CN107286280A - The coordination polymerization preparation method of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes - Google Patents

The coordination polymerization preparation method of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes Download PDF

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CN107286280A
CN107286280A CN201610202925.3A CN201610202925A CN107286280A CN 107286280 A CN107286280 A CN 107286280A CN 201610202925 A CN201610202925 A CN 201610202925A CN 107286280 A CN107286280 A CN 107286280A
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aluminium
methylene
phenyl
isosorbide
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CN107286280B (en
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崔冬梅
李世辉
刘博�
刘东涛
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Changchun Institute of Applied Chemistry of CAS
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    • C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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Abstract

The present invention relates to a kind of coordination polymerization preparation method of the poly- 3 methylene cyclopentene of Isosorbide-5-Nitrae, belong to catalyst technical field.The catalyst solution that the preparation method that the present invention is provided is constituted using the rare earth compound shown in formula (A), the organic boron salt of co-catalyst and alkyl aluminum compound, the polymerization of 3 methylene cyclopentenes is set to prepare the poly- 3 methylene cyclopentene of crystal type Isosorbide-5-Nitrae of different molecular weight size.The preparation method that the present invention is provided can efficiently prepare number-average molecular weight 169 × 104The poly- 3 methylene cyclopentene of Isosorbide-5-Nitrae of following various molecular size ranges, the poly- 3 methylene cyclopentene Isosorbide-5-Nitrae structural unit content of resulting Isosorbide-5-Nitrae is more than 97%.

Description

The coordination polymerization preparation method of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes
Technical field
The present invention relates to catalyst technical field, and in particular to a kind of coordination polymerization system of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes Preparation Method.
Background technology
The dependence to petroleum resources is reduced, the novel high polymer material that exploitation comes from renewable resource has become macromolecule Realize the inexorable trend of sustainable development in field.For the various polyethers bioabsorbable polymer materials furtherd investigate, The exploitation of high polymer material based on terpenes, then be less subject to the concern of people.Because terpene compound structure is special Point determines that it is more difficult to prepare polymer with coordination polymerization process.Accordingly, it would be desirable to which terpene compound is changed into suitable for matching somebody with somebody The monomer of position polymerization.Recently, beta-myrcene is changed into 3- methylene basic rings by Hillymer groups in the U.S. using Grubbs catalyst Amylene, the high selectivity for then realizing 3- methylene cyclopentenes using cationic initiator polymerize, and has prepared high Isosorbide-5-Nitrae-vertical The poly- 3- methylenes cyclopentene of structure, the polymer is a kind of new high polymer material with crystal property；They are also sharp simultaneously System is triggered to realize the high 4,3- selective polymerisations of 3- methylene cyclopentenes with anion.But, this kind of catalyst system and catalyzing is obtained Polymer molecular weight it is relatively low, polymerizing condition is very harsh (J.Am.Chem.Soc.2009,131,7960).The researcher of Japan By 3- methylenes cyclopentene and maleimide combined polymerization prepared high molecular alternate copolymer (Macromolecules, 2013,46,9526).In addition, also without other documents and patent report polymerizeing about 3- methylene cyclopentenes monomer. Therefore, develop new catalyst system and catalyzing and realize controllable high selectivity polymerization of the 3- methylenes cyclopentene under gentleer process conditions, be One is significantly studied, and is also to expand that this biological source monomer applications of 3- methylene cyclopentenes are urgently to be resolved hurrily asks Topic.
The content of the invention
The purpose of the present invention is to prepare the controllable poly- 3- methylenes of 1,4- of high selectivity, molecular weight using the method for coordination polymerization Cyclopentene, and then a kind of coordination polymerization preparation method of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes is provided.
To achieve these goals, technical scheme is specific as follows：
A kind of coordination polymerization preparation method of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes, comprises the following steps：
1) under inert nitrogen gas or argon gas protection, rare earth compound, organic boron salt and alkyl aluminum compound are dissolved In organic solvent, catalyst solution is obtained；
2) using 3- methylene cyclopentene monomers as raw material, with the catalyst solution catalytic polymerization, at -30~80 DEG C Polymerisation is terminated behind lower polymerase 10 .01~48 hour, product is settled, Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes are dried to obtain；
The rare earth compound general structure is such as shown in (A)：
In formula (A)：Q is non-cyclopentadienyl or cyclopentadienyl single anion ligand；
Ln is rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；
X1And X2It is each independently selected from alkyl, silylation, aryl, silicon amido, alkylamino radical, pi-allyl, boron hydrogen, chlorine or bromine；
L is neutral Lewis base tetrahydrofuran, pyridine or glycol dimethyl ether, and w is the quantity 0,1 or 2 of lewis base；
Organic boron salt is to contain [B (C6F5)4]ˉThe organoboron reagent of anion；
The alkyl aluminum compound is alkyl aluminum, alkyl aluminium hydride, chlorination alkyl aluminum or aikyiaiurnirsoxan beta；
The mol ratio of the 3- methylenes cyclopentene monomer and the rare earth compound is (50~30000):1；
Organic boron salt and the mol ratio of the rare earth compound are (0.5~2.0)：1；
The mol ratio of the alkyl aluminum compound and the rare earth compound is (0~1000)：1.
In the above-mentioned technical solutions, the structural formula of the non-cyclopentadienyl single anion ligand is as shown in Formulas I-VI：
In Formulas I-VI, R1And R2Aryl, alkyl substituting aromatic base, halogenated aryl, alkyl, hetero atom is each independently selected to take The aryl of alkyl or the hetero atom substitution in generation；
R3For alkyl, alkenyl, alkynyl, aryl, phosphino-, alkoxy or alkane sulfydryl；
R4Represent hydrogen or alkyl；
The structural formula of the cyclopentadienyl single anion ligand is as shown in Formula VII-IX：
In Formula VII-IX, R5、R6、R7、R8And R9It is each independently selected from hydrogen, alkyl, silylation, amido, phosphino-, alcoxyl Base, alkane sulfydryl, aryl or hetero-atom substituted aryl.
In the above-mentioned technical solutions, R1And R2It is each independently selected from phenyl, p-methylphenyl, to ethylphenyl, to isopropyl Base phenyl, to tert-butyl-phenyl, an aminomethyl phenyl, an ethylphenyl, an isopropyl phenyl, o-methyl-phenyl, adjacent ethylphenyl, O-isopropyl phenyl, adjacent phenyl, mesitylene base, 2,6- 3,5-dimethylphenyls, 2,6- diethyl phenyls, 2,6- diethyls Base -4- aminomethyl phenyls, equal triethyl group phenyl, 2,6- diethyl -4- 2-methyl-2-phenylpropanes base, 2,6- diisopropyl phenyls, 2,6- diisopropyls Base -4- aminomethyl phenyls, equal triisopropyl phenyl, 2,6- di-tert-butyl-phenyls, 2,6- di-t-butyl -4- aminomethyl phenyls, 2,6- bis- Phenyl, the trifluoromethyls of 2,6- bis-, 2- fluorophenyls, 3- trifluoromethyls, p-trifluoromethyl phenyl, p-fluorophenyl or 1- naphthyls；
R3For ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, trimethylsilyl methyl, double trimethylsilyl methyl, Cyclopenta, cyclohexyl, methylcyclohexyl, adamantyl, phenyl, 4- aminomethyl phenyls, 4- ethylphenyls, 4- isopropyl phenyls, 4- Tert-butyl-phenyl, 4- phenyls, pentafluorophenyl group, 4- methoxyphenyls, o- methoxyphenyl, p- N, N- 3,5-dimethylphenyls, O- N, N- 3,5-dimethylphenyl, o- N, N- dimethyl benzyls, 2- pyridine methylenes, o- first mercaptophenyl, o- diformazan phosphino- benzene Base, 4- [1- (2,5- dimethyl pyrroles)]-phenyl, vinyl, acrylic, acetenyl, propinyl, anilino-, cyclohexylamino, four Pyridinium hydroxide base, tetrahydrochysene piperidyl, diphenylphosphino, ehtylmercapto or propyl group sulfydryl；
R4For hydrogen, methyl, ethyl, propyl group, normal-butyl, isopropyl or the tert-butyl group；
R5、R6、R7、R8And R9It is each independently selected from hydrogen, methyl, ethyl, the tert-butyl group, trimethyl silicon substrate, phenyl, diphenyl Phosphine, 2- pyridine radicals, 2- pyridine methylenes or N, N- dimethyl ethyl.
In the above-mentioned technical solutions, X1And X2It is each independently selected from CH3、CH2SiMe3、CH(SiMe3)2、o-NMe2- C6H4CH2、N(SiMe3)2、N(SiHMe2)2、1,3-C3H5、C6H5CH2Or 4-CH3C6H5CH2。
In the above-mentioned technical solutions, organic boron salt is [Ph3C][B(C6F5)4]、[NEt3H][B(C6F5)4] or [PhNMe2H][B(C6F5)4]。
In the above-mentioned technical solutions, the alkyl aluminum compound be trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three just Butyl aluminium, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, It is three p-methylphenyl aluminium, tribenzyl aluminium, three n-butylaluminum, ethyl di-p-tolyl aluminium, diethylbenzyl aluminium, dimethyl hydrogenated Aluminium, diethylaluminum hydride, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminium hydride, Diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl Aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride, ethyl p-methylphenyl aluminum hydride, dimethylaluminum chloride, diethyl chlorination Aluminium, diη-propyl aluminium chloride, di-n-butyl aluminium chloride, diisopropyl aluminium chloride, diisobutyl aluminum chloride, diamyl aluminium chloride, Dihexylaluminum chloride, dicyclohexyl aluminium chloride, dioctyl aluminium chloride, diphenyl aluminium chloride, di-p-tolyl aluminium chloride, dibenzyl Aluminium chloride, Ethylbenzyl chlorination aluminium, ethyl p-methylphenyl aluminium chloride, MAO, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta and One or more in normal-butyl aikyiaiurnirsoxan beta.
In the above-mentioned technical solutions, the concentration of the 3- methylenes cyclopentene monomer is 0.1~60g/100mL.
In the above-mentioned technical solutions, the polymerisation can carry out polymerisation in solution in the presence of solvent, can also be in nothing Polymerisation in bulk is carried out under solvent case, when using polymerisation in solution mode, organic solvent is selected from saturated alkane, aromatic hydrocarbons, halo virtue One or more in hydrocarbon and cycloalkane.
In the above-mentioned technical solutions, the organic solvent is n-hexane, normal heptane, hexamethylene, petroleum ether, benzene, toluene, two Toluene, chlorobenzene, dichloro-benzenes or trichloro-benzenes.
The beneficial effects of the invention are as follows：
A kind of coordination polymerization preparation method of Isosorbide-5-Nitrae that the present invention is provided-poly- 3- methylene cyclopentenes, is to utilize coordination first Method synthesis Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes of polymerization, therefore the preparation of the Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes of the invention provided Method has novelty very much.
The preparation method that the present invention is provided uses rare earth compound, the organic boron salt of co-catalyst and the alkane shown in formula (A) The catalyst solution of base aluminium compound composition makes 3- methylenes cyclopentene polymerize the crystal type for preparing different molecular weight size The poly- 3- methylenes cyclopentenes of 1,4-.
The preparation method that the present invention is provided can efficiently prepare number-average molecular weight 169 × 104Following various points Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes of son amount size, resulting Isosorbide-5-Nitrae-poly- 3- methylenes cyclopentene Isosorbide-5-Nitrae-structural unit content is big In 97%.
Brief description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Fig. 1 be embodiment 1 prepare the poly- 3- methylenes cyclopentenes of 1,4- nucleus magnetic hydrogen spectrum (1H NMR) and nuclear-magnetism carbon spectrum (13C NMR) figure.
Embodiment
For a further understanding of the present invention, the preferred embodiments of the invention are described with reference to embodiment, but It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention rather than the limit to the claims in the present invention System.
The coordination polymerization preparation method of the Isosorbide-5-Nitrae that the present invention is provided-poly- 3- methylene cyclopentenes, specific preparation method is as follows：
Under inert nitrogen gas or argon gas protection, rare earth compound, organic boron salt and alkyl aluminum compound are dissolved in In organic solvent, catalyst solution is obtained, then catalyst solution is added at the anaerobic for filling 3- methylene cyclopentene monomers In the aggregation container of reason；The 3- methylene cyclopentene monomers added rub with the rare earth compound in described catalyst solution You are than being 50:1~30000:1, polymerisation is carried out 0.01~48 hour at -30~80 DEG C, and it is 10% to add volumetric concentration Ethanol solution hydrochloride terminate polymerisation, by reaction solution pour into methanol settle, obtain Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes； The obtained polymer is placed in vacuum drying chamber again and dried, obtains drying Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes of constant weight.Institute The mol ratio for stating organic boron salt and the rare earth compound is (0.5~2.0)：1；The alkyl aluminum compound and the rare earth The mol ratio of compound is (0~1000)：1.Above-mentioned polymerisation can carry out polymerisation in solution in the presence of solvent, can also be in nothing Polymerisation in bulk is carried out under solvent case.When using polymerisation in solution mode, organic solvent is selected from saturated alkane, aromatic hydrocarbons, halo virtue One or more in hydrocarbon, cycloalkane.It is preferred that n-hexane, normal heptane, petroleum ether, hexamethylene, benzene,toluene,xylene, chlorobenzene, Dichloro-benzenes or trichloro-benzenes.
The structural formula of the poly- 3- methylenes cyclopentenes of 1,4- prepared is as follows：
The rare earth compound general structure is such as shown in (A)：
In formula (A)：Q is non-cyclopentadienyl or cyclopentadienyl single anion ligand；
The structural formula of the non-cyclopentadienyl single anion ligand is as shown in Formulas I-VI：
In Formulas I-VI, R1And R2Aryl, alkyl substituting aromatic base, halogenated aryl, alkyl, hetero atom is each independently selected to take The aryl of alkyl or the hetero atom substitution in generation；It is preferred that R1And R2It is each independently selected from C6~C25 aryl and alkyl substitution virtue The aryl containing halogen of base, C6~C25, C2~C25 alkyl, the heteroatomic alkane such as the siliceous of C6~C25, oxygen, nitrogen and phosphorus Base or aryl, more preferably phenyl, p-methylphenyl, to ethylphenyl, p-isopropyl phenyl, to tert-butyl-phenyl, a methyl Phenyl, an ethylphenyl, an isopropyl phenyl, o-methyl-phenyl, adjacent ethylphenyl, o-isopropyl phenyl, adjacent phenyl, Trimethylphenyl, 2,6- 3,5-dimethylphenyls, 2,6- diethyl phenyls, 2,6- diethyl -4- aminomethyl phenyls, equal triethyl group phenyl, 2,6- diethyl -4- 2-methyl-2-phenylpropanes base, 2,6- diisopropyl phenyls, 2,6- diisopropyl -4- aminomethyl phenyls, equal triisopropylbenzene Base, 2,6- di-tert-butyl-phenyls, 2,6- di-t-butyl -4- aminomethyl phenyls, 2,6- diphenyl phenyl, the trifluoromethylbenzenes of 2,6- bis- Base, 2- fluorophenyls, 3- trifluoromethyls, p-trifluoromethyl phenyl, p-fluorophenyl or 1- naphthyls；
R3For alkyl, alkenyl, alkynyl, aryl, phosphino-, alkoxy or alkane sulfydryl；It is preferred that R3For C1~C20 alkyl, C2~ C20 alkenyl, C2~C20 alkynyl, C6~C25 substituted-phenyl, C6~C25 aralkyl, C6~C25 cycloalkyl, C2 ~C20 cyclic ethers base, C2~C20 phosphino-, C1~C20 boryl, C1~C20 alkoxy, C1~C20 alkane sulfydryl；More Preferably ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, trimethylsilyl methyl, double trimethylsilyl methyl, cyclopenta, Cyclohexyl, methylcyclohexyl, adamantyl, phenyl, 4- aminomethyl phenyls, 4- ethylphenyls, 4- isopropyl phenyls, 4- tert-butyl benzenes Base, 4- phenyls, pentafluorophenyl group, 4- methoxyphenyls, o- methoxyphenyl, p- N, N- 3,5-dimethylphenyls, o- N, N- bis- Aminomethyl phenyl, o- N, N- dimethyl benzyls, 2- pyridine methylenes, o- first mercaptophenyl, o- diformazan phosphino- phenyl, 4- [1- (2,5- dimethyl pyrroles)]-phenyl, vinyl, acrylic, acetenyl, propinyl, anilino-, cyclohexylamino, tetrahydropyridine Base, tetrahydrochysene piperidyl, diphenylphosphino, ehtylmercapto or propyl group sulfydryl.
R4Represent hydrogen or alkyl；It is preferred that R4For hydrogen or C1~C20 alkyl, more preferably R4For hydrogen, methyl, ethyl, propyl group, Normal-butyl, isopropyl or the tert-butyl group；
The structural formula of the cyclopentadienyl single anion ligand is as shown in Formula VII-IX：
In Formula VII-IX, R5、R6、R7、R8And R9It is each independently selected from as hydrogen, alkyl, silylation, amido, phosphino-, alcoxyl Base, alkane sulfydryl, aryl or hetero-atom substituted aryl；It is preferred that R5、R6、R7、R8And R9It is each independently selected from hydrogen, methyl, ethyl, uncle Butyl, trimethyl silicon substrate, phenyl, diphenylphosphine, 2- pyridine radicals, 2- pyridine methylenes or N, N- dimethyl ethyl；
Ln is rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；
X1And X2It is each independently selected from alkyl, silylation, aryl, silicon amido, alkylamino radical, pi-allyl, boron hydrogen, chlorine or bromine； It is preferred that X1And X2It is each independently selected from C1~C10 alkyl, C1~C10 silylation, C7~C10 aryl, C1~C10 Silicon amido, C1~C10 alkylamino radical, C1~C10 pi-allyl, boron hydrogen, chlorine or bromine etc.；More preferably X1And X2Select independently of one another From CH3、CH2SiMe3、CH(SiMe3)2、o-NMe2-C6H4CH2、N(SiMe3)2、N(SiHMe2)2、1,3-C3H5、C6H5CH2、4- CH3C6H5CH2、BH4, Cl or Br；
L is neutral Lewis base tetrahydrofuran, pyridine or glycol dimethyl ether, and w is the quantity 0,1 or 2 of lewis base；
Organic boron salt B is to contain [B (C6F5)4]ˉThe organoboron reagent of anion, selected from [Ph3C][B(C6F5)4]、 [NEt3H][B(C6F5)4] or [PhNMe2H][B(C6F5)4]；
The alkyl aluminum compound C is alkyl aluminum, alkyl aluminium hydride, chlorination alkyl aluminum or aikyiaiurnirsoxan beta；Preferably trimethyl Aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminums, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, three Cyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, three n-butylaluminum, ethyl di-p-tolyl It is aluminium, diethylbenzyl aluminium, dimethyl hydrogenated aluminium, diethylaluminum hydride, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, two different Propyl group aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl hydrogenation Aluminium, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride, the hydrogenation of ethyl p-methylphenyl Aluminium, dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminium chloride, di-n-butyl aluminium chloride, diisopropyl aluminium chloride, two Isobutyl group aluminium chloride, diamyl aluminium chloride, dihexylaluminum chloride, dicyclohexyl aluminium chloride, dioctyl aluminium chloride, diphenyl chlorination Aluminium, di-p-tolyl aluminium chloride, dibenzyl aluminium chloride, Ethylbenzyl chlorination aluminium, ethyl p-methylphenyl aluminium chloride, methyl alumina One or more in alkane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta；More preferably trimethyl aluminium, three second Base aluminium, three n-butylaluminums, tri-n-n-propyl aluminum, triisobutyl aluminium, triisopropylaluminiuand, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, Diethylaluminum hydride, diisobutyl aluminium hydride or MAO.
According to the present invention, the preparation method of the catalyst solution is：By rare earth compound, organoboron reagent and alkyl aluminum Compound, is well mixed in organic solvent according to a certain ratio, obtains catalyst solution.
According to the present invention, the one kind or many of the organic solvent in saturated alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon, cycloalkane Kind.It is preferred that n-hexane, normal heptane, hexamethylene, petroleum ether, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes or trichloro-benzenes.
According to the present invention, described rare earth compound is synthesized according to prior art, and those skilled in the art being capable of root Synthesized according to correlation technique data.According to the preferred compositions of patent of the present invention, our preferably following rare earth compound 1-44 are sub- to 3- Methyl cyclopentene carries out polymerization experiment：
It is the specific embodiment of the invention below, it is necessary to which explanation is that scheme to be protected of the invention is not limited in following reality Apply example.
Embodiment 1
Under the conditions of anhydrous and oxygen-free, by rare earth compound 1 (8.8mg, 10 μm of ol), [Ph3C][B(C6F5)4](9.2mg,10 μm ol) and AiiBu3The toluene solution 2mL of (0.2mL × 0.25M), at 25 DEG C, is added to 25mL and fills 3- methylene cyclopentenes In the toluene solution of (0.16g, 2mmol) monomer (3mL).After high-speed stirred is reacted 1 minute, add a small amount of ethanol solution and terminate and gather Close reaction.Then reaction solution is poured on a small quantity containing sedimentation in hydrochloric acid and stabilizer (BHT) 100ml methanol.Gained is polymerize Thing is placed in 40 DEG C of vacuum drying chambers and dried 48 hours, obtains net weight 0.16g polymer (yield 100%).Resulting polymers Nucleus magnetic hydrogen spectrum (1H NMR) and nuclear-magnetism carbon spectrum (13C NMR) as shown in Figure 1, it is known that successfully prepare Isosorbide-5-Nitrae-poly- 3- methylene basic rings Amylene.
Embodiment 2~47：The experimental procedure of the series embodiment is same as Example 1, its polymeric reaction condition and its urges The change condition of change system is described in detail in table 1.
The coordination polymerization of table 1. prepares the poly- 3- methylenes cyclopentenes of 1,4-
D in table 1 represents organic boron salt [Ph3C][B(C6F5)4], E represents organic boron salt [NEt3H][B(C6F5)4], F generations Organic boron salt [the PhNMe of table2H][B(C6F5)4]。
It is rare earth compound described in above-described embodiment, the species and its ratio of organic boron salt and alkyl aluminum compound, used Solvent can be any combination that limits in above-mentioned technical proposal, no longer enumerate here.
It can be drawn from the aggregated data of embodiment 1~47：Catalyst solution provided by the present invention is catalyzed 3- methylene During cyclopentene polymerisation, monomer can obtain 100% conversion.The number-average molecular weight of 3- methylene cyclopentenes is 1.6 × 104 ~169 × 104In the range of, molecular weight distribution is narrower.The rare-earth catalysis system can high selectivity catalysis 3- methylenes basic ring penta Alkene polymerize, and prepares high Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (9)

1. the coordination polymerization preparation method of a kind of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes, it is characterised in that comprise the following steps：
1) under inert nitrogen gas or argon gas protection, rare earth compound, organic boron salt and alkyl aluminum compound have been dissolved in In machine solvent, catalyst solution is obtained；
2) using 3- methylene cyclopentene monomers as raw material, with the catalyst solution catalytic polymerization, gather at -30~80 DEG C Polymerisation is terminated after closing 0.01~48 hour, product is settled, Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes are dried to obtain；
The rare earth compound general structure is such as shown in (A)：
In formula (A)：Q is non-cyclopentadienyl or cyclopentadienyl single anion ligand；
Ln is rare earth Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；
X1And X2It is each independently selected from alkyl, silylation, aryl, silicon amido, alkylamino radical, pi-allyl, boron hydrogen, chlorine or bromine；
L is neutral Lewis base tetrahydrofuran, pyridine or glycol dimethyl ether, and w is the quantity 0,1 or 2 of lewis base；
Organic boron salt is to contain [B (C6F5)4]-The organoboron reagent of anion；
The alkyl aluminum compound is alkyl aluminum, alkyl aluminium hydride, chlorination alkyl aluminum or aikyiaiurnirsoxan beta；
The mol ratio of the 3- methylenes cyclopentene monomer and the rare earth compound is (50~30000):1；
Organic boron salt and the mol ratio of the rare earth compound are (0.5~2.0)：1；
The mol ratio of the alkyl aluminum compound and the rare earth compound is (0~1000)：1.
2. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 1-poly- 3- methylene cyclopentenes, it is characterised in that institute The structural formula of non-cyclopentadienyl single anion ligand is stated as shown in Formulas I-VI：
In Formulas I-VI, R1And R2It is each independently selected from what aryl, alkyl substituting aromatic base, halogenated aryl, alkyl, hetero atom replaced Alkyl or the aryl of hetero atom substitution；
R3For alkyl, alkenyl, alkynyl, aryl, phosphino-, alkoxy or alkane sulfydryl；
R4Represent hydrogen or alkyl；
The structural formula of the cyclopentadienyl single anion ligand is as shown in Formula VII-IX：
In Formula VII-IX, R5、R6、R7、R8And R9It is each independently selected from hydrogen, alkyl, silylation, amido, phosphino-, alkoxy, alkane Sulfydryl, aryl or hetero-atom substituted aryl.
3. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 2-poly- 3- methylene cyclopentenes, it is characterised in that R1 And R2It is each independently selected from phenyl, p-methylphenyl, to ethylphenyl, p-isopropyl phenyl, to tert-butyl-phenyl, a methyl Phenyl, an ethylphenyl, an isopropyl phenyl, o-methyl-phenyl, adjacent ethylphenyl, o-isopropyl phenyl, adjacent phenyl, Trimethylphenyl, 2,6- 3,5-dimethylphenyls, 2,6- diethyl phenyls, 2,6- diethyl -4- aminomethyl phenyls, equal triethyl group phenyl, 2,6- diethyl -4- 2-methyl-2-phenylpropanes base, 2,6- diisopropyl phenyls, 2,6- diisopropyl -4- aminomethyl phenyls, equal triisopropylbenzene Base, 2,6- di-tert-butyl-phenyls, 2,6- di-t-butyl -4- aminomethyl phenyls, 2,6- diphenyl phenyl, the trifluoromethylbenzenes of 2,6- bis- Base, 2- fluorophenyls, 3- trifluoromethyls, p-trifluoromethyl phenyl, p-fluorophenyl or 1- naphthyls；
R3For ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, trimethylsilyl methyl, double trimethylsilyl methyl, ring penta Base, cyclohexyl, methylcyclohexyl, adamantyl, phenyl, 4- aminomethyl phenyls, 4- ethylphenyls, 4- isopropyl phenyls, the tertiary fourths of 4- Base phenyl, 4- phenyls, pentafluorophenyl group, 4- methoxyphenyls, o- methoxyphenyl, p- N, N- 3,5-dimethylphenyls, o- N, N- 3,5-dimethylphenyls, o- N, N- dimethyl benzyls, 2- pyridine methylenes, o- first mercaptophenyl, o- diformazan phosphino- phenyl, 4- [1- (2,5- dimethyl pyrroles)]-phenyl, vinyl, acrylic, acetenyl, propinyl, anilino-, cyclohexylamino, tetrahydrochysene pyrrole Piperidinyl, tetrahydrochysene piperidyl, diphenylphosphino, ehtylmercapto or propyl group sulfydryl；
R4For hydrogen, methyl, ethyl, propyl group, normal-butyl, isopropyl or the tert-butyl group；
R5、R6、R7、R8And R9Be each independently selected from hydrogen, methyl, ethyl, the tert-butyl group, trimethyl silicon substrate, phenyl, diphenylphosphine, 2- pyridine radicals, 2- pyridine methylenes or N, N- dimethyl ethyl.
4. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 1-poly- 3- methylene cyclopentenes, it is characterised in that X1 And X2It is each independently selected from CH3、CH2SiMe3、CH(SiMe3)2、o-NMe2-C6H4CH2、N(SiMe3)2、N(SiHMe2)2、1,3- C3H5、C6H5CH2Or 4-CH3C6H5CH2。
5. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 1-poly- 3- methylene cyclopentenes, it is characterised in that institute Organic boron salt is stated for [Ph3C][B(C6F5)4]、[NEt3H][B(C6F5)4] or [PhNMe2H][B(C6F5)4]。
6. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 1-poly- 3- methylene cyclopentenes, it is characterised in that institute Alkyl aluminum compound is stated for trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminums, triisopropylaluminiuand, triisobutyl Aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl Dibenzyl aluminium, ethyl di-p-tolyl aluminium, diethylbenzyl aluminium, dimethyl hydrogenated aluminium, diethylaluminum hydride, diη-propyl hydrogenation Aluminium, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, two Cyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl Aluminum hydride, ethyl p-methylphenyl aluminum hydride, dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminium chloride, di-n-butyl chlorine Change aluminium, diisopropyl aluminium chloride, diisobutyl aluminum chloride, diamyl aluminium chloride, dihexylaluminum chloride, dicyclohexyl aluminium chloride, Dioctyl aluminium chloride, diphenyl aluminium chloride, di-p-tolyl aluminium chloride, dibenzyl aluminium chloride, Ethylbenzyl chlorination aluminium, ethyl pair One or more in tolyl aluminium chloride, MAO, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta.
7. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 1-poly- 3- methylene cyclopentenes, it is characterised in that institute The concentration for stating 3- methylene cyclopentene monomers is 0.1~60g/100mL.
8. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 1-poly- 3- methylene cyclopentenes, it is characterised in that institute Polymerisation in solution can be carried out in the presence of solvent by stating polymerisation, and polymerisation in bulk can also be carried out in the case of solvent-free, when adopting During with polymerisation in solution mode, one or more of the organic solvent in saturated alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon and cycloalkane.
9. the coordination polymerization preparation method of Isosorbide-5-Nitrae according to claim 8-poly- 3- methylene cyclopentenes, it is characterised in that institute Organic solvent is stated for n-hexane, normal heptane, hexamethylene, petroleum ether, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes or trichloro-benzenes.
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