CN1342717A - Process for preparing long-chain branched polyethylene elastomer - Google Patents
Process for preparing long-chain branched polyethylene elastomer Download PDFInfo
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- CN1342717A CN1342717A CN 00124738 CN00124738A CN1342717A CN 1342717 A CN1342717 A CN 1342717A CN 00124738 CN00124738 CN 00124738 CN 00124738 A CN00124738 A CN 00124738A CN 1342717 A CN1342717 A CN 1342717A
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Abstract
A process for preparing long-chain branched polyethylene elastomer is disclosed, and features that the ethylene is used as unique monomer, the post-transistion metal compound as oligomerizing catalyst of ethylene, the metallocene or carried metallocene as copolymerizing catalyst, and the alkyl aluminium or alkyl aluminoxyane or B compound with Lewis acidity as co-catalyst. The said catalyst system has high catalytic activity.
Description
The present invention relates to a kind of process for preparing long-chain branched polyethylene elastomer.
The PE of long chain branching is the novel polyethylene kind that a class has specific performance.Owing to introduce long-chain branch in the main polymer chain, make the crystallization behavior of side chain participation and main chain, therefore make it under the situation of not damaging the product rerum natura, processing characteristics is greatly improved, and demonstrates the better moulding processability than existing LLDPE.This polymkeric substance is very sensitive to shearing rate, and melt viscosity descends soon under the high shear rate, and melt strength improves, and traditional rheological parameters can not fully be described the structure of this polymkeric substance and the relation of processing characteristics.
The PE of long chain branching has elasticity and plasticity (degree of branching is high to be elastomerics, and the degree of branching is low to be plastomer) simultaneously, and density is low, and MWD is narrow, chain length, optical property and good mechanical property.Compare with ULDPE that to have puncture resistance strong, ball falling impact intensity height, snappiness height, characteristics such as the transparency is good.Therefore, long-chain branched polyethylene has application market widely, can substitute materials such as MODIFIED PP, PVC.
The preparation of long-chain branched polyethylene adopts two kinds of methods, and a kind of method is to adopt metallocene catalyst, and ethene and alpha-olefin copolymer are obtained, and wherein related alpha-olefin is a hexene, octene, ten alkene, vinylbenzene, laurylene and octadecylene etc.Wherein with DOW[Eurpean PatentNo.416815 (1991)] the INSITE technology advocated of company finished industrialization at present, it adopts the monocyclopentadienes constrained geometry catalyst, ethene and octene copolymer are obtained, at present, the product of DOW chemical company mainly contains two big classes, and a kind of is polyolefin plastomers (POPs) and polyolefin elastomer (POEs).The octene content of POPs series is 10-19%, and density is 0.9g/cm
3This polymkeric substance has elasticity and thermoplasticity simultaneously, and the octene content of POEs is 20-40%, the low 0.8g/cm that reaches of density
3, Young's modulus and former EPDM are suitable.The INSITE technology of Dow company is similar to an ideal system, makes people can utilize computer that polymer molecular structure is designed accurately, and control has been created polymer molecule designed regular-processing characteristics not in the size that relies on MWD.
Metallocene catalyst also can catalysis high alpha-olefin and ethene generation copolymerization, R.Quijada[Macromol.Chem.Phys.200,1306 (1999)] utilize rac-Et (Ind)
2ZrCl
2/ MAO catalyst system is studied ethene and the copolymerization of 1-octadecylene, the result shows, 1-octadecylene concentration in the system has certain influence to polymerization activity, show and significantly be total to the monomer effect, be total to monomeric insertion rate also higher (6.4%), and the relevant nature of polymkeric substance is studied.
The preparation method of another kind of long-chain branched polyethylene adopts the technology of in-situ copolymerization to carry out, and this method comes from in-situ polymerization and prepares LLDPE.Wherein, Bazan[J.Am.Chem.Soc.120,7143 (1998)] design synthetic (C
6H
5B-OEt)
2ZrCl
2Can under the effect of MAO, the catalyzed ethylene oligomerisation close, obtain ethylene oligomer, and then utilize constrained geometry catalyst and in-situ copolymerization, successfully obtain long-chain branched polyethylene.
But, its maximum shortcoming is the alpha-olefin poor selectivity of its ethylene oligomerization catalyst instability that adopts and catalyzer, selectivity is 40-90%, its oligomerization product is the 1-alkene, 2-alkyl-1-alkene and 2-alkene, wherein, 2-alkyl-1-alkene and 2-alkene can not form copolymerization product with ethene.
The object of the invention is to provide a kind of new process for preparing long-chain branched polyethylene elastomer, solves the deficiency in the above-mentioned research, reaches the effect that the polymer molecule of atom economy type is cut out.
The present invention adopts a kind of promotor MAO, the in-situ polymerization system of forming with two kinds of polymerizing catalysts prepares long-chain branched polyethylene, a kind of be have good ethylene oligomerization optionally the rear transition metal system be catalyzer, another kind is the catalyst for copolymerization with excellent copolymerized characteristic, its objective is that the alpha-olefin in-situ polymerization that oligomerisation is generated generates the long-chain branched polyethylene elastomerics, its reaction synoptic diagram is as follows:
Process for preparing long-chain branched polyethylene elastomer of the present invention follows these steps to carry out:
1. with catalyst for copolymerization and promotor toluene solution, be 1 in molar ratio: 100-1: 5000 ratio, the best are 1: 500-1: 2000 are made into mixing solutions, at Ar or (N
2) protect down stirring at room 0.2-4 hour.
2. under agitation, in reaction flask, add toluene, feed ethene, keep pressure 770mmHg in the bottle through the deoxidation of sodium Metal 99.5 reflux dewatering, temperature of reaction 0-100 ℃, best 30-100 ℃.
3. add 1. promotor successively.2. catalyst for oligomerization.Wherein promotor and catalyst for oligomerization mol ratio are 5-3000, and optimum proportion is 5-2000.Carry out pre-polymerization 0-10min.
4. the mixing solutions with catalyst for copolymerization in the step 1 and promotor adds in the reaction flask, and wherein the mol ratio of catalyst for oligomerization/catalyst for copolymerization is 0.1-100, and optimum mole ratio is 0.25-5.
5. polyase 13 0-120min adds acidifying ethanol termination reaction, washing copolymer, and vacuum-drying obtains long-chain branched polyethylene (LBCPE).
Catalyst for oligomerization of the present invention refers to have the multiple tooth title complex of typical western Buddhist alkali structure part and rear transition metal formation, can generate C under the alkylaluminoxane effect
6-C
50Alpha-olefin, wherein contain two or three coordination elements such as nitrogen, oxygen or phosphorus in the part, its structural representation is:
Wherein, R
1, R
2: 2-methylbenzene, 2-isopropyl benzene, 2-ethylbenzene;
R
2, R
4: alkyl, substituted benzene, benzene;
(R=Ph, substituted benzene)
R
3：
A：N，O，P，S；
M:Fe, Co, Ni, Pd; Catalyst for copolymerization of the present invention adopts metallocene, and its general molecular formula has following structure; C
P IMR
1R
2R
3(I) C
PI-A-R
1MR
2R
3(II)
C
P IC
P IIMR
1R
2(III) C
PI-A-C
P IIMR
1R
2(IV)
Wherein M is Ti, Zr, Hf; C
P IAnd C
P IIBe the cyclopentadiene of cyclopentadiene or replacement, indenyl, the monocycle of band such as fluorenyl conjugated pi electron or the ligand of polynuclear plane all can have substituting group.R
1, R
2, R
3, be H, alkyl, halogen, silane, alkoxyl group, amido, phosphino-s etc. contain O, Si, N, P ligand compound.A is meant bridged group, refers to-(OY
2) n-,-(SiY
2) n-,-(GeY
2) n-, wherein, Y is an alkyl, halogen, alkoxyl group, silylation, amido, phosphino-.N=1-4, A also can be the ring texture group; Abutment can be the diatomic bridge, monatomic bridge, polyatom bridge construction.Metallocene also can carry out carrierization, and the configuration of surface when solving the homogeneous phase metallocene is poor, the easy shortcoming of sticking still.Wherein used carrier is inorganic carrier or organic carrier, as MgCl
2, zeolite, Al
2O
3, SiO
2, polyethylene, polystyrene resin or complex carrier, the carrier granule size is 0.1-0.6mm, specific surface area 50-1000m
2/ g, the aperture is 50-500A, pore volume is 0.3-500cc/g.
Copolymerization catalyst for ethylene of the present invention also can be Z-N catalyzer or non-metallocene catalyst.
Promoter aluminium alkyl oxygen alkane of the present invention or aluminum alkyls or the borate compounds of lewis acidity is arranged; The described promotor of preparation method of the present invention is for alkylaluminoxane has following structure: linear structure R-(AlR-O) n-AlR
2The m of ring texture-(AlR-O), n=1-40 wherein, the best is 20, m=3-40, the best is 3-20, R is a kind of C
1-C
8Alkyl, be preferably methyl, wherein generally adopt MAO, EAO, BAO or MMAO; Described aluminum alkyls or the borate compounds of lewis acidity is arranged is characterized in that described aluminum alkyls is AlR
3, R is the alkyl of C1-C6, is respectively aluminium trimethide, aluminium triethyl, aluminium isobutyl or its mixture; Described aluminum alkyls or the borate compounds of lewis acidity is arranged, the borate compounds that it is characterized in that described lewis acidity is B (C
6F
5)
3, Ph
3 +B (C
6F
5)
- 4, (C
6F
5)
2BH or B (2-C
6F
5-C
6F
4)
3
The catalyst system of preparation method's gained of the present invention has following superiority:
1. the method for making of catalyst for copolymerization of the present invention is that metallocene is at first carried out alkylating reaction with alkylaluminoxane, forms stable catalytic active species, and these species are difficult for destroyed.Typical metallocene catalyst commonly used more of the present invention is Cp
2ZrCl
2, Et (Ind)
2ZrCl
2, Me
2Si (Ind)
2ZrCl
2, Et (Ind)
2ZrCl
2, Cp
*Me
2Nt-BuZrCl
2, Cp
*Me
2N
T-BuTiCl
2And non-metallocene catalyst such as Z-N catalyzer etc.Catalyst for copolymerization also can be supported catalyst, and its carrier is for being generally porous material.As MgCl
2, zeolite, Al
2O
3, SiO
2, polyethylene, polystyrene resin, or complex carrier.The carrier granule size is 0.1-0.6mm, specific surface area 50-1000m
2/ g, the aperture is 50-500A, pore volume is 0.3-500cc/g.
2. to use catalyst for oligomerization be the structure with typical rear transition metal feature in the present invention; The catalyst for oligomerization consumption is few, and minimum content is 0.5 μ mol; Can under the promotor activation, carry out ethylene oligomerization prepared in reaction high alpha-olefin, be C
6=-C
50 =, selectivity is greater than 90%, and activity can reach 10
7GC
2H
4/ molZr.h.
3. alkylaluminoxane comprises methylaluminoxane MAO (MMAO), ethyl aikyiaiurnirsoxan beta EAO, and isobutyl aluminium alkoxide BAO etc. wherein are best with MAO.Keep Al/ metal=5-5000, the best is 100-3000, and its consumption is few.
This catalyst system can utilize ethene can prepare the multipolymer of ethene and alpha-olefin for one step of only monomer; Have advantages of high catalytic activity, its activity be use metallocene catalyst separately 2-3 doubly; Be total to monomer insertion rate height, its insertion rate is (15-5) mol-%.Monomer being evenly distributed in Polyethylene Chain has the degree of crystallinity lower than low melting point altogether, and its melting range is 40-133 ℃, and its degree of crystallinity scope is 5-90%, and its molecular weight is 70-8 ten thousand, Mw/Mn=1.5-3.9.
Polymkeric substance
13The CNMR data analysis shows that this polymkeric substance is a long-chain branched polyethylene, at δ 39.74,38.28,38.24 be independent tertiary carbon structure, δ 34.63,34.23,34.14 δ 30.74, δ 27.48,26.79 three groups of peaks show the α of the carbon of adjacent branch point, γ, three kinds of structures of β, δ 14.42,14.38, the terminal methyl group of 11.39 long-chains.
Embodiment
Embodiment 1.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Et (Ind)
2ZrCl
2
C: promotor: MAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polymerization 10min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 2.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
2Si (Ind)
2ZrCl
2
C: promotor: BAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 3.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
5CpMe
2Nt-BuTiCl
2
C: promotor: MMAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 4.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A. catalyst for oligomerization:
B: catalyst for copolymerization: Cp
2ZrCl
2
C: promotor: EAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 5.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
2Si (Ind)
2ZrCl
2
C: promotor: MAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 6.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
2Si (Ind)
2ZrCl
2
C: promotor: MAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 7.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
2Si (Ind)
2ZrCl
2
C: promotor: MAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 8.
1. all under the condition of anhydrous oxygen, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
2Si (Ind)
2ZrCl
2
C: promotor: MAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 9.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
2Si (Ind)
2ZrCl
2
C: promotor: MAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Embodiment 10.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization:
B: catalyst for copolymerization: Me
2Si (Ind)
2ZrCl
2
C: promotor: MAO
3. in the there-necked flask of a 250ml, add 100ml toluene and stir adding a certain proportion of (C) down, add then (A), carry out pre-oligomerisation certain hour at a certain temperature, then (B) being added in the reactor, is under the condition of 770mmHg at the pressure of ethene, polyase 13 0min, add acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance, and vacuum-drying, its operational condition and polymerization property are listed in the table 1.
Polymerizing condition among table 1. embodiment and aggregated data embodiment catalyst for oligomerization catalyst for copolymerization temperature promotor C activity
A (mol) B (μ mol) (℃) Al/A+B (mol) 10
6GPE/molZr.h embodiment 124 50 3,000 4.45 embodiment 224 50 2,000 4.61 embodiment 314 50 1,000 6.63 embodiment 4 0.5 4 60 700 4.92 embodiment 5 0.25 4 60 600 5.75 embodiment 644 60 600 4.50 embodiment 7 0.1 2 70 560 4.22 embodiment 821 70 900 11.4 embodiment 924 70 900 4.75 embodiment 10 24 75 800 6.72
Claims (11)
1. process for preparing long-chain branched polyethylene elastomer comprises following these steps to carry out:
1) be 1 with mol ratio: 100-1: 5000 catalyst for copolymerization and promotor solution, under protection of inert gas, stirred 0.2-4 hour, form the mixing solutions of catalyst for copolymerization and promotor;
2) under agitation, in reaction flask, add the toluene of dehydration and deoxidation, feed ethene, keep 0-100 ℃ of temperature of reaction;
3) add promotor and catalyst for oligomerization successively, carry out prepolymerization;
4) mixing solutions with catalyst for copolymerization in the step 1) and promotor adds in the reaction flask, and wherein the mol ratio of catalyst for oligomerization/catalyst for copolymerization is 0.1-100;
5) after polyase 13 0-120 minute, the acidifying termination reaction, washing copolymer, vacuum-drying obtains long-chain branched polyethylene;
Wherein said catalyst for oligomerization is the multiple tooth title complex with typical western Buddhist alkali structure part and rear transition metal formation, wherein contains two or three coordination elements in the part, and its general structure is:
Wherein, R
1, R
2: 2-methylbenzene, 2-isopropyl benzene, 2-ethylbenzene;
R
2, R
4: alkyl, substituted benzene, benzene;
(R=Ph, substituted benzene)
R
3：
A：N，O，P，S；
M:Fe, Co, Ni, Pd; Wherein said catalyst for copolymerization is metallocene catalyst or supported metallocene catalyst, and its general molecular formula has following structure;
C
P IMR
1R
2R
3(I) C
PI-A-R
1MR
2R
3(II)
C
P IC
P IIMR
1R
2(III) C
PI-A-C
P IIMR
1R
2(IV)
Wherein M is Ti, Zr, Hf; C
P IAnd C
P IIBe the cyclopentadiene of cyclopentadiene or replacement, indenyl, fluorenyls etc. are with the monocycle of conjugated pi electron or the ligand of polynuclear plane, choose wantonly to have substituting group; R
1, R
2, R
3, be H, alkyl, halogen, silane, alkoxyl group, amido, phosphino-s etc. contain O, Si, N, P ligand compound; A is meant bridged group, refers to-(OY
2) n-,-(SiY
2) n-,-(GeY
2) n-, wherein, Y is an alkyl, halogen, alkoxyl group, silylation, amido, phosphino-; N=1-4, A are the ring texture group; Abutment is the diatomic bridge, monatomic bridge, polyatom bridge construction;
Wherein said promoter aluminium alkyl oxygen alkane or aluminum alkyls or the borate compounds of lewis acidity is arranged.
2. according to the process of claim 1 wherein that the used carrier of described supported metallocene catalyst is inorganic carrier or organic carrier, comprise MgCl
2, zeolite, Al
2O
3, SiO
2, polyethylene, polystyrene resin or complex carrier, the carrier granule size is 0.1-0.6mm, specific surface area 50-1000m
2/ g, the aperture is 50-500A, pore volume is 0.3-500cc/g.
3. according to the process of claim 1 wherein that described alkylaluminoxane is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide.
4. according to the process of claim 1 wherein that described aluminum alkyls is AlR
3, R is C
1-C
6Alkyl.
5. according to the method for claim 4, wherein said aluminum alkyls is an aluminium trimethide, aluminium triethyl, aluminium isobutyl or its mixture.
6. according to the process of claim 1 wherein that the borate compounds of described lewis acidity is B (C
6F
5)
3, Ph
3 +B (C
6F
5)
- 4, (C
6F
5)
2BH or B (2-C
6F
5-C
6F
4)
3
7. according to the process of claim 1 wherein that the catalyst for copolymerization in the step 1) and the mol ratio of promotor are 1: 500-1: 2000.
8. according to the process of claim 1 wherein step 2) in temperature of reaction be 30-100 ℃.
9. according to the process of claim 1 wherein that promotor and catalyst for oligomerization mol ratio are 5-3000 in the step 3).
10. according to the method for claim 12, wherein promotor and catalyst for oligomerization mol ratio are 5-2000.
11. according to the process of claim 1 wherein in the step 4) that wherein the mol ratio of catalyst for oligomerization and catalyst for copolymerization is 0.25-5.
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|---|---|---|---|
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|---|---|---|---|
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ID=4590627
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| JP2014528940A (en) * | 2011-09-20 | 2014-10-30 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Nickel-containing hydrosilylation catalyst and composition containing the catalyst |
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| CN105622803A (en) * | 2014-11-17 | 2016-06-01 | 中国科学院化学研究所 | Novel purpose of random hyperbranched polyethylene |
| CN105622803B (en) * | 2014-11-17 | 2018-08-24 | 中国科学院化学研究所 | A kind of new application of random hyperbranched polyethylene |
| CN106432357A (en) * | 2015-08-10 | 2017-02-22 | 中国科学院化学研究所 | Phenyl-2,9-diimine pyridine-cycloheptane iron and cobalt complex catalyst and preparing method and application thereof |
| CN106432357B (en) * | 2015-08-10 | 2019-03-08 | 中国科学院化学研究所 | Benzene generation -2,9- bis-imine pyridine and cycloheptane iron and cobalt complex catalyst and the preparation method and application thereof |
| CN113248643A (en) * | 2021-06-22 | 2021-08-13 | 天津科技大学 | Polyolefin elastomer and preparation method thereof |
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