201011048 六、發明說明： 【發明所屬之技術領域】 本發明係關於具有高乙烯基芳族含量之官能化二稀棒 膠及關於其製造，關於橡膠混合物，其包含這些具有高乙 烯基芳族含量之官能化二稀橡膠，以及關於其用於製造橡 膠硫化物(rubber vulcanisate)之用途，該硫化橡膠更特別地 用於製造高強化橡膠模造物。特佳者為於製造具有特別低 鲁 的滾動阻力、和特別高的抗濕滑性、和耐磨性的輪胎之用 途。 【先前技術】 在輪胎中一想要的重要性質為乾和濕表面之良好黏 著。在此非常難以改良輪胎防滑性而沒有同時地增加滾動 阻力和磨耗。低滾動阻力對於低燃料消耗是重要的，且高 耐磨性對於長輪胎壽命是決定性因素。 φ 輪胎之抗濕滑性、滾動阻力和耐磨性主要視用以構造 輪胎之橡膠的動態機械性質而定。為了減少滾動阻力，在 相對較高溫度下具有回彈性之橡膠被使用於輪胎胎面。另 一方面’在低溫下具有高阻尼因數之橡膠對改良抗濕滑性 是有利的。由各種橡膠組成之混合物被使用於胎面以便遵 從此複雜需求輪廓。通常使用之材料為一種或多種具有相 對較高玻璃轉移溫度之橡膠(例如苯乙烯_丁二烯橡膠)和一 種或多種具有相對較低玻璃轉移溫度之橡膠（例如具有低 乙烯基含量的聚丁二烯）的混合物。 3 201011048 包含雙鍵之陰離子性聚合溶液橡膠，例如聚丁二烯溶 液橡膠和笨乙烯-丁二烯溶液橡膠，在製造低-滾動阻力輪胎 胎面方面優於對應的乳液液橡膠。該等優點尤其發現於乙 烯基含量的可控性、和與其相關的玻璃轉移溫度及分子分 支。在實際應用中，此結果在輪胎的抗濕滑性和滾動阻力 之間的關係特別有利。舉例來說，US-A 5 227 425揭述從溶-液SBR和矽石製造輪胎胎面。為了使性質進一步改良，已 經發展很多用於端基修飾的方法’例如如EP-A 334 042中 所述，使用二甲胺基丙基丙烯胺，或如EP-A 447 066中所® 述，藉由使用矽烷基醚類。然而，端基基團的重量比例很 小，因為橡膠的高的分子量，和因此端基基團不能夠對填 料和橡膠分子之間的相互作用有很大的影響。US 2005/0 256 284 A1揭述由二烯和官能化乙烯基芳族單體組成之共 聚物。在官能化乙烯基芳族單體的複雜合成方面和在選擇 官能基的嚴格限制方面發現該等共聚物的缺點，因為可用 之官能基僅為該等在陰離子聚合方法期間不與引發劑開始 任何反應者。更特別地，不可能使用具有能夠形成氫鍵且❹ 其因此可發展在橡膠混合物中加入填料（諸如碳黑或矽石） 的表面上與極性基團之特別有利的相互作用之氫原子的官 能基。EP-A1 000 971揭示包含羧基且由乙烯基芳烴和二稀 類組成的相對較高官能化之共聚物，具有至多60%含量之 1，2-鍵結之二烯（乙烯基含量)和至多40%含量之乙烯基芳族 化合物。官能基係在陰離子聚合方法結束之後，經由適當 試劑對延橡膠中之聚合物鍵的雙鍵之加成反應引入。藉由 201011048 此方法可逹成的官能化度係高於藉由端基修飾逹成的官能 化度，且可能引入可形成氫鍵之官能基。此類型之官能基 在加入填料之表面與極性基團特別有利地互相作用。 已知輪胎之防滑性可藉由在輪胎胎面中使用具有高苯 乙烯含ΐ之苯乙稀-丁二稀共聚物改良，例如如US-A 5082901和US-A 7193004中所述。然而，防滑性之改良通 常伴隨滾動阻力增加。此類塑具有高苯乙烯含量之苯乙烯_ 丁一烯共聚物因此較佳地使用於跑車輪胎和高性能輪胎， 其中良好黏著(也在高速度下）’是決定性的，且高滾動阻力 較不重要。 【發明内容】 因此一個目的為提供沒有先前技藝的缺點且提供高防 滑性和低滾動阻力的橡膠混合物。 令人驚訝地，現已發現相較於具有較低乙烯基芳族含 量的官能化二烯橡膠，當本發明的具有高乙烯基芳族含量 ❹ 1官能化二賴膠併人輪胎巾，該等輪胎顯示該等性質和 顯示不只抗濕滑性改良且顯示滾動阻力和磨耗之改良。相 較於具有高乙稀基芳族含量之非官能化二稀橡膠，本發明 之橡膠也顯示優越性質。 本發明因此提供新穎具有高乙烯基芳族含量之官能化 二烯橡膠’ ^特徵在於其具有從3〇至6〇重量％(較佳地從 30至45重量/。)之共聚合乙烯基芳族單體含量，和具有從 40至70重量％(較佳地從55至7〇重量％)之二稀類含量， 201011048 其中在一烯類中1，2_鍵結之二烯類的含量（ 從〇.5至95重量。/〇’較佳地從1〇至85重量％，且全部)由 共聚合乙烯基絲單體和二烯類組成產生總數為磐。，和 該橡膠具有從G.G2至3重量％，較佳地從⑽5至2重量％ 之官能基及/或其鹽類，以刚重量％之二稀橡膠為基準。201011048 6. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to functionalized dilute sticks having a high vinyl aromatic content and for their manufacture, with regard to rubber mixtures, which contain these high vinyl aromatic content A functionalized dilute rubber, and for its use in the manufacture of rubber vulcanisate, which is more particularly useful in the manufacture of highly reinforced rubber moldings. It is particularly advantageous for the manufacture of tires having particularly low rolling resistance and particularly high wet skid resistance and abrasion resistance. [Prior Art] A desirable important property in a tire is good adhesion to dry and wet surfaces. It is very difficult to improve the tire slip resistance here without increasing the rolling resistance and wear at the same time. Low rolling resistance is important for low fuel consumption, and high wear resistance is a decisive factor for long tire life. The wet skid resistance, rolling resistance and wear resistance of φ tires are mainly determined by the dynamic mechanical properties of the rubber used to construct the tire. In order to reduce the rolling resistance, rubber having resilience at a relatively high temperature is used for the tire tread. On the other hand, a rubber having a high damping factor at a low temperature is advantageous for improving wet skid resistance. A mixture of various rubbers is used for the tread to conform to this complex demand profile. Commonly used materials are one or more rubbers having a relatively high glass transition temperature (for example, styrene-butadiene rubber) and one or more rubbers having a relatively low glass transition temperature (for example, polybutyl having a low vinyl content). a mixture of dienes). 3 201011048 Anionic polymeric solution rubbers containing double bonds, such as polybutadiene solution rubber and stupid ethylene-butadiene solution rubber, are superior to the corresponding emulsion rubber in the manufacture of low-rolling resistance tire treads. These advantages are particularly found in the controllability of the vinyl content, and the glass transition temperature and molecular branch associated therewith. In practical applications, this result is particularly advantageous in the relationship between the wet skid resistance of the tire and the rolling resistance. For example, US-A 5 227 425 discloses the manufacture of tire treads from solution-liquid SBR and vermiculite. In order to further improve the properties, a number of methods have been developed for the modification of the end groups, for example as described in EP-A 334 042, using dimethylaminopropyl acrylamide, or as described in EP-A 447 066, By using a decyl ether. However, the weight ratio of the terminal groups is small because of the high molecular weight of the rubber, and thus the terminal groups are not able to have a large influence on the interaction between the filler and the rubber molecules. A copolymer composed of a diene and a functionalized vinyl aromatic monomer is disclosed in US 2005/0 256 284 A1. The disadvantages of such copolymers are found in the complex synthesis of functionalized vinyl aromatic monomers and in the strict limitations of the selection of functional groups, since the functional groups available are only those that do not start with the initiator during the anionic polymerization process. Responder. More particularly, it is not possible to use a functional group having a hydrogen atom capable of forming a hydrogen bond and thereby developing a particularly advantageous interaction with a polar group on the surface of a filler such as carbon black or vermiculite in a rubber mixture. base. EP-A1 000 971 discloses relatively highly functionalized copolymers comprising a carboxyl group and consisting of a vinyl arene and a disaccharide, having a 1,2-bonded diene (vinyl content) of at most 60% and at most 40% content of vinyl aromatic compound. The functional group is introduced after the end of the anionic polymerization process by the addition reaction of the double bond of the polymer bond in the rubber by a suitable reagent. The degree of functionalization which can be obtained by this method by 201011048 is higher than the degree of functionalization by the modification of the terminal group, and it is possible to introduce a functional group capable of forming a hydrogen bond. Functional groups of this type interact particularly advantageously with polar groups on the surface of the filler. The slip resistance of the tires is known to be improved by the use of a styrene-butadiene-diene copolymer having a high styrene-containing cerium in the tire tread, as described in, for example, US-A 5, 829, 091 and US-A 7, 193, 004. However, the improvement in slip resistance is usually accompanied by an increase in rolling resistance. Such a styrene-butadiene copolymer having a high styrene content is therefore preferably used in sports tires and high performance tires, in which good adhesion (also at high speed) is decisive and high rolling resistance is higher. unimportant. SUMMARY OF THE INVENTION It is therefore an object to provide a rubber compound that does not have the disadvantages of the prior art and that provides high slip resistance and low rolling resistance. Surprisingly, it has now been found that when the functionalized diene rubber having a lower vinyl aromatic content is compared to the present invention having a high vinyl aromatic content ❹ 1 functionalized bismuth and a human tire towel, Such tires exhibit these properties and show improved not only wet skid resistance but also improved rolling resistance and wear. The rubber of the present invention also exhibits superior properties compared to non-functionalized dilute rubber having a high ethylene aromatic content. The present invention thus provides novel functionalized diene rubbers having a high vinyl aromatic content, characterized by having a copolymerized vinyl aryl group from 3 Å to 6 重量% by weight, preferably from 30 to 45 重量%. a monomer content, and a disaccharide content of from 40 to 70% by weight (preferably from 55 to 7% by weight), 201011048 wherein the content of 1,2_bonded diene in an olefin (from 〇.5 to 95 wt. / 〇 'preferably from 1 85 to 85% by weight, and all) is composed of a copolymerized vinyl silk monomer and a diene to give a total of 磐. And the rubber has a functional group and/or a salt thereof from G.G2 to 3% by weight, preferably from (5) 5 to 2% by weight, based on the weight percent of the dilute rubber.
#可使用於聚合反應的乙稀基芳族單體之可提及的例子 為苯乙烯、鄰·、間_及/或對_曱基苯乙烯、對-三級·丁基苯 ^稀、α-曱基苯乙稀、乙稀基萘、二乙稀基笨、三乙稀基 笨及/或二乙烯基萘。特佳的是使用苯乙烯。 較佳二烯類為1，3-丁二烯、異戊二烯、u_戊二烯、2,3_ 二曱基丁二烯、1-笨基]，3_丁二烯及/或13_己二稀。特佳 的疋使用1，3-丁 一稀及/或異戊二稀。 本發明之橡膠，以二烯類為主和以乙烯基芳族單體為 主，且具有從0.02至3重量％之官能基含量，較佳地具有 從50 000至2 000 〇〇〇克/莫耳’較佳地從1〇〇 〇〇〇至1 〇〇〇 〇〇〇克/莫耳之平均莫耳質量（數量平均），和從_6〇°c至 +20°C ’較佳地從-40°C至0°C之玻璃轉移溫度，以及從1〇❹ 至200 ’較佳地從30至150之孟納(Mooney)黏度ML 1+4 (100oC)。 本發明之橡膠可具有下列官能基及/或其鹽類：羧基、 羥基、胺、羧酸酯、羧醯胺或續酸基團。較佳者為羧基或 羥基基團。較佳鹽類為鹼金屬羧酸鹽類、鹼土金屬羧酸鹽 類、羧酸鋅類和羧酸銨類、以及鹼金屬磺酸鹽類、鹼土金 屬磺酸鹽類、磺酸鋅類和磺酸銨類。 201011048 在一本發明之特佳具體實例中，乙烯基芳族單體為笨 乙稀’二婦為1，3_丁二烯和官能基為緩基或經基。 本發明之橡膠在此較佳地經由二烯類和乙烯基芳埃翠 體在溶液中之共聚合作用和接著引入官能基而製得。 本發明也提供一種製造本發明橡膠之方法，根據該方 法二烯類和乙烯基芳族單體在溶液中共聚合而產生橡膠， 和然後將官能基或其鹽類引入二烯橡膠中和然後於從5〇至 鲁 200°C之溫度下，如果適當在真空中使用熱水及/或蒸汽除 去溶劑。 用於本發明橡膠混合物之本發明橡膠較佳地經由陰離 子溶液聚合作用或經由利用配位觸媒之聚合作用製造。就 此而論’配位觸媒為戚格勒_納他觸媒或單金屬觸媒系統。 較佳配位觸媒為等以Ni、Co、Ti、Nd、V、Cr或Fe為主 者。 用於陰離子溶液聚合反應之引發劑為該等以鹼金屬為 _ 主或以鹼土金屬為主者，例如正丁基鋰。也可能使用已知 用於聚合物之微結構的無規化劑(rand〇miser)和控制劑，例 如三級-戊醇鉀和三級-丁氧基乙氧基乙烷。此類型之溶液聚 合反應為已知且舉例來說揭述於I. Franta Elastomers andPossible examples of the ethylene-based aromatic monomer which can be used for the polymerization reaction are styrene, o-, m- and/or p-menthylstyrene, p-tertiary butylbenzene, Α-mercaptostyrene, ethylene naphthalene, diphenyl stupid, triethyl stupid and/or divinylnaphthalene. Particularly preferred is the use of styrene. Preferred dienes are 1,3-butadiene, isoprene, u-pentadiene, 2,3-didecylbutadiene, 1-phenylidene, 3-butadiene and/or 13 _ already dilute. A particularly good hydrazine is 1,3-butadiene and/or isoprene. The rubber of the present invention is mainly a diene type and a vinyl aromatic monomer, and has a functional group content of from 0.02 to 3% by weight, preferably from 50 000 to 2 000 g / Moore' preferably has an average molar mass (number average) from 1 〇〇〇〇〇 to 1 gram/mole, and preferably from _6 〇 °c to +20 ° C ' The glass transition temperature from -40 ° C to 0 ° C, and the Mooney viscosity ML 1+4 (100 ° C) from 1 〇❹ to 200 ', preferably from 30 to 150. The rubber of the present invention may have the following functional groups and/or salts thereof: a carboxyl group, a hydroxyl group, an amine, a carboxylate, a carboguanamine or a repeating acid group. Preferred are carboxyl or hydroxyl groups. Preferred salts are alkali metal carboxylates, alkaline earth metal carboxylates, zinc carboxylates and ammonium carboxylates, and alkali metal sulfonates, alkaline earth metal sulfonates, zinc sulfonates and sulfonates. Ammonium acid. In a particularly preferred embodiment of the invention, the vinyl aromatic monomer is stupid and the di- and di-diene is a stilbene or a trans-group. The rubber of the present invention is preferably produced by copolymerization of a diene and a vinyl aromatic eutectic in solution and subsequent introduction of a functional group. The present invention also provides a process for producing the rubber of the present invention, according to which a diene and a vinyl aromatic monomer are copolymerized in a solution to produce a rubber, and then a functional group or a salt thereof is introduced into the diene rubber and then From 5 Torr to a temperature of 200 ° C, the solvent is removed using hot water and/or steam as appropriate in a vacuum. The rubber of the present invention used in the rubber mixture of the present invention is preferably produced by anionic solution polymerization or by polymerization using a coordination catalyst. In this connection, the coordination catalyst is the 戚格勒_纳他catamer or single metal catalyst system. The preferred coordination catalyst is such that Ni, Co, Ti, Nd, V, Cr or Fe is dominant. The initiator used in the anionic solution polymerization is such that the alkali metal is predominantly or alkaline earth metal, such as n-butyllithium. It is also possible to use rand〇miser and control agents known for the microstructure of polymers, such as tertiary-potassium pentoxide and tertiary-butoxyethoxyethane. This type of solution polymerization is known and is exemplified by I. Franta Elastomers and
Rubber Compounding Materials 中；Elsevier 1989，第 113-131 頁中，於 Houben-Weyl，Methoden der Organischen Chemie [Methods of Organic Chemistry]，Thieme Verlag， Stuttgart，196卜第 XIV/1 冊第 645 至 673 頁，或於第 E 20 冊（1987)，第114至134頁和第134至153頁中，以及於 201011048Rubber Compounding Materials; Elsevier 1989, pp. 113-131, in Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Thieme Verlag, Stuttgart, 196, Division XIV/1, pages 645 to 673, or In Volume E 20 (1987), pages 114 to 134 and pages 134 to 153, and on 201011048
Comprehensive Polymer Science，第 4 冊，第 Π 部(pergamon 出版有限公司，牛津1989)，第53-108頁中。 此處所使用之溶劑較佳地包含惰性非質子溶劑，例如石 蠟烴類’諸如異構戊烷類、己烷類、庚烷類、辛烷類、癸 烧類、環戊烧、環己烧、甲基環己烧、乙基環己烧或1，4_ 二甲基環己烷、或芳族烴類，諸如苯、甲苯、乙基苯、二 曱苯、二乙苯或丙苯。該等溶劑可個別使用或組合使用。 較佳者為環己烧和正己烧。同樣地可能與極性溶劑摻合。 在本發明方法中溶劑之量通常從1000至100克，較佳® 地從700至200克，以1〇〇克的所使用之單體的全部量為 基準。然而’也可能在沒有溶劑存在下聚合所使用之單體。 聚合溫度可廣泛改變，和通常範圍在從〇〇C至2〇〇〇C， 較佳地從40°C至130。(：。反應時間同樣地廣泛地改變，從 幾分鐘到幾個小時。聚合反應通常進行從約3〇分鐘至多8 小時’較佳地從1至4小時之期間。其可在大氣壓或加壓(從 1至10巴）下進行。 在本文中官能基係根據先前技藝以單一-或多步驟反❹ 應經由適當官能化試劑對橡膠之雙鍵的加成反應，或經由 烯丙氫原子之摘取(abstraction)及後來與官能化試劑之反應 而引入。 有各種將羧基引入橡膠的方式。舉例來說，將羧基-予 體化合物(諸如C〇2)加至金屬化橡膠，或使用從先技藝得知 的過渡金屬-催化之氫羧基化方法，或用包含羧基之化合物 (例如包含羧基之硫醇類)處理該橡膠。 8 201011048 羧基含量可藉由已知方法測定，例如游離酸之滴定、 光譜法或元素分析。 較佳的是該羧基係在所使用之單體的聚合作用已經在 溶液中完成之後，經由所得聚合物，如果適當在自由基引 發劑存在下，與下式之羧基硫醇類的反應併入橡膠中 HS - W-COOX 或(HS - RLCOOhX， 其中 R1為直鏈、支鏈或環狀C卜C36-伸烷基或-伸烯基，如果適 當，其可具有經至多3個另外的羧基之取代，或可具有 被氮原子、氧原子或硫原子之中斷，或為芳基，和 X為氫或金屬離子，例如Li、Na、K、Mg、Zn、Ca或銨離 子’如果適當經C1-C36-烷基、-烯基、環烷基或芳基取 代。 較佳羧基硫醇類為硫代乙醇酸、2-巯基丙酸（硫代乳 酸）、3-魏基丙酸、4-疏基丁酸、疏基己酸、酼基辛酸、魏 基癸酸、毓基十一酸、酼基十二酸、巯基十八酸、2_酼基 號泊酸’以及它們之驗金屬的鹽類、驗土金屬的鹽類、鋅 的鹽類或銨的鹽類。特佳者為2-和3-巯基丙酸、疏基丁酸 和2_巯基琥珀酸，以及它們之鋰鹽類、鈉鹽類、鉀鹽類、 鎂鹽類、約鹽類、鋅鹽類或銨鹽類。非常特佳者為3_皴基 丙酸，以及它們之鋰鹽類、鈉鹽類、鉀鹽類、鎂鹽類、鈣 鹽類、辞鹽類或銨鹽類、乙基銨鹽類、二乙基銨鹽類、三 乙基銨鹽類、硬脂基錢鹽類和環己基錢鹽類。 羧基硫醇類與橡膠之反應通常係在溶劑(例如烴類，諸 9 201011048 如戊烷、己烷、環己烷、苯及/或曱苯）中、於從4〇至15〇〇c 之溫度下、在自由基引發劑(例如過氧化物，特別是醯基過 氧化物，諸如過氧化二月桂醯基和過氧化二苯甲醯基在 下和在縮酮過氧化物（諸如1，1_二(三級_ 丁基過氧基)_3,3,5一 二甲基環己烷)存在下、或者偶氮引發劑，諸如偶氮二異丁 腈、苯頻那醇(benzpinacoi)石夕烷基醚、或在光引發劑和可見 光或UV光存在下進行。 欲使用之羧基硫醇類的量視在本發明二烯橡膠中羧基 或其鹽類之所要含量而定。 · 羧酸鹽類也可在羧酸基團引入橡膠之後藉由將其中和 而產生。 ^將羥基基團引入橡膠的方法之例子為環氧化橡膠和然 後使環氧基基團開環，將該橡膠硼氫化，和然後混合鹼性 過氧化氫溶液，或用包含羥基基團之化合物(例如包含羥基 基團之硫醇類)處理橡膠。 較佳的是該羧基基團係在所使用之單體的聚合作用已 經在溶液中完成之後，經由所得聚合物，如果適當在自由〇 基引發劑存在下，與下式之祕石荒醇類的反應引入橡膠中 HS - R2-〇h » 其中 Κ ^直鏈、支鏈或環狀C卜C36-伸烷基或-伸烯基，如果適 當，其可具有經至多3個另外的羥基基團之取代，或可 具有被氮原子、氧原子或硫原子之中斷或可具有芳基取 代基，或為芳基。 201011048 較= 呈基硫醇類為硫代乙醇、2_疏基丙醇、3猶丙 二H醇、6撼己醇、縣辛醇、縣癸醇、· 2 醇、酼基十八醇。特佳者為魏基乙醇、 2-和3-巯基丙醇和巯基丁醇。 經基硫_與橡膠之反應通常是藉由與絲破醇類相 同的方法在溶劑中進行。Comprehensive Polymer Science, Volume 4, Part per (pergamon Publishing Co., Oxford, 1989), pp. 53-108. The solvent used herein preferably comprises an inert aprotic solvent such as a paraffinic hydrocarbon such as isomeric pentanes, hexanes, heptanes, octanes, anthraquinones, cyclopentenes, cyclohexanes, Methylcyclohexane, ethylcyclohexane or 1,4-dimethylcyclohexane, or an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, diphenylbenzene, diethylbenzene or propylbenzene. These solvents may be used singly or in combination. Preferred are cyclohexane and normal calcined. It is likewise possible to blend with polar solvents. The amount of the solvent in the process of the present invention is usually from 1,000 to 100 g, preferably from 700 to 200 g, based on 1 gram of the total amount of the monomers used. However, it is also possible to polymerize the monomers used in the absence of a solvent. The polymerization temperature can vary widely, and typically ranges from 〇〇C to 2〇〇〇C, preferably from 40°C to 130°. (: The reaction time is likewise varied widely, from a few minutes to a few hours. The polymerization is usually carried out from about 3 minutes to more than 8 hours', preferably from 1 to 4 hours. It can be at atmospheric pressure or pressurized. (from 1 to 10 bar). The functional groups herein are based on prior art processes in a single- or multi-step reaction via addition of a suitable functionalizing agent to the double bond of the rubber, or via an allyl hydrogen atom. Extraction and subsequent introduction with a functionalizing agent. There are various ways to introduce a carboxyl group into the rubber. For example, a carboxyl-host compound (such as C〇2) is added to the metallized rubber, or The transition metal-catalyzed hydrocarboxylation process known in the art, or the treatment of the rubber with a compound containing a carboxyl group (for example, a thiol containing a carboxyl group). 8 201011048 The carboxyl group content can be determined by known methods, such as free acid. Titration, spectroscopy or elemental analysis. It is preferred that the carboxyl group is passed through the resulting polymer after the polymerization of the monomer used has been completed in solution, if appropriate in the free radical initiator In the following, the reaction with a carboxy thiol of the following formula is incorporated into the rubber HS-W-COOX or (HS - RLCOOhX, wherein R1 is a linear, branched or cyclic C-C36-alkylene or -alkylene group If appropriate, it may have a substitution of up to 3 additional carboxyl groups, or may be interrupted by a nitrogen atom, an oxygen atom or a sulfur atom, or an aryl group, and X is a hydrogen or a metal ion such as Li, Na, K, Mg, Zn, Ca or ammonium ion 'if appropriate substituted with C1-C36-alkyl, alkenyl, cycloalkyl or aryl. Preferred carboxy thiols are thioglycolic acid, 2-mercaptopropionic acid (thiolactic acid), 3-weisylpropionic acid, 4-mercaptobutyric acid, sulfopyranoic acid, decyloctanoic acid, thioglycolic acid, decylundecanoic acid, decyldodecanoic acid, decyl octadecanoic acid, 2 _酼基号泊酸' and their metal salts, soil-salt metal salts, zinc salts or ammonium salts. Particularly preferred are 2- and 3-mercaptopropionic acid, sulfosyl butyric acid And 2_mercaptosuccinic acid, and their lithium salts, sodium salts, potassium salts, magnesium salts, about salts, zinc salts or ammonium salts. Very particularly preferred is 3_mercaptopropionic acid, And their Salts, sodium salts, potassium salts, magnesium salts, calcium salts, salt or ammonium salts, ethyl ammonium salts, diethyl ammonium salts, triethyl ammonium salts, stearyl groups Money salts and cyclohexyl money salts. The reaction of carboxy thiols with rubber is usually carried out in a solvent (for example, hydrocarbons, 9 201011048 such as pentane, hexane, cyclohexane, benzene and/or toluene). At temperatures from 4 〇 to 15 〇〇c, in free radical initiators (such as peroxides, especially thiol peroxides, such as dilauroyl peroxide and benzoyl peroxide) a ketal peroxide (such as 1,1_bis(tris-butylperoxy)-3,3,5-dimethylcyclohexane) or an azo initiator such as azobisisobutyl Nitrile, benzpinacoi, or in the presence of a photoinitiator and visible or UV light. The amount of the carboxy thiol to be used depends on the desired content of the carboxyl group or its salt in the diene rubber of the present invention. • Carboxylates can also be produced by neutralization after the introduction of the carboxylic acid groups into the rubber. An example of a method of introducing a hydroxyl group into a rubber is an epoxidized rubber and then ring-opening an epoxy group, hydroboring the rubber, and then mixing an alkaline hydrogen peroxide solution, or a compound containing a hydroxyl group The rubber is treated (for example, a thiol containing a hydroxyl group). Preferably, the carboxyl group is after the polymerization of the monomer used has been completed in solution, via the resulting polymer, if appropriate in the presence of a free sulfhydryl initiator, with the following formula The reaction is introduced into the rubber HS-R2-〇h » wherein Κ ^ straight chain, branched or cyclic C 卜 C36-alkylene or —extended alkenyl, if appropriate, may have up to 3 additional hydroxyl groups The group may be substituted or may be interrupted by a nitrogen atom, an oxygen atom or a sulfur atom or may have an aryl substituent or be an aryl group. 201011048 Compared with the = mercaptothiol is thioethanol, 2 - thiopropanol, 3 acetyl propylene glycol, 6 hexanol, octanol, sterol, · 2 alcohol, decyl stearyl alcohol. Particularly preferred are Wei Ke ethanol, 2- and 3-mercaptopropanol and mercaptobutanol. The reaction of the sulfhydryl group with the rubber is usually carried out in a solvent by the same method as the snail alcohol.
竣酸醋基團和胺基基團可從下列通式之錄誠酯類 和巯基胺類對應地引入 HS 一 R3-COOR4、 HS - R3-NR5R6 其中 R ^直鏈、支鏈或環狀（^_C36_伸烷基或_伸烯基如果適 當，其可具有經至多3個另外的羧酸酯或胺基基團之取 代，或可具有被氮原子、氧原子或硫原子之中斷、或為 芳基，和 R4為直鏈、支鏈或環狀C1-C36-烷基或-婦基基團，如果適 當’其可具有被氮原子、氧原子或硫原子之中斷，或為 5苯基基團’其可具有至多5個烷基取代基或芳族取代基， R和R6為氫或直鏈、支鏈或環狀C;i-C36-烷基或-烯基 基團’如果適當，其可具有被氮原子、氧原子或硫原子 之中斷’或為苯基基團，其可具有至多5個烷基取代基 或芳族取代基。 本發明也提供包含本發明二烯橡膠以及從10至5〇〇重 量份的填料（以100重量份之二烯橡膠為基準）之橡膠混合 物。 201011048 工素Γί::本發明橡膠混合物之填料為任何使用於橡膠 填:的已知填料。這些不但包含活性填料而且也包括惰性 可提及之例子為： 矽石，舉例來說其經由從矽酸鹽類之溶液沈 H具有從5至麵米2/克之比表面積_表 嗜佳地從20至400米2/克，和具有從10至働奈 之火广水解而製得。如果適當，财石也可 2 = t 如 A1、Mg、Ca、Ba、Zn、Zr 或 Ti 之氧化物）的混合氧化物之形式；The citric acid vine group and the amine group may be introduced into HS-R3-COOR4, HS-R3-NR5R6 from the group of the following formulas and mercaptoamines, wherein R^ is linear, branched or cyclic ( ^_C36_alkylene or _alkylene may, if appropriate, be substituted with up to 3 additional carboxylate or amine groups, or may be interrupted by a nitrogen, oxygen or sulfur atom, or Is an aryl group, and R4 is a linear, branched or cyclic C1-C36-alkyl or-glycosyl group, if appropriate 'which may have a disruption by a nitrogen atom, an oxygen atom or a sulfur atom, or 5 benzene The group 'which may have up to 5 alkyl substituents or aromatic substituents, R and R6 are hydrogen or straight chain, branched or cyclic C; i-C36-alkyl or -alkenyl group' if Suitably, it may have an interruption by a nitrogen atom, an oxygen atom or a sulfur atom or may be a phenyl group which may have up to 5 alkyl substituents or aromatic substituents. The invention also provides a diene rubber comprising the invention And a rubber mixture of 10 to 5 parts by weight of the filler (based on 100 parts by weight of the diene rubber). 201011048 素素:: The rubber of the present invention The filler of the compound is any known filler used for rubber filling. These include not only the active filler but also inertness. Examples of which may be mentioned are: vermiculite, for example, by sinking H from a solution of a phthalate The specific surface area from 5 to 2 m/g is preferably from 20 to 400 m 2 /g, and is obtained by extensive hydrolysis from 10 to 働. If appropriate, the fossil can also be 2 = t a form of a mixed oxide of an oxide of A1, Mg, Ca, Ba, Zn, Zr or Ti);
你f成矽酸鹽類’諸如矽酸鋁、或鹼土金屬矽酸鹽， ^如石夕㈣或㈣鹽舞，具有從2G i 4 表面積且具有從10至4〇〇夺米之一 4粒7卞兄I 魏鹽類，諸如高嶺土石U他天然 鋁 Φ 乳化鲜、氧化鈣、氧化鎂或氧化 諸如碳酸鎂，或破酸鋅； :氧化"或氫氧化鎮； 法 J 的，奴黑為藉由炭黑（flame-black) 或電孤法製造之碳黑，其=、表法面藉熱f炭黑法、乙炔f法 1表面積為從9至200米2/克， 例如超耐細SAF)、中_、中_低結構(isaf_ls)、 12 201011048 中SAF高模數(ISAF-HM)、中SAF低模數(ISAF-LM)、中 SAF高結構(ISAF-HS)、導電爐(CF)、超導電爐(SCF)、高 磨耗爐(HAF)、高磨耗爐低結構(HAF-LS)、HAF-HS、細爐 高結構(FF-HS)、半補强爐(SRF)、超導電爐(XCF)、快速擠 壓爐（FEF)、快速擠壓爐低結構(FEF-LS)、快速擠壓爐高 結構(FEF-HS)、通用爐(GPF)、GPF-HS、多用途爐(APF)、 SRF-LS、SRF-LM、SRF-HS、SRF-HM 和中粒熱裂(MT)碳 黑、或下列依據ASTM分類之類型：N110、N219、N220、 N231、N234、N242、N294、N326、N327、N330、N332、 N339、N347、N35卜 N356、N358、N375、N472、N539、 N550、N568、N650、N660、N754、N762、N765、N774、 N787和N990碳黑； -橡膠凝膠’特別是該等以聚丁二烯、丁二烯_苯乙烯 共聚物、丁二烯·•丙烯腈共聚物和聚氣平為主者。 較佳使用之填料為細粒矽石及/或碳黑。 所提及之填料可單獨使用或以混合物使用。在一特佳 具體實例中，橡膠包含作為另外的填料組分之一種由淺色 填料(諸如細粒矽石）和碳黑組成的混合物，其中淺色填料對 破黑之混合比係從0.01 : 1至5〇 : 1，且較佳從〇 〇5 :丄至 20 : 1。此較佳地也表示從〇 〇5至2〇，較佳地從〇丨至15。 在本文中填料所使用之量範圍在從1〇至5〇〇重量份之 填料，以100重量份的橡膠為基準。較佳者為使用從2〇至 200重量份。 本發明之橡膠混合物可不只包含所提及之官能化二烯 13 201011048 橡膠且也包含其他橡膠’諸如天然橡膠，或者其他合成橡 膠。這些之量通常在從0.5至85重量％，較佳地從10至70 重量％之範圍’以在橡膠混合物中橡膠之全部量為基準。額 外加入橡膠之量視本發明橡膠混合物之個別所要用途而 定。 額外橡膠之例子為天然橡膝以及合成橡膠。 從文獻得知的合成橡膠係以例子列於本文中。它們尤. 其包含 BR -聚丁二婦 { ABR- 丁一婦-Cw烧基丙烯酸g旨共聚物 CR -聚氣平 IR -聚異戊二烯 SBR -具有從1至60重量％，較佳地從2〇至5〇重量〇/〇的 苯乙烯含量之苯乙烯丁二烯共聚物， IIR-異丁烯-異戊二烯共聚物 NBR-具有從5至60重量％，較佳地從1〇至4〇重量％ 的丙稀腈含量之丁二稀-丙埽腈共聚物 1 HNBR-部份地氫化或完全氫化NBR橡膠 EPDM-乙烯-丙烯-二烯三聚物 以及這些橡耀·之混合物。用於製造機動車輛輪胎的興趣材 料更特別為天然橡膠、乳液SBR以及溶液SBR，其具有 _5〇°C以上之玻璃轉移溫度、具高順式含量(> 90%)之聚丁 稀橡勝、使用以Ni、Co、Ti威抑為主之備化劑製迭以 及具有至多80%的乙烯基含量之聚丁二烯橡膠，以及=此 201011048 之混合物。 當然，本發明之橡膠混合物也可包含其他橡膠助劑， 舉例來說其改良橡膠混合物之加工性質，或用於橡膠混a 物的交聯（交咖）、或為了其特定所要用途改良從本發明^ 膠混合物製造之硫化橡膠的化學及/或物理性質、或改 膠和填料之間的相互作用、或用於將橡膠偶合至填料。'^ 橡膠助劑之例子為交聯劑，例如硫或硫-予體化合物、 反應加速劑、抗氧化劑、熱安㈣、光安定劑、抗臭^劑、 加：助劑塑化劑、膠黏劑、發泡劑、染料、顏料、蟻、 增量劑、有機酸、魏、阻滯劑、金屬氧化物、以及 劑。 乂致於本發明之橡膠混合物也包含填料、油及/或另外 的助劑，這些舉例來說可經由在適當混合裝置（諸如捏合 機、報機或擠製機）中或上掺合製得。 ^發明之橡膠混合物較佳地係藉由首先在溶液中聚合 所述單體’將官能基引入具有高乙烯基芳族含量之二烯^ 膠’且在聚合方法完成和官能基引人之後，在適當溶劑中 混合本發明之二埽橡膠與抗氧化劑，且如果適當，於適當 量之加工處理油、填料、另外的橡膠和另外的橡膠助劑， 及’在混合步驟期間或之後，於從50至200°C之溫度下， 如果適當在真空中，藉由使用熱水及/或蒸汽除去該溶劑而 製得。 在本發明之另一具體實例中’官能化方法之後，加入 填料及/或加工處理油，且如果適當，另外的橡膠和橡膠助 15 201011048 劑。較佳使用之加工處理油為DAE(蒸餾芳族萃取物， Distillate Aromatic Extract)油、TDAE(經處理之蒸餾芳族萃 取物）油、MES(輕萃取溶劍合物，Mild Extraction Solvate) 油、RAE(殘餘芳族萃取物，Residual Aromatic Extract)油、 TRAE(經處理之殘餘芳族萃取物）油、環烷油、和重環烷油。 在本發明方法之另一具體實例中，二烯類和乙烯基芳 族單體係在溶液中共聚合而產生橡膠，和然後將官能基或-其鹽類引入二烯橡膠中，及然後該包含溶劑之橡膠與加工 處理油混合，且，在混合步雜期間或之後’該溶劑在此藉錄 由於從50至200°C之溫度下，如果適當在真空中，使用熱 水及/或蒸汽除去。在本發明之另一具體實例中，官能化方 法之後’加入填料及/或加工處理油’且如果適當，另外的 橡膠和橡膠助劑。 在本發明之另一具體實例中，該填料係與工處理油一 起在引入官能基之後加入。 本發明也提供本發明橡膠混合物用於製造硫化橡膠之 用途’該硫化橡膠轉而用以製造高強化橡膠模造物，特別❹ 是用於製造輪胎。 下述實例作為本發明之說明，但沒有產生任何限制效果。 【實施方式】 實例 實例1 :具有高苯乙烯含量之苯乙烯-丁二烯橡膠的合成（比 較例） 201011048 將8.5 a斤的己燒、93G克的1，3_丁二稀、，克的苯乙 婦、1〇.3毫莫耳的三級-丁氧基乙氧基乙燒、1.1毫莫耳的三 級戊醇鉀以及u亳莫耳的丁基鐘進料至惰性化2〇升反應 器中和將内谷物加熱至7『c。然後將混合物在7〇〇c下聚 合1小時，並授拌。然後將橡膠溶液卸料且經由加入3克的 响臟⑧⑽(來自Ciba AG之认雙(辛硫基曱基)·6甲基 紛)穩定’及藉相蒸汽汽提除去關。將碎粒橡膠在真空 中於65°C下乾燥。 乙烯基含1(用IR光譜法）：22重量％ •，苯乙烯含量（用 IR光4法）.38重量％，玻璃轉移溫度(DSC) : _34〇c ;數量 平均莫耳質量Mn (GPC ’ PS標準物）：212 _克/莫耳； Mw/Mn ： 1.60 實例2 ·具有高笨乙稀含量之官能化苯乙稀·丁二稀橡勝的 合成(在本發明中） 將8·5公斤的已烷、930克的l，3-丁二烯、570克的苯 乙烯、10.3毫莫耳的三級_丁氧基乙氧基乙烷、丨丨毫莫耳 的二級-戍醇鉀以及16 5毫莫耳的丁基鋰進料至惰性化2〇 升反應器中’和將内容物加熱至7〇〇c：。然後將混合物在 7〇°C下聚合1小時’並授拌。然後加人1() 6克的3_疏基丙 酸，且將反應器内容物加熱至1〇5〇c，和然後加入丨46毫 升之二（三級-丁基過氧基)_3,3,5_三甲基環己烷(5〇%濃 度溶液）。將混合物加熱至1〇5£3(：經2小時。然後將橡膠溶 液卸料且經由加入3克的.Irganox® 1520穩定，及藉由用蒸 汽π提除去溶劑。將碎粒橡膠在真空中於65。<：下乾燥。 17 201011048 乙烯基含量（用IR光譜法）：22.5重量％;苯乙烯含量（用 IR光譜法）：37.5重量％，玻璃轉移溫度(DSC) : -32.5〇C ; 數量平均莫耳質量Mn (GPC，PS標準物）：217 000克/莫耳； Mw/Mn : 1.76 ; COOH官能化度（用曱醇KOH溶液滴定）： 48毫當量/公斤 實例3:具有相對較低苯乙烯含量之官能化苯乙烯_丁二稀_ 橡膠的合成（比較例） 將8·5公斤的己烷、1122克的1，3-丁二烯、399克的苯 乙烯、26.3毫莫耳的三級_丁氧基乙氧基乙烷、0.8毫莫耳❹ 的三級-戊醇鉀以及16.1毫莫耳的丁基鋰進料至惰性化2〇 升反應器中’和將内容物加熱至70〇C。然後將混合物在 70°C下聚合1小時’並攪拌。然後加入1〇 6克的3_毓基丙 酸，且將反應器内容物加熱至l〇5°C，和然後加入2.74毫 升之1，1-二（三級-丁基過氧基)_3,3,5_三曱基環己烷(5〇%濃 度溶液）。將混合物加熱至1〇5cC經2小時。然後將橡膠溶 液卸料且經由加入3克的Irganox®152〇穩定，及藉由用蒸 提除去溶劑。將碎粒橡膠在真空中於65〇c下乾燥。❹ 乙烯基含量（用1R光譜法）：38重量％;苯乙烯含量（用 IR光譜法）：24重量。/。，玻璃轉移溫度(DSC) : ;數量 平均莫耳質量Mn(GPC，PS標準物）：239000克/莫耳； Mw/Mn : 1.62 ; COOH官能化度（用曱醇KOH溶液滴定）： 55毫當量/公斤 實例4a-c :橡膠混合物 製造橡膠混合物’其包含來自實例1的具有高苯乙烯 201011048 含量之苯乙烯-丁二烯橡膠(橡膠混合物4a)、來自實例2的 本發明具有高苯乙烯含量之官能化苯乙烯-丁二烯橡膠（橡 膠混合物4b)以及來自實例3的具有相對較低苯乙烯含量之 官能化苯乙烯-丁二烯橡膠(橡膠混合物4c)。表1列出混合 物之組分。混合物（沒有硫和加速劑)係在1.5升捏合機中製 造。然後下列混合物之組分係在40°C下使用輥機混合：硫 和加速劑。You f are citrates such as aluminum citrate or alkaline earth metal citrate, ^such as Shi Xi (four) or (iv) salt dance, having a surface area from 2G i 4 and having one from 10 to 4 〇〇 4 grains 7卞兄 I Wei salt, such as kaolinite U he natural aluminum Φ emulsified fresh, calcium oxide, magnesium oxide or oxidation such as magnesium carbonate, or zinc sulphate;: oxidation " or oxidized town; method J, slave black For carbon black produced by flame-black or electric orphan method, the surface area of the surface is from 9 to 200 m 2 /g, such as super resistance. Fine SAF), medium _, medium_low structure (isaf_ls), 12 201011048, SAF high modulus (ISAF-HM), medium SAF low modulus (ISAF-LM), medium SAF high structure (ISAF-HS), conductive Furnace (CF), superconducting furnace (SCF), high wear furnace (HAF), high wear furnace low structure (HAF-LS), HAF-HS, fine furnace high structure (FF-HS), semi-reinforcing furnace (SRF ), superconducting furnace (XCF), rapid extrusion furnace (FEF), rapid extrusion furnace low structure (FEF-LS), rapid extrusion furnace high structure (FEF-HS), general purpose furnace (GPF), GPF-HS Multi-purpose furnace (APF), SRF-LS, SRF-LM, SRF-HS, SRF-HM and medium thermal cracking (MT) Black, or the following types according to ASTM classification: N110, N219, N220, N231, N234, N242, N294, N326, N327, N330, N332, N339, N347, N35, N356, N358, N375, N472, N539, N550, N568, N650, N660, N754, N762, N765, N774, N787 and N990 carbon blacks; - rubber gels - especially these are polybutadiene, butadiene styrene copolymers, butadiene propylene Nitrile copolymers and gas gathering are the main ones. Preferred fillers are fine-grained vermiculite and/or carbon black. The fillers mentioned may be used singly or as a mixture. In a particularly preferred embodiment, the rubber comprises, as an additional filler component, a mixture of light colored fillers (such as fine vermiculite) and carbon black, wherein the mixing ratio of the light colored filler to black is from 0.01: 1 to 5〇: 1, and preferably from 〇〇5:丄 to 20:1. This preferably also means from 〇 5 to 2 〇, preferably from 〇丨 to 15. The filler is used herein in an amount ranging from 1 Torr to 5 Torr by weight based on 100 parts by weight of the rubber. It is preferably used from 2 Å to 200 parts by weight. The rubber mixture of the present invention may contain not only the functionalized diene 13 201011048 rubber mentioned but also other rubbers such as natural rubber or other synthetic rubber. These amounts are usually in the range of from 0.5 to 85% by weight, preferably from 10 to 70% by weight, based on the total amount of the rubber in the rubber mixture. The amount of additional rubber added depends on the individual intended use of the rubber mixture of the present invention. Examples of additional rubber are natural rubber knees and synthetic rubber. Synthetic rubbers known from the literature are listed herein by way of example. They include BR-polybutanin { ABR-Ding Yi - Cw-based acrylic acid g-copolymer CR - polygas flat IR - polyisoprene SBR - having from 1 to 60% by weight, preferably A styrene butadiene copolymer having a styrene content of from 2 Torr to 5 Å by weight, and an IIR-isobutylene-isoprene copolymer NBR- having from 5 to 60% by weight, preferably from 1 Torr To 4% by weight of acrylonitrile content of butadiene-acrylonitrile copolymer 1 HNBR - partially hydrogenated or fully hydrogenated NBR rubber EPDM-ethylene-propylene-diene terpolymer and mixtures of these rubber . The materials of interest for the manufacture of motor vehicle tires are more particularly natural rubber, emulsion SBR and solution SBR, which have a glass transition temperature of _5 〇 ° C or higher, a high cis content (> 90%) of polybutyl rubber Win, use Ni, Co, Ti-based preparation of the preparation agent and polybutadiene rubber with a vinyl content of up to 80%, and = this 201011048 mixture. Of course, the rubber mixture of the present invention may also contain other rubber auxiliaries, for example, to improve the processing properties of the rubber mixture, or to crosslink the rubber mixture, or to improve the specific use thereof. Invention ^ Chemical and/or physical properties of a vulcanized rubber produced by a gum mixture, or interaction between a rubber and a filler, or for coupling a rubber to a filler. '^ Examples of rubber additives are cross-linking agents, such as sulfur or sulfur-excipient compounds, reaction accelerators, antioxidants, heat (four), light stabilizers, anti-odor agents, additives: plasticizers, glues Adhesives, foaming agents, dyes, pigments, ants, extenders, organic acids, Wei, retarders, metal oxides, and agents. The rubber mixture of the present invention also contains fillers, oils and/or additional auxiliaries which can be prepared, for example, by blending in or on a suitable mixing device such as a kneader, a press or an extruder. . The inventive rubber mixture is preferably obtained by first polymerizing the monomer in a solution to introduce a functional group into a diene having a high vinyl aromatic content and after the polymerization process is completed and the functional group is introduced. Mixing the bismuth rubber of the present invention with an antioxidant in a suitable solvent, and if appropriate, processing the oil, filler, additional rubber and additional rubber auxiliaries in an appropriate amount, and 'during or after the mixing step, At a temperature of 50 to 200 ° C, if appropriate, in a vacuum, the solvent is removed by using hot water and/or steam. In another embodiment of the invention, after the 'functionalization process', a filler and/or processing oil is added, and if appropriate, additional rubber and rubber aids. The processing oils preferably used are DAE (Distillate Aromatic Extract) oil, TDAE (treated distilled aromatic extract) oil, MES (Mild Extraction Solvate) oil, RAE (Residual Aromatic Extract) oil, TRAE (treated residual aromatic extract) oil, naphthenic oil, and heavy naphthenic oil. In another embodiment of the process of the invention, the diene and vinyl aromatic mono system are copolymerized in solution to produce a rubber, and then the functional group or its salts are introduced into the diene rubber, and then the inclusion The solvent rubber is mixed with the processing oil, and during or after the mixing step, the solvent is hereby borrowed due to the temperature from 50 to 200 ° C, if appropriate in a vacuum, using hot water and/or steam to remove . In another embodiment of the invention, the functionalization process is followed by 'addition of filler and/or processing oil' and, if appropriate, additional rubber and rubber auxiliaries. In another embodiment of the invention, the filler is added with the process oil after introduction of the functional group. The present invention also provides the use of the rubber mixture of the present invention for the manufacture of vulcanized rubber. The vulcanized rubber is used in turn to produce highly reinforced rubber moldings, particularly for the manufacture of tires. The following examples are illustrative of the invention, but do not produce any limiting effect. [Examples] Example 1: Synthesis of styrene-butadiene rubber having a high styrene content (Comparative Example) 201011048 8.5 a kg of hexane, 93 g gram of 1,3-butadiene, gram of Benzene, 1 〇.3 mmol of tertiary-butoxy ethoxyethane, 1.1 mmol of potassium tertiary pentoxide, and 亳 亳 butyl butyl feed to inertization 2〇 In the riser reactor and heat the inner grain to 7 "c. The mixture was then polymerized at 7 ° C for 1 hour and mixed. The rubber solution was then discharged and stabilized by the addition of 3 grams of smear 8 (10) (from Ciba AG's bis (octylthio fluorenyl) · 6 methyl sulphate) and by phase steam stripping. The granulated rubber was dried in a vacuum at 65 °C. Vinyl contains 1 (by IR spectroscopy): 22% by weight •, styrene content (by IR light 4 method). 38% by weight, glass transition temperature (DSC): _34〇c; number average molar mass Mn (GPC) 'PS standard': 212 gram/mole; Mw/Mn: 1.60 Example 2 · Synthesis of functionalized styrene-butadiene rubber with high stupid ethylene content (in the present invention) 5 kg of hexane, 930 g of l,3-butadiene, 570 g of styrene, 10.3 mmol of tertiary _butoxyethoxyethane, 丨丨mole secondary 戍Potassium alkoxide and 16 5 millimoles of butyl lithium were fed into the inert 2 liter reactor and the contents were heated to 7 〇〇 c:. The mixture was then polymerized at 7 ° C for 1 hour' and stirred. Then add 1 () 6 g of 3 - thiopropionic acid, and heat the reactor contents to 1 〇 5 〇 c, and then add 丨 46 ml of bis (tertiary-butylperoxy) _3, 3,5-trimethylcyclohexane (5% concentration solution). The mixture was heated to 1 〇 5£3 (: over 2 hours. The rubber solution was then discharged and stabilized by the addition of 3 grams of .Irganox® 1520, and the solvent was removed by steam π. The granulated rubber was in a vacuum Drying at 65. <: 17 201011048 Vinyl content (by IR spectroscopy): 22.5 wt%; styrene content (by IR spectroscopy): 37.5 wt%, glass transition temperature (DSC): -32.5 〇C Quantity average molar mass Mn (GPC, PS standard): 217 000 g/mole; Mw/Mn: 1.76; COOH functionalization (titration with decyl KOH solution): 48 meq/kg Example 3: with Synthesis of functionalized styrene-butadiene rubber with relatively low styrene content (comparative example) 8. 5 kg of hexane, 1122 g of 1,3-butadiene, 399 g of styrene, 26.3 Millograms of tertiary _butoxyethoxyethane, 0.8 millimoles of potassium tertiary pentoxide, and 16.1 millimoles of butyllithium are fed to the inerting 2 liter reactor' and The contents were heated to 70 ° C. The mixture was then polymerized at 70 ° C for 1 hour' and stirred. Then 1 〇 6 g of 3 - mercaptopropionic acid was added. The reactor contents were heated to 10 ° C, and then 2.74 ml of 1,1-di(tertiary-butylperoxy)_3,3,5-tridecylcyclohexane (5 〇%) was added. Concentration solution). The mixture was heated to 1 〇 5 cC for 2 hours. The rubber solution was then discharged and stabilized by the addition of 3 g of Irganox® 152 ,, and the solvent was removed by evaporation. The granulated rubber was vacuumed. Drying at 65 ° C. 乙烯基 Vinyl content (by 1R spectroscopy): 38% by weight; styrene content (by IR spectroscopy): 24% by weight, glass transition temperature (DSC): ; number average molar mass Mn (GPC, PS standard): 239000 g/mole; Mw/Mn: 1.62; COOH functionalization (titration with decyl KOH solution): 55 meq/kg Example 4a-c: Rubber mixture to make rubber mixture' It comprises a styrene-butadiene rubber (rubber mixture 4a) having a high styrene 201011048 content from Example 1, a functionalized styrene-butadiene rubber (rubber mixture) of the invention having a high styrene content from Example 2. 4b) and functionalized styrene-butyl from Example 3 having a relatively low styrene content Ethylene rubber (rubber mixture 4c). The components of the mixture are listed in Table 1. The mixture (without sulfur and accelerator) was made in a 1.5 liter kneader. The components of the following mixture were then mixed at 40 ° C using a roller machine. : Sulfur and accelerators.
19 201011048 (拿啉制丨龄綠傘¥侧00Ϊ#:鳍碱W'K:<-Iqd =)令屑》龚^躂： 比較例4c cz> 〇 〇 卜 CO CO CO m CO i—H CVJ <>a CM CM (M 卜 Cvj (>i CO 1-H CO 1—H O 丨本發明之實例4b <Ξ5 CD § 卜 CO CO CO in CO CNI (M CM ca CM 卜 <NI cvi CO r*H cn T-H oa o 比較例4a 1_ Ο Ο 〇 s 卜 CO CO CO ΙΛ CO I-i CvJ <NI CM CSI 卜 03 03 CO r-H CO 〇 具有高苯乙烯含量之苯乙烯-丁二烯橡膠，來自實例1 具有高苯乙烯含量之官能化苯乙烯-丁二烯橡膠，來自實例2 具有相對較低苯乙烯含量之官能化苯乙烯-丁二烯橡膠，來自實例3 具有高順式含量的聚丁二稀（來自Lanxess Deutschland GmbH之BUNATli CB 24) 石夕石（Ultrasil® 7000) 碳黑（Vulcan® J/N 375) TDAE 油（Vivatec 500) 辞皂（Aktiplast GT) /—N CD CD 1—H oo σ> oo r—i u 〇 c o c*a 镏 a)〇x «2 抗氧化劑（來自 Lanxess Deutschland GmbH 之 Vulkanox® 4020/LG) 抗氧化劑（來自 Lanxess Deutschland GmbH 之 Vulkanox® HS/LG) 氧化鋅（Rotsiegel辞白） *|.(Anti lux 654) 石夕烷（來自 Evonik Degussa AG 之 Si 69®) 二苯基脈（來自 Lanxess Deutschland GmbH 之 Vulkacit® D/C) 次確醯胺（來自 Lanxess Deutschland GmbH 之 Vulkacit® NZ/EGC) 硫（Chancel 90/95 磨碎硫） 續醯胺（Vulkalent® E/C) 201011048 ±l、w-atnp货 w^。«令0〇〇^焯卜：}。091蛘荽Φ^Μ 3-与¥駟-&-1—|<檠鉍趄龄蜂^饽：o-a S苳駟 ❿ 比較例5c 在硫化橡膠中之苯乙烯-丁二烯橡膠： X 硫化橡膠性質： CO LO oo ίη r—H CO r*H 0. 305 〇 I Η d 445 CO C=5 (NJ 1 4 OO 本發明之實例5b X ο CO oo LO 0.155 0. 533 0. 096 1___ _____ __ . 〇〇 <ΝΙ LO OO oo 卜 比較例5a Χί oo οα 05 0.202 0.306 0.128 CO oo m 寸 C3 C<I σ5 0¾ 具有高苯乙烯含量之苯乙烯-丁二烯橡膠，來自實例1 OJ 势 装 Ί 卜 1 裝 Ο {on φ| 伞 〇 W: 具有相對較低苯乙烯含量之官能化苯乙烯-丁二烯橡膠，來自實例3 於23°C之回彈性[%] 於60°C之回彈性[°/〇] tan <5最大值（MTS振幅掃猫，在1Hz、60X下） 於0°C之tan (5 (動態阻尼，在10Hz下） 於60°C之tan (5(動態阻尼，在10Hz下） 斷裂伸長度（S2試樣）[%] 斷裂伸長度（S2試樣）[MPa] 磨耗（DIN 53516)[毫米 3] 201011048 輪胎應用需要低滾動阻力，如果在硫化橡膠中測得之 於60 C之回彈性的值為高的和於高溫度（6〇(>c)下在動態 阻尼方面之tan<5為低的和在振幅掃瞄方面之tan 5最大 值為低的’則獲得低滚動阻力。從表2可知，本發明之實 例5b的硫化橡膠特徵為於6(rc之高回彈性，於6〇乂之動 態阻尼的低值和在振幅掃晦方面之低_ 5最大值… 要高抗濕雜，如果硫化橡膠具有於低· 脱度（0 c)下在動態阻尼方面之高tand值則獲得退 滑性。從表2可知，本發明之實例％ =二 〇。。之動態阻尼的高仏以值。 l化橡膠特徵為於❽ 輪胎應用此外需要高耐磨性。從表2可知 5b的硫化橡膠特徵為低DIN磨耗。 發月之實例 【圖式簡單說明】 無 【主要元件符號說明】 無 2219 201011048 (The 啉 绿 绿 绿 绿 ¥ 侧 Ϊ Ϊ : : : : : : : : : : : : : : : : : : : : : : : : : : : : 》 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较CVJ <> a CM CM (M 卜 Cvj (> i CO 1-H CO 1 - HO 实例 Example 4b of the present invention < Ξ 5 CD § 卜 CO CO CO in CO CNI (M CM ca CM 卜 < NI cvi CO r*H cn TH oa o Comparative Example 4a 1_ Ο 〇 〇s BU CO CO CO ΙΛ CO Ii CvJ <NI CM CSI 卜 03 03 CO rH CO 苯乙烯 Styrene-butadiene with high styrene content Rubber, from Example 1 a functionalized styrene-butadiene rubber having a high styrene content, from Example 2, a functionalized styrene-butadiene rubber having a relatively low styrene content, from Example 3 having a high cis content Polybutylene (from BUNATli CB 24 from Lanxess Deutschland GmbH) Shirshi (Ultrasil® 7000) Carbon black (Vulcan® J/N 375) TDAE oil (Vivatec 500) Soap (Aktiplast GT) /—N CD CD 1—H oo σ> oo r—iu 〇coc*a 镏a)〇x «2 Antioxidant (Vulkanox® 4020/LG from Lanxess Deutschland GmbH) Antioxidant (from Lanxess Deu Vulkanox® HS/LG from tschland GmbH Zinc Oxide (Rotsiegel Remarks) *|. (Anti lux 654) Oxalane (Si 69® from Evonik Degussa AG) Diphenyl veins (Vulkacit® D from Lanxess Deutschland GmbH /C) Sub-decalamine (Vulkacit® NZ/EGC from Lanxess Deutschland GmbH) Sulfur (Chancel 90/95 ground sulfur) Continued guanamine (Vulkalent® E/C) 201011048 ±l, w-atnp goods w^. «令0〇〇^焯卜:}.091蛘荽Φ^Μ 3- and ¥驷-&-1—|<檠铋趄岁蜂^饽:oa S苳驷❿ Comparative Example 5c in vulcanized rubber Styrene-butadiene rubber: X vulcanized rubber Properties: CO LO oo ίη r—H CO r*H 0. 305 〇I Η d 445 CO C=5 (NJ 1 4 OO Example 5b of the invention X ο CO oo LO 0.155 0. 533 0. 096 1___ _____ __ . 〇〇<ΝΙ LO OO oo 卜 Comparative Example 5a Χί oo οα 05 0.202 0.306 0.128 CO oo m inch C3 C<I σ5 03⁄4 Styrene with high styrene content Butadiene rubber, from Example 1 OJ potential decoration 1 1 decoration {on φ| Umbrella W: Functionalized styrene-butadiene rubber with relatively low styrene content, Resilience from Example 3 at 23 ° C [%] Resilience at 60 ° C [° / 〇] tan < 5 maximum (MTS amplitude sweeping cat, at 1 Hz, 60X) at 0 ° C tan ( 5 (dynamic damping at 10 Hz) tan at 60 ° C (5 (dynamic damping at 10 Hz) elongation at break (S2 sample) [%] elongation at break (S2 sample) [MPa] wear (DIN) 53516)[mm3] 201011048 Tire applications require low rolling resistance if the value of resilience measured at 60 C in vulcanized rubber is high and at high temperatures (6 〇 (> c) in terms of dynamic damping Tan<5 is low and the tan 5 maximum in amplitude sweep is low', resulting in low rolling resistance. As can be seen from Table 2, the vulcanized rubber of Example 5b of the present invention is characterized by a high resilience of 6 (rc, a low value of dynamic damping at 6 和 and a low value of _ 5 in amplitude sweeping). Miscellaneous, if the vulcanized rubber has a high tand value in terms of dynamic damping at a low degree of desorption (0 c), the slippery property is obtained. As can be seen from Table 2, the example of the present invention is % 〇. The value of the rubber is characterized by the high wear resistance of the tire application. It can be seen from Table 2 that the vulcanized rubber of 5b is characterized by low DIN wear. Examples of the moon [simple description of the drawings] No [main symbol description] None twenty two