CN117777412A - Cycloolefin composition and application thereof - Google Patents
Cycloolefin composition and application thereof Download PDFInfo
- Publication number
- CN117777412A CN117777412A CN202311836268.4A CN202311836268A CN117777412A CN 117777412 A CN117777412 A CN 117777412A CN 202311836268 A CN202311836268 A CN 202311836268A CN 117777412 A CN117777412 A CN 117777412A
- Authority
- CN
- China
- Prior art keywords
- cycloolefin
- composition
- cycloolefin copolymer
- catalyst
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 150000001925 cycloalkenes Chemical class 0.000 title claims abstract description 61
- 229920001577 copolymer Polymers 0.000 claims abstract description 142
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 150000004678 hydrides Chemical class 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 56
- 230000003287 optical effect Effects 0.000 claims description 37
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 10
- -1 alicyclic hydrocarbon Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- 239000003759 ester based solvent Substances 0.000 claims description 6
- 239000004210 ether based solvent Substances 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000007868 Raney catalyst Substances 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 17
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002834 transmittance Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 238000003756 stirring Methods 0.000 description 37
- 238000010438 heat treatment Methods 0.000 description 23
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 22
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 22
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 21
- 229910001873 dinitrogen Inorganic materials 0.000 description 17
- 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 14
- 239000011521 glass Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 11
- 150000002978 peroxides Chemical class 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 239000012986 chain transfer agent Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000007142 ring opening reaction Methods 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 1
- ZVENKBGRIGHMRG-UHFFFAOYSA-M carbon monoxide chloro(hydrido)ruthenium triphenylphosphane Chemical compound [C-]#[O+].[H][Ru]Cl.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 ZVENKBGRIGHMRG-UHFFFAOYSA-M 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011984 grubbs catalyst Substances 0.000 description 1
- PKMNZOFQIRXQDO-UHFFFAOYSA-N heptane;hexane Chemical compound CCCCCC.CCCCCCC PKMNZOFQIRXQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a cycloolefin composition and application thereof. The cycloolefin composition includes compounds represented by formula D and formula C. According to the invention, the cycloolefin composition is used as a starting material, ring-opening metathesis copolymerization reaction can be realized under the action of a proper catalyst, the glass transition temperature of the obtained cycloolefin copolymer is 185-210 ℃, the thermal deformation temperature is 158-178 ℃, the light transmittance is 91%, the PDI is 1.75-2.30, the molecular weight distribution is uniform, and the cycloolefin copolymer hydride is obtained after further hydrogenation reaction, and the cycloolefin copolymer hydride has excellent heat resistance, excellent polymer light transmittance and proper water absorption and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of cycloolefin polymers, and particularly relates to a cycloolefin composition and application thereof.
Background
The cyclic olefin copolymer obtained by copolymerizing the cyclic olefin has excellent optical properties, mechanical properties, thermal properties and other properties, and has high glass transition temperature, and is widely applied to the material fields of DVD lenses, imaging lenses of smart phones, storage discs, optical fibers and the like.
Currently, polyolefin-type optical resin materials obtained from cyclic olefin-based copolymers having the above-mentioned excellent properties are an important development direction in recent years, and such resin materials are mainly prepared from cycloolefin compositions by ring-opening metathesis polymerization followed by hydrogenation. Thus, the properties and preparation of cycloolefin compositions are critical.
CN109134755a discloses a heat-resistant cycloolefin copolymer and a preparation method thereof, in particular to a copolymer of norbornene derivative 5-ethylidene-2-norbornene, 1-hexene-and 1-octene-and other long chain alpha olefins, the preparation method of the invention has the advantages of mild reaction condition, short period, simple operation and the like, and the catalyst Cpket used for the copolymerization has very good catalytic activity and thermal stability, and has great industrial application value and good application prospect. However, the cycloolefin copolymer obtained by the present invention needs to be further improved in heat resistance to meet the demands of some high-grade electronic devices or display devices.
CN106905483B discloses a cycloolefin copolymer, which is obtained by copolymerization of a comonomer under the action of a metathesis polymerization catalyst, wherein the comonomer is cycloolefin and bismaleimide, and the glass transition temperature Tg of the obtained cycloolefin copolymer is higher than 144 ℃. The invention also discloses a preparation method of the cycloolefin copolymer, and the bismaleimide with a specific structure is added into cycloolefin monomers, so that the heat resistance of the cycloolefin copolymer obtained by polymerization can be improved, the copolymer can be prepared under relatively mild conditions, and the production cost of the cycloolefin copolymer is reduced. However, the reaction raw materials of the invention have complex structure, are not easy to obtain, have a glass transition temperature higher than 144 ℃, cannot meet the requirements of the existing high-grade electronic equipment, and are required to further improve heat resistance and transparency.
CN109593160a discloses a preparation method of cycloolefin copolymer, which belongs to the field of organic materials, the preparation steps of the invention are that inert organic solvent, cycloolefin and ethylene are respectively added into a reactor under the conditions of temperature of 40-95 ℃ and pressure of 0.1-5.0 MPa; wherein the molar ratio of cycloolefin to ethylene is 1-50:1; then adding or not adding a chain transfer agent; finally, adding a catalyst to carry out solution polymerization reaction, wherein the polymerization reaction time is 0.1-10h. The polymer prepared by the method has high activity, and the prepared ethylene-cycloolefin copolymer has lower molecular weight than ethylene-cycloolefin copolymers prepared by other catalyst systems. But the heat resistance and transparency of the resulting polymer are poor.
Disclosure of Invention
In view of the above, the present invention is directed to a cycloolefin composition and an application thereof. The cycloolefin composition has easily available raw materials, and the prepared cycloolefin copolymer hydride has excellent heat resistance and light transmittance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a cycloolefin composition comprising a compound represented by formula C and a compound represented by formula D;
wherein, in the formula C,represents an alkyl chain of 3 to 7 carbons, and at least one double bond is present in the alkyl chain;
the mass percentage of the formula D in the cycloolefin composition is 0.01-3.0%.
Preferably, the mass percentage of the compound (1) in the cycloolefin composition is 0.05 to 1.5%.
In a second aspect, the present invention provides a composition for optical materials comprising the above cycloolefin composition, and other olefin components.
Preferably, the mass percentage of the other olefin components in the composition for optical material is 5-95%.
Preferably, the other olefin component includes, but is not limited to, any one or more of 1-octene, 1-hexene, norbornene, a compound represented by formula a, or a compound represented by formula B;
wherein R is 1 ～R 4 Represents an alkyl chain of 3 to 7 carbons, and at least one double bond is present in the alkyl chain.
In a third aspect, the present invention also provides a cycloolefin copolymer obtained by polymerizing the composition for an optical material.
In a fourth aspect, the present invention also provides a preparation method of the above cycloolefin copolymer, comprising the steps of:
the composition for the optical material is prepared by polymerization reaction in the presence of a catalyst and a solvent.
Preferably, the catalyst is selected from any one or more of Grubbs I, grubbs II or Grubbs III.
Preferably, the solvent is selected from any one or more of aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, carboxylic acid ester solvents or ether solvents.
Preferably, the mass percentage of the catalyst is 0.001 to 0.2% of the total mass of the composition for optical material.
Preferably, the mass percentage of the solvent is 60 to 95% of the total mass of the cycloolefin composition and the solvent in the composition for an optical material.
Preferably, the temperature of the polymerization reaction is 50-180 ℃ and the time is 0.1-10h.
In a fifth aspect, the present invention also provides a cycloolefin copolymer hydride obtained by hydrogenating the cycloolefin copolymer.
Preferably, the weight average molecular weight of the cycloolefin copolymer hydride is 5000 to 10000; the glass transition temperature of the cycloolefin copolymer hydride is 110-230 ℃; the hydrogenation rate of the cycloolefin copolymer hydride is 90% -100%.
In a sixth aspect, the present invention also provides a method for preparing the cycloolefin copolymer hydride, wherein the cycloolefin copolymer is obtained by hydrogenation in the presence of a catalyst and a solvent.
Preferably, the catalyst is selected from Raney nickel and/or palladium on carbon.
Preferably, the solvent is selected from any one or more of aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, carboxylic acid ester solvents or ether solvents.
Preferably, the catalyst is used in an amount of 0.5 to 5% by mass of the whole reaction system.
Preferably, the mass percentage of the solvent is 60 to 95% of the total mass of the cycloolefin composition and the solvent in the composition for an optical material.
Preferably, the temperature of the hydrogenation reaction is 150-200 ℃ and the time is 2-12 h.
In a seventh aspect, the present invention also provides an optical material comprising the above cycloolefin copolymer hydride.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a cycloolefin composition, which comprises compounds shown in a formula C and a formula D, and the cycloolefin composition is prepared by ring-opening metathesis polymerization and hydrogenation of four cycloolefin monomers shown in a formula A, a formula B, a formula C and a formula D, and belongs to non-crystalline polymers. Compared with the common cycloolefin copolymer, the glass transition temperature and the thermal deformation temperature are wide in regulation range, the heat resistance is excellent, the light transmittance of the polymer is excellent, the polymer has proper water absorption and mechanical properties, raw materials are easy to obtain, the glass transition temperature of the cycloolefin copolymer is 185-210 ℃, the thermal deformation temperature is 158-178 ℃, the light transmittance reaches 91%, the PDI is 1.75-2.30, and the molecular weight distribution is uniform;
the invention takes four cycloolefin monomers of formula A, formula B, formula D and formula C as starting materials, ring-opening metathesis copolymerization can be realized under the action of a proper catalyst, and the prepared copolymer main chain retains a large number of double bonds, and the existence of the double bonds can lead the copolymer to be not yellowing-resistant and not heat-resistant, so that the unsaturated double bonds are required to be converted into saturated carbon-carbon bonds through further hydrogenation reaction, thereby obtaining the cycloolefin copolymer hydride with excellent heat resistance.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In view of the deficiencies of the prior art, the present invention provides a cycloolefin composition comprising a compound represented by formula C and a compound represented by formula D;
wherein, in the formula C,represents an alkyl chain of 3 to 7 carbons, which may be any of 3, 4, 5, 6 or 7 carbons, and at least one double bond is present in the alkyl chain.
In some embodiments of the invention, the cycloolefin composition has a mass% of the formula D of 0.01 to 3.0%, preferably 0.05 to 1.5%. The cycloolefin composition provided by the invention can obviously improve the softening temperature and the impact resistance of a resin material on the basis of conventional cycloolefins, especially on the basis of containing the formula C, so that the content of the formula D reaches a certain range.
The invention provides a composition for optical materials, which comprises the cycloolefin composition and other olefin components. The other olefin component includes, but is not limited to, any one or more of 1-octene, 1-hexene, norbornene, a compound represented by formula a, or a compound represented by formula B, preferably includes any one or more of norbornene, a compound represented by formula a, or a compound represented by formula B, more preferably tetracyclododecene and dicyclopentadiene. In some embodiments of the present invention, the amount of the other olefin component in the composition for optical material is 5 to 95% by mass, preferably 20 to 70% by mass.
Wherein R is 1 ～R 4 Represents an alkyl chain of 3 to 7 carbons, which may be 3, 4, 5, 6, 7 carbons, and at least one double bond is present in the alkyl chain.
In a third aspect, the present invention also provides a cycloolefin copolymer obtained by polymerizing the composition for an optical material.
In some embodiments provided herein, it is preferred to obtain a cycloolefin copolymer from four cycloolefin monomers of the formula A, the formula B, the formula D and the formula C by ring opening metathesis polymerization and hydrogenation.
The cycloolefin copolymer provided by the invention is an amorphous polymer obtained by ring-opening metathesis polymerization and hydrogenation of four cycloolefin monomers including a formula A, a formula B, a formula D and a formula C. The ester bond and the alicyclic group in the formula D provide more rigid groups for the copolymer, namely, the copolymer is endowed with higher glass transition temperature and heat distortion temperature, but if the content of the formula D is too high, the copolymer becomes brittle, so that the ratio of four structural units is controlled within a proper range by being matched with other cycloolefin monomers, and the excellent heat resistance of the polymer is endowed, and meanwhile, the mechanical properties and other properties of the polymer are not influenced.
Compared with the common cycloolefin copolymer, the cycloolefin copolymer provided by the invention has the advantages of wide glass transition temperature and thermal deformation temperature regulation range, excellent heat resistance, excellent polymer light transmittance, low water absorption and proper mechanical properties, and easily available raw materials.
The invention also provides a preparation method of the cycloolefin copolymer, which comprises the following steps:
the composition for the optical material is prepared by polymerization reaction in the presence of a catalyst and a solvent.
In the present invention, the composition for an optical material is preferably polymerized in the presence of a catalyst, a solvent and a chain transfer agent to obtain a cycloolefin copolymer. Wherein the catalyst is selected from any one or more of Grubbs 1st, grubbs 2nd or Hoveyda-Grubbs. The solvent is selected from any one or more of aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, carboxylic ester solvents or ether solvents. Wherein the mass percentage of the catalyst is 0.001-0.2% of the total mass of the composition for optical material, preferably 0.005-0.1%. The mass percentage of the solvent is 60 to 95% of the total mass of the cycloolefin composition and the solvent in the composition for an optical material, and preferably 70 to 80%. The polymerization reaction temperature is 50-180 ℃, preferably 80-120 ℃ and the time is 0.1-10h, preferably 2-5 h.
In some embodiments of the present invention, the method for preparing the cycloolefin copolymer includes the steps of:
(1) Mixing the cycloolefin composition, the solvent and the chain transfer agent, stirring for the first time, adding the catalyst 1, stirring for the second time, adding the chain terminator, and stirring for the third time to obtain cycloolefin ring-opening polymer reaction liquid;
(2) Adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid, stirring uniformly, putting into a high-pressure reaction kettle, using nitrogen to replace air in the kettle, pressurizing by using hydrogen, stirring for the fourth time, heating, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, releasing pressure, and discharging to obtain cycloolefin copolymer solution;
(3) Mixing the cycloolefin copolymer solution obtained in the step (2) with a water-soluble extractant solution, stirring and heating for the fifth time, adding a peroxide water solution, stirring for the sixth time and reacting at constant temperature, cooling, and reserving a cycloolefin copolymer solution phase;
(4) Adding a precipitant into the cycloolefin copolymer solution phase obtained in the step (3) for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.
In the present invention, the cycloolefin composition and the solvent in the step (1) are described in the above-mentioned related contents, and are not described in detail herein. The cycloolefin composition according to the present invention is preferably 5 to 40% by mass of the solvent because the concentration of the cycloolefin composition is too low, the production efficiency is too low, the concentration of the cycloolefin composition is too high, the solution viscosity is too high after the ring-opening metathesis polymerization, gelation is easily generated, and the hydrogenation reaction is difficult.
The chain transfer agent comprises an alpha-olefin compound, preferably any one or a combination of at least two of 1-pentene, 1-hexene, 1-heptene or 1-octene. The molar ratio of the chain transfer agent to the cycloolefin composition is 1 (100 to 1000), for example 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, etc. In the present invention, the ring-opening metathesis polymerization in step (1) is preferably carried out under nitrogen protection. In the present invention, it is preferable that the cycloolefin composition, the solvent and the chain transfer agent are mixed under the protection of nitrogen gas, and then stirred for the first time while controlling the temperature at 0 to 30℃such as 1℃and 5℃and 10℃and 15℃and 20℃and 25℃and 28 ℃. The time for the first stirring is preferably 10 to 120 minutes, more preferably 30 to 60 minutes.
After the end of the first stirring, the catalyst 1 is preferably dissolved in a solvent and added dropwise to the reaction system. The catalyst 1 comprises Grubbs 1st and Grubbs 2 nd Or any one or more of Hoveyda-Grubbs. The mass ratio of the catalyst 1 to the cycloolefin composition is 1 (10) 4 ～10 5 ) For example, 1:11000, 1:15000, 1:16000, 1:17000, 1:18000, 1:20000, 1:30000, 1:40000, 1:50000, 1:60000, 1:70000, 1:80000, 1:90000, and the like. The solvent is selected from hydrocarbons such as pentane, hexane heptane, octane, etc., and benzene, tolueneAromatic solvents such as chlorobenzene. Wherein the temperature is preferably controlled to be not higher than 35℃such as 15℃and 16℃and 17℃and 18℃and 19℃and 20℃and 21℃and 22℃and 23℃and 24℃and 25℃and 26℃and 27℃and 28℃and 29℃and 30℃and 31℃and 32℃and 33℃and 34℃in the course of adding the catalyst 1. After the addition of catalyst 1 is completed, a second stirring is preferably carried out. The second stirring time is 0.5-2 h, for example 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, etc.
The invention preferably uses the specific Grubbs catalyst to catalyze the ring-opening metathesis polymerization, the catalyst has high activity, low catalyst addition amount and high cycloolefin conversion rate, the catalyst can directly catalyze hydrogenation reaction without further treatment after reaction, and the optical cycloolefin copolymer can be prepared through simple post treatment, and the whole process is simple and easy to operate.
In the present invention, the ring-opening metathesis polymerization in step (1) is terminated by a chain terminator, which may be specifically selected from olefins such as 1-octene, 1-hexene or 1-heptene. The molar ratio of the chain terminator to the cycloolefin composition is 1 (1000 to 10000), for example 1:2000, 1:3000, 1:4000, 1:5000, 1:6000, 1:7000, 1:8000, 1:9000 and the like. In the present invention, it is preferable to add the chain terminator to the mixture after completion of the second stirring and to perform the third stirring. The third stirring time is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 25min, 26min, 28min, 29min, etc.
In the present invention, step (1) preferably specifically includes: vacuumizing a reaction bottle, introducing nitrogen to replace air, adding the cycloolefin composition, the solvent and the chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving the catalyst 1 in the solvent, dripping the solvent into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dripping, adding the chain terminator, and stirring for the third time for 10-30 minutes to obtain cycloolefin ring-opening polymer reaction liquid.
Then, according to the present invention, step (2) is performed. The step (2) is preferably to add a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid for hydrogenation reactionShould be. The catalyst 2 comprises a homogeneous catalyst comprising RuHCl (CO) (PPh 3 ) 3 And/or Rh (PPh) 3 ) 3 Cl, preferably Rh (PPh 3) 3 Cl and PPh 3 Is matched with PPh 3 Is added to Rh (PPh) 3 ) 3 The mass of Cl is 1 to 5 times, for example, 2 times, 3 times, 4 times, etc. The catalyst 2 is added in an amount of 0.05 to 0.5% by mass, for example, 0.06%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.48% by mass, etc., based on the cycloolefin composition. In the present invention, the cycloolefin ring-opening polymer reaction solution and the catalyst 2 are preferably stirred uniformly and then put into a high-pressure reaction vessel, the air in the vessel is replaced with nitrogen, and then pressurized with hydrogen, preferably to 5 to 10MPa, for example, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa, 9.5MPa and the like. And stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, releasing pressure, and discharging to obtain the cycloolefin copolymer solution.
Then, according to the present invention, step (3) is carried out, that is, the cycloolefin copolymer solution obtained in step (2) is preferably mixed with the water-soluble extractant solution, stirred and warmed for the fifth time, the peroxide aqueous solution is added, stirred and reacted at a constant temperature for the sixth time, cooled, and the cycloolefin copolymer solution phase is retained. The step (3) aims at removing the catalyst, and the system consisting of the water-soluble extractant/peroxide is used for participating in the catalyst removal reaction together, so that the effect is excellent, the removal rate can reach 99.0% at the highest, and the highest recovery rate of noble metal and the best polymer product quality are realized.
In the present invention, it is preferable to mix the cycloolefin copolymer solution with a solution of a water-soluble extractant including any one or more of formic acid, acetic acid, ethylenediamine, propylenediamine, monoethanolamine, diethanolamine or triethanolamine, preferably triethanolamine. The mass concentration of the water-soluble extractant in the water-soluble extractant solution is 2-20%, such as 3%, 4%, 5%, 8%, 10%, 12%, 14%, 16%, 18% and the like. The amount of the water-soluble extractant solution added is 25 to 100% by mass, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% by mass, of the cycloolefin copolymer solution obtained in the step (2). Then, the mixture is stirred for the fifth time and heated, and the target temperature for heating is preferably 80 to 110 ℃, for example, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃, or the like. An aqueous peroxide solution is then added, the peroxide in the aqueous peroxide solution comprising an organic peroxide compound and/or an inorganic peroxide, preferably any one or a combination of at least two of hydrogen peroxide, peracetic acid and ammonium persulfate, preferably hydrogen peroxide. In the present invention, the mass concentration of the peroxide in the aqueous peroxide solution is preferably 5 to 30%, for example, 6%, 8%, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 25%, 28%, etc. The amount of the peroxide aqueous solution to be added is 25 to 100% by mass, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% by mass, of the cycloolefin copolymer solution obtained in the step (2). Then, a sixth stirring and a constant temperature reaction are performed, and cooling is performed to retain the cycloolefin copolymer solution phase. The reaction time at constant temperature is 0.5-2 h, for example 0.6h, 0.7h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, etc.
In the present invention, the step (3) specifically includes the steps of: adding a water-soluble extractant solution into the cycloolefin copolymer solution obtained in the step (2), stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting at constant temperature for 0.5-2 h, cooling, and reserving a cycloolefin copolymer solution phase.
Then, according to the present invention, after the completion of the step (3), the step (4) is performed, preferably, a precipitant is added to the cycloolefin copolymer solution phase obtained in the step (3) to precipitate, and the solid phase is collected, washed and dried to obtain the cycloolefin copolymer. The precipitating agent preferably comprises any one or more of isopropanol, methanol, ethanol or acetone.
In summary, in some embodiments of the present invention, the preparation method of the cycloolefin copolymer includes the steps of:
(1) Vacuumizing a reaction bottle, introducing nitrogen to replace air, adding the cycloolefin composition, other olefin components, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the solvent into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding, adding a chain terminator, and stirring for the third time for 10-30 minutes to obtain cycloolefin ring-opening polymer reaction liquid;
(2) Adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid, stirring uniformly, putting into a high-pressure reaction kettle, using nitrogen to replace air in the kettle, using hydrogen to pressurize to 5-10 MPa, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, releasing pressure, and discharging to obtain cycloolefin copolymer solution;
(3) Adding a precipitant into the cycloolefin copolymer solution phase for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.
The invention also provides a cycloolefin copolymer hydride which is obtained by hydrogenating the cycloolefin copolymer. Wherein the weight average molecular weight of the cycloolefin copolymer hydride is preferably 5000 to 10000, more preferably 6000 to 8000; the glass transition temperature of the cycloolefin copolymer hydride is preferably 110 to 230 ℃, more preferably 140 to 200 ℃; the hydrogenation rate of the cycloolefin copolymer is preferably 90% to 100%, more preferably 99% to 100%.
The invention also provides a preparation method of the cycloolefin copolymer hydride, and the cycloolefin copolymer is obtained by hydrogenation reaction in the presence of a catalyst and a solvent.
Wherein the catalyst is selected from Raney nickel and/or palladium carbon. The solvent is selected from any one or more of aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, carboxylic ester solvents or ether solvents. The mass percentage of the catalyst is preferably 0.5 to 5% of the whole reaction system, more preferably 1 to 3%. The mass percentage of the solvent is 60-95% of the total mass of the cycloolefin composition and the solvent in the composition for optical materials. The temperature of the hydrogenation reaction is preferably 50 to 180 ℃, more preferably 80 to 120 ℃; the time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.
In some embodiments of the invention, it is preferred to add the resulting cycloolefin copolymer and catalyst to the glass reactor using a stirrer. Then, a solvent is added, and hydrogenation is performed at a certain temperature. Pouring the hydrogenation reaction solution into a large amount of precipitant (such as methanol), completely precipitating cycloolefin copolymer hydride, filtering, and drying.
The invention also provides a molding material comprising the cycloolefin copolymer hydride. In the present invention, the molding material is preferably a medical packaging material and/or an optical material.
The invention also provides an optical material which is obtained by processing and molding (such as film forming and the like) the cycloolefin copolymer hydride.
Taking film forming as an example, the method for processing the cycloolefin copolymer into a film comprises the following steps:
taking a certain amount of cycloolefin copolymer hydride in a sample bottle, heating and dissolving the cycloolefin copolymer hydride in a solvent to prepare a solution with the mass concentration of 5-15%, pouring the solution onto a clean glass plate, casting the solution into a film, heating the film in an oven at 80 ℃ for 4-6 hours, volatilizing most of the solvent, heating the film in a vacuum drying oven at 70 ℃ for 8-12 hours, naturally cooling the film to room temperature, placing the glass plate in deionized water, removing the film, and drying the film in an oven at 100 ℃ to prepare the heat-resistant cycloolefin copolymer hydride optical film.
The invention also provides an application of the optical material, and the optical material is applied to an optical device. The optical device preferably comprises a lens or a liquid crystal display.
Further, the optical material can be also applied to a light guide plate or a polarizing film of an optical device.
In order to further illustrate the present invention, the following examples are provided. The reagents and starting materials used in the following examples of the present invention are all commercially available. Wherein TCD is tetracyclododecene, DCPD is dicyclopentadiene, grubbs 1st is a first generation platinum catalyst.
The glass transition temperature T is as follows g The testing method comprises the following steps: a DSC differential scanning calorimeter (model: DSC200F3, manufacturer: german Chi Co.) is adopted, the sample amount is 10mg, and the test temperature interval is 30-300 ℃.
The following relates to a water absorption test method: GB/T1034-2008;
the following refractive index test method is involved: GB/T614-2021;
the following molecular weight Mw and molecular weight distribution PDI test methods are involved: a high temperature gel permeation chromatograph (model: agilent PL gel MIXED-BLS, manufacturer: agilent, md.) was used, the mobile phase was 1,2, 4-trichlorobenzene, the column temperature was 150deg.C, the flow rate was 1mL/min, the sample injection volume was 200. Mu.L, and the standard was narrow-distribution polystyrene.
Example 1
Mixing C-1 obtained by rectification with formula D to obtain 0.01%,0.1%,1%,3%,5% of formula D, denoted as A 1 ,A 2 ,A 3 ,A 4 ,A 5 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the rectified C-2, C-3, C-4, C-5 with formula D to obtain 1% of formula D mixture, denoted as B 1 ,B 2 ,B 3 ,B 4 。
1.1 polymerization reaction
The polymerization reactor is pumped four times by high-purity nitrogen, the air in the reactor is discharged, then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD (TCD) are added under the protection of nitrogen, 13.2g (0.1 mol) of DCPD and A 1 19.8g of Grubbs 1st is dissolved in 10mL of toluene after stirring is started, and the mixture is placed in a material transferring tank after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; 7.8mg of Grubbs 1st was dissolved in 10mL of toluene, and the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70℃for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, ethanol is used for stopping the reaction, white powdery solid is precipitated, ethanol is used for washing and suction filtration,the cycloolefin copolymer was obtained and dried in vacuo at 70℃for 8h. The cycloolefin copolymer was 46.55g and had a weight average molecular weight of 48641.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 2
1.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and A were added under the protection of nitrogen gas 2 19.8g of Grubbs 1st was dissolved in 10mL of toluene with stirring, and placed in a transfer pot after stirring thoroughly; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The cycloolefin copolymer was 46.1g and had a number average molecular weight of 46572.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 3
1.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and A were added under the protection of nitrogen gas 3 19.8g of the mixture was stirred and then successively added (C) 2 H 5 ) 3 Al 22.8mg(0.2mmol)12.02mg (0.2 mmol) of isobutanol; moCl is added to 5 54.64mg (2.0 mmol) of the mixture is dissolved in 26g of toluene, and the mixture is placed in a material transfer pot after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; 7.8mg of Grubbs 1st was dissolved in 10mL of toluene, and the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70℃for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The cycloolefin copolymer was 45.6g and had a number average molecular weight of 44867.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 4
1.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and A were added under the protection of nitrogen gas 4 19.8g of Grubbs 1st is dissolved in 10mL of toluene after stirring is started, and the mixture is placed in a material transferring tank after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. 44.6g of a cycloolefin copolymer was obtained, and the number average molecular weight was 45394.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 5
1.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and A were added under the protection of nitrogen gas 5 19.8g of Grubbs 1st is dissolved in 10mL of toluene after stirring is started, and the mixture is placed in a material transferring tank after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The cycloolefin copolymer was 46.3g and had a number average molecular weight of 46184.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 6
1.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and B were added under the protection of nitrogen gas 1 19.8g of Grubbs 1st is dissolved in 10mL of toluene after stirring is started, and the mixture is placed in a material transferring tank after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The cycloolefin copolymer was 46.7g and had a number average molecular weight of 48246.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 7
7.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and B were added under the protection of nitrogen gas 2 19.8g of Grubbs 1st is dissolved in 10mL of toluene after stirring is started, and the mixture is placed in a material transferring tank after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The cycloolefin copolymer was 48.1g and had a number average molecular weight of 46418.
7.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 8
8.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and B were added under the protection of nitrogen gas 3 19.8g of Grubbs 1st is dissolved in 10mL of toluene after stirring is started, and the mixture is placed in a material transferring tank after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; transferring catalyst to reaction by feed pumpIn the reactor, the reactor was then warmed to 70℃for 3h, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The cycloolefin copolymer was 48.1g and had a number average molecular weight of 46418.
8.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Example 9
9.1A polymerization reactor was evacuated four times with high purity nitrogen gas, and the air in the reactor was evacuated, and then 120g of anhydrous toluene and 16.0g (0.1 mol) of TCD, 13.2g (0.1 mol) of DCPD and B were added under the protection of nitrogen gas 4 19.8g of Grubbs 1st is dissolved in 10mL of toluene after stirring is started, and the mixture is placed in a material transferring tank after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The cycloolefin copolymer was 48.3g and had a number average molecular weight of 46468.
9.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol, and the completely precipitated cycloolefin copolymer hydride was then filtered off and then dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%.
Comparative example 1
1.1 the polymerization reactor was first evacuated four times with high purity nitrogen and the air in the reactor was vented, howeverThen 120g of anhydrous toluene and 16.0g (1.0 mol) of TCD, 13.2g (1.0 mol) of DCPD and 19.8g of C-2 are added under the protection of nitrogen, stirring is started, and then (C) 2 H 5 ) 3 Al 22.8mg (0.2 mmol), isobutanol 12.02mg (0.2 mmol); moCl is added to 5 54.64mg (2.0 mmol) of the mixture is dissolved in 26g of toluene, and the mixture is placed in a material transfer pot after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The mass of the cycloolefin copolymer was 47.6g and the number average molecular weight was 43289.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol and the completely precipitated cycloolefin copolymer hydride was filtered off and dried at 40℃for 24 hours. The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%. .
Comparative example 2
11 polymerization reaction kettle is pumped four times with high-purity nitrogen, the air in the kettle is discharged, then 120g of anhydrous toluene, 16.0g (1.0 mol) of TCD-C, 13.2g (1.0 mol) of DCPD-C and norbornene, 9.4g of norbornene are added under the protection of nitrogen, stirring is started, and then (C) 2 H 5 ) 3 Al 22.8mg (0.2 mmol), isobutanol 12.02mg (0.2 mmol); moCl is added to 5 54.64mg (2.0 mmol) of the mixture is dissolved in 26g of toluene, and the mixture is placed in a material transfer pot after being fully stirred until the mixture is completely dissolved; the material transferring tank is connected with the reaction kettle through a feed pump; the catalyst was transferred into the reaction vessel by a feed pump, and then the reaction vessel was warmed to 70 ℃ for 3 hours, stopped heating and cooled to 25 ℃. After the polymerization reaction is finished, the reaction is stopped by ethanol, white powdery solid is precipitated, the cyclic olefin copolymer is obtained by washing and suction filtration by ethanol, and the cyclic olefin copolymer is dried in vacuum at 70 ℃ for 8 hours. The mass of the cycloolefin copolymer was 37.6g and the number average molecular weight was 45621.
1.2 to a glass reactor were added 15g of the cycloolefin copolymer obtained and 0.5g of 10% palladium on charcoal with a stirrer. Then, 500ml of paraxylene was added, and hydrogenation reaction was performed at 125℃for 5 hours. The hydrogenation reaction solution was poured into a large amount of methanol and the completely precipitated cycloolefin copolymer hydride was filtered off and dried at 40℃for 24 hours.
The hydrogenation rate of the obtained cycloolefin copolymer hydride is more than 99%. When the melting point of the hydride was measured, the melting point was 259 ℃, the amount of heat of fusion was 62J/g, and the onset temperature of melting was 268 ℃.
Performance testing
The properties of the cycloolefin copolymer hydrides obtained in examples and comparative examples were examined and are shown in Table 1:
TABLE 1
As can be seen from the data in Table 1, the water absorption of the cycloolefin copolymer is 0.06%, the refractive index is more than 1.53nD, and the cycloolefin copolymer is obviously superior to other cycloolefin copolymer, and completely meets the requirements of subsequent processing and use.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (13)
1. A cycloolefin composition comprising a compound represented by the formula C and a compound represented by the formula D;
wherein, in the formula C,represents an alkyl chain of 3 to 7 carbons, and at least one double bond is present in the alkyl chain;
the mass percentage of the formula D in the cycloolefin composition is 0.01-3.0%.
2. The cycloolefin composition according to claim 1, characterized in that the mass percentage of the formula D in the cycloolefin composition is 0.05 to 1.5%.
3. A composition for optical materials, comprising the cycloolefin composition according to claim 1 or 2, and other olefin components.
4. The composition for optical materials according to claim 3, wherein the mass percentage of the other olefin component in the composition for optical materials is 5 to 95%.
5. The composition for an optical material according to claim 3 or 4, wherein the other olefin component includes, but is not limited to, any one or more of 1-octene, 1-hexene, norbornene, a compound represented by formula a, or a compound represented by formula B;
wherein R is 1 ～R 4 Represents an alkyl chain of 3 to 7 carbons, and at least one double bond is present in the alkyl chain.
6. A cycloolefin copolymer obtained by polymerizing the composition for an optical material according to any one of claims 3 to 5.
7. A process for preparing cycloolefin copolymers as claimed in claim 6, comprising the following steps:
the composition for optical material according to any one of claims 3 to 5, which is obtained by polymerizing in the presence of a catalyst and a solvent.
8. The method of claim 7, wherein the catalyst is selected from any one or more of Grubbs i, grubbs ii, or Grubbs iii;
the solvent is selected from any one or more of aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, carboxylic ester solvents or ether solvents;
the mass percentage of the catalyst is 0.001-0.2% of the total mass of the composition for the optical material;
the mass percentage of the solvent is 60-95% of the total mass of the cycloolefin composition and the solvent in the composition for optical materials;
the temperature of the polymerization reaction is 50-180 ℃ and the time is 0.1-10h.
9. Cycloolefin copolymer hydride, characterized in that it is obtained after hydrogenation of the cycloolefin copolymer according to claim 6 or of the cycloolefin copolymer prepared by the preparation process according to claim 7 or 8.
10. The cycloolefin copolymer hydride according to claim 9, characterized in that the cycloolefin copolymer hydride has a weight average molecular weight of 5000 to 10000; the glass transition temperature of the cycloolefin copolymer hydride is 110-230 ℃; the hydrogenation rate of the cycloolefin copolymer hydride is 90% -100%.
11. The process for producing a cycloolefin copolymer according to claim 9 or 10, characterized in that the cycloolefin copolymer according to claim 6 or the cycloolefin copolymer produced by the production process according to claim 7 or 8 is hydrogenated in the presence of a catalyst and a solvent.
12. The method of preparation according to claim 11, wherein the catalyst is selected from raney nickel and/or palladium on carbon;
the solvent is selected from any one or more of aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, carboxylic ester solvents or ether solvents;
the dosage of the catalyst is 0.5-5% of the mass of the whole reaction system;
the mass percentage of the solvent is 60-95% of the total mass of the cycloolefin composition and the solvent in the composition for optical materials;
the temperature of the hydrogenation reaction is 150-200 ℃ and the time is 2-12 h.
13. An optical material comprising the cycloolefin copolymer hydride according to claim 9 or 10 or the cycloolefin copolymer hydride produced by the production method according to claim 11 or 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311836268.4A CN117777412A (en) | 2023-12-28 | 2023-12-28 | Cycloolefin composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311836268.4A CN117777412A (en) | 2023-12-28 | 2023-12-28 | Cycloolefin composition and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117777412A true CN117777412A (en) | 2024-03-29 |
Family
ID=90392436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311836268.4A Pending CN117777412A (en) | 2023-12-28 | 2023-12-28 | Cycloolefin composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117777412A (en) |
-
2023
- 2023-12-28 CN CN202311836268.4A patent/CN117777412A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110776618B (en) | Cycloolefin copolymer and preparation method and application thereof | |
| CN110669207B (en) | Cycloolefin copolymer and preparation method and application thereof | |
| Ramakrishnan et al. | Poly (5-hydroxyoctenylene) and its derivatives: synthesis via metathesis polymerization of an organoborane monomer | |
| CN114395063B (en) | Cycloolefin copolymer with polar group and preparation method thereof | |
| CN111777702A (en) | Modified cycloolefin random copolymer and preparation method thereof | |
| CN112646126B (en) | Method for preparing cycloolefin polymer by hydrogenation ring-opening metathesis polymerization method | |
| CN117777412A (en) | Cycloolefin composition and application thereof | |
| JP5597643B2 (en) | Polymer purification method and polymer | |
| US20090292088A1 (en) | Process for production of cyclic olefin addition polymer | |
| CN112480374A (en) | Polar cycloolefin copolymer and preparation method thereof | |
| Guo et al. | Ruthenium catalyzed regioselective copolymerization of anthrone, fluorenone, or xanthone with α, ω-dienes | |
| JP5187314B2 (en) | Norbornene polymer or copolymer and method for producing the same | |
| CN113354776B (en) | Preparation method of cycloolefin copolymer and application of cycloolefin copolymer in preparation of heat-resistant optical material | |
| CN115785443B (en) | Optical polymer and preparation method and application thereof | |
| JP5109247B2 (en) | Method for producing cyclic olefin ring-opening polymer hydride | |
| CN117624473A (en) | Preparation method of hydrogenated cycloolefin copolymer | |
| JPH0597719A (en) | Isomerization of aromatic group-containing norbornene compound end isomer to exo isomer, mixture of aromatic group-containing norbornene compound isomers and its production | |
| CN111153773A (en) | Preparation method of benzyl vinyl ether and monomer copolymer thereof | |
| JPH0625213B2 (en) | Method for producing hydrogenated dicyclopentadiene-ethylene copolymer | |
| JP2004149704A (en) | Cyclodiene monomer, polymer, and preparation processes for those | |
| CN115850581B (en) | Cycloolefin copolymer and preparation method and application thereof | |
| KR101142687B1 (en) | Preparation method of polynobornene including polar substituents | |
| CN117986421A (en) | Preparation method of cycloolefin copolymer | |
| CN117777413A (en) | Cycloolefin copolymer hydride and preparation method and application thereof | |
| JP2010159404A (en) | Method for producing hydrogenated product of cyclic olefin-based ring-opened (co)polymer and the resultant hydrogenated product of cyclic olefin-based ring-opened (co)polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |