CN107216444B - A kind of transparent, high heat resistance cyclic olefine copolymer and preparation method thereof - Google Patents
A kind of transparent, high heat resistance cyclic olefine copolymer and preparation method thereof Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 138
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 34
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 15
- 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
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 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
- 150000004945 aromatic hydrocarbons 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
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 50
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 230000009477 glass transition Effects 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 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
- 239000000047 product Substances 0.000 description 34
- 238000005481 NMR spectroscopy Methods 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 32
- 238000001914 filtration Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000007795 chemical reaction product Substances 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 17
- 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
- 239000000178 monomer Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- 150000001925 cycloalkenes Chemical group 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 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 12
- 238000005292 vacuum distillation Methods 0.000 description 11
- 238000001291 vacuum drying 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
- 238000005406 washing Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 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
- 238000001514 detection method Methods 0.000 description 7
- 238000004455 differential thermal analysis Methods 0.000 description 7
- 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
- 239000003708 ampul Substances 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
- 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
- 230000008859 change Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 C20 aromatic hydrocarbons Chemical class 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 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
- 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
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 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
- 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
- 239000012299 nitrogen atmosphere 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
- 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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- 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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- 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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- 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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- 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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Abstract
The present invention provides a kind of transparent, high heat resistance cyclic olefine copolymer and preparation method thereof, cyclic olefine copolymer provided by the invention is by selecting specific structure, so that cyclic olefine copolymer glass transition temperature provided by the invention is precisely adjustable, range 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% thermal decomposition temperature be all larger than 410 DEG C, with good thermal stability.Preparation method provided by the invention so that catalytic conversion reaches 100%, and does not crosslink by selecting specific catalyst and waits side reactions；And co-catalyst is not needed, polymerization tolerance is fine, and molecular weight distribution is adjustable, has a good application prospect.
Description
Technical field
Polymeric material field of the present invention, more particularly to a kind of transparent, high heat resistance cyclic olefine copolymer and preparation method thereof.
Background technique
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 size, heat resistance ratio PC is also high.COC has low-k (insulating properties), glass
Glass temperature adjustability, translucency are greater than 91%, and heat resistance has preferable 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'use nontoxicity monomer is raw material, polymer
Very high purity, water permeability is very low, cell-free toxin, no induction mutant organism, nonirritant, meets FDA standard.Cause
This, cyclic olefine copolymer is widely used in the various optics of manufacture, information, electric appliance, medical material etc..
The heat resistance and thermal stability of cyclic olefine copolymer are the important performances of this material.In certain higher temperatures
Under use environment, if the heat resistance of cyclic olefine copolymer is poor, the rulers such as cyclic olefine copolymer can be distorted and deform
Variation on very little, 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, heat resistance and thermal stability are provided
Good cyclic olefine copolymer is the important topic studied at present.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in provide a kind of transparent, high heat resistance cyclic olefine copolymer
And preparation method thereof, the heat resistance that cyclic olefine copolymer provided by the invention has not only had, but also the thermostabilization having had
Property.
The present invention provides a kind of cyclic olefine copolymers, have structure shown in formula (I),
Wherein, 140≤m≤220,170≤n≤280,1≤x≤4.
Preferably, the m is 170≤m≤190.
Preferably, the n is 170≤n≤190.
Preferably, the x is 2≤x≤3.
The present invention also provides a kind of preparation methods of cyclic olefine copolymer, comprising:
1) compound of the compound and formula (III) structure that will have formula (II) structure is made in the catalyst of formula (IV) structure
Polymerization reaction is carried out under, obtains polymer；
Wherein, x is 1≤x≤4；
2) obtained polymer is subjected to hydro-reduction reaction with heterogeneous metallic catalyst, obtains cyclic olefine copolymer.
Preferably, the molar ratio of the compound of the compound and formula (III) structure of formula (II) structure be (9~
1)∶1。
Preferably, the solvent of the polymerization reaction is the ring of the alkane of C1~C15, the halogenated hydrocarbons of C1~C15, C3~C15
The aromatic hydrocarbons of alkane or C5~C20.
Preferably, the temperature of the polymerization reaction is 10~50 DEG C, and the time of the polymerization reaction is 4~12h.
Preferably, the total mole number of the compound of the compound and formula (III) structure of formula (II) structure and the formula
(IV) molar ratio of the catalyst of structure is (25~1000): 1.
Preferably, the heterogeneous metallic catalyst is 5~10% wet palladium carbons, 10%Pd/C, Pd/C/BaSO4Or Pt/
SiO2。
Compared with prior art, the present invention provides a kind of transparent, high heat resistance cyclic olefine copolymers and preparation method thereof, originally
The cyclic olefine copolymer that invention provides is by selecting specific structure, so that cyclic olefine copolymer vitrifying provided by the invention turns
Temperature is precisely adjustable, and range is 105-169 DEG C, and solution coating, for material transmissivity up to 91%, extension test shows the material
With excellent mechanical performance, between 25-50MPa, stretch modulus 1600-2800MPa, elongation at break exists tensile strength
Between 2.5-5.4%, and 10% thermal decomposition temperature is all larger than 410 DEG C, has good thermal stability.
In addition, the present invention also provides a kind of transparent, high heat resistance cyclic olefine copolymer cyclic olefine copolymer preparations
Method, preparation method provided by the invention is by using the bis- (thricyclohexyls of benzylidene dichloro with formula (IV) structure
Phosphine) close catalyzed by ruthenium complexes have formula (II) structure polynary cyclic annular cycloolefin monomers (TCPD) and formula (III) structure have 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 system indefinite compared to structure, Mo series catalysts, polymerization of the invention do not need co-catalysis
Agent, polymerization tolerance is fine, and molecular weight distribution is adjustable.Hydro-reduction is carried out to gained Romp polymer, main chain can be obtained
Fully saturated polymer.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram for the product that the embodiment of the present invention 1 obtains；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram for the product that the embodiment of the present invention 2 obtains；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram for the polymeric reaction product hydrogenation front and back that the embodiment of the present invention 3 obtains；
Fig. 4 is the embodiment of the present invention 3, embodiment 4, embodiment 5, the cyclic olefine copolymer that embodiment 6 and embodiment 7 obtain
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 exist
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 obtain；
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram for the polymeric reaction product hydrogenation front and back that the embodiment of the present invention 4 obtains；
Fig. 8 is the hydrogen nuclear magnetic resonance spectrogram for the polymeric reaction product hydrogenation front and back that the embodiment of the present invention 5 obtains；
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram for the polymeric reaction product hydrogenation front and back that the embodiment of the present invention 6 obtains；
Figure 10 is the hydrogen nuclear magnetic resonance spectrogram for the polymeric reaction product hydrogenation front and back that the embodiment of the present invention 7 obtains.
Specific embodiment
The present invention provides a kind of cyclic olefine copolymers, have 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 are 1.4~2.0, and glass transition temperature is 105~169 DEG C.
Cyclic olefine copolymer provided by the invention is by selecting specific structure, so that cycloolefin copolymer provided by the invention
Object glass transition temperature is precisely adjustable, and range is between 105~169 DEG C, and cyclic olefin polymer film is with a thickness of 50~120 μm
When light transmittance be greater 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% thermal decomposition temperature is all larger than 410 DEG C, has hot steady well
It is qualitative.
The present invention also provides a kind of preparation methods of cyclic olefine copolymer, comprising:
1) compound of the compound and formula (III) structure that will have formula (II) structure is made in the catalyst of formula (IV) structure
Polymerization reaction is carried out under, obtains polymer；
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 will have formula (II) structure compound and formula (III) structure compound in formula
(IV) polymerization reaction is carried out under the catalyst action of structure, obtains polymer；The compound of formula (II) structure and the formula
(III) molar ratio of the compound of structure is preferably (9~1): 1, it is more preferably (7~2): and 1, most preferably (6~
3):1；The total mole number of the compound of the compound and formula (III) structure of formula (II) structure and the formula (IV) structure
The molar ratio of catalyst is preferably (25~1000): 1, more preferably (50~100): 1；The temperature of the polymerization reaction is preferably
10~50 DEG C, more preferably 25~30 DEG C；The time of the polymerization reaction is preferably 4~12h, and more preferably 7~9 hours；Institute
It states polymerization reaction and is additionally added chain terminating agent and terminates and react, 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, compound and the compound of formula (III) structure of the present invention preferably first with formula (II) structure and molten
Agent mixing；Wherein, the concentrated polymer solution concentration is preferably 5~15wt%, more preferably 8~10wt%.The present invention couple
Mixed mode is required without special, hybrid mode well known in the art, wherein the time stirred when the mixing is preferably
5 minutes~15 minutes, more preferably 8 minutes~12 minutes, most preferably 10 minutes.The solvent is preferably the polymerization reaction
Solvent be preferably the alkane of C1~C15, the halogenated hydrocarbons of C1~C15, the cycloalkane of C3~C15 or C5~C20 aromatic hydrocarbons, it is more excellent
It is selected as the aromatic hydrocarbons of the alkane of C5~C8, the halogenated hydrocarbons of C1~C5, the cycloalkane of C5~C8 or C6~C15, most preferably dichloromethane
Alkane；The present invention does not have particular/special requirement to the source of solvent, it is only necessary to anhydrous airfree solvent, the anhydrous no air solvent
Processing mode preferably use liquid nitrogen frozen~thawing processing mode to be handled.
Polymerization reaction of the present invention preferably carries out under drying, oxygen free condition, and the present invention does not have the device of polymerization reaction
There is particular/special requirement, can be carried out in Braun (Mbraun) glove box, Xi Laike (Schlenk) skill of standard can also be used
Art carries out under the protection of nitrogen.
According to the present invention, after the completion of the polymerization reaction, present invention preferably employs stopping stirrings terminating the polymerization reaction,
Obtain polymeric reaction solution；By the polymeric reaction solution and precipitant mix, precipitated product is obtained；By the precipitated product mistake
Filter, washing, drying, obtain polymeric reaction product.Wherein, the precipitating reagent is preferably anhydrous methanol；The present invention is to the precipitating
The method that product is filtered, washed and dried does not have special limitation, is filtered, washed and is done using well known to those skilled in the art
Dry technical solution.In the present invention, the reagent of the precipitated product washing is preferably ethyl alcohol.In the present invention, described
The number of precipitated product washing is preferably 2 times~4 times, more preferably 3 times.In the present invention, the dry side of the precipitated product
Method is preferably dried in vacuo.In the present invention, the dry temperature of the precipitated product be 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 precipitated product dry time is preferably 12 hours~24 hours,
More preferably 16 hours~20 hours, most preferably 18 hours.
The present invention does not have special limitation to the source of the compound with Formula II and III structure, using this field
There is the method for Formula II and III structural compounds to be prepared for preparation known to technical staff.In the present invention, the tool
There is the preparation method of the compound of Formula II structure preferred are as follows:
Dicyclopentadiene and 2,6-di-tert-butyl p-methylphenol are reacted, the chemical combination with Formula II structure is obtained
Object.Wherein, the molar ratio of the dicyclopentadiene and 2,6-di-tert-butyl p-methylphenol is preferably (800~1200): 1, more
Preferably (900~1100): 1, most preferably (1000~1100): 1.The atmosphere of the reaction is preferably vacuum or nitrogen atmosphere
It encloses；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 reaction was completed, the present invention is preferably double by what is obtained for the dicyclopentadiene and 2,6-di-tert-butyl p-methylphenol
Cyclopentadiene and 2,6-di-tert-butyl p-methylphenol reactant is cooling, vacuum distillation, be added to residue alcohol, cross filter out it is insoluble
Object, low temperature recrystallization, are precipitated after solid and are recrystallized again with alcohol low temperature, obtain the compound with Formula II structure.The present invention couple
The method that the cooling, vacuum distillation, filtering and low temperature recrystallize does not have special limitation, using known to 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 does not have special limitation to the source with formula III structural compounds, using those skilled in the art
There is the method for formula III structural compounds to be prepared for preparation known to member.In the present invention, described that there is formula III knot
The preparation method of the compound of structure is preferred are as follows:
Dicyclopentadiene, methyl acrylate and 2,6-di-tert-butyl p-methylphenol are reacted, obtained with formula III
The compound of structure；The reaction preferably carries out under vacuum or nitrogen protection atmosphere；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.In the present invention, the time of the reaction is preferably 4 small
When~8 hours, more preferably 5 hours~7 hours, most preferably 6 hours.
After the reaction was completed, the present invention is excellent for the dicyclopentadiene, methyl acrylate and 2,6-di-tert-butyl p-methylphenol
It selects the dicyclopentadiene that will be obtained, methyl acrylate and the cooling of 2,6-di-tert-butyl p-methylphenol reaction product, stand, 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 the technical solution of cooling well known to those skilled in the art, standing and vacuum distillation.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
It is selected 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
Fraction, the fraction are the compound with formula III structure.
According to the present invention, obtained polymer is also carried out hydro-reduction with heterogeneous metallic catalyst by the present invention, is obtained
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
It is selected as 22~24 hours.After completion of the reaction, reaction solution is preferably poured slowly into industrial alcohol by the present invention, and it is solid that a large amount of whites are precipitated
Body, filtering, repeated washing are put into vacuum drying oven at 60 DEG C dry 12~24 hours afterwards three times up to cyclic olefine copolymer.
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 of the cyclic olefine copolymer provided by the invention, by using the benzene methylene with formula (IV) structure
Base dichloro bis- (tricyclohexyl phosphines) closes the polynary cyclic annular cycloolefin monomers (TCPD) that catalyzed by ruthenium complexes has formula (II) structure
Random copolymerization is carried out with the norbornene monomer (NBMA) with short-chain ester key of formula (III) structure, not only trigger rate is fast,
Catalytic conversion reaches 100%, and does not crosslink equal side reactions；W system indefinite compared to structure, Mo series catalysts, this
The polymerization of invention does not need co-catalyst, and polymerization tolerance is fine, and molecular weight distribution is adjustable.To gained ring-opening metathesis polymerization
Object carries out hydro-reduction, and the fully saturated polymer of main chain can be obtained.And the present invention can be by controlling the polymerization reaction raw material
The glass transition temperature of cyclic olefine copolymer that is prepared of dosage.The cyclic olefine copolymer that the present invention is prepared
In with Formula II structure compound it is more, the glass transition temperature of cyclic olefine copolymer is higher.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The anhydrous and oxygen-frees such as methylene chloride, toluene solvent is by MBraun SPS solvent purification processing system controlling in following embodiment
?；The method preparation of used Grubbs first generation catalyst reference literature (JACS, 1996,118,100~110) description,
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) the method preparation of description.Other raw materials are commercial product.
The application is surveyed during detecting to the high-performance cyclic olefine copolymer of preparation using NMR spectrum
Determine the molecular structure of copolymer；Using the melting temperature of differential thermal analysis measurement polymer；It is poly- using gel permeation chromatography measurement
Close the molecular weight and molecular weight distribution index of object.Wherein, NMR spectrum refers to polymer1H and13C H NMR spectroscopy by
The type of Varian Unity~400 nuclear magnetic resonance chemical analyser measures at 25 DEG C, and TMS is internal standard, and deuterated chloroform is solvent.Show differential thermal
Analysis (DSC) refers to that the glass transition temperature of polymer is surveyed by Perkin~ElmerPyrisl DSC differential scanning calorimeter
Fixed, temperature rate is 20 DEG C/min, rescan.Thermal weight loss (TGA) is by 1 type Instrument measuring of Perkin-Elmer Pyris.
Light transmittance using UV~3600 Shimadzu it is ultraviolet~visible light~near infrared spectrometer measures, measurement wavelength is 400~
800nm.Stretching experiment: the mechanical property characterization of polymer is carried out on INSTRON 1121, Canton, MA instrument, with
GB/T1040~1992 are standard, and batten folder is away from for 20.0mm, test rate 5mm/min, each sample at least test 8 times with
Guarantee the reliability of data.Gel permeation chromatography (GPC) refer to the molecular weight and molecualr weight distribution index of polymer by
The measurement of waters1525 type gel permeation chromatograph；Using RI~Laser detector, solvent is tetrahydrofuran (THF), test
Temperature is 35 DEG C, and flow velocity 1.0mL/min uses PS~1 PL EasiCal for standard specimen.
Embodiment 1
1.5 liters of dicyclopentadienes, 1 gram of 2,6-di-tert-butyl p-methylphenol, to institute are sequentially added into 2 liters of single port bottles
It states single port bottle and repeats 3 operations for vacuumizing rear inflated with nitrogen；The single port bottle bottle is heated to 200 DEG C, makes the single port
Substance in bottle carries out reaction in 16 hours under stirring conditions.
It is described after reaction, obtained reaction product is cooled to 25 DEG C, vacuum distillation obtains low-boiling unreacted
1100 grams of object.1 liter of ethyl alcohol is added into residue, crosses filtrate after filtering out insoluble matter and freezes 3 hours.The solid was filtered after recrystallization
389 grams, 315 grams of solid are obtained with 800 milliliters of ethyl alcohol recrystallizations again.Product is prepared in the method that the embodiment of the present invention 1 provides
Yield be 78%.
Product obtained above is subjected to nuclear magnetic resonance spectroscopy 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 obtains 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 phenol repeats 3 operations for vacuumizing rear inflated with nitrogen to the autoclave；By the autoclave
200 DEG C are heated to, the reaction for carrying out the substance in the autoclave under stirring conditions 16 hours.
After reaction, obtained reaction product is cooled to 25 DEG C, carries out decompression steaming at 65 DEG C after standing 12 hours
It evaporates, collects unreacted dicyclopentadiene and cyclopentadiene；The product obtained after vacuum distillation is subtracted again at 100 DEG C
Pressure distillation, collects fraction when vacuum distillation, obtains 114 grams of products.Product is prepared in the method that the embodiment of the present invention 2 provides
Yield is 70%.
Product obtained above is subjected to nuclear magnetic resonance spectroscopy 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 obtains are with formula III structure
Compound.
Embodiment 3
At room temperature, in dry polymerisation bottle, 0.12gTCPD monomer and 0.01gNBMA monomer is added, 50ml is added
10min is sufficiently stirred in methylene chloride, claims 2.5mg (5ml methylene chloride is added in small ampulla in G1, and ultrasonic 3min makes sufficiently molten
Solution, imported into polymerization bottle, and polymerization starts, and in five minutes, solution gradually becomes orange-yellow from purple, continues stirring 7 hours, adds
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stirs half an hour.Reaction solution is poured into anhydrous methanol, is precipitated a large amount of
White polymer.The product being obtained by filtration is 12 hours dry to be put into vacuum drying oven after acetone washing 3 times at 40 DEG C.It weighs
0.13g polymer, yield 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 alcohol, a large amount of white solids are precipitated, filtering is drained, and uses the heating of 40ml toluene molten again gained white solid
Solve half an hour, after be slowly added drop-wise in 300ml industrial alcohol, filtering is drained, which is put into vacuum drying oven after being repeated 2 times
In, it is 12 hours dry at 60 DEG C, 0.12g product, yield 92.3% are obtained, purity is greater than 99.9%.
The cyclic olefine copolymer obtained to the embodiment of the present invention 3 carries out nuclear magnetic resonance spectroscopy detection, testing result such as Fig. 3,
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 3 obtains, curve 1 in Fig. 3
The nuclear magnetic resonance spectroscopy of the polymeric reaction product obtained before hydrogenating for the embodiment of the present invention 3, curve 2 are 3 hydrogen of the embodiment of the present invention
The nuclear magnetic resonance spectroscopy of the cyclic olefine copolymer obtained after change, as seen from Figure 3, the polymerization that the embodiment of the present invention 3 obtains are anti-
Product double bond peak after hydrogenation is answered to completely disappear, hydrogenation effect is preferable.
Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 3 obtains is 1.4, and weight average molecular weight is 7.0 × 104g/mol。
Differential thermal analysis test, test result such as Fig. 4, Fig. 4 are carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains
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 obtains,
It is amorphous state, the present invention by curve 1 in Fig. 4 it is found that the cyclic olefine copolymer that the embodiment of the present invention 3 obtains does not have melting temperature
The glass transition temperature for the cyclic olefine copolymer that embodiment 3 obtains is 169 DEG C.The cycloolefin that the embodiment of the present invention 3 is obtained
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, example 4, example 5, example 6, reality
Thermogravimetric curve of the cyclic olefine copolymer that example 7 obtains in nitrogen, curve 1 is the cycloolefin that the embodiment of the present invention 3 obtains in 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 obtains is at 410 DEG C
Resolution ratio is 10%, thermal stability with higher.
The mechanical property for the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is tested, test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 3 obtains is 2.5%, tensile strength 25MPa, and stretch modulus is
1600MPa。
The transparency for the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is tested, test result such as Fig. 6, Fig. 6 are
The light transmittance for the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 obtain, curve 1 is that the present invention is real in Fig. 6
The light transmittance for the cyclic olefine copolymer that example 3 obtains is applied, it will be appreciated from fig. 6 that the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is saturating
Light rate > 91%.
Embodiment 4
At room temperature, in dry polymerisation bottle, 0.21gTCPD monomer and 0.04gNBMA monomer is added, 50ml is added
10min is sufficiently stirred in methylene chloride, claims 10mg (5ml methylene chloride is added in small ampulla in G1, and ultrasonic 3min makes sufficiently molten
Solution, imported into polymerization bottle, and polymerization starts, and in five minutes, solution gradually becomes orange-yellow from purple, continues stirring 7 hours, adds
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stirs half an hour.Reaction solution is poured into anhydrous methanol, is precipitated a large amount of
White polymer.The product being obtained by filtration is 12 hours dry to be put into vacuum drying oven after acetone washing 3 times at 40 DEG C.It weighs
0.25g polymer, yield 100%.
In dry autoclave, above-mentioned polymer 0.25g is sequentially added, 5% wet palladium carbon 1g (4eqv), a little BHT,
40ml cyclohexane solvent, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, reaction solution is slowly dropped to 100ml after filtering
In industrial alcohol, a large amount of white solids are precipitated, filtering is drained, and uses 40ml toluene to dissolve by heating again half gained white solid
Hour, after be slowly added drop-wise in 300ml industrial alcohol, filtering is drained, which is put into vacuum drying oven after being repeated 2 times, 60 DEG C
Lower drying 12 hours, obtains 0.24g product, yield 96%, and purity is greater than 99.9%.
The cyclic olefine copolymer obtained to the embodiment of the present invention 4 carries out nuclear magnetic resonance spectroscopy detection, testing result such as Fig. 7,
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 4 obtains, curve 1 in Fig. 4
The nuclear magnetic resonance spectroscopy of the polymeric reaction product obtained before hydrogenating for the embodiment of the present invention 4, curve 2 are 4 hydrogen of the embodiment of the present invention
The nuclear magnetic resonance spectroscopy of the cyclic olefine copolymer obtained after change, as seen from Figure 7, the polymerization that the embodiment of the present invention 4 obtains are anti-
Product double bond peak after hydrogenation is answered to completely disappear, hydrogenation effect is preferable.
Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 4 obtains is 1.4, and weight average molecular weight is 9.4 × 104g/mol。
Differential thermal analysis test, test result such as Fig. 4, Fig. 4 are carried out to the cyclic olefine copolymer that the embodiment of the present invention 4 obtains
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 obtains,
It is amorphous state, the present invention by curve 2 in Fig. 4 it is found that the cyclic olefine copolymer that the embodiment of the present invention 4 obtains does not have melting temperature
The glass transition temperature for the cyclic olefine copolymer that embodiment 4 obtains is 154 DEG C.The cycloolefin that the embodiment of the present invention 4 is obtained
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, example 4, example 5, example 6, reality
Thermogravimetric curve of the cyclic olefine copolymer that example 7 obtains in nitrogen, curve 2 is the cycloolefin that the embodiment of the present invention 4 obtains in 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 obtains is at 413 DEG C
Resolution ratio is 10%, thermal stability with higher.
The mechanical property for the cyclic olefine copolymer that the embodiment of the present invention 4 obtains is tested, test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 4 obtains is 2.8%, tensile strength 32MPa, and stretch modulus is
2200MPa。
Embodiment 5
At room temperature, in dry polymerisation bottle, 0.76gTCPD monomer and 0.25gNBMA monomer is added, 50ml is added
10min is sufficiently stirred in methylene chloride, claims 20mg (5ml methylene chloride is added in small ampulla in G1, and ultrasonic 3min makes sufficiently molten
Solution, imported into polymerization bottle, and polymerization starts, and in five minutes, solution gradually becomes orange-yellow from purple, continues stirring 7 hours, adds
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stirs half an hour.Reaction solution is poured into anhydrous methanol, is precipitated a large amount of
White polymer.The product being obtained by filtration is 12 hours dry to be put into vacuum drying oven after acetone washing 3 times at 40 DEG C.It weighs
1.01g polymer, yield 100%.
In dry autoclave, above-mentioned polymer 1.01g is sequentially added, 5% wet palladium carbon 4g (4eqv), a little BHT,
40ml cyclohexane solvent, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, reaction solution is slowly dropped to 100ml after filtering
In industrial alcohol, a large amount of white solids are precipitated, filtering is drained, and uses 40ml toluene to dissolve by heating again half gained white solid
Hour, after be slowly added drop-wise in 300ml industrial alcohol, filtering is drained, which is put into vacuum drying oven after being repeated 2 times, 60 DEG C
Lower drying 12 hours, obtains 9.9g product, yield 98.1%, and purity is greater than 99.9%.
The cyclic olefine copolymer obtained to the embodiment of the present invention 5 carries out nuclear magnetic resonance spectroscopy detection, testing result such as Fig. 8,
Fig. 8 is the hydrogen nuclear magnetic resonance spectrogram of polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 5 obtains, curve 1 in Fig. 8
The nuclear magnetic resonance spectroscopy of the polymeric reaction product obtained before hydrogenating for the embodiment of the present invention 5, curve 2 are 5 hydrogen of the embodiment of the present invention
The nuclear magnetic resonance spectroscopy of the cyclic olefine copolymer obtained after change, as seen from Figure 8, the polymerization that the embodiment of the present invention 5 obtains are anti-
Product double bond peak after hydrogenation is answered to completely disappear, hydrogenation effect is preferable.
Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 5 obtains is 1.4, and weight average molecular weight is 11.8 × 104g/mol。
Differential thermal analysis test, test result such as Fig. 4, Fig. 4 are carried out to the cyclic olefine copolymer that the embodiment of the present invention 5 obtains
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 obtains,
It is amorphous state, the present invention by curve 1 in Fig. 4 it is found that the cyclic olefine copolymer that the embodiment of the present invention 3 obtains does not have melting temperature
The glass transition temperature for the cyclic olefine copolymer that embodiment 5 obtains is 147 DEG C.The cycloolefin that the embodiment of the present invention 5 is obtained
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, example 4, example 5, example 6, reality
Thermogravimetric curve of the cyclic olefine copolymer that example 7 obtains in nitrogen, curve 3 is the cycloolefin that the embodiment of the present invention 5 obtains in 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 obtains is at 415 DEG C
Resolution ratio is 10%, thermal stability with higher.
The mechanical property for the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is tested, test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 5 obtains is 3.1%, tensile strength 36MPa, and stretch modulus is
2400MPa。
The transparency for the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is tested, test result such as Fig. 6, Fig. 6 are
The light transmittance for the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 obtain, curve 2 is that the present invention is real in Fig. 6
The light transmittance for the cyclic olefine copolymer that example 5 obtains is applied, it will be appreciated from fig. 6 that the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is saturating
Light rate > 91%.
Embodiment 6
At room temperature, in dry polymerisation bottle, 0.7gTCPD monomer and 0.3gNBMA monomer is added, 50ml bis- is added
Chloromethanes, is sufficiently stirred 10min, claim 20mg (5ml methylene chloride is added in small ampulla in G1, and ultrasonic 3min makes sufficiently to dissolve,
It imported into polymerization bottle, polymerization starts, and in five minutes, solution gradually becomes orange-yellow from purple, continues stirring 7 hours, is added
Vinyl ethyl ether EVE (500 equivalent) terminates polymerization, stirs half an hour.Reaction solution is poured into anhydrous methanol, is precipitated a large amount of white
Color polymer.The product being obtained by filtration is 12 hours dry to be put into vacuum drying oven after acetone washing 3 times at 40 DEG C.Weigh to obtain 1g
Polymer, yield 100%.
In dry autoclave, above-mentioned polymer 1g, 5% wet palladium carbon 4g (4eqv), a little BHT, 40ml are sequentially added
Cyclohexane solvent, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, and reaction solution is slowly dropped to 100ml industry after filtering
In ethyl alcohol, a large amount of white solids are precipitated, filtering is drained, and uses 40ml toluene to dissolve by heating again gained white solid half small
When, after be slowly added drop-wise in 300ml industrial alcohol, filtering is drained, which is put into vacuum drying oven after being repeated 2 times, at 60 DEG C
It is 12 hours dry, 0.96g product, yield 96% are obtained, purity is greater than 99.9%.
The cyclic olefine copolymer obtained to the embodiment of the present invention 6 carries out nuclear magnetic resonance spectroscopy detection, testing result such as Fig. 9,
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 6 obtains, curve 1 in Fig. 9
The nuclear magnetic resonance spectroscopy of the polymeric reaction product obtained before hydrogenating for the embodiment of the present invention 6, curve 2 are 6 hydrogen of the embodiment of the present invention
The nuclear magnetic resonance spectroscopy of the cyclic olefine copolymer obtained after change, as seen from Figure 9, the polymerization that the embodiment of the present invention 6 obtains are anti-
Product double bond peak after hydrogenation is answered to completely disappear, hydrogenation effect is preferable.
Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 6 obtains is 1.4, and weight average molecular weight is 13.9 × 104g/mol。
Differential thermal analysis test, test result such as Fig. 4, Fig. 4 are carried out to the cyclic olefine copolymer that the embodiment of the present invention 6 obtains
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 obtains,
It is amorphous state, the present invention by curve 4 in Fig. 4 it is found that the cyclic olefine copolymer that the embodiment of the present invention 6 obtains does not have melting temperature
The glass transition temperature for the cyclic olefine copolymer that embodiment 6 obtains is 131 DEG C.The cycloolefin that the embodiment of the present invention 6 is obtained
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, example 4, example 5, example 6, reality
Thermogravimetric curve of the cyclic olefine copolymer that example 7 obtains in nitrogen, curve 4 is the cycloolefin that the embodiment of the present invention 6 obtains in 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 obtains is at 415 DEG C
Resolution ratio is 10%, thermal stability with higher.
The mechanical property for the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is tested, test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 6 obtains is 3.7%, tensile strength 402MPa, and stretch modulus is
2400MPa。
Embodiment 7
At room temperature, in dry polymerisation bottle, 0.6gTCPD monomer and 0.44gNBMA monomer is added, 50ml is added
10min is sufficiently stirred in methylene chloride, claims 20mg (5ml methylene chloride is added in small ampulla in G1, and ultrasonic 3min makes sufficiently molten
Solution, imported into polymerization bottle, and polymerization starts, and in five minutes, solution gradually becomes orange-yellow from purple, continues stirring 7 hours, adds
Enter vinyl ethyl ether EVE (500 equivalent) and terminate polymerization, stirs half an hour.Reaction solution is poured into anhydrous methanol, is precipitated a large amount of
White polymer.The product being obtained by filtration is 12 hours dry to be put into vacuum drying oven after acetone washing 3 times at 40 DEG C.It weighs
1.04g polymer, yield 100%.
In dry autoclave, above-mentioned polymer 1.04g is sequentially added, 5% wet palladium carbon 4g (4eqv), a little BHT,
40ml cyclohexane solvent, boost 5.8Mp, is warming up to 130 DEG C, stirs 24 hours, reaction solution is slowly dropped to 100ml after filtering
In industrial alcohol, a large amount of white solids are precipitated, filtering is drained, and uses 40ml toluene to dissolve by heating again half gained white solid
Hour, after be slowly added drop-wise in 300ml industrial alcohol, filtering is drained, which is put into vacuum drying oven after being repeated 2 times, 60 DEG C
Lower drying 12 hours, obtains 1g product, yield 96.1%, and purity is greater than 99.9%.
The cyclic olefine copolymer obtained to the embodiment of the present invention 7 carries out nuclear magnetic resonance spectroscopy detection, testing result such as Figure 10,
Figure 10 is the hydrogen nuclear magnetic resonance spectrogram of polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 7 obtains, song in Figure 10
Line 1 is the nuclear magnetic resonance spectroscopy of the polymeric reaction product obtained before the embodiment of the present invention 7 hydrogenates, and curve 2 is the embodiment of the present invention 7
The nuclear magnetic resonance spectroscopy of the cyclic olefine copolymer obtained after hydrogenation, as seen from Figure 10, the polymerization that the embodiment of the present invention 7 obtains
Reaction product double bond peak after hydrogenation completely disappears, and hydrogenation effect is preferable.
Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 7 obtains, test result is this hair
The molecular weight distribution for the cyclic olefine copolymer that bright embodiment 7 obtains is 2.0, and weight average molecular weight is 15.5 × 104g/mol。
Differential thermal analysis test, test result such as Fig. 4, Fig. 4 are carried out to the cyclic olefine copolymer that the embodiment of the present invention 7 obtains
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 obtains,
It is amorphous state, the present invention by curve 5 in Fig. 4 it is found that the cyclic olefine copolymer that the embodiment of the present invention 7 obtains does not have melting temperature
The glass transition temperature for the cyclic olefine copolymer that embodiment 7 obtains is 105 DEG C.The cycloolefin that the embodiment of the present invention 5 is obtained
Copolymer carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3, example 4, example 5, example 6, reality
Thermogravimetric curve of the cyclic olefine copolymer that example 7 obtains in nitrogen, curve 5 is the cycloolefin that the embodiment of the present invention 7 obtains in 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 obtains is at 418 DEG C
Resolution ratio is 10%, thermal stability with higher.
The mechanical property for the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is tested, test result is the present invention
The elongation at break for the cyclic olefine copolymer that embodiment 7 obtains is 5.4%, tensile strength 50MPa, and stretch modulus is
2800MPa。
The transparency for the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is tested, test result such as Fig. 6, Fig. 6 are
The light transmittance for the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 obtain, curve 3 is that the present invention is real in Fig. 6
The light transmittance for the cyclic olefine copolymer that example 7 obtains is applied, it will be appreciated from fig. 6 that the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is saturating
Light rate > 91%.
Specifically, the reaction condition that feeds intake in 3~embodiment of the embodiment of the present invention 7 is shown in Table 1；
Table 1
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of cyclic olefine copolymer has structure shown in formula (I),
Wherein, 140≤m≤220,170≤n≤280,1≤x≤4；
The molecular weight distributing index of the cyclic olefine copolymer is 1.4~2.0.
2. cyclic olefine copolymer according to claim 1, which is characterized in that the m is 170≤m≤190.
3. cyclic olefine copolymer according to claim 1, which is characterized in that the n is 170≤n≤190.
4. cyclic olefine copolymer according to claim 1, which is characterized in that the x is 1≤x≤2.
5. a kind of preparation method of cyclic olefine copolymer, comprising:
1) compound of the compound and formula (III) structure that will have formula (II) structure is under the catalyst action of formula (IV) structure
Polymerization reaction 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, which is characterized in that the compound of formula (II) structure and the formula
(III) molar ratio of the compound of structure is (9~1): 1.
7. preparation method according to claim 5, which is characterized in that the solvent of the polymerization reaction is the alkane of C1~C15
Hydrocarbon, the halogenated hydrocarbons of C1~C15, the cycloalkane of C3~C15 or C6~C15 aromatic hydrocarbons.
8. preparation method according to claim 5, which is characterized in that the temperature of the polymerization reaction is 10~50 DEG C, institute
The time for stating polymerization reaction is 4~12h.
9. preparation method according to claim 5, which is characterized in that the compound and formula (III) of formula (II) structure
The molar 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, which is characterized in that the heterogeneous metallic catalyst is 5~10% wet
Palladium carbon, 10%Pd/C, Pd/C/BaSO4Or Pt/SiO2。
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| CN104910329A (en) * | 2015-06-04 | 2015-09-16 | 天津大学 | Polar cycloolefin copolymer and preparation method thereof |
| CN105348442A (en) * | 2015-10-26 | 2016-02-24 | 中国科学院长春应用化学研究所 | Cycloolefine copolymer and preparation method thereof |
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| CN105418863A (en) * | 2014-09-12 | 2016-03-23 | Jsr株式会社 | Block copolymer and preparation method thereof and membrane |
| CN104910329A (en) * | 2015-06-04 | 2015-09-16 | 天津大学 | Polar cycloolefin copolymer and preparation method thereof |
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