶液 -11Ζ°氫氧化鉀水湓湓__ 消泡劑：單體回收操作期間加入 L乳膠 _ _ 軟水 j a 1 C 0 - E X χ 〇 η E C 9 0 6 0 A 消泡 #1 0 0B V. Description of the invention (45) Printed pinane hydrogen peroxide (44% active) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 100.00 Active solution: 6 5.59 Soft water 9 8.69 2 0% Ferrous sulfate aqueous solution 0.4 1 4 0 % Ethylenediamine tetraacetic acid tetrasodium 0.56 sodium formaldehyde sulfoxylate 0.34 modifier (chain transfer agent): 0.29 tertiary dodecyl mercaptan 100,00 oxygen scavenger solution; 2.46 soft water 9 7.00 sodium bisulfite 3.00 second Stage: Butadiene monomer added to the 5th CSTR stream: 13 9.76 1,3-butadiene 90.00 impurities (mixed butene, isobutylene, isobutylene, 4-vinylcyclohexene, etc.) 10.00 benzene Ethylene monomer: 5 7.28 Styrene-. 9 1.00 Impurities (4-vinylcyclohexene, ethylbenzene, mixed xylene, etc.) 9.00 Modifier (chain transfer agent) 0.20 Tertiary dodecyl mercaptan 100.00 Speed Stopper: added after the first CSTR, the conversion rate is 6 2% (or 22.6% solids) 4 2.56 ---------- ¢ ------ 1T ----- -1 (please-first M # t. © * of >! 'Italian matters <: writing (-4S " this paper wave scale is applicable to Chinese countries Standard (CNS) A4 specification (210 X 297 mm) 424106 A7 B7 Five 'invention description soft water *' " 'II —t- diethylhydroxylamine Yongru __ 40% sodium dimethyldithiocarbamate aqueous solution 12% potassium sulfonate aqueous solution -11Z ° potassium hydroxide hydrazone __ defoaming agent: L latex added during monomer recovery operation _ _ soft water ja 1 C 0-EX χ 〇η EC 9 0 6 0 A defoaming # 1 0 0
經濟部智態財產局員工消f合作社印製 所製得乳膠自第1 3個反應器連績取出 〜亚通過濾益而除 去凝塊。濾器係由具直徑约3 / 8吋（9.5其（， i米）孔洞之籃式 粗濾器紕成。然後使乳膠通過回收殘留 、 ., hJ、丁二歸單體念 戍料箱。將表辨識之消泡劑於物流自洩料# 叮相輸出後加入发 中。然後使乳膠物流通過第一閃蒸箱，其被施予約3 ^ 5?5丨8(1.2以051>&至真空。接著通過真空二 22吋汞拄（Z.4xl04Pa)設置之第二閃蒸箱。乳膠然後通過 1 2碟蒸汽汽提管柱，其中丨5 p s i g蒸汽注入管柱底部，約 22兮水柱（7.4x10 Pa)被施於管柱上端。在未反應單體在 蒸汽汽提而自此穩定乳膠中被移除後τ經發現其固體含量 為20.8百分比，苯乙烯含量為2 3 4百分比，M〇〇ney M L 1 + 4黏度為1 〇5 »乳膠在通過蒸汽汽提管柱後被儲存 於容量約45,000加侖之儲槽。 -49- 本紙張尺度適用中國國家標準（CNS ) A4規格{ 210X297公楚） 計 424106 A7 B7 — 五、發明説明（） 具備低黏度及高結合笨乙烯含量之第二乳膠亦於類似製 備高黏度乳膠之反應器系統中合成。用於合成低黏度乳膠 之反應器連鎖组態敘述於下表中： ---------装------,玎------0 (請^閲讀"-面之注意事項^寫本X ) ( 經濟部智慧財產局員工消費合作社印製 -50 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）Printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the cooperative. The latex produced was removed from the 13th reactor in a row. ~ The clot was removed by filtering. The filter is formed by a basket-type coarse filter with a diameter of about 3/8 inches (9.5 m (, i meters)). Then, the latex is passed through the residual,., HJ, and succinimide monomer container. The table The identified defoamer is added to the hair after the stream is discharged from the material from the leaking material #. Then the latex stream is passed through the first flash tank, which is administered about 3 ^ 5? 5 丨 8 (1.2 to 051 > & to vacuum Then pass the second flash tank set with 22 inches of mercury (Z.4xl04Pa) in vacuum. The latex then passes through a 12-disc steam stripping column, of which 5 psig steam is injected into the bottom of the column, about 22 ° water column (7.4 x10 Pa) was applied to the upper end of the column. After the unreacted monomer was removed from the stable latex by steam stripping, τ was found to have a solid content of 20.8 percent, a styrene content of 2 34 percent, and 〇ney ML 1 + 4 has a viscosity of 1 〇 5 »The latex is stored in a storage tank with a capacity of approximately 45,000 gallons after passing through the steam stripping column. Chu) Count 424106 A7 B7 — V. Description of the invention () With low viscosity and high binding stupid ethylene content The second latex is also synthesized in a reactor system similar to the preparation of high viscosity latex. The chain configuration of the reactor used to synthesize the low viscosity latex is described in the following table: --------- 装 ----- -, 玎 ------ 0 (please ^ read " -the above notes ^ written X) (printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -50-this paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm)
a 2 厶' 〇 6 . ’ AT B7 ---^-- 五、發明説明（） I I— In I - I I · 經濟部智慧財產局8工消費合作社印製 RV 曳態 體積 (加命） Pzm 溫度(°F) .攪拌: 攪拌機型態7 速度(rpm) 0 管式· 150 63 1 CSTR 3 750 50 抽流丨1¾輪 107 2 CSTR 3750 50 轴流渦輪 107 3 CSTR 3750 50 布魯Π金择拌機 71 4 CSTR 7500 50 布魯Π金攪拌機 71 5 CSTR 7500 50 布魯門金携拌機 71 6 CSTR 3750 50 軸流渦輪 107 7 CSTR 3750 50 相流滿輪 107 8 CSTR 3750 50 抽流滿輪 107 9 CSTR 3750 50 抽流满輪 107 ---------装-- (請t閲讀背面之汶意事項'ί 馬本頁) 訂 線 -βί Ina 2 厶 '〇6.' AT B7 --- ^-V. Description of the invention () II— In I-II · RV trailing volume (plus life) printed by RV Cooperative Society of Intellectual Property Bureau of the Ministry of Economy (° F) .Stirring: Stirring mode 7 Speed (rpm) 0 Tube type · 150 63 1 CSTR 3 750 50 Pumping flow 丨 1¾ wheel 107 2 CSTR 3750 50 Axial turbine 107 3 CSTR 3750 50 Brui gold optional mixing Machine 71 4 CSTR 7500 50 BruJin Mixer 71 5 CSTR 7500 50 Blumenkin Blender 71 6 CSTR 3750 50 Axial Turbine 107 7 CSTR 3750 50 Phase Flow Full Wheel 107 8 CSTR 3750 50 Pumping Full Wheel 107 9 CSTR 3750 50 Pumping full round 107 --------- equipment-(Please read the Wen Yi matters on the back 'ί Ma page) Thread-βί In
In - i - 11 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公煃） 06. ^ A7 B7 五、發明説明（” 經濟部智慧財產局員工消費合作社印製 以連續方式將以下物流被加入此反應器組態。 質量流量率 (磅/分鐘） 物流组合 (%) 第一味段：添加入管式反應器之物流 丁二烯單體： 3 8.02 1，3 - 丁二烯 9 0.00 雜質（混合丁烯，異丁烯，異伸 丁基，4 -乙烯基環己烯等） 10.00 苯乙烯單體： 5 4.10 苯乙 '烯 9 1.00 雜質（4 -乙烯基環己烯，乙基苯 ，混合二甲苯等） 9.00 皂溶液： 40.62 軟水 7 9.33 4 5 %氫氧化鉀水溶液 2.04 4 0 %鱗酸三钾水溶液 2.06 2 0 %氣氧.化钾水溶液 1.71 混合之風化牛脂脂防酸 8.21 4 7 %莫績酸鋼水溶液 1.70 歧化妥爾油松香之鉀皂（8 0 %活 性） 1.95 2 3 %十二基苯績酸鋼水溶液 3.00 軟水 217.15 100.00 -52- (請七閲讀背面之注意事項又冯本頁) -裝- 訂 線 本紙張尺度適用令國國家標準（CNS ) A4规格（210X297公釐） 424106 ~ * • A7 B7 50五、發明説明（） 經濟部智葸財產局員工消費合作社印製 起始劑： 0.20 蒎烷過氧化氫（4 4 %活性） 100.00 活性劑溶液： 17.68 款水 9 8.69 2 0 %硫酸亞鐵水溶液 0.41 4 0 %乙烯二胺四乙酸四鈉 0.56 甲醛次硫酸鈉 0.34 改質劑（鏈轉移劑）： 0.19 三級十二基硫酵 10 0.0 氧淨化剖溶液； 0.65 軟水 9 7.00 亞硫酸氫納 3.00 第二階段：添加至第3個C S T R之物流 丁二烯單體： 25.34 1，3 - 丁二烯 90.00 雜質（混合丁烯，異丁烯，異伸 丁基，4 -乙烯基環己缔等） 10.00 苯乙晞單_體.-二 3 6.07 苯乙缔 9 1.00 雜質（4 -乙烯基環己烯，乙基苯 ，混合二曱苯等） 9.00 改質劑（鏈轉移劑） 0.12 三級十二基硫酵 100.00 速止劑：第1 3個C S T R後添加， 13.31 -53 - ---------钟水— (請先聞讀背面之注意事項广〉寫本頁) 訂 線 本紙張尺度適用中國國家橾準（CNS ) A4規格（210 X 297公嫠） 424 1 〇6 A7 B7 五、發明説明（ 轉化率為62%(或21,6%固體、 軟水 8 5 %二乙羥基胺水溶液 40/ό —甲一疏胺基甲酸納水溶 液 4 7 %莫續酸钾水溶液 4 5 %氳氧化卸水溶液 消泡劑：單體回收操作期間加入乳膠In-i-11 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 gong) 06. ^ A7 B7 V. Description of the invention ("Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the following logistics is Add this reactor configuration. Mass flow rate (lbs / min) Stream combination (%) First taste stage: Stream butadiene monomer added to the tube reactor: 3 8.02 1,3-butadiene 9 0.00 Impurities (mixed butene, isobutylene, isobutylene, 4-vinylcyclohexene, etc.) 10.00 Styrene monomer: 5 4.10 Styrene'ene 9 1.00 Impurities (4-vinylcyclohexene, ethylbenzene, Mixed xylene, etc.) 9.00 Soap solution: 40.62 Soft water 7 9.33 4 5% potassium hydroxide aqueous solution 2.04 4 0% tripotassium tribasic acid aqueous solution 2.06 2 0% gas-oxygen. Potassium hydroxide aqueous solution 1.71 mixed weathered tallow grease anti-acid 8.21 4 7 % Mochi acid steel aqueous solution 1.70 Disproportionated tall oil rosin potassium soap (80% active) 1.95 2 3% Dodecyl benzoic acid steel aqueous solution 3.00 Soft water 217.15 100.00 -52- (Please read the precautions on the back again and Feng (This page) -pack- The paper size of the guideline applies the national standard (CNS) A4 specification (210X297 mm) 424106 ~ * • A7 B7 50 V. Description of the invention () Printing agent for employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs: 0.20 蒎Alkyl hydrogen peroxide (44% active) 100.00 Active solution: 17.68 water 9 8.69 2 0% ferrous sulfate aqueous solution 0.41 40% ethylene diamine tetraacetic acid tetrasodium 0.56 sodium formaldehyde hyposulfite 0.34 modifier (chain transfer Agent): 0.19 tertiary dodecyl thiolase 10 0.0 oxygen purification profile solution; 0.65 soft water 9 7.00 sodium bisulfite 3.00 second stage: added to the third CSTR stream butadiene monomer: 25.34 1,3- Butadiene 90.00 Impurities (mixed butene, isobutylene, isobutylene, 4-vinylcyclohexyl, etc.) 10.00 Phenylethylene monomer.-Di 3 6.07 Styrene 9 1.00 Impurities (4-vinyl ring Hexene, ethylbenzene, mixed diphenylbenzene, etc.) 9.00 Modifier (chain transfer agent) 0.12 Tertiary dodecyl thiolase 100.00 Quick stop agent: added after the 13th CSTR, 13.31 -53---- ------ Zhongshui— (Please read and read first (Notes on this page are wide> write this page) The size of the book is applicable to the Chinese National Standard (CNS) A4 size (210 X 297 cm) 424 1 〇6 A7 B7 V. Description of the invention (the conversion rate is 62% (or 21 , 6% solids, soft water 8 5% diethylhydroxylamine aqueous solution 40 / ό —Sodium methylmonosulfamate aqueous solution 4 7% potassium molybdate aqueous solution 4 5% oxidative dewatering solution defoamer: during monomer recovery operation Add latex
Nalco-Exxon EC9060A 消泡劑 〇.〇5 9 7.08 0.38 0.80 0.89 0.85 --.-------^ — (請先聞讀背面之ii-意事項一·'--寫本頁) 100,00 在未反應單體在蒸汽汽提而自此穩定乳膠中被移除後， 經發現其固體含量為20.5百分比，苯乙烯含量為5〇 6百 分比，Mooney ML 1+4黏度為13 » 222,646磅（10〇992公斤）高黏度乳膠及1S 4,8 2 8磅 (83,838公斤）低黏度乳膠之摻合物（55百分比：45百分 比乾重摻合物）係製備於攪拌槽中。添加至乳膠摻合物I 2 105 ..镑（>9 5 5公斤）50百分比活性G〇〇dyear W i n g s t a y ® C抗氧化劑乳液。 此乳膠在傳統連績方法中經絮凝及乾燥。此乳跟以8〇〇 磅/分鐘（3 6 2公斤/分鐘）之速率進行絮凝。添加硫酸至絮 凝槽以維持p Η 3，7。也以2 9磅/分鐘（丨3公斤/分鐘）之速 率添加鹽水（2 3百分比氣化鈉水溶液）及以〇 〇 6镑/分鐘之 速率添加Ρ Μ 1 9 6 9乙婦胺混合物（u n i 0 n c a r b i d e )至絮 54 ‘ 本紙張尺度適用中國國家標準（CNS ) A4規格（2! 〇 X 2Θ7公嫠） -訂 線- 經濟部智慧財產局員工消費合作社印製 經濟部智葸財產局員工消資合作杜印製 4241u b A7 B7 五、發明説明（5’ ^ 一" 凝韁。自聚合物c r u m b洗除絮凝劑，然後在單螺桿擠出機 中脫水。然後使聚合物在2 1 0 F。之單一通道、燃燒煤氣之 裙式乾燥機中乾燥，減少0.5百分比濕氣含量。最終聚合 物之結合苯乙烯含量為35.7百分比，Mooney ML 1+4 黏度為52。 實例1 1至1 3 此實驗中，製備傳統乳化聚合所製得高分子量乳化S B R 及傳統乳化聚合所製得低分子量乳化S B R之摻合物，經混 鍊成為標準輪胎面橡膽~ a此橡膠經硬化，其物理性質與標 準乳化S β R及標準溶液S B R所製得類似橡膠化合物作比 較。摻合物中高分子量SBR含23.5百分比結合苯乙埽， 數目平均分子f為130,000 ’ Mooney ML 1+4黏度約 為111。摻合物中低分子量SBR含50百分比結合苯乙烯 ’ Mooney ML 1+4黏度约為15 〇接合物中高分子量 S B R對低分子量S B R之重量比例為5 〇 : 5 0。 橡膠化合物係製備於混合7 0份三種不同5 B R橡膠與 37.5份向度順-1，4 -聚丁二烯橡膠（含75份高度芳族加工 油），60份^石，在作為載體之5份N33〇碳黑上之5份 Si-69矽石^偶合劑，2 6.2 5份高度芳族加工油，之份 Agerite樹脂D抗氧化劑（聚合U2-二氫_2,24_三甲基峻 #) ’ 3份氧化鋅’ 1.25份Wingstay® 1〇〇對-苯二胺 抗氧化劑，I . 8份N -環己基-2 -苯并n塞唑亞磺醯胺，1 . 4 5 份二苯基脈促造劑及1.6份硫。然後，橡膠調配物硬化， 經評估以測定物理性質。經硬化橡膠摻合物在〇 ^及6〇 本紙中_家標準（CNS) A4规格（210><297公瘦）~ ---——— ^ 裝^ 訂 線 * · /' (Itit'閲讀t.面之注t事項A (ΪΤ本頁) 一 424106 A7 B7 五、發明説明（53) 1之tan delta記載於表ΠΙ e ian deUa係使用動態機 械試驗機以抗張模式於u赫及ϋ (π至】百分比之應變範 圍測定的。 表III 實例 tan delta — tan delta @0 °C 6 0 T, 1 1 -新乳化S B R 0.2 6 0 0 6 12 -標準溶液SBR 0.09 0 0 7 1 3 - F I Μ 乳化 S B R ο.ιί 0.07 ---------裝-- W ' -* * ' f (請it·閱讀背1&之汶意事項又¾本f > 經濟部智慧財產局員工消費合作社印袈 使用，發明乳化SBR摻合物於載入矽石之混鍊橡膠會 在〇 °C得到高tan delta值及在6 0 °c得到低tan de：ita值 。此係象徵優良牽引特徵，滾動阻力及胎面耐磨。以本發 明乳化橡膠製得之硬化橡膠摻合物在〇它之t a n d e丨t a值 高於由傳統乳化SBR製得硬化橡膠者。顯著的是，以本發 明乳化SBR製得之硬化橡膠摻合物在6〇它之Un delu 值幾乎與標準溶液S B R製得硬化橡膠一樣高。 本發..明.苯^乙晞-丁二烯橡膠一般在含70份重量苯乙浠_ 丁二烯橡膠，30份重量高度順-1，4 -聚丁二缔橡膠， 33.75份重量高度芳族加工油，60份矽石，在作為載體 之5份N 3 3 0碳黑上之5份S i - 6 9矽石偶合劑，2 6 2 5份 高度芳族加工_，2份A g e r i t e樹脂D抗氧化劑（聚八 1，2-二氫-2,24 -三甲基p查1#)， 3偷氧化鋅，j 25份 W i n g s t a y ® 1 0 0對-苯二胺抗氧化劑，1 . 8份n -環己基_ -56 - — 本紙張尺度適用中國國家標準（CNS } A4規格（210X297公釐） "^ - 訂 線 -I ί ί 12 4 10 6 1 A7 B7 五、發明説明（ 2 -苯并11塞唑亞磺醯胺，1 . 4 5份二苯基胍促進劑及1 . 6份 硫之橡膠摻合物中硬化後，在0 eC之t a n d e 11 a範圍為 0.20 至 0.40 ，而在 60 °C 之 tan delta 範圍為 0‘03 至 0 . 1 ο 5大部份情況下，本發明苯乙婦，丁二烯橡膠组合物 在此橡膠摻合物中硬化後’在〇 °c之t a n d e 11 a範圍為 0.22至0.35 ’而在60 C之tan delta範圍為0,〇4至 0 · ο 8 。本發明苯乙烯·丁二烯橡膠組合物在此橡膠摻合物 中硬化後’一般較佳在ο X：之tan delta範圍為0.25至 〇.. 27 ’ 而在 60。(：之 tan delta 範園為 〇〇5 至 0.〇7。 雖然為了例示本發明而顯示某些代表性具體實施例及詳 細内容’對熟習此項技藝人士而言各種改變及修飾係顚^ 易見的’而不會偏離本發明範圍。 ’ (請£'聞讀背面之注’意事項1 寫本頁} -裝. 訂 線 經.濟部智慧財產局員工消費合作杜印製 -57- 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ29?公釐）Nalco-Exxon EC9060A Defoamer 0.05 9 7.08 0.38 0.80 0.89 0.85 --.------- ^-(Please read the ii-Issue 1 on the back of the page first; '-write this page) 100 0,00 After the unreacted monomer was removed from the stable latex by steam stripping, it was found that its solid content was 20.5 percent, styrene content was 50 percent, and Mooney ML 1 + 4 viscosity was 13 »222,646 A blend of 55 pounds (10,992 kg) of high viscosity latex and 1S 4,8 2 8 pounds (83,838 kg) of low viscosity latex (55%: 45% dry weight blend) was prepared in a stirred tank. Added to Latex Blend I 2 105... Pounds (> 955 kg) 50% active GODyear W yn t y ® C antioxidant emulsion. This latex is flocculated and dried in a traditional continuous method. This heel was flocculated at a rate of 800 pounds per minute (362 kg / minute). Add sulfuric acid to the flocculation tank to maintain p Η 3,7. Brine (23% aqueous sodium gas solution) was also added at a rate of 29 lbs / min (3 kg / min) and PM 1 9 6 9 ethionamine mixture (uni 0 ncarbide) to 54 'This paper size applies to Chinese National Standards (CNS) A4 specifications (2! 〇X 2Θ7 Gong)-Order-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, printed by the Ministry of Economic Affairs, the Intellectual Property Bureau, staff consumption Cooperative production of printed 4241u b A7 B7 V. Description of the invention (5 '^ a " Condensate. The flocculant is washed from the polymer crumb, and then dewatered in a single screw extruder. Then the polymer is dehydrated in 2 1 0 F. Dry in a single-pass, gas-fired skirt dryer to reduce the moisture content by 0.5%. The final polymer has a combined styrene content of 35.7% and Mooney ML 1 + 4 viscosity of 52. Examples 1 1 to 1 3 In this experiment, a blend of high molecular weight emulsified SBR prepared by traditional emulsification polymerization and low molecular weight emulsified SBR prepared by traditional emulsification polymerization was prepared and mixed into a standard tire tread rubber bladder. A This rubber is hardened and its physical properties versus Quasi-emulsified S β R and standard solution SBR prepared similar rubber compounds for comparison. The high-molecular-weight SBR in the blend contains 23.5 percent bound phenethylhydrazone, and the number average molecular f is 130,000 'Mooney ML 1 + 4 viscosity is about 111. Blended The low-molecular weight SBR in the compound contains 50% bound styrene. The Mooney ML 1 + 4 has a viscosity of about 15 〇 The weight ratio of high-molecular-weight SBR to low-molecular-weight SBR in the joint is 50: 50. The rubber compound is prepared in a mixture of 7 0 Parts of three different 5 BR rubbers and 37.5 parts of cis-1,4-polybutadiene rubber (containing 75 parts of highly aromatic processing oil), 60 parts of spar, 5 parts of N33 carbon black as a carrier 5 parts Si-69 silica ^ coupling agent, 2 6.2 5 parts highly aromatic processing oil, parts Agerite resin D antioxidant (Polymer U2-dihydro_2,24_trimethyljun #) '3 parts zinc oxide '1.25 parts of Wingstay® 100 p-phenylenediamine antioxidant, 1.8 parts of N-cyclohexyl-2 -benzon thiazolyl sulfenamide, 1.4 parts of diphenyl pulse generator and 1.6 parts of sulfur. Then, the rubber formulation is hardened and evaluated to determine physical properties. The hardened rubber blend is between 0 and 60. In the paper _ home standard (CNS) A4 specification (210 > < 297 male thin) ~ --------^ binding ^ order line * · / '(Itit' read t. Face note t matter A (ΪΤ 本Page) A 424106 A7 B7 V. Description of the invention (53) The tan delta of Table 1 is described in Table III. The I ian deUa is determined by using a dynamic mechanical testing machine in a tensile mode at a strain range of u Hz and ϋ (π to) percentage. Table III Examples tan delta — tan delta @ 0 ° C 6 0 T, 1 1-new emulsified SBR 0.2 6 0 0 6 12-standard solution SBR 0.09 0 0 7 1 3-FI Μ emulsified SBR ο.ι 0.07 --- ------ Installation-W '-* *' f (Please read · I read the “Issues” and 本 this f > Use of the seal of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, invented the emulsified SBR blend. The mixed-chain rubber loaded with silica will get a high tan delta value at 0 ° C and a low tan de: ita value at 60 ° c. This symbolizes excellent traction characteristics, rolling resistance and tread wear resistance. The hardened rubber blend prepared from the emulsified rubber of the present invention has a tande value that is higher than those obtained from the conventional emulsified SBR. Significantly, the hardened rubber blend prepared from the emulsified SBR of the present invention At 60, its Un delu value is almost as high as that of the hardened rubber made by the standard solution SBR. The hair .. Ming. Styrene-butadiene rubber generally contains 70 parts by weight of styrene-butadiene rubber, 30 parts by weight highly cis-1,4-polybutadiene rubber, 33.75 parts by weight highly aromatic processing oil, 60 parts silica, 5 parts N 3 as carrier 5 parts Si-6 9 silica coupling agent on 30 carbon black, 2 6 2 5 parts highly aromatic processing, 2 parts A gerite resin D antioxidant (poly 1,2, dihydro-2, 24 -Trimethyl pcha 1 #), 3 stolen zinc oxide, j 25 parts Wingstay ® 1 0 p-phenylenediamine antioxidant, 1.8 parts n-cyclohexyl_ -56-— This paper size applies to China National Standard (CNS) A4 Specification (210X297 mm) " ^-Thread-I ί 12 4 10 6 1 A7 B7 V. Description of the Invention After curing in a rubber blend of 1.6 parts of diphenylguanidine accelerator and 1.6 parts of sulfur, the tande 11 a ranges from 0.20 to 0.40 at 0 eC, and the tan delta ranges from 0'03 to 0 at 60 ° C. 1 ο In most cases, the styrene-butadiene and butadiene rubber composition of the present invention is hardened in this rubber blend, with a tande 11 a range of 0.2 ° to 0.35 at 0 ° C and a temperature of 60 ° C. The tan delta range is from 0.04 to 0. ο 8. The styrene butadiene rubber composition of the present invention is generally hardened after curing in this rubber blend. X: The tan delta range is from 0.25 to 〇 .. 27 'while at 60 . (: The tan delta range is from 0.05 to 0.07. Although some representative specific embodiments and details are shown to illustrate the present invention, various changes and modifications are made to those skilled in the art. It is easy to see 'without departing from the scope of the present invention.' (Please read 'Notes on the back of the note' Note 1 Write this page}-Binding. Thread Script. Ministry of Economic Affairs Intellectual Property Bureau staff consumer cooperation Du-57 -This paper size is in accordance with China National Standard (CNS) A4 (21〇29? Mm)
Claims (1)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11366398P | 1998-03-11 | 1998-03-11 | |
| US7978998P | 1998-03-28 | 1998-03-28 | |
| US10475598P | 1998-10-19 | 1998-10-19 | |
| US10953098P | 1998-11-23 | 1998-11-23 | |
| US11730599P | 1999-01-26 | 1999-01-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW424106B true TW424106B (en) | 2001-03-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW088103716A TW424106B (en) | 1998-03-11 | 1999-03-11 | Emulsion styrene-butadiene rubber compositions, styrene-butadiene rubber latex and tire treads and tires comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TW424106B (en) |
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1999
- 1999-03-11 TW TW088103716A patent/TW424106B/en active
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