English:
[0009] Japanese Published Patent Application No. JP2001 -031716 A, published February 26, 2001, discloses the synthesis of epoxy-ethylenedicyclopentadiene (E/DCPD) copolymers having 16, 27, and 40 mole % epoxy-DCPD units and Tgs of, respectively, 56, 112, and 178 0C. These materials are derived from E/DCPDs synthesized using a μ-(CH2CH2)bis(l- indenyl)ZrCl2 catalyst and having GPC molecular weights of Mw < 150,000 (versus polystyrene standards). The exemplified epoxidation of the copolymer is carried out in a toluene solvent using a premixed combination of formic acid and hydrogen peroxide as an epoxidizing agent. IR and NMR analysis of the resulting epoxidized copolymer is said to show that 100 mol % of the unsaturated bonds in the copolymer are converted to epoxy groups.
[0015] Although the preceding discussion demonstrates that epoxidation has been widely used to functionalize olefins and olefin polymers, it is believed that epoxidation and/or hydroxylation has to date never been suggested as a route for effecting in-situ functionalization and impact modification of a rigid cyclic diene copolymer, such as E/DCPD, in admixture with a flexible or elastomeric copolymers derived from dienes such as 7-methyl-l,6-octadiene (MOD), 4-vinyl-l-cyclohexene (VCH), and 1,4-hexadiene. The in- situ epoxidation can be conducted on a solution of the rigid and elastomeric copolymers, thereby resulting in co-precipitation of the epoxidized (and possibly also hydroxylated) products and hence avoiding the need for the melt mixing conventionally used to effect impact modification of cyclic olefin copolymers. Moreover, the resultant epoxidized material typically retains the high and low Tg values associated with the rigid and elastomeric precursors respectively. In addition, the process can be selectively controlled in such a way that the rigid cyclic olefin copolymer, such as E/DCPD, forms an epoxide, while the flexible elastomer, such as an ethylene-propylene-diene monomer (EPDM) copolymer rubber, forms epoxide ring opened products, such as diols or copolymers with both hydroxyl and ester groups.
[0048] The most preferred types of elastomeric polymeric materials for use in the copolymer mixtures herein are of three basic types. These threes types are the polymerized conjugated linear dienes, olefm/nonconjugated diene copolymers, and aromatic vinyl/conjugated diene copolymers.
[0053] The elastomeric polymers and copolymers used in the present invention are conventional materials and can be prepared using any of the polymerization procedures known in the art to be useful for synthesis of materials of this type. Polymer and copolymer properties such as Tg, molecular weight, diene content, etc., can be adjusted by selecting appropriate reactant types, reactant concentrations, and polymerization reaction conditions to realize any desired set of elastomer characteristics.
[0063] Another preferred type of oxidizing agent for use in the process herein is hydrogen peroxide itself. Hydrogen peroxide has the chemical formula H2O2 and is a strong oxidizing agent. It is a raw material which is readily commercially available in a variety of forms.
[0072] The MTOZH2O2 system has relatively high acidity, and such high acidity can promote hydrolysis of epoxidized products to hydroxylated, diol products. Accordingly, when the epoxidized copolymer is the desired primary reaction product, it may be appropriate to add one or more basic ligands to the MTO complex. Such basic ligands can, for example, be nitrogen-containing compounds such as ammonia or primary, secondary or tertiary amines including those described in U.S. Patent No. 5,155,247, incorporated herein by reference. Such ligands can be reacted with the MTO complex prior to the introduction of the MTO-based catalyst into the common liquid reaction medium used in the process herein. Alternatively, ligand forming-compounds such as pyridine, bipyridine or other pyridine derivatives can be added to the common liquid reaction medium along with the reactants, MTO catalyst and reaction solvents.
[0076] In another aspect of the present invention, the mixtures of rigid α-olefm/diene copolymers and elastomeric diene-based polymeric materials as hereinbefore described are converted using the oxidizing agents and optional catalyst materials also hereinbefore described to hydroxylated copolymers by subjecting the common liquid reaction medium containing these reactants to reaction conditions which convert from about 50% to 100% of the double bonds in the diene-derived co-monomers to diol moieties. (One or both of the hydroxyl groups in such diol moieties can be further converted to other oxygen-containing functional moieties such as ester, ether or acid groups.) Certain types and concentrations of reactants and catalysts, as well as relatively higher reaction temperatures and relatively longer reaction times, tend to favor conversion of the unsaturated copolymers to hydroxylated, diol-containing functionalized copolymers.
[0086] Preferred compositions will utilize as the rigid copolymer component, the ethylene/dicyclopentadiene (E/DCPD) materials hereinbefore described with respect to preferred process embodiments herein. Such preferred rigid copolymers have been at least partially epoxidized in-situ within the common liquid reaction medium. Preferred compositions herein will also utilize the preferred elastomeric polymers and copolymers hereinbefore described with respect to the preferred process embodiments herein.
[0095] 1.2835 g of ethylene/dicyclopentadiene copolymer (E/DCPD) containing about 43.6 mole % DCPD (FW 132.20, bp 170 0C 0.00757 moles, Mn 119,000; Mw 213,000) and 1.283 g of ethylene / 1-octene/ 4-vinyl-l-cyclohexene copolymer (E/O/VCH) containing about 13.8 mole % VCH (0.00295 moles) are charged into a reaction flask and dissolved in 200 ml of chloroform. To the polymer solution is added 9.6847 g of formic acid (FW 46.03; 0.2104 mole, 20-fold excess) followed by 1.2522 g of 30% hydrogen peroxide (FW 34.02, 0.01105 moles, 5% excess). The solution is stirred at room temperature for 18 hours. The reaction mixture is poured into 500 ml methanol and the solid precipitate is filtered, washed with methanol, and dried under vacuum (0.1 mm) at 60 0C overnight. The yield of the product is 2.6 g.
[0096] The IR spectrum of the products from Example 1 show absorption peaks due to both epoxidized DCPD and ring opened product of E/O/VCH (formate). In the proton spectrum, the unreacted DCPD and VCH can be determined from the olefmic peals at 5.5 (DCPD only) and 5.7 (DCPD and VCH) ppm. The differential between the peak areas is used to calculate the VCH contribution. VCH formate hemiester is quantified from the peaks at 8.1 and 5.1-4.9 ppm. The cluster of peaks from 4.0-3.0 ppm is corrected for contributions from VCH formate, DCPD olefin, and methanol. The residual integral in the region is assigned to DCPD epxoide.
[00105] 2.1 g of ethylene/dicyclopentadiene copolymer (E/DCPD) containing about 43.6 mole % DCPD (FW 132.20, bp 170 0C 0.01239 moles) and 0.900 g of EPDM containing about 3 mole % ethylidene norbornene (0.00067 moles) are charged into a reaction flask and dissolved in 300 ml of chloroform. To the polymer solution is added 12.01964 g of formic acid (FW 46.03; 0.26112 moles, 20-fold excess) followed by 1.5341 g of 30% hydrogen peroxide (FW 34.02, 0.01371 mole, 5% excess). The solution is stirred at room temperature for 18 hours. The reaction mixture is poured into 750 ml methanol and the solid precipitate is filtered, washed with methanol, and dried under vacuum (0.1 mm) at 50 0C overnight. The yield of the product is 3.08 g.
[00106] The GPC analysis of the product shows Mn 139,000 and Mw 250,000 (polydispersity Mw/Mn 1.80). The DSC analysis of the product shows one T8 at 174.47 0C.
[00109] 8.4 g of ethylene/dicyclopentadiene copolymer (E/DCPD) containing about 45.7 mole % DCPD (FW 132.20, bp 170 0C 0.0508 moles) and 3.6 g of EPDM containing about 5 wt. % ethylidene norbornene (0.0015 moles) are charged into a reaction flask and dissolved in 500 ml of chloroform. To the polymer solution is added 48.15 g of formic acid (FW 46.03; 1.046 mole, 20-fold excess) followed by 14.82 g of 30% hydrogen peroxide (FW 34.02, 0.13 mole, 5% excess). The solution is stirred at room temperature for 18 hours. The reaction mixture is poured into 2500 ml methanol and the solid precipitate was filtered, washed with methanol, and dried under vacuum (0.1 mm) at 60 0C overnight. The yield of the product is 12.0O g. [00110] The impact of the material is 2.7 vs. 0.2 for E/NB copolymer (topaz).
[00111] 1.8 g of ethylene/dicyclopentadiene copolymer (E/DCPD) containing about 45.7 mole % DCPD (FW 132.20, bp 170 0C 0.011 moles) and 0.2 g of polybutadiene copolymer (36 % cis, 55 % trans, 9 % 1,2, Aldrich, mw 420,000, Tg -95 0C) (0.0037 moles) are charged into a reaction flask and dissolved in 40 ml of chloroform. To the polymer solution is added 13.5 g of formic acid (FW 46.03; 20-fold excess) followed by 4.5 g of 30% hydrogen peroxide (FW 34.02, 5% excess). The solution is stirred at room temperature for 18 hours. The reaction mixture is poured into 500 ml methanol and the solid precipitate is filtered, washed with methanol, and dried under vacuum (0.1 mm) at 50 0C overnight. The yield of the product is 1.93 g.

中文:
[0009]日本2001年2月26日已公开的专利申请JP2001-031716A中公开了环氧乙烯/二环戊烯(E/DCPD)共聚物的合成,该共聚物具有16,27和40mol%环氧-DCPD单元和分别为56,112和178°C的Tg值。这些材料衍生自使用μ-(CH2CH2)双(1-茚基)ZrCl2催化剂合成和GPC法测得的分子量MW≤150,000(以聚苯乙烯为标准)的聚E/DCPD。该共聚物的例示环氧化反应在甲苯溶剂中进行,反应使用预混合的甲酸和过氧化氢作为环氧化剂。对得到的环氧化共聚物进行的IR和NMR分析结果显示在该共聚物中100摩尔%的不饱和键转化成环氧基。
[0015]虽然前面的讨论展示了环氧化已经广泛被用来官能化烯烃和烯烃聚合物,人们相信环氧化和/或羟基化迄今为止从来没有被建议作为进行在与衍生自二烯烃例如7-甲基-1,6-辛二烯(MOD),4-乙烯基-1-环己烯(VCH),和1,4-己二烯的柔性或弹性共聚物的掺混物中,刚性环状二烯烃共聚物例如E/DCPD的原位官能化和冲击改性的途径。可以对该刚性的和弹性共聚物的溶液进行原位环氧化,从而得到环氧化(还可能羟基化)产物的共沉淀和因此避免了通常用于进行环烯烃共聚物冲击改性的熔融混合的需要。此外,得到的环氧化的材料通常保持了分别与刚性和弹性体前体相关的高或低Tg值。此外,该方法可以是有选择地控制使得刚性环烯烃共聚物,例如E/DCPD形成环氧化物,而柔性弹性体例如乙烯-丙烯-二烯烃单体(EPDM)共聚物橡胶形成环氧化物开环的产物,例如二醇或同时含有羟基和酯基的共聚物。
[0048]用于本发明共聚物混合物的最优选类型的弹性体聚合物材料是三个基本类型。该三个基本类型是聚合的共轭线性二烯烃,烯烃/非共轭二烯烃共聚物,和芳族乙烯基/共轭二烯烃共聚物。
[0053]本发明使用的弹性聚合物和共聚物是常规的材料和可以使用任何本领域已知的用于合成这类材料的任何聚合方法制备。聚合物和共聚物性能例如Tg,分子量,二烯烃含量等等可以通过选择适当反应物类型,反应物浓度,和聚合反应条件来调整以获得要求的成套弹性体特性。
[0063]本发明方法中使用的另一种类型的优选氧化剂为过氧化氢自身。过氧化氢具有化学式H2O2和是强氧化剂。它是容易在市场上以各种形式商购的原材料。
[0072]MTO/H2O2体系具有相对高的酸性,并且此种高酸性能够促进环氧化产物水解成羟基化二醇产物。因此,当环氧化共聚物是所需的主要反应产物时,添加一种或多种碱性配体到MTO络合物中可能是合适的。这样的碱性配体可以例如是含氮化合物例如氨或伯、仲或叔胺,包括美国专利5,155,247中描述的那些,该文献在此引入作为参考。这样的配体可以在将基于MTO的催化剂引入本文方法中使用的反应介质中之前与MTO络合物反应。或者,可以将形成配体的化合物如吡啶、联吡啶或其它吡啶衍生物与反应物、MTO催化剂和反应溶剂一起添加到普通液体反应介质中。
[0076]在本发明的另一方面中,使用上文中描述过的氧化剂和任选催化剂材料通过如下方式将上文描述的刚性α-烯烃/二烯烃共聚物和弹性二烯烃基聚合物材料的混合物转化以使共聚物羟基化:使含有这些反应物的普通液体反应介质经历将二烯衍生的共聚单体中双键的大约50%至100%转化成二醇结构部分的反应条件。(这些二醇结构中的一个或者两个羟基可以进一步转化成其它的含氧官能结构部分如酯、醚或者酸基)。反应物和催化剂的某些类型和浓度,以及相对较高的反应温度和相对较长的反应时间,倾向于有利于所述不饱和共聚物转化成羟基化的、含二醇的官能化共聚物。
[0086]优选的组合物使用以上关于本发明优选方法实施方案描述的乙烯/二环戊二烯(E/DCPD)材料作为刚性聚合物组分。这些优选的刚性共聚物已经在普通液体反应介质中至少部分地原位环氧化。本发明的优选组合物也采用以上关于本发明优选方法实施方案描述的优选弹性聚合物和共聚物。
[0095]1.2835克包含约43.6mol�PD(FW 132.20,bp 170°C0.00757摩尔,Mn119,000;Mw213,000)的乙烯/二环戊二烯共聚物(E/DCPD)和1.283克包含约13.8mol%VCH(0.00295摩尔)的的乙烯/1-辛烯/4-乙烯基-1-环己烯共聚物(E/O/VCH)加入反应烧瓶并溶于200毫升的氯仿中。在聚合物溶液中添加9.6847克甲酸(FW 46.03;0.2104摩尔,20倍过量),接着加入1.2522克的30%过氧化氢(FW34.02,0.01105摩尔,5%过量)。溶液在室温下搅拌18小时。将反应混合物倾入500毫升甲醇中,并将固体沉淀物过滤,用甲醇洗涤,60°C真空干燥(0.1毫米)过夜。产物的产量为2.6g。
[0096]来自实施例1产物IR光谱显示由于环氧化的DCPD和E/O/VCH的开环产物(甲酸酯)两者的吸收峰。在质子光谱中,该未反应的DCPD和VCH可以由5.5(仅DCPD)和5.7(DCPD和VCH)ppm的烯属峰确定。峰面积之差被用来计算VCH贡献。VCH甲酸酯半酯的量由在8.1和5.1-4.9ppm的峰计算。将来自4.0-3.0ppm峰的晶簇校正来自VCH甲酸酯,DCPD烯烃,和甲醇的贡献。该区域的残留积分分配给DCPD环氧化物。
[00105]2.1克的乙烯/二环戊二烯共聚物(E/DCPD),其包含约43.6mol�PD(FW 132.20,bp 170°C0.01239摩尔)和0.900克包含约3mol%亚乙基降冰片烯(0.00067摩尔)的EPDM加入反应烧瓶并溶于300毫升氯仿。在聚合物溶液中添加12.01964克甲酸(FW 46.03;0.26112摩尔,20倍过量),接着加入1.5341克的30%过氧化氢(FW34.02,0.01371摩尔,5%过量)。溶液在室温下搅拌18小时。将反应混合物倾入750毫升甲醇中,并将固体沉淀物过滤,用甲醇洗涤,50°C真空干燥(0.1毫米)过夜。该产物的产量是3.08克。
[00106]产物的GPC分析显示Mn139,000和Mw250,000(多分散性Mw/Mn1.8)。该产物的DSC分析一个Tg,为174.47°C。
[00109]8.4克的乙烯/二环戊二烯共聚物(E/DCPD),其包含约45.7mol�PD(FW 132.20,bp 170°C0.0508摩尔)和3.6g包含约5wt%的亚乙基降冰片烯(0.0015摩尔)的EPDM加入反应烧瓶中并溶解于500毫升的氯仿。在聚合物溶液中添加48.15克甲酸(FW 46.03;1.046摩尔,20倍过量),接着加入14.82克的30%过氧化氢(FW34.02,0.13摩尔,5%过量)。溶液在室温下搅拌18小时。将反应混合物倾入2500毫升甲醇中,并将固体沉淀物过滤,用甲醇洗涤,60°C真空干燥(0.1毫米)过夜。该产物的产量是12.00克。
[00111]1.8克的乙烯/二环戊二烯共聚物(E/DCPD),其包含约45.7mol�PD(FW 132.20,bp 170°C 0.011摩尔)和0.2克的聚丁二烯共聚物(36%顺式,55%反式,9%1,2,Aldrich,mw 420,000,Tg-95°C)(0.0037摩尔)加入反应烧瓶中并溶于40毫升的氯仿。在聚合物溶液中添加13.5克甲酸(FW 46.03;20倍过量),接着加入4.5克的30%过氧化氢(FW 34.02,5%过量)。溶液在室温下搅拌18小时。将反应混合物倾入500毫升甲醇中,并将固体沉淀过滤,用甲醇洗涤,50°C真空干燥(0.1毫米)过夜。该产物的产量是1.93克。