200407341 玖、發明說明： L明戶斤屬3 本發明係有關一種連續氫化不餘和性聚合物之方法。 I：先前技術3 5 不飽和性聚合物先前係使用多種催化劑及條件氣化。 過去典型氫化催化劑具有低度反應性，要求高催化劑對聚 合物比’特別用於芳香族聚合物之氫化時要求高催化劑對 聚合物比。使用多種金屬以及樓體可達成催化氣化的改 良。VIII族金屬於多孔撐體特別可用於氫化不飽和性聚合 10 物，特別例如U.s. 5,612,422所述之芳香族聚合物。但發現 此等催化劑之哥命相當短，此等.催化劑於接觸可能存在於 聚合物進料流的極性雜質時被去活化。此外，先前氫化方 法典型係以批次方法進行。但批次方法之經濟效率不佳， 難以達成產品之一致性。 15 旭公司之WO 99/64479揭示一種氫化乙烯基芳香族軏 合二烯嵌段共聚物之方法，該方法係使用一種固定床反應 器，反應器内填裝有一種氫化催化劑，包含鉑族金屬沉積 於無機撐體上。但所用催化劑之氫化速率低且需要長期反 應時間。 20 美國專利第6,395,841號說明一種氫化不飽和性聚合物 之連續方法，包含於固定床反應器上不飽和性聚合物接觸 氫化劑，其中該反應器被填裝以一種氫化催化劑，其特徵 在於該氫化催化劑包含一種νπι族金屬成分以及至少一種 抗去活化成分。雖然此種固定床方法之效果極佳，但仍然 6 200407341 需要儘可能延長催化劑壽命至最大可能程度，如此提供一 種使用可對抗去活化之催化劑，以高度氫化速率，連續氫 化不飽和性聚合物之方法。 【潑^明内容】 5 本發明為一種氫化不飽和性聚合物之連續方法之改 良，包含不飽和性聚合物於固定床反應器接觸一種氫化 劑，其中該反應器被填裝以一種氫化催化劑，其特徵在於 該氫化催化劑包含一種VIII族金屬成分以及至少〆種抗去 活化成分，其中改良部分包含利用一種具有平均孔徑至少 10 2000埃之經支載之氫化催化劑。200407341 发明. Description of the invention: L. Minghujin 3 This invention relates to a method for continuously hydrogenating surplus polymers. I: Prior art 3 5 Unsaturated polymers have previously been gasified using a variety of catalysts and conditions. In the past, typical hydrogenation catalysts had low reactivity, requiring a high catalyst-to-polymer ratio ', especially when used for the hydrogenation of aromatic polymers, requiring a high catalyst-to-polymer ratio. The use of multiple metals and buildings can improve catalytic gasification. Group VIII metals are particularly useful in porous supports for hydrogenated unsaturated polymers, such as the aromatic polymers described in U.s. 5,612,422. However, the brothers of these catalysts have been found to be relatively short-lived. These catalysts are deactivated upon contact with polar impurities that may be present in the polymer feed stream. In addition, the previous hydrogenation process is typically carried out as a batch process. However, the batch method is not economically efficient and it is difficult to achieve product consistency. 15 Asahi's WO 99/64479 discloses a method for hydrogenating vinyl aromatic bonded diene block copolymers. The method uses a fixed-bed reactor filled with a hydrogenation catalyst containing a platinum group metal. Deposited on inorganic supports. However, the catalyst used has a low hydrogenation rate and requires a long reaction time. 20 U.S. Patent No. 6,395,841 describes a continuous process for hydrogenating unsaturated polymers, comprising contacting an unsaturated polymer with a hydrogenating agent on a fixed bed reactor, wherein the reactor is packed with a hydrogenation catalyst, which is characterized in that The hydrogenation catalyst includes a metal group νπ and at least one anti-deactivation component. Although the effect of this fixed bed method is excellent, it is still necessary to extend the life of the catalyst to the maximum extent possible. This provides a catalyst that can resist deactivation and continuously hydrogenate unsaturated polymers at a high hydrogenation rate. method. [Explanations] 5 The present invention is an improvement of a continuous process for hydrogenating unsaturated polymers, which comprises contacting an unsaturated polymer with a hydrogenating agent in a fixed-bed reactor, wherein the reactor is filled with a hydrogenation catalyst It is characterized in that the hydrogenation catalyst comprises a Group VIII metal component and at least three anti-deactivation components, wherein the improved part comprises using a supported hydrogenation catalyst having an average pore size of at least 10 2000 Angstroms.
I[實施方式J 出乎意外地，經支載之氫化催化劑之大孔徑組合固定 床反應器’可提供一種極為重要且極為有效之連續氫化方 法，其中氫化速率高，可達成穩態效能，暴露於聚合物内 15部雜質時催化劑填充物對去活化有抗性；如此允許於催化 劑之使用壽命期間獲得較大生產力。 本發明之連續方法使用經支載之抗去活化之氫化催化 劑來氫化芳香族聚合物。 本發明方法為連續方法，其中包含不飽和性聚合物之 20組成物被連續饋入固定床反應器内，其中該不飽和性聚合 物經氫化，且由反應器連續移出。固定床反應器被填裝以 經過承載之氫化催化劑（後文稱作經支載之混合氫化催化 劑），其特徵在於其包含至少兩種成分之混合物。第一成分 包含任一種可提高氫化速率之金屬，包括鎳、鈷、鍺、針、 7 200407341 鈀、鉑、其它VIII族金屬或其組合。較佳使用铑及/或鉑。 但已知翻為腈類之不良氫化催化劑，故始用於氫化猜共取 物時並不佳。用於經支載之混合氫化催化劑之第二成八勹 含一種促進劑，該促進劑可抑制vm族金屬暴露於極性材料 5時的去活化，後文稱作為抗去活化成分。此種成分較佳包 含銖、鉬、鎢、鈕或鈮或其混合物。 抗去活化成分之用量至少為當VIII族金屬成分暴露於 聚合物組成物之極性雜質時可顯著抑制VIII族金屬去活化 之用量，後文稱作去活化抑制量。VIII族金屬之去活化可由 10氫化反應速率之顯著降低證實。可以兩種成分或混合成分 氮化催化劑與/、含有VIII無金屬成分之催化劑，於極性雜質 存在下於相同條件下作比較舉例說明，其中只含VIII族金屬 成分之催化劑具有氫化反應速率小於使用經支載之混合氫 化催化劑所達成之氫化速率之75%。 15 較佳抗去活化成分用量為VIII族金屬成分對抗去活化 成分之比為0·5 : 1至10 : 1，更佳為1 : 1至7 : 1及最佳為1 : 1 至5 : 1 〇 催化劑額外包含一種撐體，各成分係沉積於該撐體 上。撐體可為任一種允許各成分良好分佈之材料，製造可 20用於本發明連續方法之有效催化劑。典型地，撐體為由矽 氧、紹氧、氧化鎂或碳等材料製造之多孔材料，具有平均 孔徑至少2000埃以及狹窄孔徑分佈。 撐體之孔徑分佈、孔隙容積及平均孔隙直徑可透過水 銀孔隙計量術遵照ASTMD-4284-83之程序測量得。 7佈/、型ίτ、使用水銀孔隙計量術測定。但此種方 法僅足以測量大於6〇埃之孔隙。因此須使用額外方法來測 量小於6G埃之孔隙。其中—種方法為根據ASTMIM6⑽ 之氮解吸_於小於約6_之制:直#。窄孔徑分佈係定 義為要，至v 98/。孔隙容積係由孔隙直徑大於細。埃之孔 隙所界定；II氮解⑽對小於纖魏隙測得之孔隙容積 占水銀孔料量侧得之總减容積之·7下。出乎意外 地發現使用具有大孔隙直徑以及狹窄孔徑分佈之撐體:本 發明方法特別有利。 表面積係根據ASTM D-3663-84測定。表面積典型為1 至1〇〇且較佳為5至50平方米/克。 一具體實施{列中，至少98%孔隙容積係由孔隙直徑大 於1000埃之孔隙所界定，以及藉氮解吸附對小於⑽〇埃之 孔隙測得之孔隙容積係低於藉水銀孔隙計量術測得總孔隙 谷積之2%。另一具體實施例中，至少98%孔隙容積係由孔 隙直徑大於30〇〇埃之孔隙所界定，以及藉氮解吸附對小於 3〇〇〇埃之孔隙測得之孔隙容積係低於藉水銀孔隙計量術測 得總孔隙容積之2%。 平均孔隙直徑典型至少為1000埃，較佳至少15〇〇埃及 更佳至少2000埃。 撐體形狀並無特殊限制，撐體形狀包括球形粒子或圓 柱狀粒子。也可使用擠壓成形之撐體帶有側邊切削部、或 使用環形撐體。以球形粒子為例，催化劑大小為直徑〇2至 ⑺愛米；以圓柱形粒子為例，催化劑直徑係於〇2至1〇毫米 200407341 之範圍，其長度係於0.2至20毫米之範圍。 此等撐體之製備方法為熟諳技藝人士眾所周知。以石夕 氧撐體為佳，石夕氧撐體之製法係經由於水中組合矽酸鉀與 膠凝劑如甲醯胺，如美國專利第4，112,〇32號之舉例說明經 5 聚合以及滲濾。然後石夕氧如同於Iler，R.K.，石夕氧化學，約 翰威力父子公司，1979年539-544頁所述加水加熱煆燒，通 常包含加熱矽氧同時將飽和以水之氣體通過矽氧之上經歷 約2小時或2小時以上時間，溫度為6〇〇°C至85〇t。水熱煆 燒結果導致孔隙直徑分佈狹窄，以及平均孔隙直徑加大。 10另外，撐體可經由Iler，R.K·，矽氧化學，約翰威力父子公 司，1979年510-581頁揭示之方法製備。 經支載催化劑之製造方法也為熟諳技藝人士眾所周 知。例如經矽氧支載之撐體可使用美國專利第5，ι 1〇,779號 所述方法製造。適當金屬、金屬成分、含金屬化合物或其 15 混合物可藉氣相沉積、水性或非水性浸潰接著為煆燒、昇 華或任何其它習知方法沉積，沉積方法例如舉例說明於表 面科學及催化研究，「催化劑之成功設計」第44版，146-158 ^ 頁，1989年以及應用雜環催化劑，第75-123頁，法國石油 出版公司，1987年。至於用於固定床反應器之催化劑，較 20佳沉積活性金屬成分以及抗去活化成分，且較佳係沉積於 . 接近催化劑撐體外表面。例如具有此種經控制之金屬分佈 之催化劑可經由於金屬施用期間限制容積用量獲得。任何 其它獲得此種非均勻分佈之適當手段也為人所接受。浸潰 方法中，適當含金屬化合物可為任一種前述含金屬化合 10 200407341 物，其將產生可對抗去活化之有用的氫化催化劑。此等化 合物可為鹽類、配位錯合物、有機金屬化合物或共價錯合 物。 典型地，經支載催化劑之金屬總含量係占經支載催化 5 劑總重之0.1至10 wt%。較佳用量係占催化劑總重之0.2至8 wt%且更佳為0.5至5 wt°/〇。I [Embodiment J Unexpectedly, a large-pore combined fixed-bed reactor with a supported hydrogenation catalyst 'can provide an extremely important and effective continuous hydrogenation method, in which the hydrogenation rate is high, steady-state performance can be achieved, and exposure The catalyst filler is resistant to deactivation at 15 impurities in the polymer; this allows greater productivity during the life of the catalyst. The continuous process of the present invention uses a supported deactivation-resistant hydrogenation catalyst to hydrogenate aromatic polymers. The method of the present invention is a continuous method in which 20 compositions containing unsaturated polymers are continuously fed into a fixed-bed reactor, wherein the unsaturated polymers are hydrogenated and continuously removed from the reactor. The fixed-bed reactor is packed with a supported hydrogenation catalyst (hereinafter referred to as a supported mixed hydrogenation catalyst), which is characterized in that it contains a mixture of at least two components. The first component includes any metal that can increase the hydrogenation rate, including nickel, cobalt, germanium, needles, 7 200407341 palladium, platinum, other Group VIII metals, or a combination thereof. Rhodium and / or platinum are preferably used. However, it is known to be a poor hydrogenation catalyst for nitriles, so it is not good when it is initially used for hydrogenation. The second 28% of the supported mixed hydrogenation catalyst contains a promoter which can inhibit the deactivation of the vm group metal when exposed to the polar material 5, which is hereinafter referred to as an anti-deactivation component. Such ingredients preferably include baht, molybdenum, tungsten, buttons or niobium or mixtures thereof. The amount of the anti-deactivation component is at least an amount which can significantly inhibit the deactivation of the Group VIII metal when the Group VIII metal component is exposed to the polar impurities of the polymer composition, and is hereinafter referred to as a deactivation inhibitory amount. Deactivation of Group VIII metals can be confirmed by a significant reduction in the rate of the 10 hydrogenation reaction. Nitrogen catalysts with two components or mixed components and / or catalysts containing VIII metal-free components can be compared and exemplified under the same conditions in the presence of polar impurities. Among them, the catalyst containing only group VIII metal components has a hydrogenation reaction rate less than that used. 75% of the hydrogenation rate achieved by the supported mixed hydrogenation catalyst. 15 The preferred amount of the anti-deactivation component is a Group VIII metal component. The ratio of the anti-deactivation component is 0.5: 1 to 10: 1, more preferably 1: 1 to 7: 1 and most preferably 1: 1 to 5: The 10 catalyst additionally includes a support, and the components are deposited on the support. The support may be any material that allows a good distribution of the components, and produces an effective catalyst that can be used in the continuous process of the present invention. Typically, the support is a porous material made of materials such as silicon oxide, sodium oxide, magnesium oxide, or carbon, with an average pore size of at least 2000 angstroms and a narrow pore size distribution. The pore size distribution, pore volume, and average pore diameter of the support can be measured by mercury pore metrology in accordance with the procedure of ASTMD-4284-83. 7 cloth /, type τ, measured using mercury porosimetry. However, this method is only sufficient to measure pores larger than 60 angstroms. Therefore additional methods must be used to measure pores smaller than 6G Angstroms. Among them, one method is a system of nitrogen desorption according to ASTM6, which is less than about 6: straight. Narrow pore size distributions are defined as essential, up to v 98 /. The pore volume is determined by the pore diameter being larger than thin. It is defined by the pore space of Angstrom; II. The pore volume measured by the nitrogen hydrazone is less than 7 times the total volume reduction of the mercury pore volume measured by the fiber gap. It was unexpectedly found that the use of a support having a large pore diameter and a narrow pore size distribution: the method of the invention is particularly advantageous. The surface area is measured according to ASTM D-3663-84. The surface area is typically 1 to 100 and preferably 5 to 50 m2 / g. In a specific implementation {column, at least 98% of the pore volume is defined by pores with a pore diameter greater than 1000 angstroms, and the pore volume measured by nitrogen desorption for pores smaller than ⑽0 angstroms is lower than that measured by mercury pore metrology Get 2% of the total pore valley. In another embodiment, at least 98% of the pore volume is defined by pores with a pore diameter greater than 30,000 angstroms, and the pore volume measured by nitrogen desorption on pores smaller than 3,000 angstroms is lower than that of mercury Porostometry measures 2% of the total pore volume. The average pore diameter is typically at least 1000 Angstroms, preferably at least 1 500 Egypt and more preferably at least 2000 Angstroms. The shape of the support body is not particularly limited, and the shape of the support body includes spherical particles or cylindrical particles. It is also possible to use an extruded support with side cuts, or use an annular support. Taking spherical particles as an example, the size of the catalyst is 0 to 2 mm in diameter; taking cylindrical particles as an example, the diameter of the catalyst is in the range of 02 to 10 mm 200407341, and its length is in the range of 0.2 to 20 mm. The preparation of these supports is well known to those skilled in the art. It is better to use Shixian oxide, which is prepared by combining potassium silicate with a gelling agent such as formamidine in water, as illustrated in US Pat. No. 4,112,032. And percolation. Then Shi Xi oxygen is as described in Iler, RK, Shi Xi Oxidation, John Willy & Sons, 1979, p. 539-544. Adding water to heat sintering, usually involves heating the silicon oxygen while passing the saturated gas with water through the silicon After about 2 hours or more, the temperature is from 600 ° C to 8500t. Hydrothermal calcination results in a narrow pore diameter distribution and an increase in average pore diameter. 10 Alternatively, the support can be prepared by the method disclosed in Iler, R.K., Silicon Oxidation, John Willy & Sons, pp. 510-581, 1979. The method for manufacturing a supported catalyst is also well known to those skilled in the art. For example, a silicon-supported support can be manufactured using the method described in U.S. Patent No. 5,10,779. Appropriate metals, metal components, metal-containing compounds, or 15 mixtures thereof can be deposited by vapor deposition, aqueous or non-aqueous impregnation followed by calcination, sublimation, or any other conventional method. Examples of deposition methods are illustrated by surface science and catalytic studies "Successful Design of Catalysts", 44th edition, 146-158 ^, 1989 and Applied Heterocyclic Catalysts, pp. 75-123, French Petroleum Publishing Company, 1987. As for the catalyst used in the fixed-bed reactor, it is better to deposit active metal components and anti-deactivation components than 20, and it is preferably deposited near the outer surface of the catalyst support. For example, catalysts with such a controlled metal distribution can be obtained by limiting the volume used during metal application. Any other appropriate means of obtaining such a non-uniform distribution is also acceptable. In the impregnation method, a suitable metal-containing compound may be any of the aforementioned metal-containing compounds 10 200407341, which will produce a useful hydrogenation catalyst that is resistant to deactivation. These compounds may be salts, coordination complexes, organometallic compounds or covalent complexes. Typically, the total metal content of the supported catalyst is 0.1 to 10 wt% based on the total weight of the supported catalyst. The preferred amount is 0.2 to 8% by weight and more preferably 0.5 to 5% by weight based on the total weight of the catalyst.
促進劑如含驗金屬、驗土金屬或鑭系元素之化合物也 可用來輔助金屬成分分散於撐體，或輔助反應期間之安 定，但促進劑之使用並不佳。 10 可藉本發明方法氫化之聚合物包括任一種含有稀屬或 芳香族不飽和度之不飽和性聚合物。此種聚合物包括由烯 屬單體製造之烴聚合物，例如丁二烯或異戊間二烯之均聚 物、其共聚物、以及芳香族聚合物及共聚物。可藉本發明 方法氳化之芳香族聚合物包括任一種含有側鏈芳香族官能Accelerators such as compounds containing metals, soil metals, or lanthanides can also be used to help disperse metal components in the support or to stabilize the reaction period, but the use of accelerators is not good. 10 Polymers that can be hydrogenated by the method of the present invention include any unsaturated polymer containing rare or aromatic unsaturation. Such polymers include hydrocarbon polymers made from olefinic monomers, such as homopolymers of butadiene or isoprene, copolymers thereof, and aromatic polymers and copolymers. Aromatic polymers that can be hydrolyzed by the method of the present invention include any type of aromatic polymer containing a side chain.
15 基之聚合物料。側鏈芳香族官能基表示一種結構式其中芳 香族基為聚合物主鏈之取代基而非嵌入聚合物主鏈内部。 較佳芳香族基團為C6-20芳基且特別為苯基。此等芳香族聚 合物除了芳香族基團之外也可含有其它烯屬基團。較佳芳 香族聚合物係衍生自下式單體：15 base polymer material. The side chain aromatic functional group represents a structural formula in which the aromatic group is a substituent of the polymer main chain instead of being embedded inside the polymer main chain. Preferred aromatic groups are C6-20 aryl and especially phenyl. These aromatic polymers may contain other olefinic groups in addition to the aromatic groups. Preferred aromatic polymers are derived from monomers of the formula:
R 20 |R 20 |
Ar-C = CH2 其中R為氫或烷基；Ar為苯基、鹵苯基、烷基苯基、烷基鹵 苯基、萘基、啦啶基或蔥基，其中任一個烷基含有1至6個 碳原子且可經以例如鹵原子、硝基、胺基、氰基、魏基及 11 羧基等官能基一取代或多取代。更佳氬為苯基或烷基苯 基，且以苯基為最佳。均聚物可具有任一種立體結構包括 間規、等規或無規；但以無規聚合物為佳。此外，含有此 等芳香族單體之共聚物包括隨機、假隨機、嵌段、錐形嵌 丰又生形及接枝共聚物’此等共聚物也可經氫化。例如乙 烯基芳香族單體以及共聚單體之共聚物也可使用，共聚單 體例如係選自腈類、丙烯酸類、酸類、乙烯、丙烯、順丁 稀二酐、順丁稀二醯亞胺類、乙酸乙烯酯及氯乙稀；共聚 物例如為苯乙烯-丙烯腈、苯乙烯-甲基苯乙烯及苯乙烯_ 10乙烯。也可使用乙烯基芳香族單體之嵌段共聚物，例如苯 乙稀-α-甲基苯乙稀欲段共聚物、笨乙烯_丁二稀或苯乙稀_ 異戊間二烯嵌段共聚物、及多種多段共聚物。例如包括苯 乙烯-丁二烯、苯乙烯-異戊間二烯、苯乙烯_丁二烯_苯乙烯 以及苯乙烯-異戊間二烯-苯乙烯嵌段共聚物。其它嵌段共聚 15 物範例可參考美國專利第4,845，173、4,096,203、4,200,718、 4,201，729、4,205,016、3,652,516、3,734,973、3,390,207、 3,231，635及3,030,346號。也可使用包括含量芳香族聚合物 之經過耐衝擊改性之接枝橡膠之聚合物攙合物。 較佳欲氮化之聚合物之數目平均分子量（Μη)為10,000 20 至 3,000,000，更佳為 30,000 至 400,000 及最佳為 50,000 至 300,000，Μη係藉凝膠滲透層析術測定。 包含不飽和性聚合物之組成物（後文稱作為聚合物進 料)典型含有小量污染物，該污染物將去活化典型VIII族金 屬氫化催化劑。此等污染物包括聚合終止劑以及極性物 200407341 質、以及聚合催化劑殘餘物例如魏。即使氫化聚合物進料 含有此等污染物，本發明方法仍然允許更有效的氫化以及 更長的催化劑壽命。 本發明之連續方法利用固定床反應器，其中經支載之 5 催化劑填裝於反應器内，聚合物進料流經固定催化劑床。 任一種固定床反應器皆可使用而無任何特殊限制。多管型 反應器可用於有效去除熱。來自固定床之液體及氣體流出 物可經分離及再度循環至床，俾便更有效使用氫，或辅助 控制反應器溫度。聚合物溶液以及氫氣之流動方向可為反 10 向或同向（平行方向），但以平行流方法為佳。此種流動方向 可向上或向下。 經支載之催化劑固定床典型係於40至250°c，較佳50 至200°C及特佳50至180°C之溫度操作。反應器可以絕熱方 式操作，換言之允許反應熱由反應混合物所吸收；或反應 15器可使用業界已知之任一種添加熱量以及去除熱量之方法 操作，包括可與管反應器、具有階段間加熱或冷卻之多階 段式反應器、或冷發射添加反應器。 反應典型之進行條件如後：氫壓力為0.5至20 MPa，較 佳1至20 MPa及最佳2至15 MPa;氫氣流速/聚合物溶液流速 20比為20至7⑼當量升/升(N1/1)，較佳為20至500 N1/1及最佳為 40至350 N1/1 ;以及液體每小時空間速度(LHSV)為0.01至 15(升/小時）且較佳為〇 〇3至1〇(升/小時）及最佳為〇 〇5至 10(升/小時）。LHSV係定義為每小時液體進料速率（升)除以 催化劑床容積（升）。 13 377 200407341 已經達到目標氫化之氫化反應流出流可藉任一種方法 包括脫去揮發物以及其它分離技術分離成為氫氣、溶劑、 及氫化聚合物。 氫化反應較佳係於烴溶劑進行，聚合物可溶於該烴溶 5 劑，且該烴溶劑不會妨礙氫化反應。較佳溶劑為飽和溶劑 如環戊烷、環己烷、環庚烷、環辛烷、甲基環己烷、十氫 萘、乙基環己烷、十二烷、二氧己烷、二乙二醇二甲醚、 四氫呋喃、異戊烷、以及十氫萘或其混合物，而以環己烷 為最佳。也可使用正己烷、正庚烷與其它烴類之混合物， 10 以及與醚類、四氫呋喃、二氧己烷、二乙二醇二甲醚、醇 類、醚類或胺類之混合物。 聚合物濃度典型為5至30重量％，且較佳為5至25重量 %。Ar-C = CH2 where R is hydrogen or alkyl; Ar is phenyl, halophenyl, alkylphenyl, alkylhalophenyl, naphthyl, pyridyl, or allium, and any alkyl group contains 1 Up to 6 carbon atoms and may be mono- or poly-substituted with functional groups such as a halogen atom, a nitro group, an amine group, a cyano group, a weyl group, and an 11 carboxyl group. More preferably, argon is phenyl or alkylphenyl, and phenyl is most preferred. Homopolymers may have any of three-dimensional structures including syndiotactic, isotactic, or random; however, random polymers are preferred. In addition, copolymers containing these aromatic monomers, including random, pseudo-random, block, tapered inserts, and graft copolymers', may also be hydrogenated. For example, copolymers of vinyl aromatic monomers and comonomers can also be used. The comonomers are, for example, selected from the group consisting of nitriles, acrylics, acids, ethylene, propylene, maleic anhydride, and maleimide Copolymers such as styrene-acrylonitrile, styrene-methylstyrene, and styrene-10 ethylene. It is also possible to use block copolymers of vinyl aromatic monomers, such as styrene-α-methylstyrene copolymers, styrene-butadiene or styrene-isoprene blocks Copolymers and various multi-stage copolymers. Examples include styrene-butadiene, styrene-isoprene, styrene-butadiene-styrene, and styrene-isoprene-styrene block copolymers. For other examples of block copolymers, refer to U.S. Patent Nos. 4,845,173, 4,096,203, 4,200,718, 4,201,729, 4,205,016, 3,652,516, 3,734,973, 3,390,207, 3,231,635, and 3,030,346. Polymer admixtures of impact-modified graft rubbers containing aromatic polymers may also be used. The number average molecular weight (Mn) of the polymer to be nitrided is preferably 10,000 20 to 3,000,000, more preferably 30,000 to 400,000 and most preferably 50,000 to 300,000, and Mn is determined by gel permeation chromatography. Compositions containing unsaturated polymers (hereinafter referred to as polymer feeds) typically contain small amounts of contaminants that will deactivate typical Group VIII metal hydrogenation catalysts. These contaminants include polymerization terminators and polar substances, and the residues of polymerization catalysts such as Wei. Even if the hydrogenated polymer feed contains these contaminants, the process of the present invention allows for more efficient hydrogenation and longer catalyst life. The continuous process of the present invention utilizes a fixed bed reactor in which a supported 5 catalyst is packed in the reactor, and the polymer feed flows through the fixed catalyst bed. Any kind of fixed bed reactor can be used without any special restrictions. Multi-tube reactors can be used to effectively remove heat. Liquid and gaseous effluents from the fixed bed can be separated and recycled to the bed again, so that hydrogen can be used more efficiently, or the reactor temperature can be controlled. The polymer solution and hydrogen can flow in the opposite direction or in the same direction (parallel direction), but the parallel flow method is preferred. This direction of flow can be up or down. The supported catalyst fixed bed is typically operated at a temperature of 40 to 250 ° C, preferably 50 to 200 ° C and particularly preferably 50 to 180 ° C. The reactor can be operated adiabatically, in other words allowing the reaction heat to be absorbed by the reaction mixture; or the reactor 15 can be operated using any of the methods known in the industry for adding and removing heat, including with tube reactors, with interstage heating or cooling Multi-stage reactor, or cold launch addition reactor. The typical reaction conditions for the reaction are as follows: hydrogen pressure is 0.5 to 20 MPa, preferably 1 to 20 MPa and optimal 2 to 15 MPa; hydrogen flow rate / polymer solution flow rate 20 ratio is 20 to 7 ⑼ equivalent liters / liter (N1 / 1), preferably 20 to 500 N1 / 1 and most preferably 40 to 350 N1 / 1; and a liquid hourly space velocity (LHSV) of 0.01 to 15 (liters / hour) and preferably 0.3 to 1 0 (liters / hour) and optimally 0.05 to 10 (liters / hour). LHSV is defined as the liquid feed rate (liters) per hour divided by the catalyst bed volume (liters). 13 377 200407341 The hydrogenation reaction effluent that has reached the target hydrogenation can be separated into hydrogen, solvent, and hydrogenated polymer by any method including volatiles removal and other separation techniques. The hydrogenation reaction is preferably performed in a hydrocarbon solvent, and the polymer is soluble in the hydrocarbon solvent, and the hydrocarbon solvent does not hinder the hydrogenation reaction. Preferred solvents are saturated solvents such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, decalin, ethylcyclohexane, dodecane, dioxane, diethyl Dimethyl ether, tetrahydrofuran, isopentane, and decalin or mixtures thereof, and cyclohexane is most preferred. Mixtures of n-hexane, n-heptane and other hydrocarbons, 10 and mixtures with ethers, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, alcohols, ethers or amines can also be used. The polymer concentration is typically 5 to 30% by weight, and preferably 5 to 25% by weight.
氫化反應典型係於氧存在下進行。典型反應容器使用 15 惰性氣體掃除而於反應開始前，由反應區去除氧。惰性氣 體包括但非限於氮、氦及氬，以氮為佳。 氫化劑可為任一種可氫化不飽和性聚合物之氫產生性 化合物。氫化劑包括但非限於氫氣、肼及调氫化鈉。較佳 具體實施例中，氫化劑為氫氣。 20 低分子量聚合物之固定床氫化實施例含括於U.S. 3,809,687。 一具體實施例中，固定床反應器包含填裝有顆粒狀氫 化催化劑之立式反應管柱。一種包含嵌段共聚物之組成物 連續通過管柱，同時接觸氫化劑。聚合物溶液與氫氣之流 14 200407341 動方向可相反或相同，但以平行流方法為佳。流動方向可 向上或向下。 氫化量係依據欲氫化之聚合物、使用之催化劑、方法 條件以及反應時間決定。用於烯屬聚合物，至少80。/。烯屬 5鍵結被氫化，而獲得氫化度為8〇%，較佳至少90%，更佳至 少95%及最佳100%。用於例如聚苯乙烯以及苯乙烯-丁二烯 共聚物等聚合物，典型之芳香族氫化反應大於80%(其中大 於80%芳香族鍵結被氫化）’較佳大於99%及更佳大於 99.5%。氫化程度可經由測定氫化聚合物之紫外光吸光比且 10 與未經氫化之標準品之吸光比作比較而測定。換言之， 99.5%之氫化聚合物之吸光比將比未經氫化之聚合物之 光比小99.5%。對例如聚α-甲基苯乙烯、苯乙稀-甲基笨己 烯共聚物及乙烯基芳香族單體與選自腈、丙烯酸酯、酸、 乙烯、丙烯、順丁烯二酐、順丁烯二醯亞胺、乙酸乙崎以 15 及乙烯氯組成的組群之共聚單體生成之共聚物等聚合物而 言，氫化程度為較低，氫化程度係依據欲氫化之聚合物決 定。典型地達成至少20%芳香族氫化，較佳至少30%，更件 至少50%及最佳至少9〇%聚合物氫化。 烯屬氫化量可使用紅外光譜術或質子NMR技術測定。 20芳香族氫化量可使用UV-VIS光譜術測定。聚苯乙烯之環己 烧溶液可對芳香環於約260.5奈米獲得極為獨特的σ及收 帶。此種吸收帶於溶液濃度為0.004980莫耳芳香族/升於1 厘米光試管時可獲得吸光比L000。吸光比係依據濃度決 疋。氫化聚合物產物典型係於較高濃度測定，原因在於 <气 15 200407341 化聚合物之產物於測量吸光比之前未經稀釋。因反應溶液 比払準叩濃縮15_3〇倍，故可準確測量小量殘餘不飽和度。 一具體實施例中，本發明方法包含一種包含至少一種 未飽和聚合物以及至少一種極性雜質之聚合物進料組成 5物，於一種經矽氧支載之混合氫化催化劑存在下，接觸氫 化劑，其特徵在於該經矽氧支載之混合氫化催化劑包含至 少一種VIII族金屬成分以及至少一種去活化抑制量之抗去 活化成刀，5亥抗去活化成分係選自由銖、鉬、鎢、鈕及銳 成分組成的組群，其中該魏具有平均孔隙直徑至少為 10 2000埃。 ^現具有類似平均分子量（Mn於50,000至12〇,〇〇〇之範 圍）之甘入^又/、來物當於固定床反應器使用粒狀催化劑而非 粉狀催化劑進行氫化時，欲段共聚物之表現不同。特別富 於本乙烯之嵌段共聚物使用平均孔隙直徑至少2〇〇〇埃之多 15孔催化d氫化時幾乎可完全氫化。雖然孔隙小於⑺⑻埃之 催化』也可在翅時間内有高轉化率，但該種催化劑於固定 木二 長吩間維持高度轉化的能力有限。此外催化劑 用於氫化田於丁二稀之嵌段共聚物時可維持高度轉化率， 即使/催化4之孔彼比用於富含苯乙稀之聚合物之催化劑 20 之孔徑更大亦如此。 牛出下列貫施例供舉例說明本發明，而非囿限其範 圍。實施例中，除韭—扣- 降非另们^曰不，否則全部份數及百分比皆 為以重量計。 芳香族_ /u胃/ 、， 、4化I係如前文說明使用UV-VIS光譜術測 16 200407341 量。稀屬氫化量可使用紅外光譜術測定。 除非另行載明’否則^^為藉凝膠滲透層析術測得之絕 對分子量。 貫施例使用之全部聚合物樣本皆具有無規立體結構。 5 實施例 比車父例1使用具有直徑500埃孔隙之催化劑氮化苯乙稀/丁 二稀(85/15)共聚物(Mn 6〇,〇〇〇) 立式有夾套的不銹鋼管（長76.2厘米，直徑1.9厘米）被 填裒50克（100¾升）ι 2毫米χ (2-8)毫米經圓柱形矽氧[諾頓 10 (N〇rt〇n)矽氧，具有單模孔徑分佈，取中於接近50奈米（500 埃）孔隙直徑，以及表面積65平方米/克]支載之催化劑粒子 (3 wt% Pt以及2 Wt% Re)。反應器於^孓丨“它溫度以及％ 巴氫壓操作。13份重量比苯乙烯/ 丁二烯共聚物溶解於87份 重量比環己烷溶劑之溶液以丨.5毫升/分鐘速率饋至反應器 15頂端，獲得液體小時空間速度(LHSV)0.9〇。氫氣係以19〇 cc/ 分鐘之速率饋入管内。 苯乙烯之轉化率係使用UV-Vis吸光比於259 8奈米波 長監視。以常規間隔每數小時取樣本，芳香族轉化率維持 大於99%經歷前30小時，於該點，催化劑之生產力為5的 2〇 克氫化聚合物/克催化劑。46小時後取次一樣本，此時催化 劑已經加工處理8.77克聚合物/克催化劑，轉化率降至 96·9%。 實施例1使用具有直徑3500埃孔隙之催化劑氯化苯乙稀/ 丁二烯(85/15)共聚物(Μη 60,000) 17 重複比較例卜反應器填裝27克（100毫升)催化劑，催化 劑包含3%Pt以及2%Re經支載於^汕篩目（1·68-〇·84ι毫米） 矽氧撐體顆粒上，矽氧撐體具有單模孔徑分佈，平均孔徑 3,50〇埃，及BET表面積18平方米/克。溫度、壓力、及進料 流速率皆係設定且控制於比較例之相同範圍。恰在啟動之 後，反應為已經達到高於99%苯乙烯轉化率；於進行12〇小 時後，測得轉化率為99.8%，催化劑已經氫化41·6克聚合物 /克催化劑。 比較例2使用具有直徑35〇〇埃孔隙之催化劑氫化苯乙烯/ 丁二稀(32/68)共聚物(Μη 63,000) 重複貫施例1，但使用27克催化劑包含3%Pt以及2%Re 支載於12,20篩目矽氧撐體顆粒上，矽氧撐體具有單模孔徑 分佈以及平均孔徑3,500埃，BET表面積18平方米/克。本比 較例之進料溶液包含12份重量比苯乙烯_丁二烯嵌段共聚 物（32 wt%苯乙烯）及88份重量比環己烷溶劑。液體進料速 率初期設定為3毫升/分鐘，液體小時空間速度為18，氫氣 進料速率為375¾升/分鐘。LHSV後來降至〇·9，轉化率維持 咼於99%，直至催化劑生產力達到6·8克聚合物/克催化劑。 轉化率維持高於98%直到生產力達到11〇克/克。轉化率由 99.1 /〇卩牛至98%較為顯著的原因在於於固定停駐時間之任 何第一次羃反應，催化劑活性係與-ln(l-X)成正比，此處χ 為反應物之分量轉化率。如此容易算出經24小時後，活性 只有#作3.5小時後之活性之85%。用於若干聚合物應用， 要求98%轉化率規定，於轉化率降至低於卯％以下之前，本 200407341 實驗可獲得11·〇克聚合物/克催化劑。 實施例2使㈣有直徑13·埃孔隙之催化錢化苯乙烯/ 丁二烯(32/68)共聚物(Mn 63，000) 反應器内填裝34·2克催化劑經支載於矽氧，矽氧具有 5平均孔隙直徑即⑼埃以及ΒΕΤ表面積4平方米/克，反應器 1 内也填裝3%Pt以及2%Re重量比。本實施例之進料溶液包含 12·4份重量比苯乙烯-丁二烯嵌段共聚物（32研。/〇苯乙烯）及 87·6份重量比環己烷溶劑。液體小時空間速度初期設定於 h8，後來降至1·2，轉化率維持高於99%，直到生產力達到 73·3克聚合物/克催化劑。即使生產力達到1〇8 8克/克，轉化 率仍然維持高於98%。出乎意外地可獲得較佳效能以及較 為緩慢的催化劑去活化。 出乎意外地發現當使用具有適合固定床反應器之粒徑 大小的催化劑時，如此處所述，具有較大平均孔隙直徑之 15 催化劑撐體可獲得改良生產力，其中該催化劑對於去活化 #極高抗性，因此具有較長的催化劑壽命。 【陶式簡單說明3 (無） 【圖式之主要元件代表符號表】 (無） 19The hydrogenation reaction is typically performed in the presence of oxygen. A typical reaction vessel is purged with 15 inert gas and oxygen is removed from the reaction zone before the reaction begins. Inert gases include, but are not limited to, nitrogen, helium, and argon, with nitrogen being preferred. The hydrogenating agent may be any hydrogen-generating compound capable of hydrogenating an unsaturated polymer. Hydrogenating agents include, but are not limited to, hydrogen, hydrazine, and sodium hydride. In a preferred embodiment, the hydrogenating agent is hydrogen. 20 Examples of fixed bed hydrogenation of low molecular weight polymers are included in U.S. 3,809,687. In a specific embodiment, the fixed-bed reactor comprises a vertical reaction tubular column packed with a particulate hydrogenation catalyst. A composition comprising a block copolymer is continuously passed through a column while being exposed to a hydrogenating agent. Polymer solution and hydrogen flow 14 200407341 The direction of movement can be opposite or the same, but the parallel flow method is preferred. The direction of flow can be up or down. The amount of hydrogenation is determined by the polymer to be hydrogenated, the catalyst used, the process conditions, and the reaction time. For olefinic polymers, at least 80. /. The olefinic 5 bond is hydrogenated to obtain a degree of hydrogenation of 80%, preferably at least 90%, more preferably at least 95% and most preferably 100%. For polymers such as polystyrene and styrene-butadiene copolymers, the typical aromatic hydrogenation reaction is greater than 80% (of which more than 80% of the aromatic bonds are hydrogenated) 'preferably greater than 99% and more preferably greater than 99.5%. The degree of hydrogenation can be determined by measuring the ultraviolet light absorbance ratio of the hydrogenated polymer and comparing the absorbance ratio of 10 with the standard without hydrogenation. In other words, the light absorption ratio of the 99.5% hydrogenated polymer will be 99.5% less than the light ratio of the unhydrogenated polymer. For example, polyα-methylstyrene, styrene-methylbenzene copolymer and vinyl aromatic monomers are selected from the group consisting of nitrile, acrylate, acid, ethylene, propylene, maleic anhydride, maleic anhydride For polymers such as ethylenediimide, acetazine acetate and comonomers composed of 15 and vinyl chloride, the degree of hydrogenation is low, and the degree of hydrogenation is determined by the polymer to be hydrogenated. Typically at least 20% of the aromatic hydrogenation is achieved, preferably at least 30%, more preferably at least 50% and most preferably at least 90% of the polymer is hydrogenated. The amount of olefinic hydrogenation can be determined using infrared spectroscopy or proton NMR techniques. The amount of 20 aromatic hydrogenation can be measured using UV-VIS spectroscopy. Polystyrene ring-fired solution can obtain extremely unique σ and band for aromatic rings at about 260.5 nm. Such an absorption band can obtain an absorption ratio L000 when the solution concentration is 0.004980 mol aromatic / liter in a 1 cm light test tube. The absorption ratio is determined by concentration. Hydrogenated polymer products are typically measured at higher concentrations because < Gas 15 200407341 The product of the hydrogenated polymer was not diluted before measuring the absorbance ratio. Because the reaction solution is 15-30 times more concentrated than 払 quasi- 叩, it can accurately measure small amounts of residual unsaturation. In a specific embodiment, the method of the present invention comprises a polymer feed composition 5 comprising at least one unsaturated polymer and at least one polar impurity, and contacting the hydrogenation agent in the presence of a silicon-supported mixed hydrogenation catalyst, It is characterized in that the silicon-supported mixed hydrogenation catalyst contains at least one Group VIII metal component and at least one deactivation inhibitory amount of anti-deactivation knife. The anti-deactivation component is selected from the group consisting of baht, molybdenum, tungsten, button and sharp. A group of ingredients, wherein the Wei has an average pore diameter of at least 10 2000 Angstroms. ^ Now there is a similar average molecular weight (manganese in the range of 50,000 to 120,000) ^ and /, when the use of granular catalyst instead of powder catalyst for hydrogenation in a fixed bed reactor, Copolymers behave differently. The block copolymers particularly rich in this ethylene can be almost completely hydrogenated when using a 15-pore catalyzed hydrogenation with an average pore diameter of at least 2000 angstroms. Although the pore size is smaller than that of ⑺⑻A catalyst, it can also have a high conversion rate in the fin time, but this catalyst has limited ability to maintain high conversion between fixed wood diphene. In addition, the catalyst can maintain a high degree of conversion when used in a hydrogenated field with a succinic block copolymer, even if the pore size of / catalyst 4 is larger than that of the catalyst 20 used for styrene-rich polymers. The following examples are presented to illustrate the invention, but not to limit its scope. In the examples, all parts and percentages are based on weight, except for chives, buckles, and drops. Aromatic _ / u stomach /,,,, and 4H are measured as described above using UV-VIS spectroscopy 16 200407341. The amount of rare hydrogenation can be measured using infrared spectroscopy. Unless stated otherwise, ^^ is the absolute molecular weight measured by gel permeation chromatography. All polymer samples used throughout the examples have a random three-dimensional structure. 5 Example is compared to car parent example 1 using a catalyst with a diameter of 500 angstroms, a styrene-nitride / butadiene (85/15) copolymer (Mn 60,000,000), a vertical jacketed stainless steel tube ( 76.2 cm in length, 1.9 cm in diameter) filled with 50 g (100 ¾ liters) 2 mm x (2-8) mm via cylindrical silica [Norton 10 (N〇rt〇n) silica, with a single-mode pore size distribution The catalyst particles (3 wt% Pt and 2 Wt% Re) supported at a pore diameter close to 50 nanometers (500 angstroms) and a surface area of 65 square meters per gram] were taken. The reactor was operated at its temperature and% bar hydrogen pressure. A solution of 13 parts by weight of a styrene / butadiene copolymer dissolved in 87 parts by weight of a cyclohexane solvent was fed at a rate of 1.5 ml / min. At the top of reactor 15, a liquid hourly space velocity (LHSV) of 0.90 was obtained. Hydrogen was fed into the tube at a rate of 190 cc / minute. The conversion of styrene was monitored using a UV-Vis absorption ratio at a wavelength of 259 8 nm. Samples were sampled every few hours at regular intervals, and the aromatic conversion rate was maintained greater than 99%. At this point, the productivity of the catalyst was 20 grams of hydrogenated polymer per gram of catalyst. Samples were taken after 46 hours. At that time, the catalyst had been processed 8.77 grams of polymer / gram of catalyst, and the conversion rate was reduced to 96.9%. Example 1 uses a catalyst having a diameter of 3,500 angstroms, a chlorinated styrene / butadiene (85/15) copolymer ( Μη 60,000) 17 Repeat the comparative example. The reactor was charged with 27 g (100 ml) of catalyst. The catalyst contained 3% Pt and 2% Re and was supported on a sieve (1.68-0.84 mm). On the body particles, the siloxane body has a single-mode pore size distribution with an average pore size. 3,50 Angstroms, and a BET surface area of 18 square meters per gram. The temperature, pressure, and feed flow rate were all set and controlled within the same range of the comparative example. Immediately after startup, the reaction was above 99% benzene Ethylene conversion; after 12 hours, the conversion was measured to be 99.8%, and the catalyst had been hydrogenated at 41.6 g of polymer per gram of catalyst. Comparative Example 2 Hydrogenated styrene / butadiene was used with a catalyst having a pore diameter of 350,000 angstroms. Dilute (32/68) copolymer (Μη 63,000) Example 1 was repeated, but using 27 g of the catalyst containing 3% Pt and 2% Re was supported on 12,20 mesh silica particles. Siloxane The body has a single-mode pore size distribution, an average pore size of 3,500 angstroms, and a BET surface area of 18 square meters per gram. The feed solution of this comparative example contains 12 parts by weight of a styrene-butadiene block copolymer (32 wt% styrene) and 88 parts by weight of cyclohexane solvent. The liquid feed rate was initially set to 3 ml / min, the liquid hourly space velocity was 18, and the hydrogen feed rate was 375¾ liters / min. The LHSV was later reduced to 0.9, and the conversion rate was maintained 咼At 99% until catalyst productivity reaches 6.8 g polymer / g The conversion rate is maintained above 98% until the productivity reaches 11 g / g. The conversion rate is from 99.1 / 0 yak to 98%. The more significant reason is that at any fixed dwell time, the first rhenium reaction, catalyst activity It is directly proportional to -ln (lX), where χ is the component conversion rate of the reactant. It is so easy to calculate that after 24 hours, the activity is only 85% of the activity after 3.5 hours. For several polymer applications, requirements The 98% conversion rate stipulates that before the conversion rate drops below 卯%, this 200407341 experiment can obtain 11.0 grams of polymer per gram of catalyst. Example 2 A catalyzed styrene / butadiene (32/68) copolymer (Mn 63,000) with a diameter of 13 angstroms was filled in a reactor with 34.2 grams of catalyst supported on silica The silicon oxide has an average pore diameter of 5 Å and the surface area of BET is 4 square meters per gram. The reactor 1 is also filled with 3% Pt and 2% Re weight ratio. The feed solution of this example contains 12 · 4 parts by weight of a styrene-butadiene block copolymer (32 mol /% styrene) and 87 · 6 parts by weight of a cyclohexane solvent. The liquid hourly space velocity was initially set at h8, and then dropped to 1.2, and the conversion rate remained above 99% until the productivity reached 73.3 grams of polymer per gram of catalyst. Even with a productivity of 108 g / g, the conversion rate remains above 98%. Unexpectedly better performance and slower catalyst deactivation were obtained. It was unexpectedly found that when using a catalyst having a particle size suitable for a fixed bed reactor, as described herein, a catalyst support having a larger average pore diameter of 15 can achieve improved productivity, where the catalyst is effective for deactivating the High resistance and therefore longer catalyst life. [Tao-style brief description 3 (none) [Representative symbols for the main elements of the diagram] (none) 19