CN103396514A - Catalyst for ternary polymerization of norbornene, maleic anhydride and pentene, and ternary polymerization method - Google Patents

Catalyst for ternary polymerization of norbornene, maleic anhydride and pentene, and ternary polymerization method Download PDF

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CN103396514A
CN103396514A CN 201310333251 CN201310333251A CN103396514A CN 103396514 A CN103396514 A CN 103396514A CN 201310333251 CN201310333251 CN 201310333251 CN 201310333251 A CN201310333251 A CN 201310333251A CN 103396514 A CN103396514 A CN 103396514A
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catalyst
ternary
polymerization
bottle
norbornene
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CN103396514B (en )
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房江华
高浩其
杨建平
胡敏杰
方烨汶
肖勋文
丛杨
王志强
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宁波工程学院
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Abstract

The invention relates to a catalyst for ternary polymerization of norbornene, maleic anhydride and pentene, and a ternary polymerization method. The catalyst is prepared by following steps: dissolving bis(cyclopentadienyl) zirconium dichloride, a ligand and an alkyl metal compound to a first solvent in a dry single-opening glass bottle in which inert gas is filled; sealing the bottle opening by an emulsion tube, keeping the bottle at a constant temperature for 5 to 15min in a water bath of 40 to 50 DEC C; and cooling so as to obtain the zirconium complex catalyst. Preparation method of the catalyst is simple. The catalyst can produce catalytic activity under a certain pressure, at a temperature and in nitrogen protection system; the norbornene, maleic anhydride and pentene are catalyzed and are subjected to ternary polymerization; and products are easy to wash and separate after being soaked by methanol. The yield of copolymer is high; the reaction temperature is low; the catalyst is low in cost and is easy to obtain; and the catalytic efficiency is high.

Description

降冰片烯类、马来酸酐和戊烯类三元共聚催化剂以及三元共聚方法 Norbornene, maleic anhydride and terpolymers pentene copolymerization process as well as ternary catalyst

技术领域 FIELD

[0001] 本发明涉及到高聚物领域,具体指一种降冰片烯类、马来酸酐和戊烯类三元共聚催化剂以及三元共聚方法。 [0001] The present invention relates to polymers, and in particular means a norbornene, maleic anhydride, and pentene terpolymers and terpolymers catalyst reduction method.

背景技术 Background technique

[0002] 聚降冰片烯是一种特殊的聚合物,具有优良的力学性能、耐热性、在有机溶剂中的可溶性及透明性,可用于193nm紫外光光刻。 [0002] polynorbornene is a special polymer, having excellent mechanical properties, heat resistance, transparency and solubility in an organic solvent, it can be used to 193nm ultraviolet lithography. 这一材料主要缺点是脆性、粘性差和分子量低等。 The main drawback of this material is brittle, poor tack and low molecular weight. 将马来酸酐插入聚降冰片烯主链中后,可提高聚合物的粘结性和可溶性,戊烯的聚入可以增加共聚物光刻材料的韧性。 After the maleic anhydride inserted polynorbornene backbone, and can improve adhesion of the soluble polymer, the poly-pentene copolymer may increase the toughness of the photoresist material. 这种三元共聚物可作为光阻材料应用于193nm影印技术。 Such terpolymers may be applied as a photoresist material 193nm photocopying technology. 而且,微电子工业的发展需要尺寸更小的成分,对适用于线宽为1.3μπι及以下线宽的曝光技术,可选择193nm光刻技术,这些技术涉及光刻工艺的各个方面,提出了新的光学材料及其制造和镀膜技术、新型抗蚀剂、用于掩模及其保护薄膜的新材料等有待于解决的问题。 Moreover, the development of the microelectronics industry requires smaller components, to apply to the following line width and line width 1.3μπι exposure technique, you can choose 193nm lithography techniques that involve all aspects of the lithography process, a new optical materials and manufacturing and coating technology, new resist mask and the new materials used for the protective film remains to solve the problem. 因此,为了获得好的光刻新材料,发展了交替共聚材料,主要发展降冰片烯与马来酸酐类二组份共聚和降冰片烯与马来酸酐、丙稀酸酯或其他组份三元共聚材料,同时应用有侧基的降冰片烯,目的是提高整个基质的抗蚀能力,提高光刻性能,增加材料的粘结性、可溶性和韧性。 Accordingly, in order to obtain good lithographic new materials, the development of materials alternating copolymerization, the main development norbornene and maleic anhydride-based copolymers and two component norbornene and maleic anhydride, acrylic esters, or other components of the three yuan copolymeric material while applications are pendant norbornene, aimed at improving the overall corrosion resistance of the matrix, to improve lithographic performance, increased material adhesion, toughness, and solubility.

[0003]目前合成这些材料的方法主要有自由基、活性自由基、金属催化剂等方法。 [0003] Current methods for synthesizing these materials are mainly free radical, living radical, metal catalysts and the like. 如Proceedings of SPIE Vol.5039 (2003)第80〜92页公开的光刻材料的合成采用了过氧化物作为自由基聚合的催化剂,Proceedings of SPIE Vol.4690(2002)第127〜135页公开的光刻材料的合成采用了AINB (偶氮二异丁腈)作为自由基聚合的催化剂。 The Proceedings of the synthesis of SPIE Vol.5039 (2003) disclosed on page 80~92 of photoresist material using a peroxide as a radical polymerization catalyst, Proceedings of SPIE Vol.4690 (2002) disclosed on page 127~135 synthetic materials using photolithography AINB (azobisisobutyronitrile) as a radical polymerization catalyst. 目前应用的这些合成方法存在反应时间长、获得共聚物收率低、共聚物分子量小、共聚物交替度低等缺点,并且国内对降冰片烯与马来酸酐、戊烯三元共聚研究开展很少。 The presence of these synthesis methods currently used long reaction time, low yield is obtained copolymer, small molecular weight copolymers, alternating copolymers of low defects, and domestic and maleic anhydride, norbornene, pentene terpolymers study was carried out less. 发明内容 SUMMARY

[0004] 本发明所要解决的技术问题是针对现有技术的现状提供一种能够降低反应温度、提高催化效率和共聚物收率的降冰片烯类、马来酸酐和戊烯类三元共聚用催化剂。 [0004] The present invention solves the technical problem of reducing the reaction temperature to provide an improved catalytic efficiency and norbornene copolymers yield of maleic anhydride, and pentene terpolymers with the current situation of the prior art catalyst.

[0005] 本发明所要解决的第二个技术问题是提供一种反应温度低、催化效率高和共聚物收率高的降冰片烯类、马来酸酐和戊烯类三元共聚的方法。 [0005] The present invention is to solve the second technical problem is to provide a low reaction temperature, high catalytic efficiency and yield of copolymer norbornene, maleic anhydride, and pentene method terpolymerized.

[0006] 本发明解决上述技术问题所采用的技术方案为:该降冰片烯类、马来酸酐和戊烯类三元共聚催化剂,其特征在于该催化剂是由下述方法制备得到的: [0006] aspect of the present invention to solve the above technical problem is: the norbornene, maleic anhydride, and pentene terpolymers catalyst, wherein the catalyst is obtained by the following method of preparation:

[0007] 在惰性气体氛围的干燥的单口玻璃瓶中,将双(环戊二烯基)二氯化锆、配体和烷基金属化合物溶解于第一溶剂中,瓶口用乳胶管密封,在40_50°C水浴中恒温5-15分钟,冷却后即得锆络合物催化剂; [0007] In a dry glass jar single inert gas atmosphere, zirconium bis (cyclopentadienyl) dichloride, and an alkyl metal ligand compound is dissolved in a first solvent, latex tube was sealed bottle, 5-15 minutes in a thermostatic water bath 40_50 ° C, after cooling to obtain a zirconium complex catalyst;

[0008] 所述双(环戊二烯基)二氯化锆与所述配体的摩尔比为10: 10〜10: 1,所述双(环戊二烯基)二氯化锆与所述烷基金属化合物的摩尔比为10: 5〜10: I ;[0009] 所述配体选自8-羟基喹啉、α,α,-联吡啶、邻二氮菲、吡啶、异喹啉、喹啉、叶啉、乙酰基丙酮或苯酰基丙酮; Molar ratio [0008] The bis (cyclopentadienyl) zirconium dichloride, the ligand is 10: 10~10: 1, the bis (cyclopentadienyl) zirconium dichloride and the the molar ratio of said alkyl metal compound is 10: 5~10: I; [0009] the ligand is selected from 8-quinolinol, α, α, - bipyridine, phenanthroline, pyridine, isoquinoline , quinoline, morpholine leaf, benzoyl acetone or acetyl acetone;

[0010] 所述烷基金属化合物选自三乙基铝、三异丁基铝、三乙基锌、二氯乙基铝中任意一种; [0010] The metal alkyl compound is selected from triethylaluminum, triisobutylaluminum, triethyl zinc, any one of ethyl aluminum dichloride;

[0011] 所述第一溶剂选自四氢呋喃、苯甲醚、1,4-二氧六环、环已酮或甲苯;所述第一溶剂的用量与所述双(环戊二烯基)二氯化锆、配体和烷基金属化合物三者总量的比例为20毫升:0.03〜0.25摩尔。 [0011] the first solvent is selected from tetrahydrofuran, anisole, 1,4-dioxane, cyclohexanone or toluene; an amount of the first solvent with the bis (cyclopentadienyl) bis zirconium chloride, the ratio of the total amount of the ligand and the metal alkyl compound is a 20 ml three: 0.03~0.25 mol.

[0012] 优选所述双(环戊二烯基)二氯化锆、配体、烷基金属化合物三者的摩尔比为10: 5: 2。 [0012] Preferably, the bis (cyclopentadienyl) zirconium dichloride, the ligand, the molar ratio of alkyl metal compound of the three 10: 5: 2.

[0013] 上述各方案中,所述配体、所述第一溶剂在使用前可以先进行干燥;其中所述配体中的固态配体的干燥是先用重结晶办法纯化然后真空干燥;所述配体中的液态配体的干燥是用氢化钙或金属钠干燥,所述溶剂采用氯化钙或氢化钙干燥。 [0013] In the above embodiment, the ligand, the first solvent can first be dried before use; dry solid ligand wherein said ligand is purified first by recrystallization and then dried in vacuo way; the drying said liquid ligands are ligands with calcium hydride or metallic sodium sulfate, and the solvent is dried using calcium hydride or calcium chloride.

[0014] 使用上述降冰片烯类、马来酸酐与戊烯类三元共聚用催化剂进行降冰片烯类、马来酸酐与戊烯三元共聚的方法,其特征在于包括下述步骤: [0014] Using the above-described norbornene, maleic anhydride and terpolymers pentene with a catalyst for the norbornene, maleic anhydride and terpolymers of pentene method, comprising the steps of:

[0015] 按照摩尔比为1:1:1取降冰片烯类、马来酸酐和戊烯类单体,将三者加入到惰性气体氛围的干燥的高压釜中,然后向该高压釜中加入第二溶剂,溶解;将所述的锆络合物催化剂加入到所述的高压釜中,在40〜100°C下恒温、0.5-5MP压力下反应0.5〜6小时; [0015] molar ratio of 1: 1: 1 and dried autoclave take norbornene, maleic anhydride, and pentene monomer, the three added to the inert gas atmosphere, and then added to the autoclave the second solvent, dissolve; the zirconium complex catalyst was added to the autoclave, temperature, reaction pressure 0.5-5MP 0.5~6 hours at 40~100 ° C;

[0016] 将得到的反应产物倾入含5wt%盐酸的甲醇溶液中,得到降冰片烯类、马来酸酐和戊烯类三元共聚物的沉淀物,将该沉淀物用甲醇洗涤至中性后,真空干燥,即得到降冰片烯类、马来酸酐和戊烯类三元共聚物; Methanol [0016] The reaction product was poured into hydrochloric acid containing 5wt%, to obtain a norbornene, maleic anhydride, and pentene terpolymer precipitate, and the precipitate was washed with methanol until neutral after vacuum drying, to obtain a norbornene, maleic anhydride, and pentene terpolymers;

[0017] 所述锆络合物催化剂的用量`为降冰片烯类、马来酸酐和戊烯类单体总重量的 [0017] The amount of zirconium complex catalyst `norbornene, maleic anhydride, and the total weight of the monomers pentene

0.03 〜1% ; 0.03 ~ 1%;

[0018] 所述第二溶剂选自四氢呋喃、苯甲醚、1,4- 二氧六环、环已酮或甲苯;所述第二溶剂的用量与聚合单体总量的比例为20毫升:0.09摩尔。 [0018] The second solvent is selected from tetrahydrofuran, anisole, 1,4-dioxane, cyclohexanone or toluene; an amount ratio of the second solvent is the total amount of the polymerizable monomer 20 ml: 0.09 mole.

[0019] 较好的,所述降冰片烯类选自二环[2,2,1]庚-2-烯、1-甲基二环[2,2,1]庚_2_稀、5_甲基二环[2,2,1]庚_2_稀、7_甲基二环[2,2,1]庚-2-稀、1-乙基二环[2,2,I]庚-2-烯、5-乙基二环[2,2,1]庚-2-烯、5,5_ 二甲基二环[2,2,I]庚-2-烯、1-苯基二环[2, 2,1]庚_2_稀、5_苯基二环[2, 2,1]庚-2-稀、5-乙稀基二环[2, 2,1]庚-2-稀、二环[2,2,I]庚-2-烯-5-甲酸甲酯或二环[2,2,I]庚-2-烯-5-甲酸特丁酯; [0019] preferably, the norbornene-based is selected from bicyclo [2,2,1] hept-2-ene, 1-methyl-bicyclo [2,2,1] hept-_2_ dilute, 5 _ methyl-bicyclo [2,2,1] hept-_2_ dilute, 7_ methyl-bicyclo [2,2,1] hept-2-dilute, 1-ethyl-bicyclo [2,2, I] hept-2-ene, 5-ethyl-bicyclo [2,2,1] hept-2-ene, 5,5_-dimethyl-bicyclo [2,2, I] hept-2-ene, 1-phenyl bicyclo [2,2,1] hept-_2_ dilute, 5_ phenyl-bicyclo [2,2,1] hept-2-dilute, 5-ethylene-yl bicyclo [2,2,1] hept - 2- dilute, bicyclo [2,2, I] hept-2-ene-5-carboxylate, or bicyclo [2,2, I] hept-2-ene-5-carboxylic acid tert ester;

[0020] 所述戍烯选自1-戍烯、2_戍烯、3-甲基-1-戍烯、4-甲基-1-戍烯、3-甲基-2-戍稀、5_环已基-1-戍稀或5_环已基-2-戍稀。 [0020] The selected from 1-pentene pentene, 2_ pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-lean Shu, 5 _ cyclohexyl-1-cyclohexyl-shu 5_ dilute or dilute Shu-2.

[0021] 与现有技术相比,本发明提供了一种新型锆络合物催化剂,制备方法简单,它能在一定压力、温度在40〜10(TC时,在氮气保护体系中产生催化活性,催化降冰片烯类、马来酸酐与戊烯类单体的三元共聚,经甲醇浸泡后,聚合产物很容易洗涤分离;具有共聚物收率高,反应温度低,催化剂廉价、易得、催化效率高等特点。 [0021] Compared with the prior art, the present invention provides a novel zirconium complex catalyst preparation method is simple, it can in certain pressure, temperature, in a nitrogen atmosphere to produce a catalytically active system at 40~10 (TC catalytic norbornene, maleic anhydride with a trihydric pentene comonomer, after soaking in methanol, the polymerization product was washed easily separated; copolymer having a high yield, low reaction temperature, the catalyst inexpensive, readily available, catalytic efficiency.

具体实施方式 detailed description

[0022] 以下结合实施例对本发明作进一步详细描述。 [0022] The following embodiments in conjunction with the present invention is described in further detail.

[0023] 下列各实施例的催化剂制备过程中,如无特别说明,在使用前均对其中的配体和溶剂进行了干燥处理。 [0023] The following catalyst preparation procedure of each of the embodiments, unless otherwise specified, before use of both ligand and a solvent in which a drying process. 具体的干燥方法是:对固体配体的干燥先用重结晶办法纯化然后再真空干燥;对液体配体是用氢化钙干燥或金属钠干燥;溶剂的干燥是用氯化钙或氢化钙干燥。 Specific drying methods are: drying of the solid ligand purified first by recrystallization and then dried again in vacuo way; liquid calcium hydride ligand with a metal sulfate or sodium sulfate; the solvent is dried with calcium chloride or calcium hydride drying.

[0024] 上述溶剂包括第一溶剂和第二溶剂。 [0024] The solvent comprises a first solvent and a second solvent.

[0025] 实施例1 [0025] Example 1

[0026] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升四氢呋喃、 [0026] After a single glass bottle was evacuated several times, flushed with nitrogen baked in 20 ml of tetrahydrofuran were added,

0.10摩尔双(环戊二烯基)二氯化锆、0.10摩8-羟基喹啉和0.05三乙基铝,在50°C水浴中恒温15分钟,冷却后即得锆络合物催化剂。 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, 0.10 mol 0.05 8-hydroxyquinoline, and triethyl aluminum, 50 ° C and a constant temperature water bath for 15 minutes and after cooling to obtain a zirconium complex catalyst.

[0027] 将0.03摩尔二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔1-戊烯加入已充氮气的高压釜中,加20ml四氢呋喃溶解。 [0027] 0.03 mol of bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of 1-pentene was added autoclave purged with nitrogen, 20ml of tetrahydrofuran was added to dissolve. 按降冰片烯、马来酸酐、1-戊烯三者的总重量计取1%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, a total weight of 1-pentene billing three 1% of the catalyst, with the syringe to the above mixture. 恒温在90°C,0.5MP压力,反应0.5小时。 Thermostated at 90 ° C, 0.5MP pressure, for 0.5 hours. 将产物倾入含5%盐酸的甲醇溶液中使降冰片烯、马来酸酐、1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,测得反应收率为36.9%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield was 36.9 measured %.

[0028] 反应收率的计算是产物重量/ (降冰片烯衍生物+马来酸酐+戊烯)的总重量。 [0028] The reaction yield was calculated weight of the product / (norbornene derivative maleic anhydride + + pentene) total weight. 下述各实施例与此相同。 Each of the following examples and the same.

[0029] 实施例2 [0029] Example 2

[0030] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升苯甲醚、0.10摩尔双(环戊二烯基)二氯化锆、0.01摩α,α ,-联吡啶和0.01摩三异丁基铝,在40°C水浴中恒温5分钟,冷却后即得锆络合物催化剂。 [0030] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of anisole, 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, 0.01 mol α, α, - bipyridine and 0.01 mol of triisobutylaluminum, 5 minute at 40 ° C water bath, after cooling to obtain a zirconium complex catalyst.

·[0031] 将0.03摩尔1-甲基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔3_甲基-1-戊烯加入已充氮气的高压釜中,加20ml苯甲醚溶解。 * [0031] 0.03 mol of 1-methyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of methyl-1-pentene 3_ been purged with nitrogen was added to the autoclave , add 20ml of anisole were dissolved. 按降冰片烯、马来酸酐、3-甲基-1-戊烯三者的总重量计取0.3%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, a total weight of 3-methyl-1-pentene three billing 0.3% of the catalyst, with the syringe to the above mixture. 恒温在90°C,5MP压力,反应6小时。 Thermostated at 90 ° C, 5MP pressure, the reaction for 6 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、3-甲基-1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率56.9%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 3-methyl-1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 56.9 %.

[0032] 实施例3 [0032] 3 Example

[0033] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升1,4_ 二氧六环、0.10摩尔双(环戊二烯基)二氯化锆、0.07摩尔邻二氮菲和0.03摩三乙基锌,在45°C水浴中恒温15分钟,冷却后即得锆络合物催化剂。 [0033] After a single glass bottle was evacuated several times, flushed with nitrogen in baking, 1,4_ were added 20 ml of dioxane, 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, 0.07 mol of o phenanthroline and 0.03 mole triethyl zinc, thermostat for 15 minutes at 45 ° C water bath, after cooling to obtain a zirconium complex catalyst.

[0034] 将0.03摩尔5-甲基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔2_戊烯加入已充氮气的高压釜中,加20mll,4-二氧六环溶解。 [0034] 0.03 mol of 5-methyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of pentene was added 2_ has autoclave purged with nitrogen, was added 20mll, 4 - dioxane was dissolved. 按降冰片烯、马来酸酐、2-戊烯三者的总重量计取0.05%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 2-pentene total weight of the three billing 0.05% of the catalyst, with the syringe to the above mixture. 恒温在100°C,IMP压力,反应4小时。 Thermostated at 100 ° C, IMP pressure, for 4 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、2-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率61.2%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 2-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield of 61.2%.

[0035] 实施例4 [0035] Example 4

[0036] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升甲苯、0.10摩尔双(环戊二烯基)二氯化锆、0.05摩吡啶和0.02摩三异丁基铝,在40°C水浴中恒温10分钟,冷却后即得锆络合物催化剂。 [0036] After a single glass bottle was evacuated several times, flushed with nitrogen in baking were added 20 ml of toluene, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.05 mole of pyridine and 0.02 moles triisobutyl aluminum group, a thermostat for 10 min at 40 ° C water bath, after cooling to obtain a zirconium complex catalyst.

[0037] 将0.03摩尔7-甲基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔4_甲基-1-戊烯加入已充氮气的高压釜中,加20ml甲苯溶解。 [0037] 0.03 mol of 7-methyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of methyl-1-pentene 4_ been purged with nitrogen was added autoclave , dissolved in toluene 20ml was added. 按降冰片烯、马来酸酐、4-甲基-1-戊烯三者的总重量计取0.8%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 4-methylpentene total weight of the three 1-billing of the catalyst of 0.8%, with the syringe to the above mixture. 恒温在100°C,6MP压力,反应5小时。 Thermostated at 100 ° C, 6MP pressure, the reaction for 5 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率89.7%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield of 89.7%.

[0038] 实施例5 [0038] Example 5

[0039] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升环已酮、0.10摩尔双(环戊二烯基)二氯化锆、0.08摩异喹啉和0.02摩二氯乙基铝,在50°C水浴中恒温5分钟,冷却后即得锆络合物催化剂。 [0039] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of cyclohexanone, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.08 and 0.02 mol isoquinoline Mount ethylaluminum dichloride, 5 minute in a water bath at 50 ° C and, after cooling to obtain a zirconium complex catalyst.

[0040] 将0.03摩尔1-乙基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔3_甲基-2-戊烯加入已充氮气的高压釜中,加20ml环已酮溶解。 [0040] 0.03 mol of 1-ethyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of 3_-2-pentene was added to the autoclave charged nitrogen , add 20ml cyclohexanone dissolved. 按降冰片烯、马来酸酐、3-甲基-2-戊烯三者的总重量计取0.5%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, a total weight of 3-methyl-2-pentene three billing 0.5% of the catalyst, with the syringe to the above mixture. 恒温在90°C,3MP压力,反应5小时。 Thermostated at 90 ° C, 3MP pressure, the reaction for 5 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、3-甲基-2-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率65.3%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 3-methyl-2-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 65.3 %.

[0041] 实施例6 [0041] Example 6

[0042] 在经过多次抽真空`、充氮气烘烤的单口玻璃瓶中,分别加入20毫升苯甲醚、0.10摩尔双(环戊二烯基)二氯化锆、0.02摩乙酰基丙酮和0.04摩三异丁基铝,在45°C水浴中恒温15分钟,冷却后即得锆络合物催化剂。 [0042] After a single glass bottle was evacuated several times `nitrogen filling baked in, respectively, 20 ml of anisole, 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, and 0.02 mol acetylacetone 0.04 mol of triisobutylaluminum, 15 minutes in a thermostat water bath at 45 ° C, after cooling to obtain a zirconium complex catalyst.

[0043] 将0.03摩尔5-乙基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔5_环已基-1-戊烯加入已充氮气的高压釜中,加20ml苯甲醚溶解。 [0043] 0.03 mol of 5-ethyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 moles 5_-cyclohexyl-1-pentene was added to the autoclave charged nitrogen , add 20ml of anisole were dissolved. 按降冰片烯、马来酸酐、5-环已基-1-戊烯三者的总重量计取0.06%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 5-cyclohexyl-1-pentene three 0.06% total weight of the catalyst taken by syringe to the above mixture. 恒温在60°C,4MP压力,反应6小时。 Thermostated at 60 ° C, 4MP pressure, the reaction for 6 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、5-环已基-1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率58.8%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 5-cyclohexyl-1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 58.8%.

[0044] 实施例7 [0044] Example 7

[0045] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升四氢呋喃、 [0045] After a single glass bottle was evacuated several times, flushed with nitrogen baked in 20 ml of tetrahydrofuran were added,

0.10摩尔双(环戊二烯基)二氯化锆、0.01摩喹啉和0.01摩三异丁基铝,在50°C水浴中恒温10分钟,冷却后即得锆络合物催化剂。 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, 0.01 mol and 0.01 mol quinoline triisobutylaluminum, thermostat 10 minutes in a water bath at 50 ° C and, after cooling to obtain a zirconium complex catalyst.

[0046] 将0.03摩尔5,5-二甲基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔5-环已基-2-戊烯加入已充氮气的高压釜中,加20ml四氢呋喃溶解。 [0046] 0.03 mol of 5,5-dimethyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of 5-cyclohexyl-2-pentene was flushed with nitrogen was added autoclave, add 20ml of tetrahydrofuran was dissolved. 按降冰片烯、马来酸酐、戊烯三者的总重量计取0.07%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride by weight of the total, three billing pentene 0.07% of the catalyst, with the syringe to the above mixture. 恒温在IOO0C, 4MP压力,反应5小时。 Thermostated at IOO0C, 4MP pressure, the reaction for 5 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、5-环已基-2-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率48.9%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 5-cyclohexyl-2-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 48.9%.

[0047] 实施例8 [0047] Example 8

[0048] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升环已酮、0.10摩尔双(环戊二烯基)二氯化锆、0.02摩α,α ,-联吡啶和0.05摩三乙基铝,在50°C水浴中恒温15分钟,冷却后即得锆络合物催化剂。 [0048] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of cyclohexanone, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.02 mol α, α, - bipyridine and 0.05 mol triethyl aluminum, 50 ° C and a constant temperature water bath for 15 minutes and after cooling to obtain a zirconium complex catalyst.

[0049] 将0.03摩尔1-苯基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔5_环已基-2-戊烯加入已充氮气的高压釜中,加20ml环已酮溶解。 [0049] 0.03 mol of 1-phenyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 moles 5_-cyclohexyl-2-pentene was added to the autoclave charged nitrogen , add 20ml cyclohexanone dissolved. 按降冰片烯、马来酸酐、5-环已基-2-戊烯三者的总重量计取0.09%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 5-cyclohexyl-2-pentene three 0.09% total weight of the catalyst taken by syringe to the above mixture. 恒温在80°C,3MP压力,反应4小时。 Thermostated at 80 ° C, 3MP pressure, for 4 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、5-环已基-2-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率64.2%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 5-cyclohexyl-2-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 64.2%. [0050] 实施例9 [0050] Example 9

[0051] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升环已酮、0.10摩尔双(环戊二烯基)二氯化锆、0.06摩卟啉和0.03摩三异丁基铝,在50°C水浴中恒温10分钟,冷却后即得锆络合物催化剂。 [0051] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of cyclohexanone, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.06 and 0.03 mole friction porphyrin triisobutylaluminum, thermostat 10 minutes in a water bath at 50 ° C and, after cooling to obtain a zirconium complex catalyst.

[0052] 将0.03摩尔1-苯基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔1-戊烯加入已充氮气的高压釜中,加20ml环已酮溶解。 [0052] 0.03 mol of 1-phenyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of 1-pentene was added autoclave purged with nitrogen, was added 20ml cyclohexyl one were dissolved. 按降冰片烯、马来酸酐、1-戊烯三者的总重量计取0.2%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 1-pentene total weight of the three billing 0.2% of the catalyst, with the syringe to the above mixture. 恒温在70°C,5MP压力,反应6小时。 Thermostated at 70 ° C, 5MP pressure, the reaction for 6 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率73.4%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield of 73.4%.

[0053] 实施例10 [0053] Example 10

[0054] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升1,4_ 二氧六环、0.10摩尔双(环戊二烯基)二氯化锆、0.03摩苯酰基丙酮和0.03摩三乙基铝,在45°C水浴中恒温8分钟,冷却后即得铁锆合物催化剂。 [0054] After a single glass bottle was evacuated several times, flushed with nitrogen in baking, 1,4_ were added 20 ml of dioxane, 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, 0.03 mol benzene acyl of acetone and 0.03 mole of triethylaluminum, temperature 45 ° C for 8 minutes in a water bath, after cooling to obtain a zirconium iron compound catalyst.

[0055] 将0.03摩尔5-苯基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔5_环已基-2-戊烯加入已充氮气的高压釜中,加20mll,4- 二氧六环溶解。 [0055] 0.03 mol of 5-phenyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 moles 5_-cyclohexyl-2-pentene was added to the autoclave charged nitrogen , add 20mll, 4- dioxane was dissolved. 按降冰片烯、马来酸酐、5-环已基-2-戊烯三者的总重量计取0.5%的上述催化剂,用注射器注入上述混和物中,恒温在60°C,4MP压力,反应2小时。 Press norbornene, maleic anhydride, 5-cyclohexyl-2-pentene total weight of the three billing 0.5% of the catalyst, the above mixture was injected with a syringe in a thermostat at 60 ° C, 4MP pressure, the reaction 2 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、5-环已基-2-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率61.6%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 5-cyclohexyl-2-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 61.6%.

[0056] 实施例11 [0056] Example 11

[0057] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升环已酮、0.10摩尔双(环戊二烯基)二氯化锆、0.06摩α,α ,-联吡啶和0.02摩三乙基锌,在50°C水浴中恒温15分钟,冷却后即得锆络合物催化剂。 [0057] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of cyclohexanone, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.06 mol α, α, - bipyridine and 0.02 mole triethyl zinc, 50 ° C and a constant temperature water bath for 15 minutes, after cooling to obtain a zirconium complex catalyst.

[0058] 将0.03摩尔5-乙烯基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔2_戊烯加入已充氮气的高压釜中,加20ml环已酮溶解。 [0058] 0.03 mol of 5-vinyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of pentene was added 2_ has autoclave purged with nitrogen, was added 20ml cyclohexyl one were dissolved. 按降冰片烯、马来酸酐、2-戊烯三者的总重量计取0.6%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 2-pentene total weight of the three billing 0.6% of the catalyst, with the syringe to the above mixture. 恒温在90°C,4.5MP压力,反应5小时。 Thermostated at 90 ° C, 4.5MP pressure, the reaction for 5 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、2-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率80.7%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 2-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield of 80.7%.

[0059] 实施例12 [0059] Example 12

[0060] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升环已酮、0.10摩尔双(环戊二烯基)二氯化锆、0.07摩乙酰基丙酮和0.04摩三乙基锌,在50°C水浴中恒温15分钟,冷却后即得锆络合物催化剂。 [0060] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of cyclohexanone, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.07 mol acetylacetone, and 0.04 Mount triethyl zinc, thermostat 15 minutes in a water bath at 50 ° C and, after cooling to obtain a zirconium complex catalyst.

[0061] 将0.03摩尔二环[2,2,1]庚_2_烯_5_甲酸甲酯、0.03摩尔马来酸酐、0.03摩尔4-环已基-1-戊烯加入已充氮气的高压釜中,加20ml环已酮溶解。 [0061] 0.03 mol of bicyclo [2,2,1] hept-ene _5_ _2_ carboxylate, 0.03 mole of maleic anhydride, 0.03 mole of 4-cyclohexyl-1-pentene has been charged nitrogen was added autoclave, add 20ml cyclohexanone dissolved. 按降冰片烯、马来酸酐、4-环已基-1-戊烯三者的总重量计取0.4%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 4-cyclohexyl-1-pentene on the total weight of the three billing 0.4% of the catalyst, with the syringe to the above mixture. 恒温70°C,3MP压力,反应4小时。 Temperature 70 ° C, 3MP pressure, for 4 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、4-环已基-1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率65.7%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 4-cyclohexyl-1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 65.7%.

[0062] 实施例13 [0062] Example 13

[0063] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升环已酮、0.10摩尔双(环戊二烯基)二氯化锆、0.09摩卟啉和0.04摩三乙基锌,在40°C水浴中恒温10分钟,冷却后即得锆络合物催化剂。 [0063] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of cyclohexanone, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.09 mol and 0.04 mol porphyrin triethyl zinc, at 40 ° C constant temperature water bath for 10 minutes and after cooling to obtain a zirconium complex catalyst.

[0064] 将0.03摩尔二环[2,2,I]庚_2_烯_5_甲酸特丁酯、0.03摩尔马来酸酐、0.03摩尔3-甲基-2-戊烯加入已充氮气的高压釜中,加20ml环已酮溶解。 [0064] 0.03 mol of bicyclo [2,2, I] hept-ene _5_ _2_ acid tert ester, 0.03 mole of maleic anhydride, 0.03 mol of 3-methyl-2-pentene has been charged nitrogen was added autoclave, add 20ml cyclohexanone dissolved. 按降冰片烯、马来酸酐、3-甲基-2-戊烯三者的总重量计取0.1%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, a total weight of 3-methyl-2-pentene three billing 0.1% of the catalyst, with the syringe to the above mixture. 恒温在80°C,3.5MP压力,反应6小时。 Thermostated at 80 ° C, 3.5MP pressure, the reaction for 6 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride,

3-甲基-2-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率73.1%。 3-methyl-2-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield of 73.1%.

[0065] 实施例14 [0065] Example 14

[0066] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升1,4_ 二氧六环、0.10摩尔双(环戊二烯基)二氯化锆、0.50摩尔喹啉和0.03摩尔二氯乙基铝,在45°C水浴中恒温10分钟,冷却后即得锆络合物催化剂。 [0066] After a single glass bottle was evacuated several times, flushed with nitrogen in baking, 1,4_ were added 20 ml of dioxane, 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, 0.50 mol quinoline morpholine and 0.03 molar ethylaluminum dichloride, a thermostat for 10 min at 45 ° C water bath, after cooling to obtain a zirconium complex catalyst.

[0067] 将0.03摩尔7-甲基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔4_甲基-1-戊烯加入已充氮气的高压釜中,加20mll,4-二氧六环溶解。 [0067] 0.03 mol of 7-methyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of methyl-1-pentene 4_ been purged with nitrogen was added autoclave , plus 20mll, 4- dioxane was dissolved. 按降冰片烯、马来酸酐、 Press norbornene, maleic anhydride,

4-甲基-1-戊烯三者的总重量计取0.6%的上述催化剂,用注射器注入上述混和物中。 Methyl-1-pentene on the total weight of the three billing 0.6% of the catalyst, with the syringe to the above mixture. 恒温在90°C,5MP压力,反应5小时。 Thermostated at 90 ° C, 5MP pressure, the reaction for 5 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、4-甲基-1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率83.5%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 4-methyl-1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 83.5 %.

[0068] 实施例15 [0068] Example 15

[0069] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升苯甲醚、0.10摩尔双(环戊二烯基)二氯化锆、0.08摩α,α ,-联吡啶和0.01摩三异丁基铝,在50°C水浴中恒温15分钟,冷却后即得锆络合物催化剂。 [0069] After a single glass bottle was evacuated several times, flushed with nitrogen baked in, respectively, 20 ml of anisole, 0.10 moles of bis (cyclopentadienyl) zirconium dichloride, 0.08 mol α, α, - bipyridine and 0.01 mol of triisobutylaluminum, temperature 50 ° C and 15 minutes in a water bath, after cooling to obtain a zirconium complex catalyst.

[0070] 将0.03摩尔5,5-二甲基二环[2,2,I]庚_2_烯、0.03摩尔马来酸酐、0.03摩尔、3-甲基-1-戊烯加入已充氮气的高压釜中,加20ml苯甲醚溶解。 [0070] 0.03 mol of 5,5-dimethyl-bicyclo [2,2, I] hept-ene _2_, 0.03 mole of maleic anhydride, 0.03 mol of 3-methyl-1-pentene was flushed with nitrogen was added autoclave, add 20ml of anisole were dissolved. 按降冰片烯、马来酸酐、3-甲基-1-戊烯三者的总重量计取0.08%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, a total weight of 3-methyl-1-pentene three billing 0.08% of the catalyst, with the syringe to the above mixture. 恒温在100°C,6MP压力,反应6小时。 Thermostated at 100 ° C, 6MP pressure, the reaction for 6 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride,

3-甲基-1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率72.2%。 3-methyl-1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield of 72.2%.

[0071] 实施例16 [0071] Example 16

[0072] 在经过多次抽真空、充氮气烘烤的单口玻璃瓶中,分别加入20毫升环已酮、0.10摩尔双(环戊二烯基)二氯化锆、0.02摩尔邻二氮菲和0.01摩尔三异丁基铝,在40°C水浴中恒温5分钟,冷却后即得锆络合物催化剂。 [0072] After repeatedly evacuated and filled with nitrogen baked single glass jar were added 20 ml of cyclohexanone, 0.10 mol of bis (cyclopentadienyl) zirconium dichloride, 0.02 mol phenanthroline and 0.01 mol of triisobutylaluminum, 5 minute at 40 ° C water bath, after cooling to obtain a zirconium complex catalyst.

[0073] 将0.03摩尔二环[2,2,I]庚_2_烯_5_甲酸甲酯、0.03摩尔马来酸酐、0.03摩尔、 [0073] 0.03 mol of bicyclo [2,2, I] hept _2_ _5_ ene carboxylate, 0.03 mole of maleic anhydride, 0.03 mol,

4-甲基-1-戊烯加入已充氮气的高压釜中,加20ml环已酮溶解。 4-methyl-1-pentene was added autoclave purged with nitrogen, was added 20ml cyclohexanone dissolved. 按降冰片烯、马来酸酐、4-甲基-1-戊烯三者的总重量计取0.3%的上述催化剂,用注射器注入上述混和物中。 Press norbornene, maleic anhydride, 4-methylpentene total weight of the three 1-billing of the catalyst of 0.3%, with the syringe to the above mixture. 恒温100°C反,5MP压力,反应3小时。 Temperature 100 ° C trans, 5MP pressure, for 3 hours. 产物倾入含5%盐酸甲醇溶液中使降冰片烯、马来酸酐、4-甲基-1-戊烯三元共聚物沉淀,沉淀物用甲醇洗涤至中性,真空干燥,反应收率69.6%。 The product was poured into methanol containing 5% hydrochloric acid solution to a norbornene, maleic anhydride, 4-methyl-1-pentene terpolymer precipitate, the precipitate was washed with methanol until neutral, dried in vacuo, the reaction yield 69.6 %.

Claims (5)

  1. 1.一种降冰片烯类、马来酸酐和戊烯类三元共聚催化剂,其特征在于该催化剂是由下述方法制备得到的: 在惰性气体氛围的干燥的单口玻璃瓶中,将双(环戊二烯基)二氯化锆、配体和烷基金属化合物溶解于第一溶剂中,瓶口用乳胶管密封,在40-50°C水浴中恒温5-15分钟,冷却后即得锆络合物催化剂; 所述双(环戊二烯基)二氯化锆与所述配体的摩尔比为10: 10〜10: 1,所述双(环戊二烯基)二氯化锆与所述烷基金属化合物的摩尔比为10: 5〜10:1; 所述配体选自8-羟基喹啉、α,α,-联吡啶、邻二氮菲、吡啶、异喹啉、喹啉、叶啉、乙酰基丙酮或苯酰基丙酮; 所述烧基金属化合物选自二乙基招、二异丁基招、二乙基锋或_■氣乙基招; 所述第一溶剂选自四氢呋喃、苯甲醚、1,4-二氧六环、环已酮或甲苯;所述第一溶剂的用量与所述双(环戊二烯基)二氯化锆、配体和烷 A norbornene, maleic anhydride, and pentene terpolymers catalyst, wherein the catalyst is obtained by the following method of preparation: the single dry glass jar in an inert gas atmosphere, bis ( cyclopentadienyl) zirconium dichloride, and an alkyl metal ligand compound is dissolved in a first solvent, latex tube was sealed bottle, a thermostat water bath at 40-50 ° C for 5-15 min, after cooling to give zirconium complex catalyst; the bis (cyclopentadienyl) zirconium dichloride the molar ratio of the ligand is from 10: 10~10: 1, the bis (cyclopentadienyl) dichloride the molar ratio of metal alkyl compound with the zirconium is from 10: 5 to 10: 1; the ligand is selected from 8-quinolinol, α, α, - bipyridine, phenanthroline, pyridine, isoquinoline , quinoline, morpholine leaf, benzoyl acetone or acetyl acetone; -based compound is selected from the burning diethyl strokes, strokes diisobutyl, di-ethyl ethyl front or gas _ ■ move; the first solvent is selected from tetrahydrofuran, anisole, 1,4-dioxane, cyclohexanone or toluene; an amount of the first solvent with the bis (cyclopentadienyl) zirconium dichloride, ligands, and alkyl 金属化合物三者总量的比例为20毫升:0.03〜0.25摩尔。 The total amount of the metal compound to 20 ml three: 0.03~0.25 mol.
  2. 2.根据权利要求1所述的降冰片烯类、马来酸酐和戊烯类三元共聚催化剂,其特征在于所述双(环戊二烯基)二氯化锆、配体、烷基金属化合物三者的摩尔比为10: 5: 2。 The norbornene according to claim 1, pentene and maleic anhydride terpolymers catalyst, wherein said bis (cyclopentadienyl) zirconium dichloride, ligands, metal alkyl the molar ratio of the three compounds is 10: 5: 2.
  3. 3.根据权利要求1或2降冰片烯类、马来酸酐和戊烯类三元共聚催化剂,其特征在于所述配体、所述第一溶剂在使用前先进行干燥;其中所述配体中的固态配体的干燥是先用重结晶办法纯化然后真空干燥;所述配体中的液态配体的干燥是用氢化钙或金属钠干燥,所述溶剂采用氯化钙或氢化钙干燥。 According to claim 1 or claim 2 norbornene, maleic anhydride, and pentene terpolymers catalyst, wherein the ligand, the first solvent and dried before use; wherein the ligand the solid was dried ligands are purified by recrystallization to approach and then dried in vacuo; the dried liquid ligand is a ligand with calcium hydride or metallic sodium sulfate, and the solvent is dried using calcium hydride or calcium chloride.
  4. 4.使用如权利要求1或2所述的降冰片烯类、马来酸酐与戊烯类三元共聚用催化剂进行降冰片烯类、马来酸酐与戊烯三元共聚的方法,其特征在于包括下述步骤: 按照摩尔比为1:1:1取降冰片烯类、马来酸酐和戊烯类单体,将三者加入到惰性气体氛围的干燥的高压釜中,然后向该高压釜中加入第二溶剂,溶解;将所述的锆络合物催化剂加入到所述的高压釜中,在40〜100°C下恒温、0.5-5MP压力下反应0.5〜6小时; 将得到的反应产物倾入含5wt%盐酸的甲醇溶液中,得到降冰片烯类、马来酸酐和戊烯类三元共聚物的沉淀物,将该沉淀物用甲醇洗涤至中性后,真空干燥,即得到降冰片烯类、马来酸酐和戊烯类三元共聚物; 所述锆络合物催化剂的用量为降冰片烯类、马来酸酐和戊烯类单体总重量的0.03〜1% ; 所述第二溶剂选自四氢呋喃、苯甲醚、1,4-二氧六环、环已酮 4. The norbornene claim 1 or claim 2, maleic anhydride-pentene and norbornene terpolymer performed, maleic anhydride and terpolymers method pentene with a catalyst, wherein comprising the steps of: a molar ratio of 1: 1: 1 and dried autoclave take norbornene, maleic anhydride, and pentene monomer, three is added to the inert gas atmosphere, and then the autoclave adding a second solvent, is dissolved; the zirconium complex catalyst was added to the autoclave, the temperature at 40~100 ° C, the reaction pressure 0.5-5MP 0.5~6 hours; the resulting reaction the product was poured into methanol containing 5wt% hydrochloric acid solution to obtain a norbornene, maleic anhydride, and pentene terpolymer precipitate, the precipitate until neutral, washed with methanol and dried in vacuo to obtain norbornene, maleic anhydride, and pentene terpolymers; the zirconium complex catalyst is used in an amount norbornene, 0.03~1% of the total weight of maleic anhydride monomer and pentene; the said second solvent is selected from tetrahydrofuran, anisole, 1,4-dioxane, cyclohexanone 甲苯;所述第二溶剂的用量与聚合单体总量的比例为20毫升:0.09摩尔。 Toluene; an amount of the second solvent with the ratio of the total amount of polymerized monomers is 20 ml: 0.09 mol.
  5. 5.根据权利要求4所述的降冰片烯类、马来酸酐与戊烯三元共聚的方法,其特征在于所述降冰片烯类选自二环[2,2,1]庚-2-烯、1-甲基二环[2,2,1]庚-2-烯、5-甲基二环[2,2,1]庚_2_ 稀、7_ 甲基二环[2,2,1]庚-2-稀、1-乙基二环[2,2,1]庚-2-稀、5-乙基二环[2,2,1]庚-2-烯、5,5_ 二甲基二环[2,2,1]庚-2-烯、1-苯基二环[2,2,1]庚_2_稀、5_苯基二环[2, 2,1]庚_2_稀、5_乙稀基二环[2, 2,1]庚-2-稀、二环[2, 2,1]庚-2-烯-5-甲酸甲酯或二环[2,2,I]庚-2-烯-5-甲酸特丁酯; 所述戍烯选自1_戍烯、2-戍烯、3-甲基-1-戍烯、4-甲基-1-戍烯、3-甲基-2-戍烯、5-环已基-1-戊烯或5-环已基-2-戊烯。 The norbornene as claimed in claim 4, wherein the maleic anhydride with the method pentene terpolymers, wherein said norbornene is selected from bicyclo [2,2,1] hept-2 alkenyl, 1-methyl-bicyclo [2,2,1] hept-2-ene, 5-methyl-bicyclo [2,2,1] hept-_2_ dilute, 7_ methyl bicyclo [2.2.1 ] hept-2-dilute, 1-ethyl-bicyclo [2,2,1] hept-2-dilute, 5-ethyl-bicyclo [2,2,1] hept-2-ene, dimethyl 5,5_ bicyclo [2,2,1] hept-2-ene, 1-phenyl-bicyclo [2.2.1] hept-_2_ dilute, 5_ phenyl-bicyclo [2,2,1] hept-_ 2_ dilute, ethylene group 5_ bicyclo [2,2,1] hept-2-dilute, bicyclo [2,2,1] hept-2-ene-5-carboxylate, or bicyclo [2, 2, I] hept-2-ene-5-carboxylic acid tert ester; is selected from the 1_ pentene-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl- pentene, 3-methyl-pentene, 5-cyclohexyl-1-pentene or 5-cyclohexyl-2-pentene.
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