CN114685715A - Crosslinkable thermoplastic cycloolefin copolymer and preparation method and application thereof - Google Patents
Crosslinkable thermoplastic cycloolefin copolymer and preparation method and application thereof Download PDFInfo
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- CN114685715A CN114685715A CN202011624903.9A CN202011624903A CN114685715A CN 114685715 A CN114685715 A CN 114685715A CN 202011624903 A CN202011624903 A CN 202011624903A CN 114685715 A CN114685715 A CN 114685715A
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- crosslinkable thermoplastic
- carbon atoms
- cycloolefin copolymer
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 77
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 59
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 47
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims abstract description 45
- 238000004132 cross linking Methods 0.000 claims abstract description 29
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 25
- 239000005022 packaging material Substances 0.000 claims abstract description 6
- -1 cyclic olefin Chemical class 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 15
- 239000012815 thermoplastic material Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 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 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a crosslinkable thermoplastic cycloolefin copolymer, a preparation method and application thereof, wherein a repeating structural unit of the cycloolefin copolymer comprises a structural unit A and a structural unit B; the source monomer a of the A structural unit is norbornene and a derivative monomer thereof; b is a repeating unit of cyclic olefin containing at least one double bond, and a source monomer B is a monomer containing two or more double bonds; the B repeat units may be crosslinked. The Tg-adjustable COC material prepared by the crosslinkable thermoplastic cyclic olefin copolymer through chain segment adjustment is easy to process, and double bonds are introduced into the molecular structure of the cyclic olefin copolymer to initiate the double bonds to perform further in-situ crosslinking reaction in the subsequent processing process to obtain a high-temperature-resistant COC material, so that the thermoplastic material is changed into a thermosetting material, and then the material is molded. The thermosetting cycloolefin copolymer can be used in various fields such as packaging materials, circuit substrates, and the like.
Description
Technical Field
The patent belongs to the field of high polymer materials, and particularly relates to a crosslinkable thermoplastic cycloolefin copolymer, and a preparation method and application thereof.
Background
The cycloolefin copolymer is a transparent high polymer having a cycloolefin structure, and is widely used in the manufacture of optical materials and electrical components.
The prior Cyclic Olefin Copolymer (COC) is mainly a copolymer obtained by taking norbornene and ethylene or alpha-olefin as monomers, belongs to thermoplastic materials, has relatively high glass transition temperature (Tg) and is not easy to process.
For example, CN108699302A provides a cyclic olefin copolymer composition comprising a cyclic olefin copolymer (m) of a cyclic nonconjugated diene having a specific amount of specific repeating units and a cyclic olefin copolymer (n) which is different from the cyclic olefin copolymer (m) and does not contain repeating units of a cyclic nonconjugated diene, and a crosslinked product thereof, which is suitable for a circuit board or the like and has excellent dielectric properties and heat resistance in a high frequency range. However, the components in the composition are complex, a specific repeating unit is designated, a free radical initiator needs to be added, the crosslinking position is only limited to the cyclic non-conjugated diene repeating unit, the glass transition temperature (Tg) of the material is not changed remarkably due to the very limited crosslinking degree, and the characteristics of the material are not changed qualitatively. The material is mainly used as a film or sheet and a laminated body, and the use mode is single, so that the use is limited.
CN108148332A provides a resin composition and a film and a circuit board using the same, wherein the resin composition contains cyclic olefin copolymer, polybutadiene, maleic anhydridized polybutadiene and a solvent, the side chains of the molecules of the cyclic olefin copolymer and the polybutadiene both have vinyl groups, and in the baking process, the vinyl groups on the side chains of the molecules of the cyclic olefin copolymer and the vinyl groups on the side chains of the molecules of the polybutadiene are chemically reacted and bonded together to form a chemically cross-linked network structure, which can further increase the cross-linking density of the resin composition, so that the chemically cross-linked network structure in the adhesive layer will not fail in the subsequent conventional processes of soldering tin and the like of the circuit board, and therefore, the adhesive layer of the circuit board prepared from the resin composition has better heat resistance and can meet the heat resistance requirement of the circuit board. However, the main resin component is the composition, and the cross-linked body is composed of two components of the cyclic olefin copolymer and the polybutadiene, so that the system is complex. However, the cross-linked body is only limited to polybutadiene, double bonds exist in different components, the ectopic cross-linking reaction process is not easy to control, the change from thermoplasticity to thermosetting is not mentioned, the processing mode is only limited to an adhesive layer, the processing mode is single, and the use of the material is limited.
In summary, the cycloolefin copolymer in the prior art mostly adopts the composition of the cycloolefin polymer, the components are complex, the processing process is not easy to control, the processability is uneven, the requirement range of the processing conditions is narrow, the use of the material of the cycloolefin copolymer is limited, and the problems that the processing mode is harsh, the precision processing is not facilitated and the like exist at the same time.
Disclosure of Invention
In order to solve the problem of poor processability of the existing cycloolefin copolymer, the invention provides a crosslinkable thermoplastic cycloolefin copolymer, a preparation method and application thereof, the crosslinkable thermoplastic cycloolefin copolymer enables the Tg point of the prepared cycloolefin copolymer to be adjustable by segment adjustment, so that the prepared COC material is easy to process, in-situ crosslinking reaction can be further carried out, a high-temperature-resistant COC material is obtained, the thermoplastic material is changed into a thermosetting material, and then molding is realized, and the thermosetting cycloolefin copolymer can be applied to different fields, such as packaging materials, circuit substrates and the like.
The repeating structural unit of the cycloolefin copolymer comprises a structural unit A and a structural unit B, wherein the structural unit A is 100 parts by mole, and the structural unit B is more than 0 part by mole; (ii) a
A is a repeating unit of a cyclic olefin copolymer, and a source monomer a of the repeating unit is norbornene and a derivative monomer a thereof;
the source monomer B of the structural unit B is a monomer containing two or more double bonds, the molecular structure of the monomer comprises a carbon atom ring, at least one double bond is distributed on the carbon atom ring, at least one double bond is in a chain, and the number of carbon atoms of the carbon atom ring is 3-11. At least one double bond of the source monomer B is subjected to polymerization reaction, and at least one double bond does not participate in the polymerization reaction to form a B structural unit containing unsaturated double bonds; the B structural unit may undergo a crosslinking reaction.
The crosslinkable thermoplastic cycloolefin copolymer is converted into a thermosetting cycloolefin copolymer by a crosslinking reaction.
Preferably, the double bond in the chain of the molecular structure of the source monomer b of the crosslinkable thermoplastic cycloolefin copolymer is separated by at least one carbon from the ring of carbon atoms. Because of this position of the double bond, the retention of the double bond of the structural unit B is achieved with a high success rate, while the rigidity of the resulting copolymerization product is reduced, and the glass transition temperature is reduced.
The crosslinkable thermoplastic cycloolefin copolymers have a glass transition temperature Tg of from 50 to 400 ℃ before crosslinking, and offer the possibility of thermal processing in a wide range.
The different glass transition temperatures facilitate better handling during the preliminary processing, and the glass transition temperature Tg of the crosslinkable thermoplastic cycloolefin copolymer can also be adjusted depending on the rigidity or toughness of the material required for the application scenario of the final material.
The toughness or rigidity of the required material is preliminarily adjusted by introducing the monomer containing two or more double bonds.
The structural formula of the norbornene derivative is in accordance with the following general formula:
in the general formula, x is 0 or 1, y is 0 or a positive integer, z is 0 or 1, R23～R42The same or different from each other, are hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atomsA substituted alkyl group, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R39～R42Each independently or in combination with each other to form a monocyclic or polycyclic ring.
The molecular structure of the source monomer a can be selected from any one of the following molecular structures:
the number of carbon atoms of the monomer b containing two or more double bonds is 10-28; the structural formula is any one of the following three structural formulas;
the first kind: the structure of the monomer b containing two or more double bonds is as follows:
in the general formula, m is 0 or a positive integer, R6～R16The alkyl group is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
the second category: the structure of the monomer b containing two or more double bonds is as follows:
in the general formula, f is 0 or 1, e is 0 or a positive integer, R17～R31The alkyl group is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms;
the type three: the structure of the monomer b containing two or more double bonds is as follows:
in the general formula, p is 0 or 1, q is 0 or a positive integer, R32～R45The alkyl group is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.
The molecular structure of the source monomer b can be selected from any one of the following structures:
preferably, the copolymerized repeating structural units of the crosslinkable thermoplastic cycloolefin copolymer contain C structural units, the molar amount of C used is 0 to 100 per mole of cycloolefin copolymer, and the higher the molar proportion of C structural units, the lower the glass transition temperature of the cycloolefin copolymer.
By introducing C structural units, the adjustable range of the Tg point of the crosslinkable thermoplastic cycloolefin copolymers is made larger.
The structure of C is as follows:
wherein R is1Is a linear or branched hydrocarbon group having 1 to 18 carbon atoms or a linear or branched hydrocarbon group having 1 to 18 carbon atoms and contains one or more of a hydroxyl group, a carboxyl group, an ester group, an amide group, a mercapto group or a ketone group.
The alpha-olefin is selected from propylene, 1-hexene, 1-octene.
The polymerization of the cycloolefin copolymer is carried out using a catalyst,
the catalyst consists of a main catalyst and an auxiliary catalyst, wherein the main catalyst is an organic titanium complex, the auxiliary catalyst is an organic boron complex, and the ratio of the main catalyst to the auxiliary catalyst is as follows: the mass ratio of the main catalyst to the cocatalyst is 1: 0.1-3, preferably 1: 0.5-2.5;
the preparation method of the crosslinkable thermoplastic cycloolefin copolymer comprises the following steps:
1) adding a solvent for reaction into a reaction kettle subjected to anhydrous and anaerobic treatment, and controlling the temperature of the reaction kettle to be 20-80 ℃; taking a source monomer a and a source monomer b, and sequentially adding the source monomers a and b into a reaction kettle; the solvent for reaction is selected from cyclohexane, dichloromethane, chloroform, toluene, xylene, chlorobenzene and/or aromatic hydrocarbon;
2) if necessary, adding a source monomer c, and adding the source monomer c;
3) stirring all monomers uniformly, and adding a main catalyst and a cocatalyst into the mixture for reaction for 5-60 min;
4) after the reaction reaches a specified time, adding a terminating solvent to terminate the reaction, repeatedly washing by using a washing solvent, and drying to obtain the crosslinkable thermoplastic cycloolefin copolymer. The terminating solvent is a solvent with the solubility of the crosslinkable thermoplastic cyclic olefin copolymer being less than or equal to 5; the washing solvent is a solvent with the solubility of the crosslinkable thermoplastic cycloolefin copolymer being more than or equal to 50.
The terminating solvent is generally ethanol.
The washing solvent is generally acetone.
The solvent for the reaction is not particularly limited, and may be cyclohexane, methylene chloride, chloroform, toluene, xylene, chlorobenzene, aromatic hydrocarbon, etc., and cyclohexane, toluene, and xylene are preferable.
Because the structural unit B has unreacted double bonds, the double bonds can be further crosslinked, so that the crosslinkable thermoplastic cyclic olefin copolymer is converted into the thermosetting cyclic olefin copolymer due to the crosslinking reaction.
The glass transition temperature Tg of the crosslinkable thermoplastic cycloolefin copolymers is from 50 to 400 ℃ and offers the possibility of thermal processing in a wide range. The crosslinkable thermoplastic cycloolefin copolymer is formed into any shape by hot melting or dissolving the crosslinkable thermoplastic cycloolefin copolymer in a solution solvent such as toluene, chlorobenzene aromatic hydrocarbon and the like, and then double bonds are subjected to crosslinking reaction, so that the crosslinkable thermoplastic cycloolefin copolymer is converted into the thermosetting cycloolefin copolymer, and the processing difficulty is reduced.
The specific crosslinking method for the crosslinking reaction is not particularly limited, and may be any method in which a suitable vulcanizing agent, a radical initiator, a hydrosilyl-containing compound, radiation-induced crosslinking, or direct crosslinking at a high temperature is added.
The radical initiator is selected from: oil-soluble initiators such as azobisisobutyronitrile in azo type initiators, benzoyl peroxide t-butyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl peroxide, diisopropyl peroxydicarbonate, oxidation-reduction initiators and the like in organic peroxy type initiators.
Further, a process for the preparation of the crosslinkable thermoplastic cycloolefin copolymers,
1) when the source monomer and the solvent for reaction are added, the temperature of the reaction kettle is preferably 30-60 ℃;
2) the reaction time after the catalyst is added is preferably 10-40 min. The ratio of the main catalyst to the cocatalyst is preferably 1: 0.5-2.5.
The crosslinkable thermoplastic cycloolefin copolymer with uniform molecular weight distribution, stable mechanical properties and high yield is obtained by limiting the temperature of the reaction kettle, further limiting the catalytic ratio and the reaction time.
The application of the crosslinkable thermoplastic cyclic olefin copolymer is preformed and converted into the thermosetting cyclic olefin copolymer through a crosslinking reaction, and the converted thermosetting cyclic olefin copolymer is used for manufacturing packaging materials, circuit substrates, lenses, packaging materials and the like.
The crosslinkable thermoplastic cycloolefin copolymer is a thermoplastic material before use, is easy to change the shape, is convenient for precise processing, can be converted into a thermosetting material through a crosslinking reaction in the processing or using process, can resist higher temperature, and has a wider application range.
Detailed Description
First, a cyclic olefin copolymer composition according to an embodiment of the present invention will be described. The cyclic olefin copolymer composition of the present embodiment contains a cyclic olefin copolymer a structure segment, a B structure segment having a ring structure with at least one double bond, and further includes a chain olefin copolymer C structure segment. The monomer source of the A structure chain segment is a, the monomer source of the B structure chain segment is B, and the monomer source of the C structure chain segment is C.
Detailed description of the preferred embodiments
Examples 1 to 6
The monomers a used are norbornene, b are vinylnorbornene and c is ethylene.
Examples 7 to 9
The monomers a used are norbornene, b are vinylnorbornene and c is 1-hexene.
Examples 10 to 12
The monomers used are monomers a is norbornene and b is
c is ethylene.
Examples 13 to 15
The monomers a used are norbornene, b are vinylnorbornene and c is 1-octene.
Example 16
The monomers a used are tetracyclododecene, b are vinylnorbornene and c are ethylene.
Example 17
The monomers a used are norbornene, b is
c is ethylene.
Comparative example 1
The monomer a used is norbornene, c is ethylene, and no monomer b is added.
Comparative example 2
The monomer b in example 1 was changed to ethylidene norbornene
Comparative example 3:
the monomer c in example 1 was changed to
Comparative example 4: a commercial CoC masterbatch, available from Mitsui chemical corporation, APL5014CL, was used as a control.
The monomer contents in the examples were adjusted as shown in Table 1, but were otherwise unchanged.
TABLE A table of monomer amounts for examples 1-17 and comparative examples 1-3
Taking example 1 as an example, the specific process is as follows:
the method comprises the following steps: carrying out anhydrous and anaerobic treatment on a high-pressure reaction kettle with the volume of 1L; controlling the temperature of the reaction system to be 40 ℃; sequentially adding 300g of toluene solvent, 11.8g of norbornene and 15.1g of vinyl norbornene, and stirring to ensure that the system is uniform; 1ml of TiBA solution, 40umol of Cs-symmetrical fluorenylaminodimethyl titanium complex solution and Ph3CB (C6F5)4/TiBA20 umol single-neck flask are sequentially filled with 3.5g of ethylene gas by an injector, after the polymerization is finished for 10min, the reaction is stopped by using a proper amount of ethanol/HCL solution, the mixture is poured into stirred ethanol solution, and the mixture is washed, filtered and placed in an oven at 60 ℃ for 6 h. And drying the product to obtain the crosslinkable thermoplastic cycloolefin copolymer, and storing, testing and using.
Step two: and (2) dissolving 1g of the obtained crosslinkable thermoplastic cycloolefin copolymer in a toluene solution under the protection of nitrogen, adding 3mg of benzoyl peroxide tert-butyl ester free radical initiator, reacting at 80 ℃ for 15min, washing the obtained solid after the reaction is finished with ethanol, and placing the solid in an oven at 60 ℃ for 6h after washing and suction filtration. And drying the product to obtain the crosslinked thermosetting cyclic olefin copolymer, and drying to observe the dissolution condition of the thermosetting cyclic olefin copolymer in the toluene solvent.
Example of application
The crosslinkable thermoplastic cycloolefin copolymers obtained in the first step of examples 1 to 17 and comparative examples 1 to 3 and the products thereof after providing a crosslinking reaction environment and comparative example 4 were subjected to the following tests.
DSC test
DSC measurements were carried out on the crosslinkable thermoplastic cycloolefin copolymers obtained in examples 1 to 17 and comparative examples 1 to 3 in step one, the thermosetting cycloolefin copolymers obtained in step two and the samples obtained in ratio 4
And (4) testing standard: ASTM D7426-2008 determines the glass transition temperature (Tg) of a polymer or elastic composite using the standard test method assigned by the plastic Differential Scanning Calorimetry (DSC) process.
The test steps and conditions are as follows: the nitrogen valve port is opened, the nitrogen flow rate is controlled between 20ml/min, and the instrument and software are opened. Weighing a proper amount of crosslinkable thermoplastic cyclic olefin copolymer and a thermosetting cyclic olefin copolymer sample after crosslinking, placing the crosslinkable thermoplastic cyclic olefin copolymer and the thermosetting cyclic olefin copolymer sample into an aluminum crucible, clamping and compacting, then placing the crucible into an instrument by using tweezers, setting a sample number and a test program, and then testing. The test method is lift to eliminate thermal history: the first heating rate is 20 ℃/min, the temperature is heated from 20 ℃ to a proper temperature, and the balance is carried out for 3 minutes; then cooling to 20 ℃, wherein the cooling rate is 20 ℃/min, and balancing for 3 minutes; finally, the temperature is raised to a proper temperature. The scanning temperature was adjusted accordingly to T g for the polymer.
2. Solubility test
Because the molecular chains of the cross-linked polymer are linked by chemical bonds to form a three-dimensional network structure, the whole material is a macromolecule and cannot be dissolved in a solvent, such as toluene. But because the network chain size is large and the solvent molecule is small, the solvent molecule can enter the chain segment to swell the material.
The resulting crosslinkable thermoplastic cycloolefin copolymers and the thermoset cycloolefin copolymers after crosslinking were tested for solubility in toluene as solvent.
TABLE two DSC test data for examples 1-17 and comparative examples 1-4
Note that the lack of a Tg point is an indication that the product obtained after crosslinking in the examples already has no glass transition state.
In the DSC test, if the double bond is subjected to crosslinking reaction, an exothermic reaction peak appears, and the product obtained in the first step of the example has a remarkable exothermic reaction peak before being treated, but after being treated, the product has no exothermic reaction peak in the DSC test, which indicates that the double bond is subjected to crosslinking reaction in the treatment process. After crosslinking, the glass transition temperature Tg is increased significantly.
In the embodiment, the product of the step one belongs to a thermoplastic material before being processed, and has good solubility in solvents such as toluene, however, after further crosslinking, the chain segments become long and are wound to form a certain network structure, and the network structure is not dissolved in solvents such as toluene, and the product of the step one is not dissolved in toluene after being processed differently (namely the product of the step two), and only a swelling phenomenon occurs. This further indicates that the double bonds in the product of step one of the examples have cross-linked in step two.
The material obtained in the first step of comparative example 1 has no unreacted activated double bonds, so that the exothermic peak is not observed to exist through DSC test, no obvious change is generated after different treatments, the Tg point can still be detected through DSC test, and the material can still be dissolved in toluene solution, thereby once again showing that the double bonds of the products obtained in the first step of examples 1 to 17 have crosslinking reaction in the second step. Comparative example 3 where monomer c having an excessively long carbon chain was introduced, glass transition temperature
3. Optical Performance testing
3.1 light transmittance test
Preparing a sample: the crosslinkable thermoplastic cyclic olefin copolymer obtained in the first step of patent examples 1-17 and the samples of comparative examples 1-3, 2g each, were dissolved in 20mL of chlorobenzene solvent, 0.001g of benzoyl peroxide tert-butyl ester was added to the solvent, the mixture was stirred until the COC sample was completely dissolved, the dissolved COC solution was poured into a mold having a length and a width of about 5cm, the mold was placed in an oven at 40 ℃ to slowly volatilize the solvent, and after about 4 hours, the mold piece was removed to obtain a thermosetting cyclic olefin copolymer film having a thickness of about 0.2 mm.
Comparative example 4 the membrane was removed directly, with a thickness of about 0.2 mm;
after the obtained membranes of examples 1 to 17 and comparative examples 1 to 4 were taken out, the membranes were covered with polyimide films on the upper and lower sides and then placed between two flat stainless steel plates each weighing about 1Kg, and the membranes of examples 1 to 17 and comparative examples 1 to 4 were placed in an oven at 200 ℃ for 12 hours with the membranes sandwiched between the stainless steel plates, so that the membranes were sufficiently thermally crosslinked. And after the time is reached, closing the oven, naturally cooling to room temperature, and taking out the membrane to obtain the membrane with the thickness of about 0.2 mm.
The test method comprises the following steps: the transmittance of each film was measured using the standard test method of astm d 1003.
TABLE TRI light transmittance results of the thermosetting cycloolefin copolymer films obtained in examples 1 to 17 and comparative examples 1 to 4
| Diaphragm numbering | Transmittance (a) |
| Example 1 | 90.8 |
| Example 2 | 91.0 |
| Example 3 | 91.5 |
| Example 4 | 91.2 |
| Example 5 | 90.9 |
| Example 6 | 91.4 |
| Example 7 | 90.7 |
| Example 8 | 91.3 |
| Example 9 | 91.1 |
| Example 10 | 90.7 |
| Example 11 | 90.2 |
| Example 12 | 90.8 |
| Example 13 | 91.3 |
| Example 14 | 90.9 |
| Example 15 | 91.4 |
| Example 16 | 91.0 |
| Example 17 | 91.2 |
| Comparative example 1 | 90.9 |
| Comparative example 2 | 91.3 |
| Comparative example 3 | 90.9 |
| Comparative example 4 | 91.3 |
The data in the above table show that the thermosetting cycloolefin copolymer obtained by the present invention has better or similar optical properties than the conventional cycloolefin copolymer on the market, and completely meets the requirements of the cycloolefin copolymer in the field of optical packaging.
3.2 light degradation resistance test
The sample preparation method is the same as that of the sample preparation for light transmittance test.
The test method comprises the following steps: a commercially available light source was purchased at a wavelength of 450nm and a power of 10W and a light-collecting area of 6cm2The diaphragm is fixed, the light source is opposite to the irradiation, and the center of the light source corresponds to the center of the diaphragm. The transmittance of the film after 500h and 1000h of irradiation was measured to evaluate the filmResistance of the sheet to deterioration under light conditions.
TABLE IV light transmittance after deterioration results of the thermosetting cycloolefin copolymer films obtained in examples 1 to 17 and comparative examples 1 to 4
| Diaphragm number | Transmittance-initial/% | Transmittance-500 h/%) | Transmittance-1000 h/%) |
| Example 1 | 90.8 | 90.5 | 90.0 |
| Example 2 | 91.0 | 90.8 | 90.3 |
| Example 3 | 91.5 | 90.3 | 89.6 |
| Example 4 | 91.2 | 90.3 | 88.6 |
| Example 5 | 90.9 | 90.7 | 90.2 |
| Example 6 | 91.4 | 90.0 | 89.6 |
| Example 7 | 90.7 | 91.0 | 90.3 |
| Example 8 | 91.3 | 90.8 | 90.1 |
| Example 9 | 91.1 | 90.1 | 89.4 |
| Example 10 | 90.7 | 90.2 | 89.5 |
| Example 11 | 90.2 | 90.4 | 89.8 |
| Example 12 | 90.8 | 90.2 | 89.4 |
| Example 13 | 91.3 | 89.8 | 89.1 |
| Example 14 | 90.9 | 90.8 | 90.2 |
| Example 15 | 91.4 | 90.7 | 89.6 |
| Example 16 | 91.0 | 90.3 | 89.8 |
| Example 17 | 91.2 | 90.6 | 89.4 |
| Comparative example 1 | 90.9 | 91.0 | 90.4 |
| Comparative example 2 | 91.3 | 91.0 | 90.6 |
| Comparison ofExample 3 | 90.9 | 90.4 | 89.9 |
| Comparative example 4 | 91.3 | 91.0 | 90.6 |
The data in the above table show that the thermosetting cycloolefin copolymer obtained by the present invention has better or similar optical properties than the conventional cycloolefin copolymer on the market, and completely meets the requirements of the cycloolefin copolymer in the field of optical packaging.
The COC polymer material has obvious advantages in the field of optical packaging besides the application field of the traditional COC.
Claims (17)
1. A crosslinkable thermoplastic cycloolefin copolymer, characterized in that: the repeating structural unit of the cycloolefin copolymer includes a structural unit A and a structural unit B; taking 100 parts by mole of the structural unit A and more than 0 part by mole of the structural unit B;
the source monomer a of the A structural unit is norbornene and a derivative monomer a thereof;
the B is a repeating unit of cyclic olefin containing at least one double bond, the molecular structure of the source monomer B comprises a carbon atom ring, at least one double bond is distributed on the carbon atom ring, at least one double bond is in the chain, and the number of carbon atoms of the carbon atom ring is 3-11.
2. Crosslinkable thermoplastic cycloolefin copolymer according to claim 1, characterized in that: the molecular structure of the source monomer b is that the double bond on the chain is separated from the carbon atom ring by at least one carbon.
3. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, characterized in that: the glass transition temperature Tg of the crosslinkable thermoplastic cycloolefin copolymers before crosslinking is from 50 to 400 ℃.
4. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, wherein the norbornene and the derivative a thereof have the formula:
in the general formula, x is 0 or 1, y is 0 or a positive integer, z is 0 or 1, R23～R42The same or different, hydrogen atom, halogen atom, alkyl group with 1-20 carbon atoms, halogenated alkyl group with 1-20 carbon atoms, naphthenic group with 3-15 carbon atoms or aromatic hydrocarbon group with 6-20 carbon atoms, R39～R42Each independently or in combination with each other to form a monocyclic or polycyclic ring.
5. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, characterized in that: the number of carbon atoms of the monomer b containing two or more double bonds is 10-28.
6. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, wherein the monomer b having two or more double bonds has the following structure:
in the general formula, m is 0 or a positive integer, R6～R16The alkyl group may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms.
7. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, wherein the monomer b having two or more double bonds has the following structure:
in the general formula, f is 0 or 1, e is 0 or a positive integer, R17～R31The alkyl group may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms.
8. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, wherein the monomer b having two or more double bonds has the following structure:
in the general formula, p is 0 or 1, q is 0 or a positive integer, R32～R45The alkyl group may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms.
9. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, wherein the copolymerized repeating structural units contain C structural units, the molar amount of C relative to the unit mol of cycloolefin copolymer being from 0 to 20, the particular amount being adjusted to the desired Tg point;
the structure of C is as follows:
wherein R is1Is hydrogen atom with carbon number of 1 to E18 is a straight or branched hydrocarbon group.
10. The crosslinkable thermoplastic cycloolefin copolymer according to claim 9, wherein the starting monomer C of the structural unit C is an alpha-olefin R1-CH＝CH2Wherein R is1Is a linear or branched hydrocarbon group having 1 to 18 carbon atoms or a linear or branched hydrocarbon group having 1 to 18 carbon atoms and contains one or more of a hydroxyl group, a carboxyl group, an ester group, an amide group, a mercapto group or a ketone group.
11. The crosslinkable thermoplastic cycloolefin copolymer according to claim 10, wherein the source monomer c is selected from the group consisting of ethylene, propylene, 1-hexene, 1-octene.
12. The crosslinkable thermoplastic cyclic olefin copolymer according to claim 1, wherein the source monomer a and the source monomer b are copolymerized to obtain the cyclic olefin copolymer, the copolymerization uses a catalyst, the catalyst is composed of a main catalyst and a cocatalyst, the main catalyst is an organic titanium complex, the cocatalyst is an organic boron complex, and the ratio of the two is: the mass ratio of the main catalyst to the cocatalyst is 1: 0.1-3.
13. The crosslinkable thermoplastic cycloolefin copolymer according to claim 12, wherein the mass ratio of procatalyst to cocatalyst mass is from 1:0.5 to 2.5.
14. The process for preparing a crosslinkable thermoplastic cycloolefin copolymer as claimed in claim 1, characterized in that it comprises the following steps:
1) adding a solvent for reaction into a reaction kettle subjected to anhydrous and anaerobic treatment, and controlling the temperature of the reaction kettle to be 20-80 ℃; taking a source monomer a and a source monomer b, and sequentially adding the source monomers a and b into a reaction kettle; the solvent for reaction is selected from cyclohexane, dichloromethane, chloroform, toluene, xylene, chlorobenzene and/or aromatic hydrocarbon;
2) stirring all monomers uniformly, adding a main catalyst and a cocatalyst, and reacting for 5-60 min;
3) after the reaction reaches a specified time, adding a terminating solvent to terminate the reaction, repeatedly washing by using a washing solvent, and drying to obtain the crosslinkable thermoplastic cyclic olefin copolymer; the terminating solvent is a solvent with the solubility of the crosslinkable thermoplastic cyclic olefin copolymer being less than or equal to 5; the washing solvent is a solvent with the solubility of the crosslinkable thermoplastic cycloolefin copolymer being more than or equal to 50.
15. The process for preparing a crosslinkable thermoplastic cycloolefin copolymer according to claim 9, characterized in that it comprises the following steps:
1) adding a solvent for reaction into a reaction kettle subjected to anhydrous and anaerobic treatment, and controlling the temperature of the reaction kettle at 20-80 ℃; taking a source monomer a and a source monomer b, and sequentially adding the source monomers a and b into a reaction kettle; the solvent for reaction is selected from cyclohexane, dichloromethane, chloroform, toluene, xylene, chlorobenzene and/or aromatic hydrocarbon;
2) adding a source monomer c;
3) stirring all monomers uniformly, adding a main catalyst and a cocatalyst, and reacting for 5-60 min;
4) after the reaction is carried out for a specified time, adding a solvent to stop the reaction, repeatedly washing the solvent, and drying to obtain the crosslinkable thermoplastic cyclic olefin copolymer; the terminating solvent is a solvent with the solubility of the crosslinkable thermoplastic cyclic olefin copolymer being less than or equal to 5; the washing solvent is a solvent with the solubility of the crosslinkable thermoplastic cycloolefin copolymer being more than or equal to 50.
16. Use of a crosslinkable thermoplastic cycloolefin copolymer according to claim 1 or 9, characterized in that the crosslinkable thermoplastic cycloolefin copolymer is converted into a thermosetting cycloolefin copolymer by a crosslinking reaction after having been shaped beforehand. The use of the crosslinkable thermoplastic cycloolefin copolymers is characterized in that the cycloolefin copolymers are shaped beforehand and converted into thermosetting cycloolefin copolymers by crosslinking.
17. Use according to claim 16, wherein the thermosetting cyclic olefin copolymer is used for the production of packaging materials, circuit substrates, lenses and packaging materials.
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