CN103304709B - A kind of solid catalyst for 1-butylene polymerization - Google Patents

A kind of solid catalyst for 1-butylene polymerization Download PDF

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CN103304709B
CN103304709B CN201310288758.5A CN201310288758A CN103304709B CN 103304709 B CN103304709 B CN 103304709B CN 201310288758 A CN201310288758 A CN 201310288758A CN 103304709 B CN103304709 B CN 103304709B
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enb
dicarboxylic acids
ester
diethyl
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CN103304709A (en
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刘宾元
董小芳
段中余
刘智博
杨敏
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Hebei University of Technology
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Hebei University of Technology
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Abstract

The present invention is a kind of solid catalyst of 1-butylene polyreaction.This catalyzer composition comprises: Primary Catalysts, promotor and external electron donor; Wherein, the composition of Primary Catalysts comprises magnesium halide, halogenated titanium and internal electron donor; Composition and ratio be quality than magnesium: titanium=0.2 ~ 22:1, the quality of halogen ion is the 20%-80% of Primary Catalysts quality, and internal electron donor mole number is the 0.1%-30% of the mole number of magnesium halide; The catalyst application that the present invention adopts the different 5-norbornylene compounds replaced to prepare as internal electron donor is in the polymerization of 1-butylene, and synthetic method is simple, productive rate is higher.When this compound is polymerized for 1-butylene as catalyzer prepared by internal electron donor, catalyzer can show higher activity, and polymkeric substance has higher taxis, higher molecular weight and wider molecular weight distribution.

Description

A kind of solid catalyst for 1-butylene polymerization
Technical field:
The present invention relates to Ziegler-Natta catalyst component and catalyzer thereof, relate generally to three kinds of catalyst components for 1-butylene polymerization and catalyzer thereof.
Technical background:
As everyone knows, MgCl 2carrier model Ziegler-Natta catalyst is a kind of important catalyst of manufacture of polyolefins, Ziegler-Natta catalyst develops into current efficient carrier type catalyst system from the first-generation, electron donor plays critical effect, finds the focus that desirable electron donor compound is Ziegler-Natta catalyst study on the synthesis always.
Internal electron donor is constantly updated and is regenerated, the earliest be aromatic series monoester class compound, especially based on aromatic series monoester class compounds such as ethyl p-methyl benzoate, ethyl benzoates (EB), aromatic diester compounds, usual n-butyl phthalate (DNBP) and diisobutyl phthalate (DIBP) (CN85100997A, CN1034736C, US6306996B1) are widely adopted in Industrial Catalysis system.
Then, people constantly attempt the internal electron donor adopting other compound as Ziegler-Natta catalyst, Himont company develop a class novel 1,3-bis-ethers (US4971937, US2004014597, EP728769) electron donor compound, the hydrogen response that the catalyzer prepared using two ethers as internal electron donor has had and higher catalytic activity, feature more outstanding is in addition that polymkeric substance still has higher degree of isotacticity when not adding external electron donor.Mo Lini etc. adopt cyano group ester compound (CN1242780A) to be internal electron donor, and the catalyzer that this compounds is prepared as electron donor is for having good hydrogen response during olefinic polymerization, the polymkeric substance of generation has comparatively broad molecular weight distribution.Morini etc. adopt the internal electron donor that diamine compounds (CN1087918) is Ziegler-Natta catalyst, and when diamine compounds is as internal electron donor, during catalyzing propone polymerization, the activity of catalyzer is generally on the low side.Beijing Chemical Research Institute successfully have developed 1,3-diol-lipid (CN1597714A) internal electron donor, and the activity of corresponding catalyzer is high, the relative molecular mass distribution of product polypropylene is wider, directional property is adjustable, and when not adding external electron donor, the polyacrylic degree of isotacticity of gained is also higher.Montell company develops a succinic acid ester compound, and the catalyst for polymerization of propylene being internal electron donor with it then has the wide feature of high directionality, the polyacrylic relative molecular mass distribution of gained.CN1597714A, CN1803864A, CN1313869A disclose the different succinate replaced as internal electron donor, but this compound structurally 2,3-bit substituents groups be not mutually bonded to ring.WO2004024785 and US6818583 discloses structurally 2,3-bit substituent groups and is mutually bonded to the succinate of ring as internal electron donor, but its synthesis difficulty, and uneconomical.CN101423571B to disclose in structure 2,3-bit substituent group is bonded to the inner mold succinate of ring mutually as internal electron donor Kaolinite Preparation of Catalyst, do not study the impact of change on catalyst performance of such succinate configuration, and he is mainly applied to the homopolymerization of propylene and the copolymerization of propylene and other alkene.Up to now, the configuration that there is not yet discuss and study norbornylene class internal electron donor affects for catalyst performance, and this is applied to the report of butene polymerization.
Summary of the invention:
The invention provides a kind of 1-butylene CH 2=CH 2cH 2cH 3the solid catalyst that polyreaction uses.The catalyst application that this catalyzer adopts the different 5-norbornylene compounds replaced to prepare as internal electron donor is in the polymerization of 1-butylene, 5-norbornylene compounds mainly contains inner mold, external form and mixed type three kinds of configurations, and this compou nd synthesis method is simple, productive rate is higher.When this compound is polymerized for 1-butylene as catalyzer prepared by internal electron donor, catalyzer can show higher activity, and polymkeric substance has higher taxis, molecular weight and wider molecular weight distribution.
Technical scheme of the present invention is:
For a solid catalyst for 1-olefinic polymerization, the composition of catalyzer comprises: Primary Catalysts, promotor and external electron donor;
Wherein, the composition of Primary Catalysts comprises magnesium halide, halogenated titanium and internal electron donor; Composition and ratio be quality than magnesium: titanium=0.2 ~ 22:1, the quality of halogen is the 20%-80% of Primary Catalysts quality, and internal electron donor mole number is the 0.1%-30% of the mole number of magnesium halide;
Described internal electron donor is have one or more of following structural compound;
or
Wherein, radicals R 1, R 2, mutually the same or different, be C 1-C 30the alkyl of straight or branched, C 3-C 30alkenyl or cycloalkyl, C 6-C 30aryl, arylalkyl or alkylaryl; R 3-R 10mutually the same or different, be C 1-C 20alkyl, the C of straight or branched 3-C 20alkenyl or cycloalkyl, C 6-C 20aryl, aralkyl or be hydrogen;
Described promotor is alkylaluminium cpd;
Described external electron donor is general formula is R 2si (OR ') 2silane compound, wherein R and R ' is alkyl, cycloalkyl, aryl, pyrrolidyl or piperidyl respectively, R and R ' is identical or different;
Catalyzer composition and ratio is: mol ratio Primary Catalysts: promotor=1000 ~ 100:1; Promotor: external electron donor=0.1 ~ 10:1, wherein, the molar weight of Primary Catalysts is with titanium atom molar amount, and the molar weight of promotor is with aluminium atomic molar gauge;
Described halogen is chlorine.
In described internal electron donor, R 1and R 2the alkyl of preferred straight or branched, alkenyl, aryl or aralkyl, be particularly preferably C 1-C 20the alkyl of straight or branched, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, neo-pentyl or isopentyl, desirably methyl, ethyl, propyl group, sec.-propyl, normal-butyl or isobutyl-.
In described internal electron donor, be preferably, R 3and R 4, R 5and R 6, R 7and R 8, R 9and R 10in have at least one group of group to be hydrogen.
Described internal electron donor is specially cis-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2-methyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2-methyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2-methyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2-methyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2-ethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2-ethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2-ethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2-ethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2-propyl group-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2-propyl group-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2-propyl group-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2-propyl group-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2-isopropyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2-isopropyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2-isopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2-isopropyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2-isopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester,Cis-2-isopropyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2-isopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2-butyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2-butyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2-butyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2-butyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2-butyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2-butyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2-butyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2,3-dimethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2,3-dimethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2,3-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2,3-dimethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2,3-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2,3-dimethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2,3-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2,3-diethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2,3-diethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2,3-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2,3-diethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2,3-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2,3-diethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2,3-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2,3-dipropyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2,3-dipropyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2,3-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2,3-dipropyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2,3-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2,3-dipropyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2,3-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2,3-diisopropyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2,3-diisopropyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2,3-diisopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2,3-diisopropyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2,3-diisopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2,3-diisopropyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2,3-diisopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-2,3-dibutyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-2,3-dibutyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-2,3-dibutyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-2,3-dibutyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-2,3-dibutyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-2,3-dibutyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-2,3-dibutyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-1-methyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-1-methyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-1-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-1-methyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-1-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-1-methyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-1-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-1-ethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-1-ethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-1-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-1-ethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-1-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-1-ethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-1-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-1-propyl group-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-1-propyl group-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-1-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl,Cis-1-propyl group-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-1-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-1-propyl group-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-1-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-1-isopropyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-1-isopropyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-1-isopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-1-isopropyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-1-isopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-1-isopropyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-1-isopropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-Isosorbide-5-Nitrae-dimethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-Isosorbide-5-Nitrae-dimethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-Isosorbide-5-Nitrae-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-Isosorbide-5-Nitrae-dimethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-Isosorbide-5-Nitrae-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-Isosorbide-5-Nitrae-dimethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-Isosorbide-5-Nitrae-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-Isosorbide-5-Nitrae-diethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-Isosorbide-5-Nitrae-diethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-Isosorbide-5-Nitrae-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-Isosorbide-5-Nitrae-diethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-Isosorbide-5-Nitrae-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-Isosorbide-5-Nitrae-diethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-Isosorbide-5-Nitrae-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-Isosorbide-5-Nitrae-dipropyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-Isosorbide-5-Nitrae-dipropyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-Isosorbide-5-Nitrae-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-Isosorbide-5-Nitrae-dipropyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-Isosorbide-5-Nitrae-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-Isosorbide-5-Nitrae-dipropyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-Isosorbide-5-Nitrae-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-5-methyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-5-methyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-5-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-5-methyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-5-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-5-methyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-5-methyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-5-ethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-5-ethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-5-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-5-ethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-5-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-5-ethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-5-ethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-5-propyl group-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-5-propyl group-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-5-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-5-propyl group-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-5-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-5-propyl group-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-5-propyl group-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-5,6-dimethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-5,6-dimethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-5,6-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-5,6-dimethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-5,6-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-5,6-dimethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-5,6-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-5,6-diethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-5,6-diethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-5,6-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-5,6-diethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-5,6-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-5,6-diethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-5,6-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-5,6-dipropyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-5,6-dipropyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-5,6-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-5,6-dipropyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-5,6-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-5,6-dipropyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-5,6-dipropyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-7,7-dimethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-7,7-dimethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-7,7-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-7,7-dimethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-7,7-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-7,7-dimethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-7,7-dimethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-7,7-diethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-7,7-diethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-7,7-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-7,7-diethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-7,7-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-7,7-diethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-7,7-diethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-1,2,3,4-tetramethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-1,2,3,4-tetramethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-1,2,3,4-tetramethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-1,2,3,4-tetramethyl-5-ENB-outer (interior)-2, 3-dicaxboxylate, cis-1, 2, 3, 4-tetramethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids dibutyl ester, cis-1, 2, 3, 4-tetramethyl-5-ENB-outer (interior)-2, 3-diisobutyl dicarboxylate, cis-1, 2, 3, 4-tetramethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids two peopentyl ester, cis-1, 2, 3, 4-tetraethyl-5-ENB-outer (interior)-2, 3-dimethyl dicarboxylate, cis-1, 2, 3, 4-tetraethyl-5-ENB-outer (interior)-2, 3-diethyl dicarboxylate, cis-1, 2, 3, 4-tetraethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids dipropyl, cis-1, 2, 3, 4-tetraethyl-5-ENB-outer (interior)-2, 3-dicaxboxylate, cis-1, 2, 3, 4-tetraethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids dibutyl ester, cis-1, 2, 3, 4-tetraethyl-5-ENB-outer (interior)-2, 3-diisobutyl dicarboxylate, cis-1, 2, 3, 4-tetraethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids two peopentyl ester, cis-2, 3, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-dimethyl dicarboxylate, cis-2, 3, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-diethyl dicarboxylate, cis-2, 3, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids dipropyl, cis-2, 3, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-dicaxboxylate, cis-2, 3, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids dibutyl ester, cis-2, 3, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-diisobutyl dicarboxylate, cis-2, 3, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids two peopentyl ester, cis-2, 3, 5, 6-tetraethyl-5-ENB-outer (interior)-2, 3-dimethyl dicarboxylate, cis-2, 3, 5, 6-tetraethyl-5-ENB-outer (interior)-2, 3-diethyl dicarboxylate, cis-2, 3, 5, 6-tetraethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids dipropyl, cis-2, 3, 5, 6-tetraethyl-5-ENB-outer (interior)-2, 3-dicaxboxylate, cis-2, 3, 5, 6-tetraethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids dibutyl ester, cis-2, 3, 5, 6-tetraethyl-5-ENB-outer (interior)-2, 3-diisobutyl dicarboxylate, cis-2, 3, 5, 6-tetraethyl-5-ENB-outer (interior)-2, 3-dicarboxylic acids two peopentyl ester, cis-1, 4, 5, 6-tetramethyl-5-ENB-outer (interior)-2, 3-dimethyl dicarboxylate, cis-1, 4, 5, 6-tetramethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, cis-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-outer (interior)-2,3-dimethyl dicarboxylate, cis-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-outer (interior)-2,3-diethyl dicarboxylate, cis-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dipropyl, cis-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-outer (interior)-2,3-dicaxboxylate, cis-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids dibutyl ester, cis-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-outer (interior)-2,3-diisobutyl dicarboxylate, cis-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-outer (interior)-2,3-dicarboxylic acids two peopentyl ester, trans-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-ENB-2,3-diethyl dicarboxylate, trans-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-ENB-2,3-dicaxboxylate, trans-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1-methyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1-methyl-5-ENB-2,3-diethyl dicarboxylate, trans-1-methyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1-methyl-5-ENB-2,3-dicaxboxylate, trans-1-methyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1-methyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1-methyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1-ethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1-ethyl-5-ENB-2,3-diethyl dicarboxylate, trans-1-ethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1-ethyl-5-ENB-2,3-dicaxboxylate, trans-1-ethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1-ethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1-ethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1-propyl group-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1-propyl group-5-ENB-2,3-diethyl dicarboxylate, trans-1-propyl group-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1-propyl group-5-ENB-2,3-dicaxboxylate, trans-1-propyl group-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1-propyl group-5-ENB-2,3-diisobutyl dicarboxylate, trans-1-propyl group-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-methyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-methyl-5-ENB-2,3-diethyl dicarboxylate, trans-2-methyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-methyl-5-ENB-2,3-dicaxboxylate, trans-2-methyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-methyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-methyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-ethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-ethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2-ethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-ethyl-5-ENB-2,3-dicaxboxylate, trans-2-ethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-ethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-ethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-propyl group-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-propyl group-5-ENB-2,3-diethyl dicarboxylate, trans-2-propyl group-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-propyl group-5-ENB-2,3-dicaxboxylate, trans-2-propyl group-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-propyl group-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-propyl group-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-isopropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-isopropyl-5-ENB-2,3-diethyl dicarboxylate, trans-2-isopropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-isopropyl-5-ENB-2,3-dicaxboxylate, trans-2-isopropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-isopropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-isopropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3-dimethyl-5-ENB-2,3-dicaxboxylate, trans-2,3-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3-diethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3-diethyl-5-ENB-2,3-dicaxboxylate, trans-2,3-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3-dipropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3-dipropyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3-dipropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3-dipropyl-5-ENB-2,3-dicaxboxylate, trans-2,3-dipropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3-dipropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3-dipropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae-diethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae-dipropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1,4-dipropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5-methyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-methyl-5-ENB-2,3-diethyl dicarboxylate, trans-5-methyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-methyl-5-ENB-2,3-dicaxboxylate, trans-5-methyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-methyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-methyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5-ethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-ethyl-5-ENB-2,3-diethyl dicarboxylate, trans-5-ethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-ethyl-5-ENB-2,3-dicaxboxylate, trans-5-ethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-ethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-ethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5-propyl group-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-propyl group-5-ENB-2,3-diethyl dicarboxylate, trans-5-propyl group-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-propyl group-5-ENB-2,3-dicaxboxylate, trans-5-propyl group-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-propyl group-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-propyl group-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5,6-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5,6-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-5,6-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5,6-dimethyl-5-ENB-2,3-dicaxboxylate, trans-5,6-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5,6-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5,6-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5,6-diethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5,6-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-5,6-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5,6-diethyl-5-ENB-2,3-dicaxboxylate, trans-5,6-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5,6-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5,6-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5,6-dipropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5,6-dipropyl-5-ENB-2,3-diethyl dicarboxylate, trans-5,6-dipropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5,6-dipropyl-5-ENB-2,3-dicaxboxylate, trans-5,6-dipropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5,6-dipropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5,6-dipropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-7,7-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-7,7-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-7,7-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-7,7-dimethyl-5-ENB-2,3-dicaxboxylate, trans-7,7-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-7,7-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-7,7-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-7,7-diethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-7,7-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-7,7-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-7,7-diethyl-5-ENB-2,3-dicaxboxylate, trans-7,7-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-7,7-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-7,7-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1,2,3,4-tetramethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1,2,3,4-tetramethyl-5-ENB-2,3-diethyl dicarboxylate, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicaxboxylate, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1,2,3,4-tetramethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1,2,3,4-tetraethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1,2,3,4-tetraethyl-5-ENB-2,3-diethyl dicarboxylate, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicaxboxylate, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1,2,3,4-tetraethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3,5,6-tetramethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3,5,6-tetramethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicaxboxylate, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3,5,6-tetramethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3,5,6-tetraethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3,5,6-tetraethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicaxboxylate, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3,5,6-tetraethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-diisobutyl dicarboxylate or trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester.
Described promotor is preferably triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine di-isopropyl aluminium, a chloro-di-isobutyl aluminum or a chlorine di-n-butyl aluminium.
Described external electron donor is specially dimethyldimethoxysil,ne, diethyldimethoxysilane, dipropyl dimethoxysilane, diisopropyl dimethoxy silane, dibutyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane, Dicyclohexyldimethoxysilane, dimethoxydiphenylsilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyl diethoxy silane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyl diethoxy silane, bicyclopentyl diethoxy silane, dicyclohexyl diethoxy silane, diphenyl diethoxy silane, methylethyl dimethoxysilane, methyl-propyl dimethoxysilane, isopropyl methyl dimethoxysilane, methyl butyl dimethoxysilane, methyl-isobutyl dimethoxysilane, methylcyclopentyl dimethoxysilane, Cyclohexylmethyldimethoxysilane, aminomethyl phenyl dimethoxysilane, ethyl propyl dimethoxysilane, ethylisopropyl base dimethoxysilane, ethyl-butyl dimethoxysilane, ethyl isobutyl base dimethoxysilane, ethylcyclopentyl dimethoxysilane, ethylcyclohexyl dimethoxysilane, ethylphenyl dimethoxysilane, propyl iso-propyl dimethoxysilane, butyl dimethoxysilane, propyl group isobutyl-dimethoxysilane, propyl group cyclopentyl dimethoxysilane, propylcyclohexyl dimethoxysilane, propyl group phenyidimethoxysilane, butyl isobutyl-dimethoxysilane, butyl cyclopentyl dimethoxysilane, butylcyclohexyl dimethoxysilane, butyl phenyl dimethoxysilane, isobutyl-cyclopentyl dimethoxysilane, isobutyl-cyclohexyl dimethoxysilane, isobutyl phenenyl dimethoxysilane, cyclopentyl cyclohexyl dimethoxysilane, cyclopentyl phenyl dimethoxysilane, cyclohexyl phenyl dimethoxysilane, dipiperidino dimethoxysilane, dipiperidino diethoxy silane, bihyrrolidinyl dimethoxysilane or bihyrrolidinyl diethoxy silane.
The preparation method of described Primary Catalysts, comprises the following steps:
(1), according to mol ratio Tetra hydro Phthalic anhydride: magnesium chloride=0.01-3.00:1, mol ratio alcohol: magnesium=0.2-10:1, mol ratio decane: magnesium chloride=1-10:1, Tetra hydro Phthalic anhydride, magnesium chloride, alcohol and decane are joined in reactor, 80-180 DEG C of reaction 4-6h, obtained alcohol and thing;
(2), be added drop-wise to by alcohol adduct in the titanium tetrachloride of-30-10 DEG C, the 1g magnesium correspondence wherein in alcohol adduct adds the titanium tetrachloride of 10-100ml, is added dropwise to complete in 1-3 hour;
(3), 80-150 DEG C is warming up to, insulation 1-4 hour;
(4), leave standstill, draw up a layer waste liquid, now temperature is down to room temperature, adds and carry out secondary with the titanium tetrachloride of step (2) same amount and carry titanium in this temperature downhill reaction device;
(5), be warming up to 50-100 DEG C, add internal electron donor compound, insulation reaction 2-3 hour, mol ratio is interior Donor compound: magnesium=0.01-10.00:1;
(6), temperature programming, to 100-160 DEG C, reacts 1-5 hour;
(7), leave standstill, filter out upper strata waste liquid, toluene wash, vacuum-drying, finally obtain Primary Catalysts.
Described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, neopentyl alcohol, n-Octanol or isooctyl alcohol.
Beneficial effect of the present invention is:
Tradition phthalic acid diisobutyl is 26.5KgPB/gTi as catalyst activity prepared by internal electron donor, polymericular weight is 73.4W, Tile Width is 5.5, cis-5-norbornylene-2, 3-dicarboxylic acid diethyl ester type is 27.3KgPB/gTi as internal electron donor Kaolinite Preparation of Catalyst activity, molecular weight is 112.1W, Tile Width is 7.8, trans-5-norbornylene-2, 3-dicarboxylic acid diethyl ester type is 22.3KgPB/gTi as internal electron donor Kaolinite Preparation of Catalyst activity, polymericular weight is 153.9W, Tile Width is 10.8, the change of internal electron donor configuration has a significant impact the molecular weight of polymkeric substance and Tile Width, wide molecular weight distribution is conducive to the processing of product, and be conducive to the exploitation of the different trade mark of polymkeric substance, simultaneously the increase of molecular weight is conducive to the raising of the mechanical property of polymeric articles.
Embodiment:
Donor compound in the norbornylene class that different configuration has been synthesized in this invention, self-control solid catalyst, have studied the impact of its configuration on catalyst performance, be polymerized by 1-butylene, obtain the reasonable polybutene of taxis, the polymericular weight simultaneously obtained is large, wider distribution, and the mechanical property that polymkeric substance has not only been had but also the processing characteristics had, be conducive to the polymeric articles developing the different trade mark simultaneously.
Following present specific embodiment so that this patent to be described, but the present invention is not limited thereto:
The internal electron donor that the present invention relates to is known material, wherein, the synthesis of logical formula I (II) compound can adopt esterification to obtain, and is namely prepared by the norbornene dicarboxylic acids acid anhydride derivative of different configuration and alcohol, also can be obtained by diels-alder reaction.The synthesis of logical formula III compound adopts diels-alder reaction to obtain, and namely to be reacted from different replacement dimethyl ester by cyclopentadiene derivant and prepares.Relevant references is see (2) Liu, D.; Canales, E.; Corey, E.J.; JournaloftheAmericanChemicalSociety.2007,129 (6), 1498-1499. (3) ChiW.HandHenryN.C.W; TetrahedronLetters.1987,28 (21), 2393-2396.
Relevant testing method:
(1) polymkeric substance degree of isotacticity test: ether boiling extracting 48 hours, namely 0.5-1g is through the polymer samples (be cut into small pieces shape) of vacuum-drying, through boiling diethyl ether extracting after 48 hours in extraction plant, carry out the vacuum-drying ratio of weight before (g) and extracting of weighing and be degree of isotacticity.
(2) percentage composition of titanium in catalyzer: by spectrophotometry.
(3) polymericular weight and molecular weight distribution MWD(MWD=M w/ M n): make standard specimen with polystyrene, 1,2,4-trichlorobenzene is sample dissolution under solvent high temperature.Test with PL-GPC220 type gel permeation chromatograph at 150 DEG C.
One, the synthesis of norbornene dicarboxylic acids ester cpds
1. the synthetic method of trans-5-norbornylene-2,3-dicarboxylic diester class is as follows:
Cyclopentadiene with amounts such as DEF is dissolved in ether under condition of ice bath, is added drop-wise in 1h-1.5h in the mixing solutions of dimethyl ester, Resorcinol and ether.Then heating reflux reaction 5h.Room temperature is cooled to, NaHCO after reaction terminates 3solution washing removing Resorcinol, is washed to neutrality, merges extraction phase, anhydrous sodium sulfate drying, filter, revolve steaming, and underpressure distillation or post are separated, and obtain target product, productive rate 70-90%.
Embodiment 1
The synthetic method of trans-5-norbornylene-2,3-diethyl dicarboxylate is as follows
In the there-necked flask of 250ml, add 32ml DEF, 0.2g Resorcinol, 20ml ether, 17ml cyclopentadiene is dissolved in 50ml ether and adopts dropping mode, is added dropwise to complete, back flow reaction 5h under condition of ice bath at 1h-1.5h.Room temperature is cooled to, NaHCO after reaction terminates 3solution washing removing Resorcinol, is washed to neutrality, merges extraction phase, anhydrous sodium sulfate drying, filter, revolve steaming, underpressure distillation, obtain oily liquids 42.8g, productive rate 90%. 1h (TMS, CDCl 3, 400MHz) and analytical results: δ 6.28 (s, 1H, alkene H); δ 6.07 (s, 1H, alkene H); δ 4.08 (m, 4H, CH 2cH 3); δ 3.36 (s, 1H, CHCO); δ 2.67 (s, 1H, CHCO); δ 3.12 (s, 1H, CH); δ 3.26 (s, 1H, CH); δ 1.61 (t, 1H, CH 2); δ 1.45 (t, 1H, CH 2); δ 1.23 (m, 6H, CH 2cH 3).
2. the preparation of cis-5-norbornylene-outer-2,3-dicarboxylic diester classes
(1) the configuration conversion of inner mold norbornene dicarboxylic acids acid anhydride:
Get 200gendo type norbornylene and carboxylic acid anhydride adds single port bottle, system through argon gas pump drainage 3 times, heating until solid all melts, 190 DEG C of back flow reaction 2h.Be cooled to about 100 DEG C, add the acetone of about 250ml, filtered while hot residue, temperature is down to room temperature and is put into refrigerator cold-storage one night.Filter, weigh.If filtrate is turned to be yellow, need to continue recrystallization 2-3 time, until obtain white crystal with acetone.Filtrate need be revolved to steam and be reclaimed solid, then uses acetone recrystallization 1-2 time, productive rate: 65%.
(2) synthetic method of cis-5-norbornylene-outer-2,3-dicarboxylic diester classes is as follows:
In there-necked flask, add exo-NA, excessive alcohol, tosic acid, back flow reaction 24h, after reaction terminates, be cooled to room temperature, NaHCO 3solution washing removing tosic acid, extracted with diethyl ether is washed to neutrality, merges extraction phase, anhydrous sodium sulfate drying, filters, revolves steaming, underpressure distillation, obtain target product, productive rate 80-95%.
Embodiment 2
The synthetic method of cis-5-norbornylene-outer-2,3-dicaxboxylate is as follows:
Synthetic method, as cis-5-norbornylene-outer-2,3-diethyl dicarboxylates, just replaces ethanol with Virahol, output 10.4g, productive rate 87%. 1h (TMS, CDCl 3, 400MHz) and analytical results: δ 6.21 (s, 2H, alkene H); δ 5.00 (m, 2H, CH 3cHCH 3); δ 3.05 (s, 2H, CH); δ 2.54 (s, 2H, CHCO); δ 2.15 (t, 1H, CH 2); δ 1.47 (t, 1H, CH 2); δ 1.23 (m, 12H, CH 3).
3. the synthetic method of cis-5-norbornylene-Nei-2,3-dicarboxylic diester class is as follows:
In there-necked flask, add endo-NA, excessive alcohol, tosic acid, back flow reaction 24h, after reaction terminates, be cooled to room temperature, NaHCO 3solution washing removing tosic acid, extracted with diethyl ether is washed to neutrality, merges extraction phase, anhydrous sodium sulfate drying, filters, revolves steaming, and underpressure distillation or post are separated, and obtain target product, productive rate 80-95%.
Embodiment 3
The synthesis of cis-5-norbornylene-Nei-2,3-diethyl dicarboxylate:
In the there-necked flask of 250ml, add 8.0gendo-NA, 35ml ethanol, 0.5g tosic acid, back flow reaction 24h, after reaction terminates, be cooled to room temperature, NaHCO 3solution washing removing tosic acid, extracted with diethyl ether is washed to neutrality, merges extraction phase, anhydrous sodium sulfate drying, filters, revolves steaming, underpressure distillation, obtain oily liquids 11.2g, productive rate 94%. 1h (TMS, CDCl 3, 400MHZ) and analytical results: δ 6.26 (s, 2H, alkene H); δ 4.08 (m, 4H, CH 2cH 3); δ 3.27 (s, 2H, CHCO); δ 3.15 (s, 2H, CH); δ 1.47 (t, 1H, CH 2); δ 1.33 (t, 1H, CH 2); δ 1.22 (m, 6H, CH 2cH 3).
Embodiment 4
(1), the preparation of catalyst component
(1) 250ml there-necked flask vacuumizes, leads to argon replaces 3 times, 3g (0.032mol) Magnesium Chloride Anhydrous is added under argon atmosphere, decane 85ml(0.44mol), Tetra hydro Phthalic anhydride 0.4g(0.0027mol), isooctyl alcohol 35ml(0.22mol), add there-necked flask successively, be warming up to 100 DEG C gradually, insulation 2h, naturally cools to room temperature under argon atmosphere, obtained alcohol and thing.
(2) 500ml five mouthfuls of bottles vacuumize, lead to argon replaces 3 times, add 50mlTiCl 4, cryosel bath cools to-30 DEG C--20 DEG C, is all added drop-wise to by the alcohol adduct of above-mentioned preparation in five mouthfuls of bottles, is added dropwise to complete in 2h.
(3) 80 DEG C are warmed up to, insulation 2h,
(4) remove supernatant liquid after leaving standstill 20min, now system temperature is room temperature substantially, adds 50mlTiCl at this temperature 4carry out secondary and carry titanium.
(5) be warmed up to 90 DEG C, add the cis-5-norbornylene of internal electron donor-Nei-2,3-diethyl dicarboxylate 1.5mmol, insulation reaction 2h.
(6) 140 DEG C are warming up to, reaction 1.5h.
(7) system leaves standstill 20min, suction filtration upper strata waste liquid, and now temperature is down to about 40 DEG C, washs: add the temperature programming of 100ml toluene system, at 85 DEG C, stir 0.5h, leaves standstill 20min, suction filtration upper strata waste liquid.Repeat toluene wash 2-3 time, then wash 4-5 time at 50 DEG C with normal hexane, catalyzer is carried out vacuum-drying.
Gained catalyst Ti content is 1.8%.The quality of halogen ion is 24.4% of Primary Catalysts quality, and internal electron donor mole number is 1.2% of the mole number of magnesium halide.
The catalyst Step prepared in embodiment 5-39 is as embodiment 4, and the internal electron donor that correspondence adds is in the secondary series of table 1, and gained catalyst Ti content is in the 3rd row of table 1
(2), butene polymerization experiment
Catalyzer prepared by embodiment 4 carries out the experiment of normal pressure butene polymerization.Concrete steps are as follows: 250ml there-necked flask is through through argon gas pump drainage 3 times, system is full of 1-butylene gas (the 1-butylene pressure in solenoid control reaction system is 0.1MP), add 50ml normal hexane, Primary Catalysts 10mg, promotor adopts triethyl aluminum, mol ratio promotor: Primary Catalysts=300, and external electron donor adopts Cyclohexylmethyldimethoxysilane, mol ratio promotor aluminium: external electron donor=30, H 23ml, reacts 2h at 30 DEG C.100ml acidic ethanol termination reaction, polymkeric substance carries out drying in 40 DEG C of vacuum drying ovens, and the polymer active of survey is 27.3KgPB/g.Ti, degree of isotacticity 95.2%, molecular weight 112.1*10 4, molecular weight distribution 7.8.The aggregated data of embodiment 5-39 is in the four-seven row of table 1
Comparative example 1
Internal electron donor, as above-mentioned, is just replaced with diisobutyl phthalate by Kaolinite Preparation of Catalyst method.Its polymerizing condition is with the polymerizing condition of embodiment 4.
Table 1
Embodiment 40-42
The preparation of Primary Catalysts is with the catalyzer in embodiment 6,4 and 5, the polymerizing condition of polymerizing condition the other the same as in Example 4, change the mol ratio (Al/Ti) of promotor and Primary Catalysts, promotor and external electron donor mol ratio (Al/Si), specific experiment data are as following table 2:
Table 2
Experimental data from above table: increase AlEt 3consumption, catalyst activity increase.A small amount of impurity may be there is in system, AlEt during polymerization 3first can consume a part with impurity reaction, cause partial-titanium not activated, catalyst activity is relatively lower.Mol ratio promotor: Primary Catalysts=300, mol ratio promotor: during external electron donor=30, catalyst activity and degree of isotacticity are relatively high.
Embodiment 43 ~ 45
The preparation of Primary Catalysts is with the catalyzer in embodiment 6,4 and 5, the polymerizing condition of polymerizing condition the other the same as in Example 4, examine or check the impact that different external electron donor is polymerized 1-butylene, external electron donor is respectively Cyclohexylmethyldimethoxysilane (CHMMS), second, isobutyl dimethoxy silane (DIBMS), dicyclopentyl dimethoxyl silane (DCPMS), diisopropyl dimethoxy silane (DIPMS), dimethoxydiphenylsilane (DDS).Aggregated data is as following table 3.
Table 3
Experimental data from above table: when second, isobutyl dimethoxy silane does external electron donor, the degree of isotacticity of polymkeric substance is relatively good.External electron donor has conclusive effect to the stereoselective raising of Z-N catalyzer taking magnesium chloride as carrier, and namely selectivity poisons random active centre, improves the degree of isotacticity of polymkeric substance.In addition, silane compound is as external electron donor, and except 2 alkoxyl groups be combined with Siliciumatom, and the degree of isotacticity of size on polymkeric substance of the alkyl volume of Siliciumatom combination also has impact, and the increase of alkyl volume is conducive to the increase of polymkeric substance degree of isotacticity.

Claims (8)

1., for a solid catalyst for 1-butylene polymerization, the composition that it is characterized by catalyzer comprises: Primary Catalysts, promotor and external electron donor;
Wherein, the composition of Primary Catalysts comprises magnesium halide alcohol and thing, halogenated titanium and internal electron donor; Composition and ratio be quality than magnesium: titanium=0.2 ~ 22:1, the quality of halogen is the 20%-80% of Primary Catalysts quality, and internal electron donor mole number is the 0.1%-30% of the mole number of magnesium halide alcohol and thing;
Described magnesium halide alcohol and the preparation method of thing comprise the steps: according to mol ratio Tetra hydro Phthalic anhydride: magnesium chloride=0.01-3.00:1, mol ratio alcohol: magnesium=0.2-10:1, mol ratio decane: magnesium chloride=1-10:1, Tetra hydro Phthalic anhydride, magnesium chloride, alcohol and decane are joined in reactor, 80-180 DEG C of reaction 4-6h, obtained alcohol and thing;
Described internal electron donor is have one or more of following structural compound;
Wherein, radicals R 1, R 2, mutually the same or different, be C 1-C 30the alkyl of straight or branched, C 3-C 30alkenyl or cycloalkyl, C 6-C 30aryl, arylalkyl or alkylaryl; R 3-R 10mutually the same or different, be C 1-C 20alkyl, the C of straight or branched 3-C 20alkenyl or cycloalkyl, C 6-C 20aryl, aralkyl or be hydrogen;
Described promotor is alkylaluminium cpd;
Described external electron donor is general formula is R 2si (OR ') 2silane compound, wherein R and R ' is alkyl, cycloalkyl, aryl, pyrrolidyl or piperidyl respectively, R and R ' is identical or different;
Catalyzer composition and ratio is: mol ratio promotor: Primary Catalysts=1000 ~ 100:1; Promotor: external electron donor=0.1 ~ 10:1, wherein, the molar weight of Primary Catalysts is with titanium atom molar amount, and the molar weight of promotor is with aluminium atomic molar gauge;
Described halogen is chlorine.
2., as claimed in claim 1 for the solid catalyst of 1-butylene polymerization, it is characterized by described internal electron donor, R 1and R 2for alkyl, alkenyl, the aryl or aralkyl of straight or branched, R 3and R 4, R 5and R 6, R 7and R 8, R 9and R 10in have at least one group of group to be hydrogen.
3., as claimed in claim 2 for the solid catalyst of 1-butylene polymerization, it is characterized by described internal electron donor, R 1and R 2for methyl, ethyl, propyl group, normal-butyl, isobutyl-, neo-pentyl or isopentyl.
4. as claimed in claim 1 for the solid catalyst of 1-butene polymerization, it is characterized by described internal electron donor and be specially trans-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-ENB-2,3-diethyl dicarboxylate, trans-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-ENB-2,3-dicaxboxylate, trans-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1-methyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1-methyl-5-ENB-2,3-diethyl dicarboxylate, trans-1-methyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1-methyl-5-ENB-2,3-dicaxboxylate, trans-1-methyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1-methyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1-methyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1-ethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1-ethyl-5-ENB-2,3-diethyl dicarboxylate, trans-1-ethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1-ethyl-5-ENB-2,3-dicaxboxylate, trans-1-ethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1-ethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1-ethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1-propyl group-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1-propyl group-5-ENB-2,3-diethyl dicarboxylate, trans-1-propyl group-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1-propyl group-5-ENB-2,3-dicaxboxylate, trans-1-propyl group-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1-propyl group-5-ENB-2,3-diisobutyl dicarboxylate, trans-1-propyl group-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-methyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-methyl-5-ENB-2,3-diethyl dicarboxylate, trans-2-methyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-methyl-5-ENB-2,3-dicaxboxylate, trans-2-methyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-methyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-methyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-ethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-ethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2-ethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-ethyl-5-ENB-2,3-dicaxboxylate,Trans-2-ethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-ethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-ethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-propyl group-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-propyl group-5-ENB-2,3-diethyl dicarboxylate, trans-2-propyl group-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-propyl group-5-ENB-2,3-dicaxboxylate, trans-2-propyl group-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-propyl group-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-propyl group-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2-isopropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2-isopropyl-5-ENB-2,3-diethyl dicarboxylate, trans-2-isopropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2-isopropyl-5-ENB-2,3-dicaxboxylate, trans-2-isopropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2-isopropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2-isopropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3-dimethyl-5-ENB-2,3-dicaxboxylate, trans-2,3-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3-diethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3-diethyl-5-ENB-2,3-dicaxboxylate, trans-2,3-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3-dipropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3-dipropyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3-dipropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3-dipropyl-5-ENB-2,3-dicaxboxylate, trans-2,3-dipropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3-dipropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3-dipropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae-diethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae-dipropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae-dipropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5-methyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-methyl-5-ENB-2,3-diethyl dicarboxylate, trans-5-methyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-methyl-5-ENB-2,3-dicaxboxylate, trans-5-methyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-methyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-methyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5-ethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-ethyl-5-ENB-2,3-diethyl dicarboxylate, trans-5-ethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-ethyl-5-ENB-2,3-dicaxboxylate, trans-5-ethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-ethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-ethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester,Trans-5-propyl group-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5-propyl group-5-ENB-2,3-diethyl dicarboxylate, trans-5-propyl group-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5-propyl group-5-ENB-2,3-dicaxboxylate, trans-5-propyl group-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5-propyl group-5-ENB-2,3-diisobutyl dicarboxylate, trans-5-propyl group-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5,6-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5,6-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-5,6-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5,6-dimethyl-5-ENB-2,3-dicaxboxylate, trans-5,6-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5,6-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5,6-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5,6-diethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5,6-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-5,6-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5,6-diethyl-5-ENB-2,3-dicaxboxylate, trans-5,6-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5,6-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5,6-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-5,6-dipropyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-5,6-dipropyl-5-ENB-2,3-diethyl dicarboxylate, trans-5,6-dipropyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-5,6-dipropyl-5-ENB-2,3-dicaxboxylate, trans-5,6-dipropyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-5,6-dipropyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-5,6-dipropyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-7,7-dimethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-7,7-dimethyl-5-ENB-2,3-diethyl dicarboxylate, trans-7,7-dimethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-7,7-dimethyl-5-ENB-2,3-dicaxboxylate, trans-7,7-dimethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-7,7-dimethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-7,7-dimethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-7,7-diethyl-5-ENB-2,3-dimethyl dicarboxylate, trans-7,7-diethyl-5-ENB-2,3-diethyl dicarboxylate, trans-7,7-diethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-7,7-diethyl-5-ENB-2,3-dicaxboxylate, trans-7,7-diethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-7,7-diethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-7,7-diethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1,2,3,4-tetramethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1,2,3,4-tetramethyl-5-ENB-2,3-diethyl dicarboxylate, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicaxboxylate, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1,2,3,4-tetramethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1,2,3,4-tetramethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-1,2,3,4-tetraethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-1,2,3,4-tetraethyl-5-ENB-2,3-diethyl dicarboxylate, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicaxboxylate, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-1,2,3,4-tetraethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-1,2,3,4-tetraethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3,5,6-tetramethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3,5,6-tetramethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicaxboxylate, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3,5,6-tetramethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3,5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-2,3,5,6-tetraethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-2,3,5,6-tetraethyl-5-ENB-2,3-diethyl dicarboxylate, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicaxboxylate, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-2,3,5,6-tetraethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-2,3,5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetramethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-Norbornene-2,3-Dicarboxylic Acid Dimethyl Ester, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-diethyl dicarboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dipropyl, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicaxboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids dibutyl ester, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-diisobutyl dicarboxylate, trans-Isosorbide-5-Nitrae, 5,6-tetraethyl-5-ENB-2,3-dicarboxylic acids two peopentyl ester.
5., as claimed in claim 1 for the solid catalyst of 1-butylene polymerization, it is characterized by described promotor is triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine di-isopropyl aluminium, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium.
6., as claimed in claim 1 for the solid catalyst of 1-butylene polymerization, it is characterized by described external electron donor is dimethyldimethoxysil,ne, diethyldimethoxysilane, dipropyl dimethoxysilane, diisopropyl dimethoxy silane, dibutyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane, Dicyclohexyldimethoxysilane, dimethoxydiphenylsilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyl diethoxy silane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyl diethoxy silane, bicyclopentyl diethoxy silane, dicyclohexyl diethoxy silane, diphenyl diethoxy silane, methylethyl dimethoxysilane, methyl-propyl dimethoxysilane, isopropyl methyl dimethoxysilane, methyl butyl dimethoxysilane, methyl-isobutyl dimethoxysilane, methylcyclopentyl dimethoxysilane, Cyclohexylmethyldimethoxysilane, aminomethyl phenyl dimethoxysilane, ethyl propyl dimethoxysilane, ethylisopropyl base dimethoxysilane, ethyl-butyl dimethoxysilane, ethyl isobutyl base dimethoxysilane, ethylcyclopentyl dimethoxysilane, ethylcyclohexyl dimethoxysilane, ethylphenyl dimethoxysilane, propyl iso-propyl dimethoxysilane, butyl dimethoxysilane, propyl group isobutyl-dimethoxysilane, propyl group cyclopentyl dimethoxysilane, propylcyclohexyl dimethoxysilane, propyl group phenyidimethoxysilane, butyl isobutyl-dimethoxysilane, butyl cyclopentyl dimethoxysilane, butylcyclohexyl dimethoxysilane, butyl phenyl dimethoxysilane, isobutyl-cyclopentyl dimethoxysilane, isobutyl-cyclohexyl dimethoxysilane, isobutyl phenenyl dimethoxysilane, cyclopentyl cyclohexyl dimethoxysilane, cyclopentyl phenyl dimethoxysilane, cyclohexyl phenyl dimethoxysilane, dipiperidino dimethoxysilane, dipiperidino diethoxy silane, bihyrrolidinyl dimethoxysilane or bihyrrolidinyl diethoxy silane.
7., as claimed in claim 1 for the preparation method of Primary Catalysts in the solid catalyst of 1-butylene polymerization, it is characterized by and comprise the following steps:
(1), according to mol ratio Tetra hydro Phthalic anhydride: magnesium chloride=0.01-3.00:1, mol ratio alcohol: magnesium=0.2-10:1, mol ratio decane: magnesium chloride=1-10:1, Tetra hydro Phthalic anhydride, magnesium chloride, alcohol and decane are joined in reactor, 80-180 DEG C of reaction 4-6h, obtained alcohol and thing;
(2), be added drop-wise to by alcohol adduct in the titanium tetrachloride of-30-10 DEG C, the 1g magnesium correspondence wherein in alcohol adduct adds the titanium tetrachloride of 10-100ml, is added dropwise to complete in 1-3 hour;
(3), 80-150 DEG C is warming up to, insulation 1-4 hour;
(4), leave standstill, draw up a layer waste liquid, now temperature is down to room temperature, adds and carry out secondary with the titanium tetrachloride of step (2) same amount and carry titanium in this temperature downhill reaction device;
(5), be warming up to 50-100 DEG C, add internal electron donor compound, insulation reaction 2-3 hour, mol ratio is interior Donor compound: magnesium=0.01-10.00:1;
(6), temperature programming, to 100-160 DEG C, reacts 1-5 hour;
(7), leave standstill, filter out upper strata waste liquid, washing, vacuum-drying, finally obtains Primary Catalysts.
8. as claimed in claim 7 for 1 ?butene polymerization solid catalyst in the preparation method of Primary Catalysts, it is characterized by described alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, neopentyl alcohol, n-Octanol or isooctyl alcohol.
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