CN107216444A - A kind of transparent, high heat-resisting cyclic olefine copolymer and preparation method thereof - Google Patents
A kind of transparent, high heat-resisting cyclic olefine copolymer and preparation method thereof Download PDFInfo
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- CN107216444A CN107216444A CN201710599333.4A CN201710599333A CN107216444A CN 107216444 A CN107216444 A CN 107216444A CN 201710599333 A CN201710599333 A CN 201710599333A CN 107216444 A CN107216444 A CN 107216444A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 137
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003863 metallic catalyst Substances 0.000 claims description 8
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- -1 alkane Hydrocarbon Chemical class 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 50
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 238000006116 polymerization reaction Methods 0.000 abstract description 25
- 230000009477 glass transition Effects 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000003426 co-catalyst Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000000047 product Substances 0.000 description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000007795 chemical reaction product Substances 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 238000001914 filtration Methods 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 16
- 238000005984 hydrogenation reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- 150000001925 cycloalkenes Chemical group 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 12
- 238000005292 vacuum distillation Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000004455 differential thermal analysis Methods 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000007707 calorimetry Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 239000003708 ampul Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011985 first-generation catalyst Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical group C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical class C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/592—Stability against heat
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
- C08G2261/724—Hydrogenation
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides one kind is transparent, high heat-resisting cyclic olefine copolymer and preparation method thereof, the cyclic olefine copolymer that the present invention is provided is by selecting specific structure, so that the cyclic olefine copolymer glass transition temperature that the present invention is provided is precisely adjustable, scope is 105 169 DEG C, solution coating, material transmissivity is up to 91%, extension test shows that the material has excellent mechanical performance, tensile strength is between 25 50MPa, stretch modulus is 1600 2800MPa, elongation at break is between 2.5 5.4%, and 10% heat decomposition temperature be all higher than 410 DEG C, with good heat endurance.The preparation method that the present invention is provided, by selecting specific catalyst so that catalytic conversion reaches 100%, and the side reaction such as do not crosslink；And co-catalyst is not needed, very well, molecular weight distribution is adjustable, with good application prospect for polymerization tolerance.
Description
Technical field
Polymeric material field of the present invention, more particularly to a kind of transparent, high heat-resisting cyclic olefine copolymer and preparation method thereof.
Background technology
Cyclic olefine copolymer (COC) is a kind of armorphous transparent copolymerized macromolecule of cycloolefin structure, is had and PMMA
The optical property of enemy, more more stable than PMMA and PC sizes, heat resistance is also higher than PC.COC has low-k (insulating properties), glass
Glass temperature adjustable, translucency is more than 91%, and heat resistance has preferably heat resisting temperature and anti-oxidation characteristics, thermal decomposition temperature
Degree is higher than 400 degree, and has good biocompatibility and high fluidity.COC materials'uses nontoxicity monomer is raw material, polymer
Very high purity, water permeability is very low, acellular toxin, no induction mutant organism, nonirritant, meets FDA standards.Cause
This, cyclic olefine copolymer is widely used in the various optics of manufacture, information, electrical equipment, medical material etc..
The heat resistance and heat endurance of cyclic olefine copolymer are the important performances of this material.In some higher temperatures
Under use environment, if the heat resistance of cyclic olefine copolymer is poor, the chi such as cyclic olefine copolymer can be distorted and deform
Change on very little, so as to directly affect the optical property and mechanical property of cyclic olefine copolymer.Therefore, cyclic olefine copolymer is improved
Heat resistance and thermal stability can greatly expand the use scope of cyclic olefine copolymer there is provided heat resistance and heat endurance
Good cyclic olefine copolymer is the important topic studied at present.
The content of the invention
In view of this, the technical problems to be solved by the invention are to provide a kind of transparent, high heat-resisting cyclic olefine copolymer
And preparation method thereof, the heat resistance that the cyclic olefine copolymer that provides of the present invention has not only had, and had it is thermally-stabilised
Property.
The invention provides a kind of cyclic olefine copolymer, with structure shown in formula (I),
Wherein, 140≤m≤220,170≤n≤280,1≤x≤4.
It is preferred that, the m is 170≤m≤190.
It is preferred that, the n is 170≤n≤190.
It is preferred that, the x is 2≤x≤3.
Present invention also offers a kind of preparation method of cyclic olefine copolymer, including：
1) compound of formula (II) structure and the compound of formula (III) structure will make in the catalyst of formula (IV) structure
Polymerisation is carried out under, polymer is obtained；
Wherein, x is 1≤x≤4；
2) obtained polymer is subjected to hydro-reduction reaction with heterogeneous metallic catalyst, obtains cyclic olefine copolymer.
It is preferred that, the mol ratio of the compound of formula (II) structure and the compound of the formula (III) structure for (9~
1)∶1。
It is preferred that, the solvent of the polymerisation is C1~C15 alkane, C1~C15 halogenated hydrocarbons, C3~C15 ring
The aromatic hydrocarbons of alkane or C5~C20.
It is preferred that, the temperature of the polymerisation is 10~50 DEG C, and the time of the polymerisation is 4~12h.
It is preferred that, total mole number and the formula of the compound of formula (II) structure and the compound of formula (III) structure
(IV) mol ratio of the catalyst of structure is (25~1000): 1.
It is preferred that, the heterogeneous metallic catalyst is 5~10% wet palladium carbons, 10%Pd/C, Pd/C/BaSO4Or Pt/
SiO2。
Compared with prior art, the invention provides transparent, high heat-resisting cyclic olefine copolymer of one kind and preparation method thereof, this
The cyclic olefine copolymer provided is invented by selecting specific structure so that the cyclic olefine copolymer vitrifying that the present invention is provided turns
Temperature is precisely adjustable, and scope is 105-169 DEG C, solution coating, and material transmissivity is up to 91%, and extension test shows the material
With excellent mechanical performance, tensile strength is between 25-50MPa, stretch modulus is 1600-2800MPa, and elongation at break exists
Between 2.5-5.4%, and 10% heat decomposition temperature is all higher than 410 DEG C, with good heat endurance.
In addition, present invention also offers a kind of transparent, high heat-resisting cyclic olefine copolymer cyclic olefine copolymer preparation
Method, the preparation method that the present invention is provided is by using the double (thricyclohexyls of benzylidene dichloro with formula (IV) structure
Phosphine) close catalyzed by ruthenium complexes have formula (II) structure polynary ring-type cycloolefin monomers (TCPD) and formula (III) structure carry it is short
The norbornene monomer of chain ester bond carries out random copolymerization, and not only trigger rate is fast, and catalytic conversion reaches 100%, and does not send out
The side reactions such as raw crosslinking；W systems indefinite compared to structure, Mo series catalysts, polymerization of the invention does not need co-catalysis
Agent, very well, molecular weight distribution is adjustable for polymerization tolerance.Hydro-reduction is carried out to gained Romp polymer, main chain is can obtain
Fully saturated polymer.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram for the product that the embodiment of the present invention 1 is obtained；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram for the product that the embodiment of the present invention 2 is obtained；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram before and after the polymeric reaction product hydrogenation that the embodiment of the present invention 3 is obtained；
Fig. 4 is the embodiment of the present invention 3, embodiment 4, embodiment 5, the cyclic olefine copolymer that embodiment 6 and embodiment 7 are obtained
Differential calorimetry curve；
Fig. 5 is the embodiment of the present invention 3, and embodiment 4, embodiment 5, embodiment 6 and embodiment 7 obtain cyclic olefine copolymer and existed
Thermogravimetric curve in nitrogen；
Fig. 6 is the light transmittance for the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 are obtained；
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram before and after the polymeric reaction product hydrogenation that the embodiment of the present invention 4 is obtained；
Fig. 8 is the hydrogen nuclear magnetic resonance spectrogram before and after the polymeric reaction product hydrogenation that the embodiment of the present invention 5 is obtained；
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram before and after the polymeric reaction product hydrogenation that the embodiment of the present invention 6 is obtained；
Figure 10 is the hydrogen nuclear magnetic resonance spectrogram before and after the polymeric reaction product hydrogenation that the embodiment of the present invention 7 is obtained.
Embodiment
The invention provides a kind of cyclic olefine copolymer, with structure shown in formula (I),
Wherein, the 140≤m≤220,170≤n≤280,1≤x≤4.
According to the present invention, the m is preferably 170≤m≤190.The n is preferably 170≤n≤190.The x is preferably 1
≤ x≤2, more preferably 1；The cyclic olefine copolymer is random copolymer；The copolymer weight average molecular weight is 7.0~15.0
×104G/mol, molecular weight distributing index is 1.4~2.0, and glass transition temperature is 105~169 DEG C.
The cyclic olefine copolymer that the present invention is provided is by selecting specific structure so that the cycloolefin copolymer that the present invention is provided
Thing glass transition temperature is precisely adjustable, and scope is between 105~169 DEG C, and cyclic olefin polymer film thickness is 50~120 μm
When light transmittance be more than 91%, good mechanical performance, tensile strength between 25~50MPa, stretch modulus be 1600~
2800MPa, elongation at break is between 2.5~5.4%, and 10% heat decomposition temperature is all higher than 410 DEG C, steady with good heat
It is qualitative.
Present invention also offers a kind of preparation method of cyclic olefine copolymer, including：
1) compound of formula (II) structure and the compound of formula (III) structure will make in the catalyst of formula (IV) structure
Polymerisation is carried out under, polymer is obtained；
Wherein, x is 1≤x≤4；
2) obtained polymer is subjected to hydro-reduction with heterogeneous metallic catalyst, obtains cyclic olefine copolymer.
According to the present invention, the present invention is by the compound of the compound with formula (II) structure and formula (III) structure in formula
(IV) polymerisation is carried out under the catalyst action of structure, obtains polymer；The compound and the formula of formula (II) structure
(III) mol ratio of the compound of structure is preferably (9~1): 1, it is more preferably (7~2): and 1, be most preferably (6~
3)∶1；The total mole number of the compound of formula (II) structure and the compound of formula (III) structure and the formula (IV) structure
The mol ratio of catalyst is preferably (25~1000): 1, more preferably (50~100): 1；The temperature of the polymerisation is preferably
10~50 DEG C, more preferably 25~30 DEG C；The time of the polymerisation is preferably 4~12h, more preferably 7~9 hours；Institute
State polymerisation and be additionally added chain terminating agent terminating reaction, the terminator is preferably vinyl ethyl ether, mole of the terminator
Number is preferably 100~500 times, more preferably 300~400 times of the catalyst molal quantity of formula (IV) structure.
Specifically, the present invention preferably has the compound of formula (II) structure and the compound of formula (III) structure and molten first
Agent is mixed；Wherein, described concentrated polymer solution concentration is preferably 5~15wt%, more preferably 8~10wt%.The present invention is right
The mode of mixing requires without special, hybrid mode well known in the art, wherein, the time stirred during the mixing is preferably
5 minutes~15 minutes, most preferably more preferably 8 minutes~12 minutes, 10 minutes.The solvent is preferably the polymerisation
Solvent be preferably C1~C15 alkane, C1~C15 halogenated hydrocarbons, C3~C15 cycloalkane or C5~C20 aromatic hydrocarbons, it is more excellent
Elect C5~C8 alkane, C1~C5 halogenated hydrocarbons, C5~C8 cycloalkane or C6~C15 aromatic hydrocarbons, most preferably dichloromethane as
Alkane；Source no particular/special requirement of the present invention to solvent, it is only necessary to anhydrous airfree solvent, it is described anhydrous without air solvent
Processing mode be preferred to use liquid nitrogen frozen~thawing processing mode and handled.
Polymerisation of the present invention is carried out preferably under drying, oxygen free condition, and the present invention does not have to the device of polymerisation
There is particular/special requirement, can be carried out in Braun (Mbraun) glove box, it would however also be possible to employ Xi Laike (Schlenk) skill of standard
Art is carried out under the protection of nitrogen.
According to the present invention, after the completion of the polymerisation, the polymerisation is terminated present invention preferably employs stopping stirring,
Obtain polymeric reaction solution；By the polymeric reaction solution and precipitant mix, precipitated product is obtained；By the precipitated product mistake
Filter, wash, dry, obtain polymeric reaction product.Wherein, the precipitating reagent is preferably absolute methanol；The present invention is to the precipitation
The method that product is filtered, washed and dried does not have special limitation, using filtering well known to those skilled in the art, washs and dry
Dry technical scheme.In the present invention, the reagent of the precipitated product washing is preferably ethanol.In the present invention, it is described
The number of times of precipitated product washing is preferably 2 times~4 times, more preferably 3 times.In the present invention, the side that the precipitated product is dried
Method is preferably vacuum drying.In the present invention, the temperature that the precipitated product is dried is preferably 20 DEG C~40 DEG C, more preferably 25
DEG C~35 DEG C, most preferably 30 DEG C.In the present invention, the time that the precipitated product is dried is preferably 12 hours~24 hours,
More preferably 16 hours~20 hours, most preferably 18 hours.
The present invention originates without special limitation to the compound with Formula II and III structures, using this area
The method with Formula II and III structural compounds is prepared known to technical staff to prepare.In the present invention, the tool
The preparation method for having the compound of Formula II structure is preferably：
Dicyclopentadiene and BHT are reacted, the chemical combination with Formula II structure is obtained
Thing.Wherein, the mol ratio of the dicyclopentadiene and BHT is preferably (800~1200): 1, more
Preferably (900~1100): 1, be most preferably (1000~1100): 1.The atmosphere of the reaction is preferably vacuum or blanket of nitrogen
Enclose；The temperature of the reaction is preferably 180 DEG C~220 DEG C, more preferably 190 DEG C~210 DEG C, most preferably 200 DEG C.It is described anti-
The time answered is preferably 14 hours~18 hours, more preferably 15 hours~17 hours.
After the completion of dicyclopentadiene and the BHT reaction, the present invention is double preferably by what is obtained
Cyclopentadiene and the cooling of BHT reactant, vacuum distillation, add to residue alcohol, cross filter out it is insoluble
Thing, low temperature recrystallization, separate out and are recrystallized again with alcohol low temperature after solid, obtain the compound with Formula II structure.The present invention is right
The method that the cooling, vacuum distillation, filtering and low temperature are recrystallized does not have special limitation, is known using those skilled in the art
Cooling, vacuum distillation, filtering and low temperature recrystallization technology scheme.In the present invention, the temperature of the cooling is preferably
20 DEG C~30 DEG C, more preferably 24 DEG C~28 DEG C.In the present invention, the temperature of the vacuum distillation is preferably 40 DEG C~80 DEG C,
More preferably 50 DEG C~60 DEG C.In the present invention, the temperature of the low temperature recrystallization is preferably~20 DEG C~0 DEG C, more preferably
~10 DEG C~~5 DEG C.
The present invention is to the originating without special limitation with formula III structural compounds, using people in the art
The method with formula III structural compounds is prepared known to member to prepare.In the present invention, it is described that there is formula III knot
The preparation method of the compound of structure is preferably：
Dicyclopentadiene, methyl acrylate and BHT are reacted, obtained with formula III
The compound of structure；The reaction preferably encloses lower progress in vacuum or nitrogen protective atmosphere；The temperature of the reaction is preferably 180 DEG C
~220 DEG C, most preferably more preferably 190 DEG C~210 DEG C, 200 DEG C.In the present invention, the time of the reaction is preferably 4 small
When~8 hours, most preferably more preferably 5 hours~7 hours, 6 hours.
After the completion of the dicyclopentadiene, methyl acrylate and BHT reaction, the present invention is excellent
Obtained dicyclopentadiene, methyl acrylate and BHT reaction product are cooled down, stood by choosing, decompression
Distillation, obtains the compound with formula III structure.The present invention is not special to the method for the cooling, standing and vacuum distillation
Limitation, using it is well known to those skilled in the art cooling, stand and vacuum distillation technical scheme.In the present invention,
The temperature of the cooling is preferably 20 DEG C~30 DEG C, more preferably 25 DEG C~28 DEG C.In the present invention, the time of the standing is excellent
Elect as 10 hours~16 hours, more preferably 12 hours~14 hours.In the present invention, the temperature of the vacuum distillation is preferably
110 DEG C~160 DEG C, more preferably 120 DEG C~150 DEG C.130 DEG C~140 DEG C when the present invention preferably collects the vacuum distillation
Cut, the cut is the compound with formula III structure.
According to the present invention, obtained polymer is also carried out hydro-reduction with heterogeneous metallic catalyst, obtained by the present invention
Cyclic olefine copolymer.Wherein, the heterogeneous metallic catalyst is preferably 5%~10% wet palladium carbon；This it is described heterogeneous
Metallic catalyst and the fluidized polymer mass ratio are preferably (3~6): 1, more preferably (5~6): 1；The solvent of the reaction
Preferably hexamethylene；The reaction is preferably additionally added a small amount of cocatalyst B HT；The pressure of the hydrogen in reaction is preferably 5.5
~6.0MPa, more preferably 5.8~5.9MPa；The temperature of the reaction is preferably 120~130 DEG C；The time of the reaction is excellent
Elect as 22~24 hours.After completion of the reaction, reaction solution is preferably poured slowly into industrial alcohol by the present invention, separates out a large amount of whites solid
Drying at 60 DEG C is put into vacuum drying oven after body, filtering, repeated washing three times and produces cyclic olefine copolymer within 12~24 hours.
More specifically, the preparation of cyclic olefine copolymer (COC) of the present invention can be carried out according to following reaction equations：
The preparation method for the cyclic olefine copolymer that the present invention is provided, by using the benzene methylene with formula (IV) structure
Base dichloro double (tricyclohexyl phosphines), which closes catalyzed by ruthenium complexes, has the polynary ring-type cycloolefin monomers (TCPD) of formula (II) structure
Random copolymerization is carried out with the norbornene monomer (NBMA) with short chain ester bond of formula (III) structure, not only trigger rate is fast,
Catalytic conversion reaches 100%, and the side reaction such as does not crosslink；W systems indefinite compared to structure, Mo series catalysts, this
The polymerization of invention does not need co-catalyst, and very well, molecular weight distribution is adjustable for polymerization tolerance.To gained ring-opening metathesis polymerization
Thing carries out hydro-reduction, can obtain the fully saturated polymer of main chain.And the present invention can be by controlling the polymerisation raw material
The glass transition temperature of cyclic olefine copolymer for preparing of consumption.The cyclic olefine copolymer that the present invention is prepared
In have Formula II structure compound it is more, the glass transition temperature of cyclic olefine copolymer is higher.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
The anhydrous and oxygen-free such as dichloromethane, toluene solvent is by MBraun SPS solvent purification processing system controllings in following examples
；Used Grubbs first generation catalyst reference literature (JACS, 1996,118,100~110) description method prepare,
The preparation of polynary shape alkene monomer (TCPD) is according to document (2010Wiley Periodicals, Inc.J Polym Sci Part
A：Polym Chem 49：938-944,2011) description method prepare.Other raw materials are commercially available prod.
The application is surveyed during being detected to the high-performance cyclic olefine copolymer of preparation using NMR spectrum
Determine the molecular structure of copolymer；The melting temperature of polymer is determined using differential thermal analysis；Determine poly- using gel permeation chromatography
The molecular weight and molecular weight distribution index of compound.Wherein, NMR spectrum refers to polymer1H and13C H NMR spectroscopies by
The type nuclear magnetic resonance chemical analyser of Varian Unity~400 is determined at 25 DEG C, and TMS is internal standard, and deuterochloroform is solvent.Show differential thermal
Analysis (DSC) refers to that the glass transition temperature of polymer is surveyed by Perkin~ElmerPyrisl DSC differential scanning calorimeters
Fixed, temperature rate is 20 DEG C/min, rescan.Thermal weight loss (TGA) is by the type Instrument measurings of Perkin-Elmer Pyris 1.
Light transmittance using Shimadzu UV~3600 it is ultraviolet~visible ray~near infrared spectrometer determines, determine wavelength be 400~
800nm.Stretching experiment：The mechanical property of polymer, which is characterized, to be carried out on INSTRON 1121, Canton, MA instruments, with
GB/T1040~1992 are standard, and batten folder is away from for 20.0mm, and test rate is 5mm/min, each sample at least test 8 times with
Ensure the reliability of data.Gel permeation chromatography (GPC) refer to the molecular weight and molecualr weight distribution index of polymer by
Waters1525 types gel permeation chromatograph is determined；Using RI~Laser detectors, solvent is tetrahydrofuran (THF), test
Temperature is 35 DEG C, and flow velocity is 1.0mL/min, uses PL EasiCal PS~1 for standard specimen.
Embodiment 1
1.5 liters of dicyclopentadienes, 1 gram of BHT, to institute are sequentially added into 2 liters of single port bottles
Single port bottle is stated to repeat to vacuumize the operation of rear inflated with nitrogen for 3 times；Single port bottle bottle is heated to 200 DEG C, makes the single port
Material in bottle carries out the reaction of 16 hours under conditions of stirring.
After the reaction terminates, obtained reaction product is cooled to 25 DEG C, vacuum distillation obtains lower boiling unreacted
1100 grams of thing.1 liter of ethanol is added into residue, crosses and filters out filtrate freezing 3 hours after insoluble matter.Solid is filtered to obtain after recrystallization
389 grams, obtain 315 grams of solid with 800 milliliters of ethyl alcohol recrystallizations again.The method that the embodiment of the present invention 1 is provided prepares product
Yield be 78%.
Product obtained above is subjected to proton nmr spectra detection, testing result such as Fig. 1, Fig. 1 are the embodiment of the present invention 1
The hydrogen nuclear magnetic resonance spectrogram of obtained product, as shown in Figure 1, the product that the embodiment of the present invention 1 is obtained are with Formula II structure
Compound.
Embodiment 2
Sequentially add 115 grams of dicyclopentadienes into 1 liter of stainless steel autoclave, 310 grams of methyl acrylates, the 2 of 1 gram,
6- di-tert-butyl methyl phenols, repeat to vacuumize the operation of rear inflated with nitrogen for 3 times to the autoclave；By the autoclave
200 DEG C are heated to, the reaction for making the material in the autoclave be carried out under conditions of stirring 16 hours.
After reaction terminates, obtained reaction product is cooled to 25 DEG C, decompression steaming is carried out after standing 12 hours at 65 DEG C
Evaporate, collect unreacted dicyclopentadiene and cyclopentadiene；The product obtained after vacuum distillation is subtracted again at 100 DEG C
Pressure distillation, collects cut during vacuum distillation, obtains 114 grams of products.The method that the embodiment of the present invention 2 is provided prepares product
Yield is 70%.
Product obtained above is subjected to proton nmr spectra detection, testing result such as Fig. 2, Fig. 2 are the embodiment of the present invention 2
The hydrogen nuclear magnetic resonance spectrogram of obtained product, as shown in Figure 2, the product that the embodiment of the present invention 2 is obtained are with formula III structure
Compound.
Embodiment 3
At room temperature, in dry polymerisation bottle, 0.12gTCPD monomers and 0.01gNBMA monomers are added, 50ml is added
Dichloromethane, is sufficiently stirred for 10min, claims 2.5mg (G1 adds 5ml dichloromethane in small ampulla, and ultrasonic 3min makes fully molten
Solution, imported into polymerization bottle, polymerization starts, in five minutes, solution is gradually changed into orange-yellow from purple, continues to stir 7 hours, plus
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stir half an hour.Reaction solution is poured into absolute methanol, separated out a large amount of
White polymer.The product being filtrated to get is put into vacuum drying oven at 40 DEG C after being washed 3 times with acetone and dried 12 hours.Weigh
0.13g polymer, yield is 100%.
In dry autoclave, above-mentioned polymer 0.13g is sequentially added, 5% wet palladium carbon 0.52g (4eqv), a little
BHT, 40ml cyclohexane solvent, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, is slowly dropped to reaction solution after filtering
In 100ml industrial alcohols, a large amount of white solids are separated out, filtering is drained, gained white solid is again molten with the heating of 40ml toluene
Solve half an hour, after be slowly added drop-wise in 300ml industrial alcohols, filtering is drained, and the process is put into vacuum drying oven after being repeated 2 times
In, dried 12 hours at 60 DEG C, obtain 0.12g products, yield 92.3%, purity is more than 99.9%.
The cyclic olefine copolymer progress proton nmr spectra detection obtained to the embodiment of the present invention 3, testing result such as Fig. 3,
Fig. 3 is curve 1 in the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 3 is obtained and cyclic olefine copolymer, Fig. 3
The proton nmr spectra of the polymeric reaction product obtained before being hydrogenated for the embodiment of the present invention 3, curve 2 is the hydrogen of the embodiment of the present invention 3
The proton nmr spectra of the cyclic olefine copolymer obtained after change, as seen from Figure 3, the polymerization that the embodiment of the present invention 3 is obtained are anti-
Product double bond peak after hydrogenation is answered to be wholly absent, hydrogenation effect is preferable.
The cyclic olefine copolymer obtained to the embodiment of the present invention 3 carries out gel permeation chromatography test, and test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 3 is obtained is 1.4, and weight average molecular weight is 7.0 × 104g/mol。
The cyclic olefine copolymer obtained to the embodiment of the present invention 3 carries out differential thermal analysis test, test result such as Fig. 4, Fig. 4
For the embodiment of the present invention 3, example 4, example 5, example 6, the differential calorimetry curve for the cyclic olefine copolymer that example 7 is obtained,
Curve 1 in Fig. 4, the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained does not have melting temperature, is amorphous state, the present invention
The glass transition temperature for the cyclic olefine copolymer that embodiment 3 is obtained is 169 DEG C.The cycloolefin obtained to the embodiment of the present invention 3
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, and example 4, example 5, example 6 is real
Curve 1 is the cycloolefin that the embodiment of the present invention 3 is obtained in thermogravimetric curve of the cyclic olefine copolymer that example 7 is obtained in nitrogen, Fig. 5
Thermogravimetric curve of the copolymer in nitrogen；As shown in Figure 5, the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained is at 410 DEG C
Resolution ratio is 10%, with higher heat endurance.
The mechanical property of the cyclic olefine copolymer obtained to the embodiment of the present invention 3 is tested, and test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 3 is obtained is 2.5%, and tensile strength is 25MPa, and stretch modulus is
1600MPa。
The transparency of the cyclic olefine copolymer obtained to the embodiment of the present invention 3 is tested, and test result such as Fig. 6, Fig. 6 are
Curve 1 is real for the present invention in the light transmittance for the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 are obtained, Fig. 6
The light transmittance for the cyclic olefine copolymer that example 3 is obtained is applied, it will be appreciated from fig. 6 that the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained is saturating
Light rate ＞ 91%.
Embodiment 4
At room temperature, in dry polymerisation bottle, 0.21gTCPD monomers and 0.04gNBMA monomers are added, 50ml is added
Dichloromethane, is sufficiently stirred for 10min, claims 10mg (G1 adds 5ml dichloromethane in small ampulla, and ultrasonic 3min makes fully molten
Solution, imported into polymerization bottle, polymerization starts, in five minutes, solution is gradually changed into orange-yellow from purple, continues to stir 7 hours, plus
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stir half an hour.Reaction solution is poured into absolute methanol, separated out a large amount of
White polymer.The product being filtrated to get is put into vacuum drying oven at 40 DEG C after being washed 3 times with acetone and dried 12 hours.Weigh
0.25g polymer, yield is 100%.
In dry autoclave, above-mentioned polymer 0.25g is sequentially added, 5% wet palladium carbon 1g (4eqv), a little BHT,
40ml cyclohexane solvents, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, reaction solution is slowly dropped into 100ml after filtering
In industrial alcohol, a large amount of white solids are separated out, filtering is drained, gained white solid is dissolved by heating half with 40ml toluene again
Hour, after be slowly added drop-wise in 300ml industrial alcohols, filtering is drained, and the process is put into vacuum drying oven after being repeated 2 times, 60 DEG C
Lower drying 12 hours, obtains 0.24g products, and yield 96%, purity is more than 99.9%.
The cyclic olefine copolymer progress proton nmr spectra detection obtained to the embodiment of the present invention 4, testing result such as Fig. 7,
Fig. 7 is curve 1 in the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 4 is obtained and cyclic olefine copolymer, Fig. 4
The proton nmr spectra of the polymeric reaction product obtained before being hydrogenated for the embodiment of the present invention 4, curve 2 is the hydrogen of the embodiment of the present invention 4
The proton nmr spectra of the cyclic olefine copolymer obtained after change, as seen from Figure 7, the polymerization that the embodiment of the present invention 4 is obtained are anti-
Product double bond peak after hydrogenation is answered to be wholly absent, hydrogenation effect is preferable.
The cyclic olefine copolymer obtained to the embodiment of the present invention 4 carries out gel permeation chromatography test, and test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 4 is obtained is 1.4, and weight average molecular weight is 9.4 × 104g/mol。
The cyclic olefine copolymer obtained to the embodiment of the present invention 4 carries out differential thermal analysis test, test result such as Fig. 4, Fig. 4
For the embodiment of the present invention 3, example 4, example 5, example 6, the differential calorimetry curve for the cyclic olefine copolymer that example 7 is obtained,
Curve 2 in Fig. 4, the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained does not have melting temperature, is amorphous state, the present invention
The glass transition temperature for the cyclic olefine copolymer that embodiment 4 is obtained is 154 DEG C.The cycloolefin obtained to the embodiment of the present invention 4
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, and example 4, example 5, example 6 is real
Curve 2 is the cycloolefin that the embodiment of the present invention 4 is obtained in thermogravimetric curve of the cyclic olefine copolymer that example 7 is obtained in nitrogen, Fig. 5
Thermogravimetric curve of the copolymer in nitrogen；As shown in Figure 5, the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained is at 413 DEG C
Resolution ratio is 10%, with higher heat endurance.
The mechanical property of the cyclic olefine copolymer obtained to the embodiment of the present invention 4 is tested, and test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 4 is obtained is 2.8%, and tensile strength is 32MPa, and stretch modulus is
2200MPa。
Embodiment 5
At room temperature, in dry polymerisation bottle, 0.76gTCPD monomers and 0.25gNBMA monomers are added, 50ml is added
Dichloromethane, is sufficiently stirred for 10min, claims 20mg (G1 adds 5ml dichloromethane in small ampulla, and ultrasonic 3min makes fully molten
Solution, imported into polymerization bottle, polymerization starts, in five minutes, solution is gradually changed into orange-yellow from purple, continues to stir 7 hours, plus
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stir half an hour.Reaction solution is poured into absolute methanol, separated out a large amount of
White polymer.The product being filtrated to get is put into vacuum drying oven at 40 DEG C after being washed 3 times with acetone and dried 12 hours.Weigh
1.01g polymer, yield is 100%.
In dry autoclave, above-mentioned polymer 1.01g is sequentially added, 5% wet palladium carbon 4g (4eqv), a little BHT,
40ml cyclohexane solvents, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, reaction solution is slowly dropped into 100ml after filtering
In industrial alcohol, a large amount of white solids are separated out, filtering is drained, gained white solid is dissolved by heating half with 40ml toluene again
Hour, after be slowly added drop-wise in 300ml industrial alcohols, filtering is drained, and the process is put into vacuum drying oven after being repeated 2 times, 60 DEG C
Lower drying 12 hours, obtains 9.9g products, and yield 98.1%, purity is more than 99.9%.
The cyclic olefine copolymer progress proton nmr spectra detection obtained to the embodiment of the present invention 5, testing result such as Fig. 8,
Fig. 8 is curve 1 in the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 5 is obtained and cyclic olefine copolymer, Fig. 8
The proton nmr spectra of the polymeric reaction product obtained before being hydrogenated for the embodiment of the present invention 5, curve 2 is the hydrogen of the embodiment of the present invention 5
The proton nmr spectra of the cyclic olefine copolymer obtained after change, as seen from Figure 8, the polymerization that the embodiment of the present invention 5 is obtained are anti-
Product double bond peak after hydrogenation is answered to be wholly absent, hydrogenation effect is preferable.
The cyclic olefine copolymer obtained to the embodiment of the present invention 5 carries out gel permeation chromatography test, and test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 5 is obtained is 1.4, and weight average molecular weight is 11.8 × 104g/mol。
The cyclic olefine copolymer obtained to the embodiment of the present invention 5 carries out differential thermal analysis test, test result such as Fig. 4, Fig. 4
For the embodiment of the present invention 3, example 4, example 5, example 6, the differential calorimetry curve for the cyclic olefine copolymer that example 7 is obtained,
Curve 1 in Fig. 4, the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained does not have melting temperature, is amorphous state, the present invention
The glass transition temperature for the cyclic olefine copolymer that embodiment 5 is obtained is 147 DEG C.The cycloolefin obtained to the embodiment of the present invention 5
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, and example 4, example 5, example 6 is real
Curve 3 is the cycloolefin that the embodiment of the present invention 5 is obtained in thermogravimetric curve of the cyclic olefine copolymer that example 7 is obtained in nitrogen, Fig. 5
Thermogravimetric curve of the copolymer in nitrogen；As shown in Figure 5, the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained is at 415 DEG C
Resolution ratio is 10%, with higher heat endurance.
The mechanical property of the cyclic olefine copolymer obtained to the embodiment of the present invention 5 is tested, and test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 5 is obtained is 3.1%, and tensile strength is 36MPa, and stretch modulus is
2400MPa。
The transparency of the cyclic olefine copolymer obtained to the embodiment of the present invention 5 is tested, and test result such as Fig. 6, Fig. 6 are
Curve 2 is real for the present invention in the light transmittance for the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 are obtained, Fig. 6
The light transmittance for the cyclic olefine copolymer that example 5 is obtained is applied, it will be appreciated from fig. 6 that the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained is saturating
Light rate ＞ 91%.
Embodiment 6
At room temperature, in dry polymerisation bottle, 0.7gTCPD monomers and 0.3gNBMA monomers are added, 50ml bis- is added
Chloromethanes, is sufficiently stirred for 10min, claim 20mg (G1 adds 5ml dichloromethane in small ampulla, and ultrasonic 3min makes fully dissolving,
It imported into polymerization bottle, polymerization starts, in five minutes, solution is gradually changed into orange-yellow from purple, continues to stir 7 hours, add
Vinyl ethyl ether EVE (500 equivalent) terminates polymerization, stirs half an hour.Reaction solution is poured into absolute methanol, separated out a large amount of white
Color polymer.The product being filtrated to get is put into vacuum drying oven at 40 DEG C after being washed 3 times with acetone and dried 12 hours.Weigh to obtain 1g
Polymer, yield is 100%.
In dry autoclave, above-mentioned polymer 1g, 5% wet palladium carbon 4g (4eqv), a little BHT, 40ml are sequentially added
Cyclohexane solvent, boosted 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, and reaction solution is slowly dropped into 100ml industry after filtering
In ethanol, a large amount of white solids are separated out, filtering is drained, gained white solid is dissolved by heating with 40ml toluene again small half
When, after be slowly added drop-wise in 300ml industrial alcohols, filtering is drained, and the process is put into vacuum drying oven after being repeated 2 times, at 60 DEG C
Dry 12 hours, obtain 0.96g products, yield 96%, purity is more than 99.9%.
The cyclic olefine copolymer progress proton nmr spectra detection obtained to the embodiment of the present invention 6, testing result such as Fig. 9,
Fig. 9 is curve 1 in the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 6 is obtained and cyclic olefine copolymer, Fig. 9
The proton nmr spectra of the polymeric reaction product obtained before being hydrogenated for the embodiment of the present invention 6, curve 2 is the hydrogen of the embodiment of the present invention 6
The proton nmr spectra of the cyclic olefine copolymer obtained after change, as seen from Figure 9, the polymerization that the embodiment of the present invention 6 is obtained are anti-
Product double bond peak after hydrogenation is answered to be wholly absent, hydrogenation effect is preferable.
The cyclic olefine copolymer obtained to the embodiment of the present invention 6 carries out gel permeation chromatography test, and test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 6 is obtained is 1.4, and weight average molecular weight is 13.9 × 104g/mol。
The cyclic olefine copolymer obtained to the embodiment of the present invention 6 carries out differential thermal analysis test, test result such as Fig. 4, Fig. 4
For the embodiment of the present invention 3, example 4, example 5, example 6, the differential calorimetry curve for the cyclic olefine copolymer that example 7 is obtained,
Curve 4 in Fig. 4, the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained does not have melting temperature, is amorphous state, the present invention
The glass transition temperature for the cyclic olefine copolymer that embodiment 6 is obtained is 131 DEG C.The cycloolefin obtained to the embodiment of the present invention 6
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, and example 4, example 5, example 6 is real
Curve 4 is the cycloolefin that the embodiment of the present invention 6 is obtained in thermogravimetric curve of the cyclic olefine copolymer that example 7 is obtained in nitrogen, Fig. 5
Thermogravimetric curve of the copolymer in nitrogen；As shown in Figure 5, the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained is at 415 DEG C
Resolution ratio is 10%, with higher heat endurance.
The mechanical property of the cyclic olefine copolymer obtained to the embodiment of the present invention 6 is tested, and test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 6 is obtained is 3.7%, and tensile strength is 402MPa, and stretch modulus is
2400MPa。
Embodiment 7
At room temperature, in dry polymerisation bottle, 0.6gTCPD monomers and 0.44gNBMA monomers are added, 50ml is added
Dichloromethane, is sufficiently stirred for 10min, claims 20mg (G1 adds 5ml dichloromethane in small ampulla, and ultrasonic 3min makes fully molten
Solution, imported into polymerization bottle, polymerization starts, in five minutes, solution is gradually changed into orange-yellow from purple, continues to stir 7 hours, plus
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stir half an hour.Reaction solution is poured into absolute methanol, separated out a large amount of
White polymer.The product being filtrated to get is put into vacuum drying oven at 40 DEG C after being washed 3 times with acetone and dried 12 hours.Weigh
1.04g polymer, yield is 100%.
In dry autoclave, above-mentioned polymer 1.04g is sequentially added, 5% wet palladium carbon 4g (4eqv), a little BHT,
40ml cyclohexane solvents, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, reaction solution is slowly dropped into 100ml after filtering
In industrial alcohol, a large amount of white solids are separated out, filtering is drained, gained white solid is dissolved by heating half with 40ml toluene again
Hour, after be slowly added drop-wise in 300ml industrial alcohols, filtering is drained, and the process is put into vacuum drying oven after being repeated 2 times, 60 DEG C
Lower drying 12 hours, obtains 1g products, and yield 96.1%, purity is more than 99.9%.
The cyclic olefine copolymer progress proton nmr spectra detection obtained to the embodiment of the present invention 7, testing result such as Figure 10,
Figure 10 is song in the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 7 is obtained and cyclic olefine copolymer, Figure 10
Line 1 is the proton nmr spectra of the polymeric reaction product obtained before the embodiment of the present invention 7 is hydrogenated, and curve 2 is the embodiment of the present invention 7
The proton nmr spectra of the cyclic olefine copolymer obtained after hydrogenation, as seen from Figure 10, the polymerization that the embodiment of the present invention 7 is obtained
Reaction product double bond peak after hydrogenation is wholly absent, and hydrogenation effect is preferable.
The cyclic olefine copolymer obtained to the embodiment of the present invention 7 carries out gel permeation chromatography test, and test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 7 is obtained is 2.0, and weight average molecular weight is 15.5 × 104g/mol。
The cyclic olefine copolymer obtained to the embodiment of the present invention 7 carries out differential thermal analysis test, test result such as Fig. 4, Fig. 4
For the embodiment of the present invention 3, example 4, example 5, example 6, the differential calorimetry curve for the cyclic olefine copolymer that example 7 is obtained,
Curve 5 in Fig. 4, the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained does not have melting temperature, is amorphous state, the present invention
The glass transition temperature for the cyclic olefine copolymer that embodiment 7 is obtained is 105 DEG C.The cycloolefin obtained to the embodiment of the present invention 5
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, and example 4, example 5, example 6 is real
Curve 5 is the cycloolefin that the embodiment of the present invention 7 is obtained in thermogravimetric curve of the cyclic olefine copolymer that example 7 is obtained in nitrogen, Fig. 5
Thermogravimetric curve of the copolymer in nitrogen；As shown in Figure 5, the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained is at 418 DEG C
Resolution ratio is 10%, with higher heat endurance.
The mechanical property of the cyclic olefine copolymer obtained to the embodiment of the present invention 7 is tested, and test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 7 is obtained is 5.4%, and tensile strength is 50MPa, and stretch modulus is
2800MPa。
The transparency of the cyclic olefine copolymer obtained to the embodiment of the present invention 7 is tested, and test result such as Fig. 6, Fig. 6 are
Curve 3 is real for the present invention in the light transmittance for the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 are obtained, Fig. 6
The light transmittance for the cyclic olefine copolymer that example 7 is obtained is applied, it will be appreciated from fig. 6 that the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained is saturating
Light rate ＞ 91%.
Specifically, the reaction condition that fed intake in 3~embodiment of the embodiment of the present invention 7 is shown in Table 1；
Table 1
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of cyclic olefine copolymer, with structure shown in formula (I),
Wherein, 140≤m≤220,170≤n≤280,1≤x≤4.
2. cyclic olefine copolymer according to claim 1, it is characterised in that the m is 170≤m≤190.
3. cyclic olefine copolymer according to claim 1, it is characterised in that the n is 170≤n≤190.
4. cyclic olefine copolymer according to claim 1, it is characterised in that the x is 1≤x≤2.
5. a kind of preparation method of cyclic olefine copolymer, including：
1) by the compound of the compound with formula (II) structure and formula (III) structure under the catalyst action of formula (IV) structure
Polymerisation is carried out, polymer is obtained；
Wherein, x is 1≤x≤4；
2) obtained polymer is subjected to hydro-reduction reaction with heterogeneous metallic catalyst, obtains cyclic olefine copolymer.
6. preparation method according to claim 5, it is characterised in that the compound and the formula of formula (II) structure
(III) mol ratio of the compound of structure is (9~1): 1.
7. preparation method according to claim 5, it is characterised in that the solvent of the polymerisation is C1~C15 alkane
Hydrocarbon, C1~C15 halogenated hydrocarbons, C3~C15 cycloalkane or C5~C20 aromatic hydrocarbons.
8. preparation method according to claim 5, it is characterised in that the temperature of the polymerisation is 10~50 DEG C, institute
The time for stating polymerisation is 4~12h.
9. preparation method according to claim 5, it is characterised in that the compound and formula (III) of formula (II) structure
The mol ratio of the total mole number of the compound of structure and the catalyst of the formula (IV) structure is (25~1000): 1.
10. preparation method according to claim 5, it is characterised in that the heterogeneous metallic catalyst is 5~10% wet
Palladium carbon, 10%Pd/C, Pd/C/BaSO4Or Pt/SiO2。
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