CN114685715B - 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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- CN114685715B CN114685715B CN202011624903.9A CN202011624903A CN114685715B CN 114685715 B CN114685715 B CN 114685715B CN 202011624903 A CN202011624903 A CN 202011624903A CN 114685715 B CN114685715 B CN 114685715B
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- cycloolefin copolymer
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 81
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 44
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000004132 cross linking Methods 0.000 claims abstract description 30
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000005022 packaging material Substances 0.000 claims abstract description 6
- -1 cyclic olefin Chemical class 0.000 claims abstract description 4
- 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 38
- 239000002904 solvent Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 13
- 150000001721 carbon Chemical group 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000012815 thermoplastic material Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 238000012360 testing method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 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
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 8
- 230000003287 optical effect Effects 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 group C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 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
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004711 α-olefin Substances 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
- 239000004342 Benzoyl peroxide Substances 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
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001782 photodegradation Methods 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
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 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
- 125000003396 thiol group Chemical group [H]S* 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 repeated structural unit of the cycloolefin copolymer comprises an A structural unit and a B structural unit; the source monomer a of the A structural unit is norbornene and derivative monomers thereof; the B is a repeating unit of cyclic olefin containing at least one double bond, and the source monomer B is a monomer containing two or more double bonds; the B repeat structural units may be crosslinked. The COC material with adjustable Tg point, which is prepared by adjusting chain segments, of the crosslinkable thermoplastic cycloolefin copolymer is easy to process, and double bonds are introduced into the molecular structure of the cycloolefin copolymer to cause further in-situ crosslinking reaction of the double bonds in the subsequent processing process, so that the high-temperature-resistant COC material is obtained, and the change from a thermoplastic material into a thermosetting material is realized, and further the molding is realized. The thermosetting cycloolefin copolymer can be applied to different fields, such as packaging materials, circuit substrates and the like.
Description
Technical Field
The patent belongs to the field of high polymer materials, and in particular relates to a crosslinkable thermoplastic cycloolefin copolymer, a preparation method and application thereof.
Background
Cycloolefin copolymers are transparent high polymer polymers of cycloolefin structure, which are widely used for the production of optical materials and electrical components.
The current cycloolefin 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 non-conjugated diene having a specific repeating unit in a specific amount, and a cyclic olefin copolymer (n) containing no cyclic non-conjugated diene repeating unit, which is different from the above cyclic olefin copolymer (m), to obtain a crosslinked body excellent in dielectric characteristics and heat resistance in a high frequency region suitable for a circuit board or the like, and a crosslinked body thereof. However, the composition is complex in composition, specific repeating units are specified, a free radical initiator is required to be added, the crosslinking site is limited to cyclic non-conjugated diene repeating units, and the glass transition temperature (Tg) of the composition is not changed significantly due to the very limited degree of crosslinking, so that the characteristics of the material are not changed. The material is mainly used as a film, a sheet or a laminate, and the use is limited because the use mode is relatively single.
CN108148332a provides a resin composition and a film and a circuit board using the resin composition, wherein the resin composition contains a cyclic olefin copolymer, polybutadiene, maleated polybutadiene and a solvent, the molecular side chains of the cyclic olefin copolymer and the polybutadiene have vinyl groups, and in the baking process, the vinyl groups on the molecular side chains of the cyclic olefin copolymer and the vinyl groups on the molecular side chains of the polybutadiene are chemically reacted and bonded together to form a chemically crosslinked network structure, so that the crosslinking density of the resin composition can be further improved, and the chemically crosslinked network structure in the adhesive layer can not fail in the subsequent conventional solder and other processes of the circuit board, 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 a composition, the cross-linked body is two components of cycloolefin copolymer and polybutadiene, and the system is complex. However, the crosslinking body is limited to polybutadiene, double bonds exist in different components, the ectopic crosslinking reaction process is not easy to control, the change from thermoplasticity to thermosetting is not mentioned, the processing mode is limited to a glue layer, and the processing mode is single, so that the use of materials is limited.
In summary, the cycloolefin copolymer in the prior art adopts a cycloolefin polymer composition, has complex components, is difficult to control in the processing process, has uneven processability, has narrow requirements on processing conditions, limits the use of cycloolefin copolymer materials, and has the problems of harsh processing mode, adverse precision processing and the like.
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, wherein the crosslinkable thermoplastic cycloolefin copolymer enables the COC material with adjustable Tg point of the prepared cycloolefin copolymer to be easy to process through chain segment adjustment, and can further undergo in-situ crosslinking reaction to obtain a high-temperature-resistant COC material, so that the thermoplastic material is changed into a thermosetting material for further molding, 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 an A structural unit and a B structural unit, wherein the A structural unit is taken as 100 mole parts, and the B structural unit is more than 0 mole parts; ;
The A is a repeating unit of a cyclic olefin copolymer, and a source monomer a 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 on a chain, and the carbon atom number 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 building blocks may undergo a crosslinking reaction.
The crosslinkable thermoplastic cycloolefin copolymer is converted into a thermosetting cycloolefin copolymer by a crosslinking reaction.
Preferably, the double bonds on the chains of the molecular structure of the source monomer b of the crosslinkable thermoplastic cycloolefin copolymer are separated from the carbon atom ring by at least one carbon. Because of this position of the double bond, the double bond retention success rate of the structural unit B is high, and at the same time, the rigidity of the obtained copolymerization product is reduced, so that the glass transition temperature is lowered.
The glass transition temperature Tg of the crosslinkable thermoplastic cycloolefin copolymers before crosslinking is from 50 to 400℃and gives 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 be adjusted according to the rigidity or toughness of the material required for the application scene of the final material.
The crosslinkable thermoplastic cycloolefin copolymers according to the invention initially regulate the toughness or rigidity of the desired materials by introducing monomers containing two or more double bonds.
The structural formula of the norbornene derivative is as follows:
In the general formula, x is 0 or 1, y is 0 or a positive integer, z is 0 or 1, R 23～R42 are the same or different from each other, and are 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, and R 39～R42 are each independently or combined with each other to form a single ring or multiple rings.
The molecular structure of the source monomer a can be selected from any one of the following molecular structures:
The carbon number 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;
category one: 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, R 6～R16 are the same or different and are hydrogen atom, halogen atom, alkyl group with 1-20 carbon atoms, halogenated alkyl group with 1-20 carbon atoms, cycloalkyl group with 3-15 carbon atoms or aromatic hydrocarbon group with 6-20 carbon atoms;
Category two: 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, R 17～R31 are the same or different and are hydrogen atom, halogen atom, alkyl group with 1-20 carbon atoms, halogenated alkyl group with 1-20 carbon atoms, cycloalkyl group with 3-15 carbon atoms or aromatic hydrocarbon group with 6-20 carbon atoms;
category 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, and R 32～R45 are the same or different and are hydrogen atom, halogen atom, alkyl group with 1-20 carbon atoms, halogenated alkyl group with 1-20 carbon atoms, cycloalkyl group with 3-15 carbon atoms or aromatic hydrocarbon group with 6-20 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 to cycloolefin copolymer per unit mole is 0 to 100, and the higher the molar ratio of C structural units, the lower the glass transition temperature of the cycloolefin copolymer.
By introducing C building blocks, the Tg of the crosslinkable thermoplastic cycloolefin copolymer can be adjusted to a greater extent.
The structure of C is as follows:
Wherein R 1 is a hydrogen atom, 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 containing 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 cycloolefin copolymer is polymerized using a catalyst,
The catalyst consists of a main catalyst and a cocatalyst, wherein the main catalyst is an organic titanium complex, the cocatalyst is an organic boron complex, and the ratio of the main catalyst to the cocatalyst is as follows: the mass ratio of the main catalyst to the cocatalyst material was 1:0.1 to 3, preferably 1:0.5 to 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 ℃; sequentially adding the source monomer a and the source monomer b into a reaction kettle; the solvent for the reaction is selected from cyclohexane, dichloromethane, chloroform, toluene, xylene, chlorobenzene and/or aromatic hydrocarbon;
2) If necessary, adding the source monomer c;
3) Stirring all monomers uniformly, adding a main catalyst and a cocatalyst, and reacting for 5-60min;
4) After the reaction is carried out for a specified time, adding a stopping solvent to stop the reaction, repeatedly washing by a washing solvent, and drying to obtain the crosslinkable thermoplastic cycloolefin copolymer. The termination solvent is a solvent with a solubility of less than or equal to 5 for the crosslinkable thermoplastic cycloolefin copolymer; the washing solvent is a solvent with the solubility of more than or equal to 50 for the crosslinkable thermoplastic cycloolefin copolymer.
The terminating solvent is typically 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., preferably cyclohexane, toluene, and xylene.
Because the B structural unit carries unreacted double bonds, double bonds can be further crosslinked, so that the crosslinkable thermoplastic cycloolefin copolymer is converted into a thermosetting cycloolefin copolymer by crosslinking reaction.
The crosslinkable thermoplastic cycloolefin copolymers have a glass transition temperature Tg of from 50 to 400℃and offer the possibility of thermal processing in a wide range. The crosslinkable thermoplastic cycloolefin copolymer is dissolved by hot melting or by solution solvents such as toluene, chlorobenzene aromatic hydrocarbon and the like, then is formed into any shape, 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 the crosslinking may be carried out either by adding a suitable vulcanizing agent, or a radical initiator, or a hydrosilyl group-containing compound, or by radiation-induced crosslinking, or by directly carrying out crosslinking at a high temperature.
The free radical initiator is selected from: oil-soluble initiators such as azobisisobutyronitrile in azo-type initiators, benzoyl peroxide, t-butyl benzoyl 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 preparing the crosslinkable thermoplastic cycloolefin copolymer,
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 addition of the catalyst is preferably 10 to 40 minutes. 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 property and high yield is obtained by limiting the temperature of the reaction kettle and further limiting the catalytic proportion and the reaction time.
The crosslinkable thermoplastic cycloolefin copolymer is used for preparing packaging materials, circuit substrates, lenses, packaging materials and the like, and is formed in advance and converted into a thermosetting cycloolefin copolymer through crosslinking reaction.
The crosslinkable thermoplastic cycloolefin copolymer disclosed by the invention is a thermoplastic material before use, is easy to change in shape, is convenient for precision machining, can be converted into a thermosetting material through a crosslinking reaction in the machining or using process, can withstand 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 structural segment, a cyclic olefin copolymer B structural segment having at least one double bond, and a chain olefin copolymer C structural 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 monomer a used is norbornene, b is vinyl norbornene and c is ethylene.
Examples 7 to 9
The monomer a used is norbornene, b is vinyl norbornene and c is 1-hexene.
Examples 10 to 12
The monomer is norbornene a and b isC is ethylene.
Examples 13 to 15
The monomer a used is norbornene, b is vinyl norbornene and c is 1-octene.
Example 16
The monomer a used is tetracyclododecene, b is vinyl norbornene and c is ethylene.
Example 17
The monomer a is norbornene and b isC is ethylene.
Comparative example 1
The monomer a is norbornene and c is ethylene, and the b-type monomer is not added.
Comparative example 2
Monomer b in example 1 was changed to ethylidene norbornene
Comparative example 3:
Monomer c in example 1 was changed to
Comparative example 4: COC master batches with the trademark APL5014CL were selected as a control.
The monomer content of each example was adjusted according to Table 1, the others being unchanged.
Tables A monomer usage table for examples 1 to 17 and comparative examples 1 to 3
Taking example 1 as an example, the specific procedure is as follows:
Step one: 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 ℃; 300g of toluene solvent, 11.8g of norbornene and 15.1g of vinyl norbornene are sequentially added, and the system is stirred uniformly; sequentially using a syringe to fill 1ml of TiBA solution, 40umol of Cs-symmetrical fluorenyl amido dimethyl titanium complex solution and 20 umol of Ph3CB (C6F 5) 4/TiBA into a single-neck flask, introducing 3.5g of ethylene gas, stopping reaction after the reaction time is 10min and polymerization is finished, using proper amount of ethanol/HCL solution, pouring the mixture into a stirring ethanol solution, washing, suction-filtering, and then placing the mixture into a 60 ℃ oven for 6h. And after the product is dried, obtaining the crosslinkable thermoplastic cycloolefin copolymer, and preserving and testing the crosslinkable thermoplastic cycloolefin copolymer.
Step two: dissolving 1g of the crosslinkable thermoplastic cycloolefin copolymer in toluene solution under the protection of nitrogen, adding 3mg of benzoyl tert-butyl peroxide free radical initiator, reacting at 80 ℃ for 15min, washing the obtained solid after the reaction with ethanol, washing, suction filtering, and placing in a baking oven at 60 ℃ for 6h. After the product is dried, the cross-linked thermosetting cycloolefin copolymer is obtained, and the dissolution of the thermosetting cycloolefin copolymer in toluene solvent is observed after drying.
(II) application example
The crosslinkable thermoplastic cycloolefin copolymers obtained in the step one of examples 1 to 17 and comparative examples 1 to 3 and the products thereof after the provision of the crosslinking reaction environment as well as comparative example 4 were subjected to the following tests.
DSC test
DSC testing of the crosslinkable thermoplastic cycloolefin copolymers obtained in step one of examples 1 to 17 and comparative examples 1 to 3 and the thermosetting cycloolefin copolymers converted in step two and the samples obtained in example 4
Test standard: ASTM D7426-2008 determines the glass transition temperature (Tg) of a polymer or elastic composite using standard test methods for plastic Differential Scanning Calorimetry (DSC) process partitioning.
Test steps and conditions: the nitrogen valve port is opened, the flow rate of nitrogen is controlled to be 20ml/min, and the instrument and the software are opened. Weighing a proper amount of crosslinkable thermoplastic cycloolefin copolymer and a thermosetting cycloolefin copolymer sample after crosslinking, placing the sample in an aluminum crucible, clamping and compacting the sample, placing the crucible into an instrument by using tweezers, setting a sample number and a test procedure, and then testing. The test method is lifting to eliminate the heat history: the first heating rate is 20 ℃/min, heating is carried out from 20 ℃ to proper temperature, and balancing is carried out for 3 minutes; then cooling to 20 ℃, wherein the cooling rate is 20 ℃/min, and balancing for 3 minutes; finally, heating to a proper temperature. The scanning temperature is adjusted accordingly according to T g of the polymer.
2. Solubility test
Because of the chemical bond linkage between the molecular chains of the crosslinked polymer, a three-dimensional network structure is formed, and the whole material is a macromolecule and can not be dissolved in a solvent, such as toluene. However, due to the large network chain size, the solvent molecules are small, and can enter the chain segments to swell the material.
The resulting crosslinkable thermoplastic cycloolefin copolymer and the thermosetting cycloolefin copolymer after crosslinking were subjected to a solubility test, and toluene was used as the solvent of choice.
Table two DSC test data for examples 1-17 and comparative examples 1-4
/>
Note that the lack of a Tg point observed means that the product obtained after crosslinking of the examples has not had a glass transition state.
In the DSC test process, if a double bond is subjected to crosslinking reaction, an exothermic reaction peak appears, and the product in the first embodiment has an obvious 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 point is markedly increased.
The product of the first step belongs to a thermoplastic material before being treated, has good solubility in solvents such as toluene, and the like, but after further crosslinking, chain segments are lengthened and wound to form a certain network structure, the product is not dissolved in solvents such as toluene, and the product of the first step is not dissolved in toluene solution after being treated differently (namely the product of the second step), and only swells. This further indicates that the double bonds in the product of example step one undergo a crosslinking reaction in step two.
The material obtained in step one of comparative example 1 has no unreacted active double bonds, so that no exothermic peak is observed by DSC test, no significant change occurs after different treatments, tg point is still detected by DSC test, and the material is still soluble in toluene solution, and again, the double bonds of the products of step one of examples 1 to 17 are crosslinked in step two. Comparative example 3 incorporating monomer c exceeding the excessively long carbon chain, glass transition temperature
3. Optical performance test
3.1 Light transmittance test
Sample preparation: 2g of each of the crosslinkable thermoplastic cycloolefin copolymer samples obtained in the step one and the samples obtained in the comparative examples 1 to 17 of this patent were dissolved in 20mL of a chlorobenzene solvent, 0.001g of benzoyl tert-butyl peroxide was added to the solvent, and stirred sufficiently until the COC sample was completely dissolved, and then the dissolved COC solution was poured into a mold having a length of 5cm by 5cm, and the mold was placed in an oven at 40℃to evaporate the solvent slowly for about 4 hours, and then the mold sheet was taken out to obtain a thermosetting cycloolefin copolymer film having a thickness of about 0.2 mm.
Comparative example 4 the film was removed directly to a thickness of about 0.2mm;
after the obtained films of examples 1 to 17 and comparative examples 1 to 4 were taken out, the films were covered with polyimide films up and down, and then placed between two planar stainless steel plates, each stainless steel plate weighing about 1Kg, the films of examples 1 to 17 and comparative examples 1 to 4 sandwiched between the stainless steel plates were placed in a 200 ℃ oven, and baked for 12 hours, so that the films were sufficiently thermally crosslinked. After the time is reached, the oven is closed, the membrane is taken out after the temperature is naturally cooled to room temperature, and the membrane with the thickness of about 0.2mm is obtained.
The testing method comprises the following steps: the transmittance of each film was tested using the standard test method of astm d 1003.
Table III light transmittance results of the thermosetting cycloolefin copolymer films obtained in examples 1 to 17 and comparative examples 1 to 4
| Film numbering | Transmittance/% |
| 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 optical properties superior to or similar to those of conventional cycloolefin copolymers on the market, and completely satisfies the requirements of cycloolefin copolymers in the field of optical packaging.
3.2 Photo degradation resistance test
The sample wafer manufacturing method is the same as that for the light transmittance test.
The testing method comprises the following steps: and (3) purchasing a commercial light source with the wavelength of 450nm, the power of 10W and the light condensing area of 6cm 2, fixing the diaphragm, and directly irradiating the light source, wherein the center of the light source corresponds to the center of the diaphragm. And testing the light transmittance of the membrane after irradiation for 500h and 1000h, and evaluating the degradation resistance of the membrane under the irradiation condition.
Table IV post-degradation light transmittance results of the thermosetting cycloolefin copolymer films obtained in examples 1 to 17 and comparative examples 1 to 4
| Film numbering | Light transmittance-initial/% | Light transmittance of-500 h/% | Transmittance of-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 |
| Comparative example 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 optical properties superior to or similar to those of conventional cycloolefin copolymers on the market, and completely satisfies the requirements of cycloolefin copolymers in the field of optical packaging.
The COC polymer material of the invention has obvious advantages in the field of optical packaging besides the traditional COC applicable field.
Claims (7)
1. A crosslinkable thermoplastic cyclic olefin copolymer characterized in that: the repeating structural unit of the cycloolefin copolymer comprises an A structural unit and a B structural unit; taking the structural unit A as 100 mole parts, and the structural unit B is more than 0 mole parts;
The source monomer a of the A structural unit is norbornene and a derivative monomer a thereof, and is selected from any one of the following;
，
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 on a chain, and the carbon atom number of the carbon atom ring is 3-11;
The structure of the monomer b containing two or more double bonds is as follows: ，
In the general formula, m is a positive integer, R 6~R16 can be the same or different and are hydrogen atom, halogen atom, alkyl with 1-20 carbon atoms and halogenated alkyl with 1-20 carbon atoms;
the copolymerized repeated structural unit contains a C structural unit, the molar amount of C compared with the unit mol of cycloolefin copolymer is 0-20, wherein the amount of the C structural unit is not zero, and the specific amount is adjusted according to the required Tg point; the source monomer C of the structural unit C is ethylene and propylene;
the double bond on the chain of the molecular structure of the source monomer b is separated from the carbon atom ring by at least one carbon.
2. The crosslinkable thermoplastic cycloolefin copolymer according to claim 1, characterized in that: the crosslinkable thermoplastic cycloolefin copolymer has a glass transition temperature Tg before crosslinking of from 50 to 400 ℃.
3. 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 to 28.
4. The process for preparing a crosslinkable thermoplastic cycloolefin copolymer according to 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 o ℃; sequentially adding the source monomer a and the source monomer b into a reaction kettle; the solvent for the 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 5-60min;
4) After the reaction is carried out for a specified time, adding a stopping solvent to stop the reaction, repeatedly washing by a washing solvent, and drying to obtain the crosslinkable thermoplastic cycloolefin copolymer; the termination solvent is a solvent with a solubility of less than or equal to 5 for the crosslinkable thermoplastic cycloolefin copolymer; the washing solvent is a solvent with the solubility of more than or equal to 50 for the crosslinkable thermoplastic cycloolefin copolymer;
The catalyst consists of a main catalyst and a cocatalyst, wherein the main catalyst is an organic titanium complex, the cocatalyst is an organic boron complex, and the ratio of the main catalyst to the cocatalyst is as follows: the mass ratio of the main catalyst to the cocatalyst is 1: 0.1 to 3.
5. The process of claim 4 wherein the ratio of the amounts of the procatalyst and the cocatalyst species is from 1:0.5 to 2.5.
6. The use of a crosslinkable thermoplastic cycloolefin copolymer according to claim 1, characterized in that the crosslinkable thermoplastic cycloolefin copolymer is preformed and converted into a thermosetting cycloolefin copolymer by crosslinking.
7. The use according to claim 6, wherein the thermosetting cycloolefin copolymer is used for producing packaging materials, circuit substrates, lenses and packaging materials.
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