201226054 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種觸媒系統，更特別是關於此觸媒系 統於氫化反應之應用。 【先前技術】 以丁二烯單體為原料所製得之聚合物/共聚物，是用途 最廣泛的合成橡膠，比如汽車輪胎、鞋底、輸送帶、橡膠 帶、戰車及拖引車履帶、運動器材或玩具的主要原料。但 丁二烯聚合物之主鏈所含的不飽和碳-碳雙鍵，降低其耐候 性與熱穩定性並限制其應用。因此過去數十年持續有關於 丁二烯高分子共聚物的選擇性氫化反應的研究，亦即只氫 化主鏈的碳-碳雙鍵而不氫化共聚物中的苯環。氫化飽和後 之丁二烯高分子共聚物具有良好的耐熱性，耐紫外線，及 耐氧化性等優良性能，可廣泛應用在石油、汽車、紡織、 與醫藥等工業。 氫化技術所使用的觸媒可分為異相觸媒與均相觸媒兩 種。早期氫化丁二烯高分子共聚物之觸媒以異相觸媒為 主，主要有Raney鎳，或形成於活性碳與氧化鋁等載體上 之過渡金屬催化劑。異相觸媒的優點是容易分離觸媒與產 德* 物，但其氫化活性低、選擇性差、再現性差且反應條件嚴 苛，常需要高溫高壓和使用大量催化劑，容易造成產物裂 解。由於異相觸媒有上述缺點，因此逐漸被具有高反應性、 高選擇性、與較溫和的反應條件等優點之均相觸媒所取代。 在丁二烯聚合物/共聚物之氫化工業中，最先使用的均 201226054 相觸媒為Ziegler-Natta系統，主要為以Fe、Co或Ni金屬 化合物與烧基金屬化合物活化之觸媒系統，其中又以Co、 Ni系統最為理想。此觸媒系統的活性高，可使丁二烯高分 子共聚物的氫化度達到95%以上，且氫化反應條件較溫 和。然而此系統所殘留在氫化產物中的觸媒會略微影響產 品性能，通常需要以酸液進行脫灰（deash)以去除殘留觸 媒，在成本考量上會是一個負擔。 因此近年來，茂金屬（metallocence)觸媒系統開始成為 • 丁二烯高分子共聚物氫化反應的研究方向。主要典型的代 表為Ti觸媒，此外還有Co、Hf、Ni等觸媒。與傳統之 Ziegler-Natta觸媒相較，茂金屬觸媒的反應活性更高，氫 化反應條件更溫和，觸媒使用量更少，故殘留在氫化產物 之灰份更少，甚至可以不予處理，可以簡化製程與降低成 本。 由於茂金屬觸媒的活性很高，但是觸媒穩定性較差。 因此尋求兼具高活性、高穩定性與高選擇性之茂金屬氫化 ® 觸媒，一直是丁二烯高分子共聚物及相關聚合物之氫化反 應所追求的目標。 【發明内容】 本發明之一實施例提供一種觸媒系統，包括1當量之 金屬錯合物、0.1至20當量之有機鋰化合以及0_1至20當 量之添加劑；其中金屬錯合物之結構如下： 201226054201226054 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalyst system, and more particularly to the application of the catalyst system to a hydrogenation reaction. [Prior Art] The polymer/copolymer prepared from butadiene monomer is the most widely used synthetic rubber, such as automobile tires, soles, conveyor belts, rubber belts, chariots and trailer tracks. The main raw material for sports equipment or toys. However, the unsaturated carbon-carbon double bond contained in the main chain of the butadiene polymer reduces its weatherability and thermal stability and limits its application. Therefore, research on the selective hydrogenation reaction of butadiene polymer copolymers has continued for the past several decades, that is, hydrogenation of only the carbon-carbon double bond of the main chain without hydrogenating the benzene ring in the copolymer. The butadiene polymer copolymer after hydrogenation has excellent heat resistance, ultraviolet resistance, oxidation resistance and the like, and can be widely used in petroleum, automobile, textile, and pharmaceutical industries. The catalyst used in the hydrogenation technique can be classified into a heterogeneous catalyst and a homogeneous catalyst. The catalyst for the early hydrogenated butadiene polymer copolymer is mainly a heterogeneous catalyst, mainly Raney nickel, or a transition metal catalyst formed on a carrier such as activated carbon and alumina. The advantage of the heterogeneous catalyst is that it is easy to separate the catalyst from the germanium, but its hydrogenation activity is low, the selectivity is poor, the reproducibility is poor, and the reaction conditions are severe. It is often required to use high temperature and high pressure and a large amount of catalyst, which is liable to cause product cracking. Since the heterogeneous catalyst has the above disadvantages, it is gradually replaced by a homogeneous catalyst having the advantages of high reactivity, high selectivity, and mild reaction conditions. In the hydrogenation industry of butadiene polymers/copolymers, the first used 201262554 catalyst is the Ziegler-Natta system, which is mainly a catalyst system activated by Fe, Co or Ni metal compounds and alkyl-based compounds. Among them, the Co and Ni systems are the most ideal. The high activity of the catalyst system allows the degree of hydrogenation of the butadiene high molecular copolymer to be above 95%, and the hydrogenation reaction conditions are mild. However, the catalyst remaining in the hydrogenation product of this system slightly affects the performance of the product, and it is usually necessary to deash the acid to remove residual catalyst, which is a burden in cost consideration. Therefore, in recent years, the metallocence catalyst system has begun to become the research direction of hydrogenation reaction of butadiene polymer copolymer. The main representative is Ti catalyst, in addition to catalysts such as Co, Hf, and Ni. Compared with the traditional Ziegler-Natta catalyst, the metallocene catalyst has higher reactivity, milder hydrogenation reaction conditions and less catalyst usage, so the ash content remaining in the hydrogenation product is less, and may even be left untreated. Can simplify the process and reduce costs. Due to the high activity of the metallocene catalyst, the stability of the catalyst is poor. Therefore, the search for a metallocene hydrogenation catalyst having high activity, high stability and high selectivity has been the goal pursued by the hydrogenation reaction of butadiene polymer copolymers and related polymers. SUMMARY OF THE INVENTION One embodiment of the present invention provides a catalyst system comprising 1 equivalent of a metal complex, 0.1 to 20 equivalents of an organolithium compound, and 0 to 20 equivalents of an additive; wherein the structure of the metal complex is as follows: 201226054
2 R2 R
X1/'X2 \ / 3 u. MIX 夕M為過渡金屬’心、1、尺3、1與1^為相同或不同， 係氫、Cy之烷基、Ci_8之烷氧基或兩兩鍵結之環狀結構化 合物’ X〗' X2與X3為環狀結構化合物、氫、氯、漠、产 基或烧氧基’其中當Χ〗、Χ2與&其中之—為環士 = 合物時，其餘兩者為相同或不同，包括氫、氯、漠了^ 或烷氧基。而有機鋰化合物具有化學式UR，R為c几土 ，。其中每一 Ri各自獨立，係H、C】-8炫基、Cl 8 = ^下或兩兩鍵結之環狀結構化合物；其中該添加劑之結構 7\ 其中Rx與Ry為相同或不同，係H 烷氧基、或0：5-(：】5芳香基。 土、C】_8 ::明另一實施例提供一種共軛二 將上述之觸媒系統加入^ 物，奋液巾錢騎歧反應。 ^ 【實施方式】 :發明一實施例提供一 屬錯合物、（U至20杏旦+ ^ 匕祜i田里之金 主α田里之之& 6烷基鋰，以 201226054 當罝之添加劑；在另一實施例中，觸媒系統，包括丨當量 之金屬錯合物、0.1至12當量之Ci_6烷基鋰；以及〇1至 12當量之添加劑。本發明發現含有添加劑的觸媒系統可在 二和的1度與氫氣壓力下進行共輛二烯類聚合物之選擇性 氫化反應，可得更佳的活性與氫化度。X1/'X2 \ / 3 u. MIX E is a transition metal 'heart, 1, 3, 1 and 1 are the same or different, hydrogen, Cy alkyl, Ci_8 alkoxy or two-bond The cyclic structural compound 'X〗' X2 and X3 are cyclic structural compounds, hydrogen, chlorine, molybdenum, base or alkoxy group, wherein when Χ, Χ2 and & The other two are the same or different, including hydrogen, chlorine, indifferent or alkoxy. The organolithium compound has the chemical formula UR, and R is c. Each of the Ri is independent of each other, and is a cyclic structural compound of H, C-8-8, Cl 8 = ^ or two or two bonded; wherein the structure of the additive is 7\ wherein Rx and Ry are the same or different, H alkoxy, or 0:5-(:]5 aromatic. Soil, C]_8: Ming another embodiment provides a conjugated two to add the above-mentioned catalyst system to the substance, Reaction [Compound]: An embodiment of the invention provides a genus complex, (U to 20 apricot + ^ 匕祜i Tianli gold master alpha Tianli & 6 alkyl lithium, to 201226054 when In another embodiment, the catalyst system comprises a ruthenium equivalent metal complex, 0.1 to 12 equivalents of Ci-6 alkyl lithium; and 〇1 to 12 equivalents of an additive. The present invention finds an additive containing an additive The medium system can carry out selective hydrogenation of a total of diene polymers under a hydrogen pressure of 1 degree and a hydrogen pressure to obtain better activity and degree of hydrogenation.
X1 x2 =中，M為過渡金屬，例如鈦、鍅或 同或不同’係氫、k之院基、C"之烧 ，或兩兩鍵結之環狀結構化合物， 二: 狀結構化合物、氫U “ 3為-％ X2與X3盆中之—直m、兀基或烷乳基，其中當X】、 或不同，包括氣氣一、=構化合師其餘兩者為相同 合物具有化學式LiR，R、^基或以基。而"有機經化 上述添加劑之結構如式2;示烷基 kyv 在弋9击 （式2)〜 一或或不同，❹、垸基、 述添加劑之結構如式35所示▲。在本發明—實施例中，上 201226054X1 x2 = medium, M is a transition metal, such as titanium, tantalum or the same or different 'hydrogen, k-based, C" burning, or a two-bonded cyclic structural compound, two: a structural compound, hydrogen U "3 is -% X2 and X3 in the basin - straight m, sulfhydryl or alkane based, where X], or different, including gas, one = the other two are the same compound with the chemical formula LiR , R, ^ base or base. And "organic chemistry" of the above additives structure of the formula 2; shows alkyl kyv in 弋 9 hit (Formula 2) ~ one or different, ruthenium, ruthenium, the structure of the additive ▲ as shown in Equation 35. In the present invention - an embodiment, on 201226054
烧氧基。 上述添加劑化合物’可包括笨乙稀(styrene)、甲基苯乙 婦(methylstyrene)、二甲基苯乙烯(dimethylstyrene)、1,1-二 苯乙稀（1,1-diphenylethylene)、1，1-二甲苯基乙晞 (1,1 -di(tolyl)ethylene) 、 1-乙烯苯基甲氧基苯 (l-(4-methoxyphenyl)-l-phenylethene)、1,1-二甲氧基苯乙烯 (1 -methoxy-4-[(4-methoxyphenyl)vinyl]benzene) 〇 所述觸媒系統可用以催化共軛二烯類聚合物的氫化反 應，比如1,3-丁二烯等共軛二烯之聚合物或共聚物。本發 明的觸媒系統中，包括1當量之金屬錯合物、0.1至20當 量之CN6烷基鋰，以及0.1至20當量之添加劑；在另一實 施例中，觸媒系統，包括1當量之金屬錯合物、0.1至12 當量之Cw烷基鋰；以及0.1至12當量之添加劑。在本發 明另一實施例中，共軛二烯類聚合物為苯乙烯-丁二烯-苯 乙烯(SBS)共聚物。上述觸媒系統具有高選擇性，只會氫化 高分子主鏈或側鏈上的碳碳雙鍵而不會氫化苯環。在氫化 反應中，所使用的氫氣壓力大體一般介於2至50大氣麼’ 在另一實施例中氫氣壓力介於2至20大氣壓之間，氫化反 應溫度大體一般介於40〜200°C ’在另一實施例中氫化反應 201226054 溫度介於40〜120。(^!之間。 與^知的金屬觸媒系統相較，具有式2所示之添加劑 的觸媒系統可在溫和的溫度與氣氣壓力下，具有更佳的活 性與氫化度。 為了讓本發明之上述和其他目的、特徵和優點能更明 顯易憧，下文特舉數實施例配合所附圖式，作詳細說明如 下： φ 【實施例】 製備例：笨乙烯_丁二烯_笨乙烯(SBS)聚合物製備 首先’將反應槽(2公升）喊體置換錢氣。接著 己華〇g)、四氫吱喃（2.如、苯乙稀(24g)與 : 1.6M溶液)置入反應样中， lmL, 液。升-至帅㈣拌速度擾拌溶 f升，皿至45C後，反應液明顯進行苯乙稀聚 為溶液會放熱升溫至約62cC。反 α因 物溶液外觀呈橘紅色。加人^鐘後取樣，聚合 #二烯聚合。待反應！小時後取樣 ）進行第二段的丁 黃色。之後，再加入苯乙烯(24克)進:…，液外觀呈微淺 合。反應過程中，溫度會由54。〇敌熱亍第一 ^又的笨乙烯聚 1小時後取樣，聚合物溶液外觀呈揭紅皿至58 C。待反應 二稀·苯乙稀(棒聚物，如式3所：色在即為苯乙烯-丁 X、及y分別為第一段笨乙烯、以 飞中nm' (vinyl group)、以I,4-雙鍵共軛聚人又鍵聚合之丁二烯 group)及第二段苯乙烯之聚合度（根之丁 一烯（backboneAlkoxy groups. The above additive compound ' may include styrene, methylstyrene, dimethylstyrene, 1,1-diphenylethylene, 1,1 -1,1-di(tolyl)ethylene, 1-(4-methoxyphenyl)-l-phenylethene, 1,1-dimethoxybenzene Ethylene (1-methoxy-4-[(4-methoxyphenyl)vinyl]benzene) 〇 The catalyst system can be used to catalyze the hydrogenation of a conjugated diene-based polymer, such as conjugated 1,3-butadiene a polymer or copolymer of an alkene. The catalyst system of the present invention comprises 1 equivalent of a metal complex, 0.1 to 20 equivalents of CN6 alkyllithium, and 0.1 to 20 equivalents of the additive; in another embodiment, the catalyst system comprises 1 equivalent of a metal complex, 0.1 to 12 equivalents of Cw alkyllithium; and 0.1 to 12 equivalents of an additive. In another embodiment of the invention, the conjugated diene-based polymer is a styrene-butadiene-styrene (SBS) copolymer. The above catalyst system has high selectivity and only hydrogenates carbon-carbon double bonds in the polymer main chain or side chain without hydrogenating the benzene ring. In the hydrogenation reaction, the hydrogen pressure used is generally between 2 and 50 atmospheres. In another embodiment, the hydrogen pressure is between 2 and 20 atmospheres, and the hydrogenation temperature is generally between 40 and 200 °C. In another embodiment, the hydrogenation reaction 201226054 has a temperature between 40 and 120. (^! Between. Compared with the metal catalyst system of the know, the catalyst system with the additive shown in Formula 2 can have better activity and degree of hydrogenation under mild temperature and gas pressure. The above and other objects, features, and advantages of the present invention will become more apparent. The following detailed description of the embodiments of the present invention will be described in detail as follows: φ [Examples] Preparation Example: Stupid Ethylene-Butadiene_Stupid Ethylene (SBS) polymer preparation First, 'replace the reaction tank (2 liters) to replace the money gas. Then hexahydrate 四g), tetrahydrofuran (2. such as styrene (24g) and: 1.6M solution) Place the reaction sample, lmL, liquid.升-到帅(四) Mixing speed disturbing the mixture f liter, after the dish reaches 45C, the reaction liquid is obviously benzene condensed into a solution which will exotherm and heat up to about 62cC. The anti-alpha factor solution is orange-red in appearance. Sampling after adding a person's clock, polymerization #diol polymerization. Waiting for reaction! Sampling after hours) The yellowing of the second stage is performed. After that, styrene (24 g) was added to:..., and the appearance of the liquid was slightly shallow. During the reaction, the temperature will be 54. After the enemy's enthusiasm, the first stupid ethylene was sampled for 1 hour, and the appearance of the polymer solution was revealed to be 58 C. The dilute styrene to be reacted (the condensate, as in the formula 3: the color is styrene-butadiene X, and y is the first stage of stupid ethylene, in the fly of nm' (vinyl group), I, 4-double bond conjugated poly-bonded butadiene group) and second-stage styrene polymerization degree (backbone)
圖譜特徵吸收峰面積積分得n + 產物SBS的1HNMR 9 y===25〜34%，m + x = 201226054 66〜75%)。The spectral characteristic absorption peak area is integrated to obtain n + product SBS of 1H NMR 9 y === 25 to 34%, m + x = 201226054 66 to 75%).
(式 3) SBS的1HNMR圖譜分析顯示，位於化學位移4.93ppm 與4.96ppm左右的吸收|為1，2-碳-碳雙鍵結構（vinyl group)，如式3中聚合度為m之重複單元中的雙鍵。位於 化學位移5.38ppm與5.55ppm左右的吸收峯為3,4-碳-碳雙 鍵結構(backbone group)，如式3中聚合度為X之重複單元 中的雙鍵。 實施例1 於手套箱中，將製備例所得之SBS共聚物溶液（1〇〇克 之15wt%溶液）置於反應釜中，加熱至60。(：後，加入CpTiCl3 觸媒甲苯溶液(0.02mmol/g polymer)，·，並隨即加入丁基鐘與 1，1，一 本乙稀（l，ldiphenylethylene)(l，ldiphenylethylene /Li/Timolarratio=3/3/l ;環己烷溶液接著將反應器内氫 軋壓力增加至l〇atm，溫度仍維持6〇{>c，劇烈攪拌i小時。 上述反應之化學式如式4所示。 201226054(Formula 3) 1H NMR spectrum analysis of SBS showed that the absorption at a chemical shift of 4.93 ppm and 4.96 ppm is a 1,2-carbon-carbon double bond structure, such as a repeating unit having a degree of polymerization of m in Formula 3 Double key in. The absorption peak at a chemical shift of 5.38 ppm and 5.55 ppm is a 3,4-carbon-carbon double bond group, such as a double bond in a repeating unit of formula 3 having a degree of polymerization of X. Example 1 In a glove box, a SBS copolymer solution (1 gram of a 15% by weight solution) obtained in the preparation example was placed in a reaction vessel and heated to 60°C. (: After adding CpTiCl3 catalyst toluene solution (0.02mmol/g polymer), ·, and then add butyl clock and 1,1, a piece of ethylene (l, ldiphenylethylene) (l, ldiphenylethylene /Li/Timolarratio=3 /3/l; The cyclohexane solution was then increased to the hydrogen pressure in the reactor to l〇atm, the temperature was maintained at 6 〇{>c, and vigorously stirred for 1 hour. The chemical formula of the above reaction is shown in Formula 4. 201226054
Ο ό (式4) 待反應結束後降溫洩壓，將系統氣體置換成氮氣。再 將氫化產物以曱醇進行凝聚沉析分離。待真空抽濾溶劑 φ 後，於60°C乾燥至少12小時以上。烘乾產物再以1HNMR(d-氯仿）測定產品氫化度，結果如表一所示。 SBS氫化度的計算，則是根據其hNMR圖譜特徵吸收 峰面積積分計算所得。將SBS氫化產物的1,2-碳-碳雙鍵結 構(vinyl group)與未氫化前SBS聚合物1,2-碳-碳雙鍵結構 (vinyl group)的質子特殊吸收峯面積進行比較，即得表一的 產物側鏈氫化度；計算SBS氫化產物的1,4-碳-碳雙鍵結構 (backbone group)與未氫化前SBS聚合物1,4-碳-碳雙鍵結 φ 構(backbone group)的質子特殊吸收峯面積比，即得表一的 產物主鏈氫化度。再依據未氫化前SBS聚合物1,2-碳-碳雙 鍵結構(vinyl group)與 1,4-碳-碳雙鍵結構(backbone group) 的莫耳比例組成，計算得產物選擇性總氫化度。 實施例2 與實施例1類似，差別在於氫化反應時間自1小時延 長到4小時。其SBS氫化度的計算方式同實施例1。 201226054 比較實施例1 與實施例2類似，差別在於觸媒系統只含有CpTiCl3 觸媒與丁基裡之甲笨溶液（Li/Ti molar ratio = 3)，不含添加 劑U-二苯乙烯。所得SBS氫化度的計算方式同實施例1。 表一 實驗編號 主鏈氫化度(％) Backbone group 側鏈氫化度(%) Vinyl eroup 總氫化度(％) 實施例1 反應1小時 94.6 99.0 95.8_ 實施例2 反應4小時 98.9 992 99,0______ 峨實施例1 反應4小時 38.0 86.5 ------ 由表1可知，在低溫低壓的反應條件下，具有添加劑 i，i-二苯乙烯之觸媒系統可更有效的選擇性曼化SBS。此即 表示，本發明觸媒系統相對於習知觸媒系統在進行含雙鍵 聚合物例如SBS的選擇性氫化反應時具有更佳的選擇氫化 效果。 雖然本發明已經以數個較佳實施例揭露如上，然其並 非用以限定本發明’任何熟習此技藝者，在不脫離本發明 之精神和範圍内’當可作任意之更動與潤飾，因此本發明 之保護範圍當視後附之申請專利範圍所界定者為準。Ο ό (Formula 4) After the reaction is completed, the temperature is released and the pressure is released, and the system gas is replaced with nitrogen. The hydrogenated product is then coagulated and separated by decyl alcohol. After vacuum filtration of the solvent φ, it is dried at 60 ° C for at least 12 hours. The product was dried and the degree of hydrogenation of the product was measured by 1H NMR (d-chloroform). The results are shown in Table 1. The calculation of the SBS hydrogenation degree is calculated based on the integral of the absorption peak area of the hNMR spectrum. Comparing the 1,2-carbon-carbon double bond structure of the SBS hydrogenated product with the proton specific absorption peak area of the 1,2-carbon-carbon double bond structure of the unhydrogenated SBS polymer, ie The product side chain hydrogenation degree of Table 1 is calculated; the 1,4-carbon-carbon double bond group of the SBS hydrogenated product is calculated and the 1,4-carbon-carbon double bond φ structure of the unhydrogenated SBS polymer (backbone) The proton-specific absorption peak area ratio of group) is the product main chain hydrogenation degree of Table 1. According to the molar ratio of the 1,2-carbon-carbon double bond structure (vinyl group) of the unhydrogenated SBS polymer to the 1,4-carbon-carbon double bond group, the product is selectively hydrogenated. degree. Example 2 Similar to Example 1, the difference was that the hydrogenation reaction time was extended from 1 hour to 4 hours. The SBS degree of hydrogenation is calculated in the same manner as in Example 1. 201226054 Comparative Example 1 Similar to Example 2, the difference is that the catalyst system contains only a CpTiCl3 catalyst and a butyl solution (Li/Ti molar ratio = 3), and no additive U-stilbene. The calculated degree of hydrogenation of SBS was calculated in the same manner as in Example 1. Table 1 Experimental No. Main Chain Hydrogenation (%) Backbone group Side Chain Hydrogenation (%) Vinyl eroup Total Hydrogenation (%) Example 1 Reaction 1 hour 94.6 99.0 95.8_ Example 2 Reaction 4 hours 98.9 992 99,0______ 峨Example 1 Reaction 4 hours 38.0 86.5 ------ It can be seen from Table 1 that under the low temperature and low pressure reaction conditions, the catalyst system with the additive i, i-stilbene can more selectively electrify the SBS. This means that the catalyst system of the present invention has a better selective hydrogenation effect when subjected to a selective hydrogenation reaction of a double bond polymer such as SBS than a conventional catalyst system. While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified as appropriate without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
C 12 201226054 【圖式簡單說明】 無。 【主要元件符號說明】 無。C 12 201226054 [Simple description of the diagram] None. [Main component symbol description] None.