CN101157742A - Catalytic system for preparing cycloolefine copolymer - Google Patents
Catalytic system for preparing cycloolefine copolymer Download PDFInfo
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- CN101157742A CN101157742A CNA2007100712862A CN200710071286A CN101157742A CN 101157742 A CN101157742 A CN 101157742A CN A2007100712862 A CNA2007100712862 A CN A2007100712862A CN 200710071286 A CN200710071286 A CN 200710071286A CN 101157742 A CN101157742 A CN 101157742A
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 title description 7
- 230000003197 catalytic effect Effects 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- -1 aluminum alkyl compound Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 16
- 150000001925 cycloalkenes Chemical class 0.000 abstract description 12
- 238000003780 insertion Methods 0.000 abstract description 4
- 230000037431 insertion Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 125000005574 norbornylene group Chemical group 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 6
- 238000012644 addition polymerization Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KLAIVBQKBUCFPH-UHFFFAOYSA-L C(CC1=CC=CC=C1)C[Zr+2](C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21.[Cl-].[Cl-] Chemical class C(CC1=CC=CC=C1)C[Zr+2](C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21.[Cl-].[Cl-] KLAIVBQKBUCFPH-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ZMPASJLCJQIVEK-UHFFFAOYSA-N 1-(4-bicyclo[2.2.1]hept-2-enyl)ethanone Chemical compound C1CC2C=CC1(C(=O)C)C2 ZMPASJLCJQIVEK-UHFFFAOYSA-N 0.000 description 1
- BBJZIVDFAGBWHH-UHFFFAOYSA-N C=CC.N#CC#N Chemical compound C=CC.N#CC#N BBJZIVDFAGBWHH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- WEDOZAVIBQNLER-UHFFFAOYSA-N [Ni].[O].[N] Chemical compound [Ni].[O].[N] WEDOZAVIBQNLER-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention discloses a catalyst system used for the preparation of a cycloolefin copolymer. The catalyst system comprises a main catalyst and an auxiliary catalyst, the main catalyst is a metallocene compound which has a structural formula of (I), and the auxiliary catalyst is an aluminum alkyl compound which has a structure of (II) or a structure of (III). A cycloolefin monomer of the cycloolefin copolymer which is prepared by the catalyst system for the preparation of cycloolefin copolymer has high insertion rate, the mole fraction can achieve 90 percent, and the heat-resistance of the cycloolefin copolymer is improved.
Description
Technical field
The present invention is a kind of catalyst system that is used to prepare cyclic olefine copolymer.
Background technology
The cycloolefin co-polymer is called for short COC (Cyclic-Olefin Copolymers), is a kind of high added value thermoplastic engineering plastic that is formed by cyclic olefin polymerization.The COC resin has very high transparency, extremely low specific inductivity, good in moist, thermotolerance, chemical stability and dimensional stability, has been widely used at present and has made various optical lens, auto bulb, LCD assembly, electronics and electric component, medicine and packaging material for food etc.In addition, the COC resin also is considered to replace the best materials that PC is used to produce high-density DVD of future generation.COC is obtained by addition polymerization by catalyzer such as metallocenes usually.
Patents such as DE P4343566, DE P4422157, DE P4304307, DE P4304293, DE P4304292 all adopt bridging type metallocene catalyst to prepare COC by the addition polymerization process, and temperature of reaction 40-80 ℃, pressure is from the normal pressure to 20bar.The general formula of bridging type metallocene catalyst can be expressed as:
In the general formula, M is titanium, zirconium; R
4, R
5Be halogen etc.R in the DE P4343566 catalyst system therefor
1, R
2Be cyclopentadienyl, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).Among the DEP4422157, R
1, R
2Be cyclopentadienyl or indenyl, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).Among the DE P4304307, R
1Be cyclopentadienyl, R
2Be indenyl, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).Among the DE P4304293, R
1Be cyclopentadienyl, R
2Be fluorenyl or indenyl, R
3Be silane (as dimethylsilane).Among the DE P4304292, R
1Be cyclopentadienyl, R
2Be fluorenyl, R
1And R
2In at least one base be substituted, R
3Be alkane (as isopropylidene) or silane (as dimethylsilane).
CN1585781, CN1592765 have adopted the catalysis of rear transition metal element catalyst and have contained the addition polymerization of ester group or acetylnorbornene.
By the synthetic late transition metal catalyst of hydroxyl imide and rear transition metal compound,, carry out the copolymerization of monomeric homopolymerization such as norbornylene, propylene cyanogen, vinylbenzene, methyl methacrylate and above-mentioned monomer and ethene among the CN1563111 by addition polymerization.
CN1563113 adopts nitrogen-oxygen nickel complex catalytic system to carry out the addition polymerization of norbornylene and derivative thereof.
CN1335325 adopts neutral catalyst for polymerization of pyrroimino nickel cycloolefine catalysis norbornylene and derivative addition polymerization thereof, preparation high-molecular-weight poly cycloolefin.
Above catalyst system is when carrying out cycloolefin monomers and the monomeric copolymerization of non-ring olefin, all there is the lower problem of cycloolefin monomers insertion rate, this had both influenced the effective rate of utilization of cycloolefin monomers, had limited the further raising of cyclic olefine copolymer resistance toheat again.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst system that helps improving the preparation cyclic olefine copolymer of cycloolefin monomers effective rate of utilization.
The catalyst system that is used to prepare cyclic olefine copolymer of the present invention comprises Primary Catalysts and promotor, and Primary Catalysts is the metallocene compound with structural formula (I)
In the formula, R
6, R
7For replacing or unsubstituted aryl, C
1-C
6Alkyl, preferable methyl, ethyl, propyl group, phenyl or naphthyl, R
6, R
7Can be identical also can be inequality, preferably identical; R
8, R
9Be hydrogen, C
1-C
12Alkyl, alkoxyl group, siloxy, aryl, aralkoxy, hydroxyl, halogen, preferred hydrogen, methyl, ethyl, propyl group, R
8, R
9The position can be in arbitrary position of cyclopentadienyl, fluorenyl; Me is a kind of element of IVB family in the periodic table of elements, preferred titanium, zirconium; Q is a halogen, preferred chlorine;
Promotor is the alkylaluminium cpd with structure (II) or structure (III)
R in the formula
20-R
24Be identical or different C
1-C
18Alkyl, aryl or hydrogen;
R in the formula
25Be identical or different C
1-C
18Alkyl, aryl or hydrogen, the preferable methyl aikyiaiurnirsoxan beta.
The method that catalyst system of the present invention is used to prepare cyclic olefine copolymer is as follows:
Under the anhydrous and oxygen-free condition, in reactor, add the straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon or aromatic hydrocarbons are as solvent, with at least a structure suc as formula (IV), polycyclic olefin monomer shown in the formula V, and structure is suc as formula the non-ring olefin monomer shown in (VI), the monomeric mol ratio of cycloolefin monomers and non-ring olefin is 0.5-50, at 30-100 ℃, the 1-50 normal atmosphere, stir and add promotor and Primary Catalysts down successively, the mol ratio of promotor and Primary Catalysts is 1000-10000, carry out polyreaction
In the formula (IV), R
16-R
19Be hydrogen, C
1-C
12Alkyl, each group can be identical also can be inequality;
In the formula V, R
20-R
25Be hydrogen, C
1-C
12Alkyl, each group can be identical also can be inequality;
In the formula (VI), R
26-R
29Be hydrogen, C
1-C
12Alkyl, each group can be identical also can be inequality.
Among the present invention, the preferred norbornylene of polycyclic olefin monomer, methyl norbornylene, tetracyclododecane or their mixture.Non-ring olefin monomer optimal ethylene, propylene, m-pentadiene or their mixture.The preferred toluene of solvent, normal hexane, hexanaphthene or their mixture.
The invention has the advantages that: adopt the metallocene catalysis system that comprises Primary Catalysts and promotor of the present invention, improved the insertion rate of cycloolefin monomers and non-ring olefin monomer copolymerizable process cycloolefin monomers, the mole fraction of cycloolefin can reach 90% in the gained cyclic olefine copolymer, the cycloolefin monomers effective rate of utilization is increased, and the cyclic olefine copolymer thermotolerance improves.
Embodiment
Further specify the present invention below by example, but the present invention is not limited thereto.
Following examples, the second-order transition temperature of polymkeric substance is measured with differential scanning calorimeter, 10 ℃/minute of temperature rise rates, 10 ℃/minute of rate of temperature fall, adopt the secondary temperature elevation curve by sweep limit 30-220 ℃.
Embodiment 1
The refining norbornylene of 3.6 grams is dissolved in 50 milliliters of refined toluene wiring solution-forming I.Solution I is joined in advance in 100 milliliters of Schlenk tubular reactors crossing with nitrogen wash, and repeatedly punching press ethene (1 normal atmosphere) makes solution saturated by ethene.Add the toluene solution that 2 ml concns are the methylaluminoxane of 1.72 mol, 1.3 milligrams of different hydrocinnamyl-(fluorenyl)-(cyclopentadienyl) zirconium dichlorides then successively.Polymerization is 1 hour under 50 ℃, 250 rev/mins agitation condition; Polymerization process is metered into ethene by replenishing, and control pressure is 1 normal atmosphere.After reaction finished, reaction solution was poured the ethanol sedimentation after-filtration into, filter cake with washing with alcohol after, drying, catalyst activity 1.2 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 2
Method by embodiment 1 prepares polymkeric substance, and refining norbornylene add-on is reduced to 0.7 gram, catalyst activity 1.5 * 10 by 3.6 grams
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 3
Method by embodiment 1 prepares polymkeric substance, and refining norbornylene add-on is restrained catalyst activity 1.0 * 10 by 3.6 gram liters to 5.4
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 4
The refining methyl norbornylene of 12 grams is dissolved in 50 milliliters of refined toluene wiring solution-forming II.Solution II is joined in advance in 100 milliliters of Schlenk tubular reactors crossing with nitrogen wash, and repeatedly punching press ethene (1 normal atmosphere) makes solution saturated by ethene.Add the toluene solution that 12.7 ml concns are the methylaluminoxane of 1.72 mol, 1.3 milligrams of different hydrocinnamyl-(fluorenyl)-(cyclopentadienyl) zirconium dichlorides then successively.Polymerization is 1 hour under 30 ℃, 250 rev/mins agitation condition; Polymerization process is metered into ethene by replenishing, and control pressure is 1 normal atmosphere.After reaction finished, reaction solution was poured the ethanol sedimentation after-filtration into, filter cake with washing with alcohol after, drying, catalyst activity 0.5 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Embodiment 5
Method by embodiment 4 prepares polymkeric substance, and refining methyl norbornylene add-on is reduced to 0.3 gram by 12 grams, 80 ℃ of following polymerization half an hour, catalyst activity 2.0 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Comparative example 1
The refining norbornylene of 3.6 grams is dissolved in 50 milliliters of refined toluene wiring solution-forming I.Solution I is joined in advance in 100 milliliters of Schlenk tubular reactors crossing with nitrogen wash, and repeatedly punching press ethene (1 normal atmosphere) makes solution saturated by ethene.Add the toluene solution that 2 ml concns are the methylaluminoxane of 1.72 mol, 0.8 milligram of rac-vinyl-(two indenyls)-zirconium dichloride then successively.Polymerization is 1 hour under 50 ℃, 750 rev/mins agitation condition; Polymerization process is metered into ethene by replenishing, and control pressure is 1 normal atmosphere.After reaction finished, reaction solution was poured the ethanol sedimentation after-filtration into, filter cake with washing with alcohol after, drying, catalyst activity 2.55 * 10
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Comparative example 2
Method by comparative example 1 prepares polymkeric substance, and refining norbornylene add-on is reduced to 0.7 gram, catalyst activity 2.86 * 10 by 3.6 grams
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Comparative example 3
Method by comparative example 1 prepares polymkeric substance, and refining norbornylene add-on is restrained catalyst activity 2.11 * 10 by 3.6 gram liters to 5.4
6Gram/(mole zirconium hour).The polymkeric substance rerum natura sees Table 1.
Table 1 polymkeric substance rerum natura
Sequence number | Cycloolefin content/mol% | Tg/℃ |
Embodiment 1 | 56.4 | 149 |
Embodiment 2 | 37.2 | 84 |
Embodiment 3 | 60.1 | 16l |
Embodiment 4 | 90.0 | 200 |
Embodiment 5 | 10.0 | 20 |
Comparative example 1 | 49.3 | 125 |
Comparative example 2 | 29.6 | 59 |
Comparative example 3 | 53.5 | 139 |
By table as seen, the cycloolefin monomers insertion rate height of the prepared cyclic olefine copolymer of the present invention, its mole fraction can reach 90%, and the cyclic olefine copolymer thermotolerance improves.
Claims (1)
1. be used to prepare the catalyst system of cyclic olefine copolymer, it is characterized in that comprising Primary Catalysts and promotor, Primary Catalysts is the metallocene compound with structural formula (I)
In the formula, R
6, R
7For replacing or unsubstituted aryl, C
1-C
6Alkyl, R
6, R
7Can be identical also can be inequality; R
8, R
9Be hydrogen, C
1-C
12Alkyl, alkoxyl group, siloxy, aryl, aralkoxy, hydroxyl, halogen, R
8, R
9The position can be in arbitrary position of cyclopentadienyl, fluorenyl; Me is a kind of element of IVB family in the periodic table of elements; Q is a halogen;
Promotor is the alkylaluminium cpd with structure (II) or structure (III)
R in the formula
20-R
24Be identical or different C
1-C
18Alkyl, aryl or hydrogen;
R in the formula
25Be identical or different C
1-C
18Alkyl, aryl or hydrogen.
Priority Applications (1)
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CNA2007100712862A CN101157742A (en) | 2007-09-11 | 2007-09-11 | Catalytic system for preparing cycloolefine copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2007100712862A CN101157742A (en) | 2007-09-11 | 2007-09-11 | Catalytic system for preparing cycloolefine copolymer |
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Publication Number | Publication Date |
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CN101157742A true CN101157742A (en) | 2008-04-09 |
Family
ID=39305989
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105669902A (en) * | 2014-12-03 | 2016-06-15 | 魏东初 | Novel cycloolefin copolymer catalyst and synthetic method thereof |
WO2021083309A1 (en) * | 2019-10-30 | 2021-05-06 | 中国石油化工股份有限公司 | Metallocene compound, and preparation method therefor and application thereof |
CN115677879A (en) * | 2021-07-31 | 2023-02-03 | 华为技术有限公司 | Catalyst for preparing cycloolefin copolymer, preparation method of cycloolefin copolymer, cycloolefin copolymer and application of cycloolefin copolymer |
-
2007
- 2007-09-11 CN CNA2007100712862A patent/CN101157742A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105669902A (en) * | 2014-12-03 | 2016-06-15 | 魏东初 | Novel cycloolefin copolymer catalyst and synthetic method thereof |
WO2021083309A1 (en) * | 2019-10-30 | 2021-05-06 | 中国石油化工股份有限公司 | Metallocene compound, and preparation method therefor and application thereof |
CN115677879A (en) * | 2021-07-31 | 2023-02-03 | 华为技术有限公司 | Catalyst for preparing cycloolefin copolymer, preparation method of cycloolefin copolymer, cycloolefin copolymer and application of cycloolefin copolymer |
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