CN116262796A - Hyperbranched cycloolefin copolymer and preparation method thereof - Google Patents
Hyperbranched cycloolefin copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN116262796A CN116262796A CN202310247299.XA CN202310247299A CN116262796A CN 116262796 A CN116262796 A CN 116262796A CN 202310247299 A CN202310247299 A CN 202310247299A CN 116262796 A CN116262796 A CN 116262796A
- Authority
- CN
- China
- Prior art keywords
- hyperbranched
- cycloolefin copolymer
- methyl
- norbornene
- titanium metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical group CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims abstract description 50
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005977 Ethylene Substances 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 30
- 229910052719 titanium Inorganic materials 0.000 claims description 27
- 238000007334 copolymerization reaction Methods 0.000 claims description 20
- -1 titanium metal complex Chemical class 0.000 claims description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000002466 imines Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 6
- DGBISJKLNVVJGD-UHFFFAOYSA-N 2-phenylsulfanylaniline Chemical group NC1=CC=CC=C1SC1=CC=CC=C1 DGBISJKLNVVJGD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims 4
- 150000001925 cycloalkenes Chemical class 0.000 abstract description 8
- 238000012660 binary copolymerization Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a hyperbranched cycloolefin copolymer and a preparation method thereof, wherein the hyperbranched cycloolefin copolymer has a structural formula shown in a formula (I):
wherein x, y, z, n is the degree of polymerization, and the mole percentage of the norbornene chain segment is y (x+y+z)>30 percent, the mol percent of the 4-methyl-1-pentene chain segment is less than or equal to 5 percent and less than or equal to 20 percent; the weight average molecular weight of the hyperbranched cycloolefin copolymer is more than 10000 g/mol; hyperbranched cycloolefin copolymersThe hyperbranched cycloolefin copolymer provided by the invention has better mechanical property and processability compared with the COC obtained by binary copolymerization of ethylene and norbornene.
Description
Technical Field
The invention belongs to the technical field of olefin catalysis, and particularly relates to a hyperbranched cycloolefin copolymer and a preparation method thereof.
Background
Homopolymers of cycloolefins are generally obtained by addition polymerization of cycloolefin monomers. Typical cycloolefin monomers such as norbornene, which have a specific rigid bicyclo structure, polynorbornenes obtained by vinyl addition polymerization have excellent chemical stability, UV light resistance, low dielectric constant, transparency, low birefringence, and the like. Although norbornene homopolymers have very good properties, they are disadvantageous for processing due to excessively high glass transition temperatures and excessively brittle products, limiting their popularization and use.
The cycloolefin copolymer (COC) prepared by the copolymerization of norbornene and olefin (usually ethylene) has the advantages that the introduction of flexible ethylene remarkably improves the characteristics of excessively high glass transition temperature and excessively brittle products of the COC copolymer on the basis of keeping the excellent performance of cycloolefin homopolymer, so that the COC copolymer has become an important engineering plastic and has important application in the fields of optical devices, medical materials and the like. Currently, commercial COCs, trade names APEL and Topas, which are products of binary copolymerization of ethylene with cycloolefin monomers, have been proposed by the three well chemical company of japan and the treasury company of japan, respectively.
The research results of the prior art show that the higher the content of the cyclic olefin monomer in COC, the more excellent the heat resistance and the optical performance of the cyclic olefin monomer are, and the cyclic olefin monomer has important application in the optical field. However, the mechanical properties of the product are too brittle, and the toughness is insufficient, so that the subsequent processing and the application of the product are not facilitated. Therefore, development of COC with high cycloolefin content while simultaneously achieving toughness and processability is an urgent problem to be solved. To improve the processability of COC, there have been related efforts to improve the processability by preparing a bimodal/broad distribution COC product, but the content of olefins in the COC has not been increased. In addition, there are related operations of copolymerizing alpha-olefins instead of ethylene monomers and cycloolefins to prepare COC containing branched chains, and improving toughness and processability of COC copolymers by using branched chains, however, the alpha-olefin has a large steric hindrance of the monomers compared with ethylene, and the copolymerization activity of the catalyst is significantly reduced.
Thus, despite the important practical application value of preparing COC copolymers with excellent optical properties and excellent mechanical and processing properties, great challenges are faced at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hyperbranched cycloolefin copolymer, which has high content of norbornene and excellent optical performance and mechanical performance.
The invention aims to provide a hyperbranched cycloolefin copolymer, which is obtained by copolymerizing norbornene, ethylene and 4-methyl-1-pentene, wherein the hyperbranched cycloolefin copolymer has a structure shown in a formula (I):
wherein x, y, z, n is polymerization degree, the mol percent of the norbornene chain segment is y (x+y+z) >30%, and the mol percent of the 4-methyl-1-pentene chain segment is less than or equal to 5% and less than or equal to 20%; the weight average molecular weight of the hyperbranched cycloolefin copolymer is more than 10000 g/mol.
The invention provides a hyperbranched cycloolefin copolymer, the mol percent of norbornene is higher than 30%, and the mol percent of 4-methyl-1-pentene is not higher than 20%. As the hyperbranched chain can enhance the rheological property and the processing property of the polymer, the mechanical property of the polymer can be improved, and compared with the COC obtained by binary copolymerization of ethylene and norbornene, the hyperbranched cycloolefin copolymer provided by the invention has better mechanical property and processing property.
Preferably, the hyperbranched cycloolefin copolymer has a weight average molecular weight of 10000 to 500000g/mol.
More preferably, the hyperbranched cycloolefin copolymer has a weight average molecular weight of 100000 ～ 300000g/mol.
Preferably, the hyperbranched cycloolefin copolymer has a norbornene segment content of 30 to 70 mol%.
More preferably, the hyperbranched cycloolefin copolymer has a norbornene segment content of 40 to 60 mol%.
Preferably, the molar percentage of the 4-methyl-1-pentene segments of the hyperbranched cycloolefin copolymer is from 5 to 20%.
More preferably, the molar percentage of the 4-methyl-1-pentene segment of the hyperbranched cycloolefin copolymer is 8 to 15%.
The invention also aims to provide a preparation method of the hyperbranched cycloolefin copolymer, which comprises the following steps:
the norbornene monomer, the ethylene monomer and the 4-methyl-1-pentene monomer are subjected to copolymerization reaction under the action of a titanium metal catalyst, so that the hyperbranched cycloolefin copolymer is obtained;
the titanium metal catalyst consists of a titanium metal complex and a cocatalyst.
Preferably, the titanium metal complex has a structure as shown in formula (II):
wherein R is hydrogen, methyl or isopropyl; preferably, R is methyl.
The research of the invention shows that the non-metallocene titanium complex with [ N, N, S ] tridentate coordination can catalyze the ternary polymerization of norbornene, ethylene and 4-methyl-1-pentene to prepare the hyperbranched cycloolefin copolymer. On the one hand, compared with a double-ligand bidentate titanium metal complex and a metallocene catalyst, the tridentate [ N, N, S ] titanium metal complex has more open space, is favorable for the coordination insertion of norbornene and 4-methyl-1-pentene monomers with large steric hindrance, and can prepare the hyperbranched cycloolefin copolymer with high norbornene content with high activity; on the other hand, the electron donating effect of the sulfur (S) coordination atom of the side arm further enhances the thermal stability and catalytic activity of the titanium catalyst, so that the hyperbranched cycloolefin copolymer can be prepared with high activity.
Preferably, the cocatalyst is selected from at least one of Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), and pumped-Dry Methylaluminoxane (DMAO).
More preferably, the cocatalyst is MAO.
Preferably, the molar ratio of the cocatalyst to the titanium metal complex is 50-500:1.
More preferably, the molar ratio of the promoter to the titanium metal complex is from 200 to 400:1.
Preferably, the temperature of the copolymerization reaction is 20 to 120 ℃.
More preferably, the temperature of the copolymerization reaction is 50 to 100 ℃.
Preferably, the pressure of the ethylene is 1 to 20atm.
More preferably, the pressure of the ethylene is 5 to 15atm.
Preferably, the molar ratio of norbornene monomer to 4-methyl-1-pentene monomer is 1 to 9:1.
More preferably, the molar ratio of norbornene monomer to 4-methyl-1-pentene monomer is from 2 to 5:1.
The invention also provides a preparation method of the titanium metal complex, which comprises the following steps:
s1: 2-fluorobenzaldehyde
And aniline->
Condensation reaction is carried out to obtain imine compound +.>
S2: imine compound and o-phenylmercaptoaniline
Substitution reaction is carried out to obtain ligand->
S3: under the action of n-butyllithium, the ligand and TiCl 4 Reacting to obtain the titanium metal complex;
wherein R is hydrogen, methyl or isopropyl.
Preferably, in S1, the molar ratio of the 2-fluorobenzaldehyde to the aniline is 1:1.05-1.15.
Preferably, in S2, the molar ratio of the imine compound to o-phenylmercaptoaniline is 1:1.
Preferably, in S3, the ligand is combined with TiCl 4 The molar ratio of (2) is 1:1.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention introduces 4-methyl-1-pentene copolymer chain segments into hyperbranched cycloolefin copolymer, so that the copolymer contains a hyperbranched structure; compared with the linear side chain structure, the hyperbranched structure can significantly improve the toughness and the processing rheological property of the copolymer.
(2) The hyperbranched structure of the hyperbranched cycloolefin copolymer provided by the invention endows the COC material with better toughness, so that the COC copolymer with higher rigidity norbornene monomer content can be prepared, and the COC material has better optical performance.
(3) Compared with linear alpha-olefin, the hyperbranched cycloolefin copolymer provided by the invention can lead the COC material to reach the same performance as the COC material with linear alpha-olefin introduced into the molecular chain by only introducing a small amount of 4-methyl-1-pentene chain segments into the molecular chain of the copolymer, and the catalytic activity of the catalyst in the preparation of the COC is higher, thus having better production benefit.
Drawings
FIG. 1 is a synthetic route diagram of a titanium complex.
FIG. 2 is a single crystal structure diagram of ligand L2.
FIG. 3 is a DSC curve of the hyperbranched cycloolefin copolymer prepared in example 11.
FIG. 4 is a graph showing the transmittance of visible light of the hyperbranched cycloolefin copolymer prepared in example 11.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The aniline, ligand and titanium metal complex of each example has a structure represented by formula (iii):
in the following examples and comparative examples, the cyclic olefin content in the polymer was measured by nuclear magnetic resonance, the polymer was dissolved by deuterated o-dichlorobenzene, and the measurement temperature was 120℃by using hexamethyldisiloxane as an internal standard. The molecular weight and molecular weight distribution of the polymer (trichlorobenzene as solvent and mobile phase, concentration 1.5g/L, flow rate 1 mL/min) were determined by high temperature gel permeation chromatograph (HT-GPC), the melting point of the polymer was determined by differential scanning calorimeter, and the mechanical properties of the polymer were characterized on a universal tensile machine, as standard GB/T1040-1992.
Example 1
The present example provides a method for producing an imine compound A1: 2-fluorobenzaldehyde (9.4 g,75.8 mmol) and aniline (8.0 g,85.9 mmol) were reacted in 40mL of n-hexane under stirring for 4 hours, and anhydrous MgSO was added 4 Dewatering and filtering to obtain a bright yellow solution, carrying out reduced pressure distillation on the obtained bright yellow solution, and collecting a fraction at 120 ℃ under 0.5cm Hg to obtain 11.5g of bright yellow viscous liquid with the yield of 76%. 1 H NMR(300MHz,CDCl 3 ):δ(ppm)8.838(s,1H,CH＝NAr),8.262(dt,1H,ph),7.543-7.123(m,8H,ph), 13 C NMR(75MHz,CDCl 3 ):δ(ppm)164.299(d,C-F),153.221(CH＝N),151.716,132.793,128.994,127.741,126.126,124.323,120.834,115.830,Anal.Calcd for C 13 H 10 FN:C,78.37；H,5.06；N,7.03.Found:C,78.16；H,5.15；N,7.03。
Example 2
The present example provides a method for producing an imine compound A2: 2-fluorobenzaldehyde (9.4 g,75.8 mmol) and 2, 6-dimethylaniline (10.0 g,82.5 mmol) were reacted in 40mL of n-hexane under stirring for 4 hours, and anhydrous MgSO was added 4 Dewatering and filtering to obtain a bright yellow solution, carrying out reduced pressure distillation on the obtained bright yellow solution, and collecting a fraction at 170 ℃ under 0.5cm Hg to obtain 13.4g of bright yellow viscous liquid with the yield of 78%. 1 H NMR(300MHz,CDCl 3 ):δ(ppm)8.582(s,1H,CH＝NAr),8.289(dt,1H,ph),7.522(q,1H,ph),7.303(t,1H,ph),7.238-7.061(m,3H,ph),7.004(t,1H,ph),2.121(s,6H,CH 3 ). 13 C NMR(75MHz,CDCl 3 ):δ(ppm)164.283(d,C-F),156.124(CH＝N),151.006,132.916,127.943,127.460,126.874,124.332,123.764,115.949,18.350.Anal.Calcd for C 15 H 14 FN:C,79.27；H,6.21；N,6.16.Found:C,79.37；H,6.22；N,6.13。
Example 3
The present example provides a method for producing an imine compound A3: 2-fluorobenzaldehyde (11.7 g,94.4 mmol) and 2, 6-diisopropylaniline (17.6 g,99.4 mmol) were reacted in 40mL of n-hexane under stirring for 4h, and anhydrous MgSO was added 4 Removing water; the resulting bright yellow solution was filtered and frozen at-10℃to give 17.7g of bright yellow crystals in 66% yield. 1 H NMR(300MHz,CDCl 3 ):δ(ppm)8.531(s,1H,CH＝NAr),8.243(dt,1H,ph),7.518(q,1H,ph),7.298(t,1H,ph),7.238-7.085(m,4H,ph),2.988(sp,2H,CH of i Pr),1.226(d,12H,CH 3 ). 13 C NMR(75MHz,CDCl 3 ):δ(ppm)164.334(d,C-F),155.534(CH＝N),149.151,137.426,132.904,127.619,124.469,124.220,123.713,122.953,116.022,28.031,23.562.Anal.Calcd for C 19 H 22 FN:C,80.53；H,7.82；N,4.94.Found:C,80.54；H,7.67；N,4.73。
Example 4
The present embodiment provides a method for preparing ligand L1: 2-phenylthioaniline (7.71 g,38.3 mmol) was dissolved in THF (50 mL) under the protection of nitrogen, the solution was placed in a freezer at-78℃and after the temperature was equilibrated, a 2.86M n-hexane solution of n-butyllithium (13.4 mL,38.3 mmol) was slowly added dropwise with a syringe, the reaction system was slowly warmed to room temperature under uniform stirring, stirring was continued overnight to give a tan suspension, a solution of imine compound A1 (7.63 g,38.3 mmol) in THF (20 mL) was added to the suspension, and the reaction was continued at room temperature for 24 hours, the system color became dark red. Terminating the reaction with distilled water (20 mL), adding 20mL of n-hexane, extracting with separating funnel, washing the organic phase with distilled water three times, removing inorganic salt, and removing the organic phase with anhydrous MgSO 4 Removing water, filtering, placing the solution on a rotary evaporator to spin-dry the solvent to obtain brown oily matter, cooling or adding a small amount of ethanol to obtain yellow powder precipitate, and recrystallizing with ethanol to obtain yellow massive crystals with 6.36g and 44% yield. 1 H NMR(300MHz,CDCl 3 ):δ(ppm)11.395(s,1H,N-H)；8.519(s,1H,CH＝N)；7.598(d,1H,Ar-H)；7.283-6.851(m,16H,Ar-H)；6.807(t,1H,Ar-H). 13 C NMR(75MHz,CDCl 3 ):δ(ppm)161.511,153.199,150.560,144.996,142.034,134.565,132.321,131.407,130.857,129.300,128.832,126.400,126.133,125.670,123.198,121.196,120.967,119.720,117.808,113.433.Anal.Calcd for C 25 H 20 N 2 S:C,78.91；H,5.30；N,7.36,Found:C,78.82；H,5.63；N,7.46。
Example 5
The present embodiment provides a method for preparing ligand L2: 2-phenylthioaniline (4.20 g,20.9 mmol) was dissolved in THF (50 mL) under the protection of nitrogen, the solution was placed in a freezer at-78deg.C, after equilibration at temperature, a 2.86M n-hexane solution of n-butyllithium (7.3 mL,20.9 mmol) was slowly added dropwise with a syringe, the reaction system was slowly warmed to room temperature with uniform stirring, stirring was continued overnight to give a tan suspension, and imidization was added to the suspensionA solution of Compound A2 (4.75 g,20.9 mmol) in THF (20 mL) was reacted at room temperature for 24h, and the system color became dark red. Terminating the reaction with distilled water (20 mL), adding 20mL of n-hexane, extracting with separating funnel, washing the organic phase with distilled water three times, removing inorganic salt, and removing the organic phase with anhydrous MgSO 4 Removing water, filtering, placing the solution on a rotary evaporator to spin-dry the solvent to obtain brown oily matter, cooling or adding a small amount of ethanol to obtain yellow powder precipitate, and recrystallizing with ethanol to obtain yellow massive crystals 4.86g with 57% yield. 1 H NMR(300MHz,CDCl 3 ):δ(ppm)11.165(s,1H,N-H)；8.249(s,1H,CH＝N)；7.683,(d,1H,Ar-H)；7.252-7.443(m,5H,Ar-H)；6.964-7.103(m,9H,Ar-H)；6.863(t,1H,Ar-H)；2.118(s,6H,CH 3 ). 13 C NMR(75MHz,CDCl 3 ):δ(ppm)164.856,150.395,145.286,142.039,135.519,134.962,134.432,131.494,128.669,127.752,127.568,126.309,125.874,123.578,123.345,121.618,119.277,117.676,113.593,18.607.Anal.Calcd for C 27 H 24 N 2 S:C,79.37；H,5.92；N,6.86.Found:C,79.21；H,6.15；N,6.64。
Example 6
The present embodiment provides a method for preparing ligand L3: 2-phenylthioaniline (5.33 g,26.5 mmol) was dissolved in THF (50 mL) under the protection of nitrogen, the solution was placed in a freezer at-78℃and after the temperature was equilibrated, a 2.86M n-hexane solution of n-butyllithium (9.3 mL,26.6 mmol) was slowly added dropwise with a syringe, the reaction system was slowly warmed to room temperature under uniform stirring, stirring was continued overnight to give a tan suspension, a THF (20 mL) solution of imine compound A3 (7.51 g,26.5 mmol) was added to the suspension, and the reaction was continued at room temperature for 24 hours, the system color became dark red. Terminating the reaction with distilled water (20 mL), adding 20mL of n-hexane, extracting with separating funnel, washing the organic phase with distilled water three times, removing inorganic salt, and removing the organic phase with anhydrous MgSO 4 Removing water, filtering, spin-drying the solution on rotary evaporator to obtain brown oily substance, cooling or adding small amount of ethanol to obtain yellow powderThe starch was recrystallized from ethanol to give 6.33g of yellow bulk crystals in 51% yield. 1 H NMR(300MHz,CDCl 3 ):δ(ppm)11.063(s,1H,N-H)；8.245(s,1H,CH＝N)；7.576(d,1H,Ar-H)；7.350(d,1H,Ar-H)；7.296-7.046(m,12H,Ar-H)；6.981(t,1H,Ar-H)；6.823(t,1H,Ar-H)；3.054(sp,2H,CH of i Pr)；1.131(d,12H,CH 3 ). 13 CNMR(75MHz,CDCl 3 ):δ(ppm)164.835,148.570,145.762,141.019,138.069,134.977,134.512,133.372,131.622,130.447,128.840,128.643,127.982,126.608,124.226,123.805,122.830,122.427,118.971,117.563,113.438,27.995,23.737.Anal.Calcd for C 31 H 32 N 2 S:C,80.13；H,6.94；N,6.03.Found:C,80.30；H,7.18；N,6.00。
Example 7
The present embodiment provides a preparation method of a complex Ti 1: ligand L1 (0.65 g,2.2 mmol) was weighed under nitrogen atmosphere and dissolved in 30mL dry toluene, reacted with 2.86M n-BuLi (0.8 mL,2.2 mmol) at-78deg.C, slowly warmed to room temperature, stirred for 2h, then cooled to-78deg.C again, then TiCl was slowly added dropwise with a syringe 4 (2.2 mmol) toluene solution (10 mL), naturally warmed to room temperature and stirred for 24h, and filtered through a filter ball under nitrogen atmosphere to remove inorganic salts. The solid insoluble matter was washed 3 times with 10mL of dry toluene, the filtrate was evacuated to a volume of about 2mL left, 50mL of dry n-hexane was added to precipitate to obtain a reddish brown solid, the solid was washed 3 times with 10mL of dry n-hexane, and evacuated under vacuum to obtain 0.67g of a brown solid in 57% yield. ESI-MS (M/z): 497,498,499,500 (isope, [ M-Cl)] + ).Anal.Calcd for C 25 H 19 Cl 3 N 2 STi:C,56.26；H,3.59；N,5.25.Found:C,57.36；H,3.78；N,5.60。
Example 8
The present embodiment provides a preparation method of a complex Ti 2: ligand L2 (0.82 g,2.0 mmol) was weighed into 30mL of dry toluene under nitrogen atmosphere, reacted with 2.86M n-BuLi (0.7 mL,2.0 mmol) at-78deg.C, slowly warmed to room temperature, stirred for 2h, cooled to-78deg.C again, and then TiCl was slowly added dropwise with a syringe 4 (2.0 mmol) toluene solution (10 mL), naturally warmed to room temperature and stirred for 24h, and filtered through a filter ball under nitrogen atmosphere to remove inorganic salts. The solid insoluble matter was washed 3 times with 10mL of dry toluene, the filtrate was evacuated to a volume of about 2mL left, 50mL of dry n-hexane was added to precipitate to obtain a reddish brown solid, the solid was washed 3 times with 10mL of dry n-hexane, and evacuated under vacuum to obtain 0.58g of a brown solid in 52% yield. ESI-MS (M/z): 525,526,527,528,529, (isope, [ M-Cl)] + ).Anal.Calcd for C 27 H 23 Cl 3 N 2 STi:C,57.73；H,4.13；N,4.99.Found:C,58.95；H,4.81；N,4.62。
Example 9
The present embodiment provides a preparation method of a complex Ti 3: ligand L3 (0.92 g,2.0 mmol) was weighed into 30mL of dry toluene under nitrogen atmosphere, reacted with 2.86M n-BuLi (0.7 mL,2.0 mmol) at-78deg.C, slowly warmed to room temperature, stirred for 2h, cooled to-78deg.C again, and then TiCl was slowly added dropwise with a syringe 4 (2.0 mmol) toluene solution (10 mL), naturally warmed to room temperature and stirred for 24h, and filtered through a filter ball under nitrogen atmosphere to remove inorganic salts. The solid insoluble matter was washed 3 times with 10mL of dry toluene, the filtrate was evacuated to a volume of about 2mL left, 50mL of dry n-hexane was added to precipitate to obtain a reddish brown solid, the solid was washed 3 times with 10mL of dry n-hexane, and evacuated under vacuum to obtain 0.73g of brown powder in 59% yield. ESI-MS (M/z): 581,582,583,584, (isope, [ M-Cl)] + ).Anal.Calcd for C 31 H 31 Cl 3 N 2 STi:C,60.26；H,5.06；N,4.53.Found:C,61.13；H,5.43；N,4.60。
Examples 10-22 provide hyperbranched cycloolefin copolymers obtained by copolymerization of norbornene, ethylene and 4-methyl-1-pentene catalyzed by a titanium catalyst, the specific reaction steps being as follows:
the copolymerization reaction is carried out in a 100mL stainless steel pressure kettle with a stirring device, the pressure kettle is baked in vacuum for more than 2 hours at 110 ℃ to be completely dried before the polymerization reaction, after the pressure kettle is cooled to the polymerization temperature, toluene solution of a cocatalyst, toluene solution of Norbornene (NB) and 4-methyl-1-pentene (4 MP) monomers are sequentially injected into the pressure kettle from a feed valve by a syringe, the whole polymerization system volume is kept at 75mL, ethylene (E) gas is introduced to normal pressure, after the reaction system is fully stirred for 10 minutes at the set polymerization temperature, toluene solution of a titanium metal complex is added into the pressure kettle from the feed valve, the pressure of ethylene is increased to be the pressure set by polymerization, the pressure of ethylene is kept unchanged in the whole polymerization process, the ethylene is stopped from being introduced after the polymerization reaction reaches the set time, the pressure is slowly released, the pressure kettle is opened, ethanol is added into the reactor to stop the reaction, the product is soaked in hydrochloric acid/ethanol, filtered, and the polymer is placed into a vacuum drying box at 60 ℃ to be dried to constant weight after the polymer is washed for a plurality of times by absolute ethanol.
Examples 10-14 provide the copolymerization results of norbornene, ethylene and 4-methyl-1-pentene catalyzed by a different titanium catalyst. Specific reaction conditions and polymerization results are shown in Table 1, microstructure characterization is shown in Table 4, and performance test of a part of samples is shown in Table 5.
Table 1 results of copolymerization of norbornene, ethylene and 4-methyl-1-pentene catalyzed by different titanium catalysts.
Polymerization conditions: catalyst 2 μmol, al/ti=300, polymerization time 30 minutes.
As is clear from Table 1, under the same polymerization conditions, the polymerization activity of the complex Ti2 was the highest and reached 7.82X 10 6 g/(molTi h), while with different cocatalysts, MAO has the best cocatalyst effect and the highest polymerization activity.
Examples 15-22 provide the copolymerization results of a titanium complex Ti2 catalyzing norbornene, ethylene and 4-methyl-1-pentene at different Al/Ti, different temperatures, different ethylene pressures and different monomer feed ratios. Specific reaction conditions and polymerization results are shown in Table 2, microstructure characterization is shown in Table 4, and partial sample performance tests are shown in Table 5.
Table 2 titanium complex Ti2 catalyzes the copolymerization of norbornene, ethylene and 4-methyl-1-pentene.
Polymerization conditions: 2. Mu. Mol of complex, cocatalyst MAO, and polymerization time of 30 minutes.
From examples 11 and 2 of table 1, it is clear that the polymerization activity was optimal when Al/ti=300 using MAO as the cocatalyst for the complex Ti 2. The polymerization activity is highest at 80 ℃ between 20 ℃ and 120 ℃. In the range of 1 to 20atm of ethylene pressure, as the ethylene pressure increases, the polymerization activity increases, with the activity being highest at 20 atm; however, table 4 shows that the ethylene content is increased and the NB content is low. In connection with the performance test of Table 5, the refractive index was reduced to 1.50 and the light transmittance was reduced to 85%, indicating that the optical properties thereof were deteriorated, and thus the ethylene pressure was optimized to 10atm. In the range of 1 to 9:1 feed mole ratio of the two monomers norbornene to 4-methyl-1-pentene, as the amount of norbornene added increases, the copolymerization activity increases, table 4 shows that the COC norbornene content also increases, but in combination with the performance test of Table 5, the processing temperature increases to 240℃and the elongation at break decreases to 23.4%, indicating a deterioration in toughness, and thus an optimized feed mole ratio of norbornene to 4-methyl-1-pentene of 4:1.
Comparative examples 1 to 3 are the results of copolymerization of ethylene and norbornene, copolymerization of 1-hexene and norbornene, and ternary polymerization of ethylene, norbornene and 1-hexene, respectively. Specific reaction conditions and polymerization results are shown in Table 3, microstructure characterization is shown in Table 4, and performance test of a part of the samples is shown in Table 5.
Comparative example 1
An ethylene and norbornene copolymer is provided that differs from example 11 in that: the comonomers were ethylene and norbornene, and the amount of norbornene was 0.5mol.
Comparative example 2
There is provided a copolymer of 1-hexene and norbornene, which is different from example 11 in that: the comonomers were 1-hexene and norbornene, and the amount of 1-hexene was 0.1mol.
Comparative example 3
An ethylene, norbornene and 1-hexene terpolymer is provided that differs from example 11 in that: the 4-methyl-1-pentene monomer was replaced with branched alpha-olefin 1-hexene of the same carbon number.
Table 3 copolymerization results of comparative examples 1 to 3.
Polymerization conditions: 2. Mu. Mol of complex, al/Ti=300, polymerization time 30 minutes.
As is clear from Table 3, in comparative example 1, the activity of copolymerization was reduced without adding the third comonomer of 4-methyl-1-pentene under the same polymerization conditions as that of the complex Ti 2. In comparative example 2, however, the copolymerization activity was greatly reduced because the steric hindrance of 1-hexene and norbornene monomers was large without adding ethylene monomer. In contrast, comparative example 3, in which 1-hexene monomer was used instead of 4-methyl-1-pentene monomer, showed substantially no difference in copolymerization activity.
Table 4 microstructure analysis data of COC copolymers.
Table 5COC copolymer performance data.
As can be seen from Table 5, the hyperbranched cycloolefin copolymer material prepared in example 11 has a better elongation at break, a lower processing temperature and refractive index and light transmittance due to the hyperbranched structure as compared with comparative examples 1 to 3.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present invention after reading the present specification, and these modifications and variations do not depart from the scope of the invention as claimed in the pending claims.
Claims (10)
1. The hyperbranched cycloolefin copolymer is characterized by having a structural formula shown in a formula (I):
wherein x, y, z, n is polymerization degree, the mol percent of the norbornene chain segment is y (x+y+z) >30%, and the mol percent of the 4-methyl-1-pentene chain segment is less than or equal to 5% and less than or equal to 20%; the weight average molecular weight of the hyperbranched cycloolefin copolymer is more than 10000 g/mol.
2. The hyperbranched cycloolefin copolymer according to claim 1, characterized in that the molar percentage of norbornene segments of the hyperbranched cycloolefin copolymer is from 30 to 70%; the molar percentage content of the 4-methyl-1-pentene chain segment of the hyperbranched cycloolefin copolymer is 5-20%.
3. The hyperbranched cycloolefin copolymer according to claim 1, characterized in that the hyperbranched cycloolefin copolymer has a weight average molecular weight ranging from 10000 to 500000g/mol.
4. A process for the preparation of hyperbranched cyclic olefin copolymers according to any one of claims 1 to 3, characterised in that it comprises the following steps:
the norbornene monomer, the ethylene monomer and the 4-methyl-1-pentene monomer are subjected to copolymerization reaction under the action of a titanium metal catalyst, so that the hyperbranched cycloolefin copolymer is obtained;
the titanium metal catalyst consists of a titanium metal complex and a cocatalyst.
5. The method for preparing hyperbranched cyclic olefin copolymer according to claim 4, wherein the titanium metal complex has a structure as shown in formula (II):
wherein R is hydrogen, methyl or isopropyl.
6. The method for preparing hyperbranched cyclic olefin copolymer according to claim 4, wherein the cocatalyst is at least one selected from Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), and pumped methylaluminoxane (DMAO).
7. The method for preparing hyperbranched cycloolefin copolymer according to claim 4, characterized in that the molar ratio of the cocatalyst to the titanium metal complex is 50 to 500:1.
8. The method for preparing hyperbranched cycloolefin copolymer according to claim 4, characterized in that the temperature of the copolymerization reaction is 20 to 120 ℃; the pressure of the ethylene is 1 to 20atm.
9. The process for preparing hyperbranched cycloolefin copolymers according to claim 3, characterized in that the molar ratio of norbornene monomer to 4-methyl-1-pentene monomer is from 1 to 9:1.
10. The method for preparing the hyperbranched cyclic olefin copolymer according to claim 3, wherein the preparation of the titanium metal complex comprises the following steps:
s1: 2-fluorobenzaldehyde
And aniline->
Condensation reaction is carried out to obtain imine compound +.>
S2: imine compound and o-phenylmercaptoaniline
Substitution reaction is carried out to obtain ligand->
S3: under the action of n-butyllithium, the ligand and TiCl 4 Reacting to obtain the titanium metal complex;
wherein R is hydrogen, methyl or isopropyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310247299.XA CN116262796A (en) | 2023-03-14 | 2023-03-14 | Hyperbranched cycloolefin copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310247299.XA CN116262796A (en) | 2023-03-14 | 2023-03-14 | Hyperbranched cycloolefin copolymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116262796A true CN116262796A (en) | 2023-06-16 |
Family
ID=86723833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310247299.XA Pending CN116262796A (en) | 2023-03-14 | 2023-03-14 | Hyperbranched cycloolefin copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116262796A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254438A (en) * | 1997-06-05 | 2000-05-24 | 埃克森化学专利公司 | Electrical devices including ethylene, alpha-olefin, vinyl norbornene elastomers andethylene alpha-olefin polymers |
| CN1286704A (en) * | 1997-11-21 | 2001-03-07 | 埃克森化学专利公司 | Ethylene polymer compositions with norbornene comonomer |
| KR20040065110A (en) * | 2003-01-15 | 2004-07-21 | 삼성아토피나주식회사 | Long-Chain Branched α-olefin/cycloolefin/diene Copolymers and Method for Preparing the Same |
| CN101824110A (en) * | 2010-04-15 | 2010-09-08 | 复旦大学 | [N^N^S] type tridentate ligand and titanium metal coordinated olefin polymerization catalyst and preparation method thereof |
| KR20140061608A (en) * | 2012-11-13 | 2014-05-22 | 에스케이이노베이션 주식회사 | Α-olefinic copolymer compositions |
| CN112745431A (en) * | 2020-12-23 | 2021-05-04 | 广东新华粤石化集团股份公司 | Cycloolefin copolymer and preparation method thereof |
| CN114805654A (en) * | 2022-05-16 | 2022-07-29 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN115028763A (en) * | 2022-07-28 | 2022-09-09 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN115734975A (en) * | 2020-06-29 | 2023-03-03 | 宝理塑料株式会社 | Method for producing cyclic olefin copolymer, and catalyst composition for copolymerization of norbornene monomer and ethylene |
-
2023
- 2023-03-14 CN CN202310247299.XA patent/CN116262796A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254438A (en) * | 1997-06-05 | 2000-05-24 | 埃克森化学专利公司 | Electrical devices including ethylene, alpha-olefin, vinyl norbornene elastomers andethylene alpha-olefin polymers |
| CN1286704A (en) * | 1997-11-21 | 2001-03-07 | 埃克森化学专利公司 | Ethylene polymer compositions with norbornene comonomer |
| KR20040065110A (en) * | 2003-01-15 | 2004-07-21 | 삼성아토피나주식회사 | Long-Chain Branched α-olefin/cycloolefin/diene Copolymers and Method for Preparing the Same |
| CN101824110A (en) * | 2010-04-15 | 2010-09-08 | 复旦大学 | [N^N^S] type tridentate ligand and titanium metal coordinated olefin polymerization catalyst and preparation method thereof |
| KR20140061608A (en) * | 2012-11-13 | 2014-05-22 | 에스케이이노베이션 주식회사 | Α-olefinic copolymer compositions |
| CN115734975A (en) * | 2020-06-29 | 2023-03-03 | 宝理塑料株式会社 | Method for producing cyclic olefin copolymer, and catalyst composition for copolymerization of norbornene monomer and ethylene |
| CN112745431A (en) * | 2020-12-23 | 2021-05-04 | 广东新华粤石化集团股份公司 | Cycloolefin copolymer and preparation method thereof |
| CN114805654A (en) * | 2022-05-16 | 2022-07-29 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN115028763A (en) * | 2022-07-28 | 2022-09-09 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106397264B (en) | A kind of diimide ligand compound, complex and application | |
| KR101623485B1 (en) | Metallocene compound, catalyst composition comprising the same, and method for preparation of olefin-based polymer using the same | |
| KR102028063B1 (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same | |
| CN108794545B (en) | Tert-butyl-containing asymmetric α -diimine nickel complex for preparing ultra-high molecular weight polyethylene elastomer, preparation method and application | |
| CN110423306B (en) | Heterocycle-containing hexa-coordination disalicylimine metal catalyst, and preparation method and application thereof | |
| KR19990006927A (en) | Ethylene Polymerization Method and Heterogeneous Catalyst System | |
| EP1417213A1 (en) | Method for making late transition metal catalysts for olefin polymerization | |
| CN111909196A (en) | IVB group-containing bimetallic complex catalyst and preparation method and application thereof | |
| CN106397263B (en) | Ligand compound, it is prepared and the complex containing the ligand compound | |
| CN116262796A (en) | Hyperbranched cycloolefin copolymer and preparation method thereof | |
| KR100958676B1 (en) | Synthesis, Characterization, and Polymerization of dinuclear CGC Complexes | |
| CN111116790A (en) | Propylene polymer and preparation method and application thereof | |
| KR101471155B1 (en) | New transition metal compound, new organic ligand compound, catalysts composition comprising the transition metal compound and preparation method of poly-olefin using the catalysts composition | |
| US7888522B2 (en) | Oxygen-bridged bimetallic complex and polymerization process | |
| KR101828001B1 (en) | Organometalic compound with two central metal, catalyst composition comprising the same, and method for preparing olefin polymer using the same | |
| CN110386953B (en) | Seven-membered ring pyridine imine complex containing high-steric-hindrance cycloalkane, and preparation method and application thereof | |
| CN115260365B (en) | Branched olefin polymer, preparation method and application thereof | |
| CN112724288B (en) | Catalyst for ethylene polymerization and application thereof | |
| CN110964049B (en) | Transition metal compound, olefin polymerization catalyst composition containing same, preparation method and application | |
| WO2005042592A1 (en) | Ethylene polymerization employing bis-imino pyridinyl transition metal catalyst components | |
| CN116854856A (en) | Preparation method of norbornene, long-chain olefin and methyl acrylate ternary polymerization under single-metallocene titanium catalyst | |
| CN107266638B (en) | A kind of block copolymer and preparation method thereof | |
| CN117624030A (en) | Bidentate pyridinylamino ligand hafnium catalyst, preparation method and application thereof | |
| CN118126078A (en) | Metallocene complex containing amidine structure, preparation method thereof and application thereof in catalyzing ethylene/alpha-olefin copolymerization | |
| CN117903199A (en) | Phosphine-phenol transition metal complex, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |