CN116333218A - Cycloolefin copolymer, optical product and electronic device - Google Patents
Cycloolefin copolymer, optical product and electronic device Download PDFInfo
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- CN116333218A CN116333218A CN202310326321.XA CN202310326321A CN116333218A CN 116333218 A CN116333218 A CN 116333218A CN 202310326321 A CN202310326321 A CN 202310326321A CN 116333218 A CN116333218 A CN 116333218A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 79
- 230000003287 optical effect Effects 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 cyclic olefin Chemical class 0.000 claims abstract description 26
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 238000003780 insertion Methods 0.000 claims description 16
- 230000037431 insertion Effects 0.000 claims description 16
- 239000004711 α-olefin Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910007926 ZrCl Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 150000003613 toluenes Chemical class 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- C08F232/02—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 no condensed rings
- C08F232/04—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 no condensed rings having one carbon-to-carbon double bond
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F220/70—Nitriles; Amides; Imides
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a cycloolefin copolymer, an optical product and an electronic device, wherein a comonomer of the cycloolefin copolymer comprises a polar monomer A and a cyclic olefin B, wherein the polar monomer A contains (CH 3 ) 2 -N-and-N-CO-groups, said cyclic olefin B containing a benzene ring. The comonomer of the cycloolefin copolymer according to the invention is obtained by introducing highly polar benzene rings in the cyclic olefin B and by introducing (CH) 3 ) 2 The introduction of-N-, -N-CO-contributes to an increase in refractive index, and the cycloolefin polymers according to the invention achieve a high refractive index and a low Abbe numberFills the blank of the optical application field.
Description
Technical Field
The present invention relates to the technical field of cycloolefin copolymers, and more particularly, to a cycloolefin copolymer, an optical product including the cycloolefin copolymer, and an electronic device including the optical product.
Background
Cycloolefin copolymers (COC) are novel thermoplastic optical plastics, are mainly formed by copolymerizing cycloolefin monomers with alpha-olefins and the like, and become important engineering plastics in various fields of optics, information, electric appliances, medical materials and the like.
However, it is difficult to achieve properties such as high refractive index and low abbe number of the cycloolefin copolymer in the prior art.
Disclosure of Invention
An object of the present invention is to provide a cycloolefin copolymer that can solve the technical problem that the cycloolefin copolymer in the prior art is difficult to achieve the properties of high refractive index, low abbe number, and the like.
It is still another object of the present invention to provide an optical article prepared by the above cycloolefin copolymer.
It is a further object of the present invention to provide an electronic device comprising the optical article described above.
In order to achieve the above object, the present invention provides the following technical solutions.
According to an embodiment of the first aspect of the present invention, the comonomer of the cycloolefin copolymer comprises a polar monomer A and a cyclic olefin B, wherein the polar monomer A contains (CH 3 ) 2 -N-and-N-CO-groups, said cyclic olefin B containing a benzene ring.
Of the comonomers of the cycloolefin copolymers according to the examples of the invention, the incorporation of highly polar benzene rings in the cyclic olefins B and the incorporation of (CH 3 ) 2 The introduction of the-N-, -N-CO-is beneficial to the improvement of the refractive index, and the cycloolefin polymer provided by the invention has high refractive index and low Abbe number, so that the blank of the optical application field is filled.
According to one embodiment of the present invention, the polar monomer a contains a carbon-carbon single bond capable of free rotation.
According to one embodiment of the present invention, the polar monomer a has the formula:
wherein k is 1, 2, 3, 4 or 5, R 1 Is hydrogen or alkyl or cycloalkyl with 1-20 carbon atoms.
According to one embodiment of the invention, the cyclic olefin B has the formula:
according to one embodiment of the invention, the comonomer of the cycloolefin copolymer also comprises an alpha-olefin having less than 20 carbon atoms.
According to one embodiment of the invention, the insertion rate of the alpha-olefin is 1% to 99%, the insertion rate of the polar monomer A is 1% to 70%, and the insertion rate of the cyclic olefin B is 1% to 70%.
According to one embodiment of the invention, the cycloolefin copolymer has a weight average molecular weight of 100000 ～ 800000.
According to one embodiment of the invention, the glass transition temperature of the cycloolefin copolymer ranges from 110℃to 220 ℃.
According to one embodiment of the present invention, the cycloolefin copolymer has a refractive index of 1.54 to 1.70 at a wavelength of 589nm and an Abbe number of 16 to 42 in a state that the cycloolefin copolymer is injection molded into a flat plate having a size of 100 mm. Times.50 mm. Times.3 mm.
According to an embodiment of the present invention, the cyclic olefin copolymer has an elongation at break of 1% to 25% in a state of being injection molded into a flat plate having a size of 100mm×10mm×1 mm.
An optical article according to an embodiment of the second aspect of the present invention is prepared from any of the cyclic olefin copolymers described above.
An electronic device according to an embodiment of the third aspect of the present invention comprises an optical article as described in any one of the above.
Other features of the present invention and its advantages will become apparent from the following detailed description of exemplary embodiments of the invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail. It should be noted that: the relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise.
The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of exemplary embodiments may have different values.
The cycloolefin copolymer (COC) according to the present invention will be described in detail with reference to specific examples.
The comonomer of the cycloolefin copolymer according to the embodiment of the present invention contains the polar monomer A and the cyclic olefin B, wherein the polar monomer A contains (CH 3 ) 2 -N-and-N-CO-groups, the cyclic olefin B containing a benzene ring.
In the polar monomer A (CH 3 ) 2 The introduction of-N-, -N-CO-is helpful for improving the refractive index, and the benzene ring contained in the annular olefin B can improve the aggregation density and polarization degree of the polymer.
Thus, the comonomer of the cycloolefin copolymer according to the embodiment of the present invention is obtained by introducing a highly polar benzene ring in the cyclic olefin B and introducing (CH 3 ) 2 The introduction of the-N-, -N-CO-is beneficial to the improvement of the refractive index, and the cycloolefin polymer provided by the invention has high refractive index and low Abbe number, so that the blank of the optical application field is filled.
According to one embodiment of the invention, the polar monomer a contains a freely rotatable carbon-carbon single bond. The molecular structure of the cycloolefin polymer has a large number of carbon-carbon single bonds capable of rotating freely, so that rigid alicyclic rings and aromatic rings are compensated, the flexibility of molecular chains is enhanced, and the toughness of the obtained cycloolefin copolymer is improved. That is, the cycloolefin copolymer prepared in this example has a high refractive index, a low Abbe number and good mechanical properties.
In some embodiments of the invention, the polar monomer a has the formula:
wherein in formula (I), k is 1, 2, 3, 4 or 5, R 1 Is hydrogen or alkyl or cycloalkyl with 1-20 carbon atoms.
It should be noted that the value of k is 1, 2, 3, 4 or 5, on the one hand, k is not zero, since it is not possible for one C atom to form a single bond with N and at the same time form a double bond with O, C, respectively; on the other hand, the k is not more than 5, and the volume of the monomer can be limited, so that the introduction of the monomer is convenient. R is R 1 The number of carbon atoms is limited to 20 or less, and the volume of the monomer is also limited. The C=C double bond and the C-C single bond on the left and right sides can rotate freely, and after the high molecular chain is introduced, the flexibility of the product is greatly improved, which is beneficial to the mechanical property of the product. At the same time (CH) 3 ) 2 N-, -N-CO-are all groups with higher polarity, and play a positive role in improving the refractive index of the product.
In the polar monomer A (CH 3 ) 2 The introduction of N-, -N-CO-contributes to the increase of the refractive index. In addition, the polar monomer A of the cycloolefin polymer has a large number of carbon-carbon single bonds capable of rotating freely in the molecular structure, so that rigid alicyclic rings and aromatic rings are compensated, the flexibility of a molecular chain is enhanced, and the toughness of the obtained cycloolefin copolymer is improved.
Alternatively, the structures of the polar monomers A are exemplified by the following formulas (II) to (VI).
It should be noted that the chemical formulas of the polar monomer a include, but are not limited to, the above formulas (ii) to (vi), and are not described herein.
According to one embodiment of the invention, the cyclic olefin B has the formula:
it can be seen that the benzene ring contained in the ring-shaped olefin B in this example has a high molecular aggregation density and a degree of polarization, and the introduction of the highly polar benzene ring contributes to the improvement of refractive index.
According to one embodiment of the invention, the comonomer of the cycloolefin copolymer also comprises an alpha-olefin having up to 20 carbon atoms. That is, the cycloolefin copolymer according to the embodiment of the present invention is copolymerized from an α -olefin having 20 or less carbon atoms, a polar monomer A and a cyclic olefin B. In the present embodiment, the number of carbon atoms of the α -olefin is 20 or less, and on the one hand, the monomer having a carbon chain length is not easily introduced; on the other hand, even if the polymer is introduced, the polymer is used as a side chain, and the long side chain does not contain a polar group and has a large volume, so that the polymer does not increase the refractive index but increases the steric hindrance. That is, by limiting the number of carbon atoms of the α -olefin to 20 or less, not only is the preparation of the cycloolefin copolymer facilitated, but also the mechanical properties of the product are advantageously ensured.
According to one embodiment of the invention, the insertion rate of the alpha-olefin is 1% to 99%, the insertion rate of the polar monomer A is 1% to 70%, and the insertion rate of the cyclic olefin B is 1% to 70%. In this example, the cycloolefin copolymer is copolymerized from an α -olefin having 20 or less carbon atoms, a polar monomer having an A structure, and a cyclic olefin having a B structure. Wherein the insertion rate of the alpha-olefin is 1% or more and 99% or less, for example, 1%, 10%, 15%, 20%, 30%, 50%, 60%, 90%, 99% or more. The insertion rate of the polar monomer a is 1% or more and 70% or less, for example, 1%, 5%, 10%, 20%, 30%, 50%, 60%, 70%, or the like. The insertion rate of the cyclic olefin B is 1% or more and 70% or less, for example, 1%, 5%, 10%, 20%, 30%, 50%, 60%, 70%, or the like. In this embodiment, the above range is selected by limiting the insertion rate, so that the cycloolefin copolymer according to the present invention has more structural design possibilities.
Optionally, the preparation method adopted by the invention comprises the following steps:
mixing polar monomer A, annular olefin B and solvent, introducing alpha-olefin, heating, adding mixed main catalyst and cocatalyst, and reacting to obtain the cycloolefin copolymer. The reaction temperature is 50-130 deg.c, the pressure is maintained at 0.05-2 MPa and the reaction time is 10-300 min.
Wherein, the solvent can be one of n-hexane, cyclohexane, cyclopentane, methylcyclohexane, benzene, toluene, xylene, etc.
In this embodiment, the selection criteria of the solvent include: firstly, the dissolubility is good, and raw materials and catalysts for experiments can be dissolved; secondly, the stability is good, and physical and chemical reactions can not occur under the reaction condition; thirdly, water-immiscible (MAO fails in water); fourth, it is readily available.
In combination, the usual hydrocarbon solvents may meet the requirements.
In addition, the main catalyst may be metallocene, cp 2 ZrCl 2 、(Ind) 2 ZrCl 2 、rac-[Et(Ind) 2 ]ZrCl 2 、rac-[Et(Ind-H 4 ) 2 ]ZrCl 2 、rac-[Me 2 Si(Ind) 2 ]ZrCl 2 、rac-[Ph 2 Si(Ind) 2 ]ZrCl 2 、[Me 2 C(Flu)(Cp)]ZrCl 2 、[Me 2 Si(Flu)(3- t BuCp)]ZrCl 2 、[Me 2 C(Flu)(3- t BuCp)]ZrCl 2 One of them. The cocatalyst can be Methylaluminoxane (MAO).
Advantages of using the catalyst system described above in this example include, but are not limited to: high activity; the active center is single, and the structure and the performance of the polymer are easy to control; the molecular weight distribution of the produced polymer is narrow, and the composition of the copolymer is uniform.
In some embodiments of the invention, the cycloolefin copolymer has a weight average molecular weight of 100000 ～ 800000. The weight average molecular weight is the sum of the weight fractions of the molecules of the respective different molecular weights multiplied by their corresponding molecular weights. For example, the weight average molecular weight of the cycloolefin copolymer is 100000, 300000, 400000, 600000, 800000, or the like. The higher the molecular weight, the better the copolymer physical properties, and the weight average molecular weight in this example was selected in this range because the mechanical properties of 100000 or more were excellent, but it was difficult to achieve 800000 or more.
In this example, the weight average molecular weight of the cycloolefin copolymer was between 100000 ～ 800000, and the higher the molecular weight, the better the copolymer physical properties.
According to one embodiment of the invention, the glass transition temperature of the cycloolefin copolymer is in the range from 110℃to 220 ℃. The transition between the glassy state and the high-elastic state is generally referred to as a glass transition, and the transition temperature corresponding to the transition temperature is referred to as a glass transition temperature (Tg). In this example, the higher the glass transition temperature (Tg) is between 110℃and 220℃the better the copolymer thermal properties. However, the cyclic olefin/polar monomer insertion rate causes contradiction between the molecular weight and Tg, and the higher the insertion rate, the higher the Tg, but the polymerization activity decreases and the molecular weight decreases. Therefore, in the present embodiment, by limiting the glass transition temperature of the cycloolefin copolymer to the above range, both the thermal properties and the mechanical properties of the copolymer can be ensured.
In some embodiments of the present invention, the cycloolefin copolymer has a refractive index of 1.54 to 1.70, for example, a refractive index of 1.54, 1.60, 1.65, 1.70, etc. at a wavelength of 589nm in a state of being injection molded into a flat plate having a size of 100mm×50mm×3 mm; the Abbe number is 16 to 42, for example, the Abbe number is 16, 20, 30, 40 or 42, etc. That is, the cycloolefin copolymer obtained was injection molded into a flat plate of 100 mm. Times.50 mm. Times.3 mm, and the refractive index at a wavelength of 589nm was 1.54 to 1.70, and the Abbe number was 16 to 42. It can be seen that the cycloolefin copolymer according to the present embodiment achieves a higher refractive index and a lower Abbe number characteristic.
In addition, refractive index (n D ) Is the ratio of the propagation speed of light in vacuum to the propagation speed of light in the medium. In general, the refractive index of a material used as an optical lens does not exceed 1.6 because the larger the refractive index is, the more serious the dispersion is, but in achromatism, a series of materials having refractive indices from low to high are required, and a material having a refractive index > 1.6 greatly facilitates the elimination of chromatic aberration. Since the refractive index is closely related to the polarity of the groups, and the introduction of the polar groups is relatively difficult in the preparation of the cycloolefin copolymer, the structure of the cycloolefin copolymer is difficult to improve, and the cycloolefin copolymer with the refractive index of more than or equal to 1.6 in the prior art is still blank. In this example, the refractive index of the cycloolefin copolymer was very close to 1.6 even if it was less than 1.6, and it was possible to achieve a refractive index of 1.6 or more by controlling the selection of the raw materials, the catalyst, the reaction conditions, and the like.
According to an embodiment of the present invention, the cycloolefin copolymer has an elongation at break of 1% to 25%, for example, an elongation at break of 1.0%, 5%, 10%, 15%, 20%, 25%, etc., in a state of being injection molded into a flat plate having a size of 100mm×10mm×1 mm. The existing COC has poor toughness and low elongation at break due to the fact that the molecular structure of the COC contains rigid rings, and is relatively brittle. In this example, the cycloolefin copolymer was molded into a sheet-like molded article of 100 mm. Times.10 mm. Times.1 mm, and the elongation at break was 1% to 25%, and toughness and mechanical properties were improved by increasing the elongation at break.
The invention also provides an optical article which can be prepared by the cycloolefin copolymer according to any of the embodiments. Since the cycloolefin copolymer according to the embodiment of the present invention has both the properties of high refractive index and low abbe number, the optical product according to the present invention has the same advantages and will not be described herein.
The invention also provides an electronic device comprising the optical product of any embodiment, and the electronic device has the same advantages in that the optical product has good optical performance
The cycloolefin polymer according to the present invention is described in detail below with reference to specific examples.
Example 1
High-purity nitrogen is pumped and discharged three times for exhausting air, polar monomer A
6.36g (0.05 mol) and a cyclic olefin B +>
14.52g (0.05 mol) of the mixture is added into 190mL of dehydrated toluene, the mixture is evenly mixed, and is injected into a reaction kettle under nitrogen atmosphere, ethylene is introduced until the pressure is 0.15MPa, the temperature is raised to 70 ℃, and Cp-containing catalyst is added 2 ZrCl 2 1.14mg (4. Mu. Mol) of MAO 464.12mg (containing Al 8 mmol) of toluene solution (10 mL) and stopping heating after reacting for 30min, and stopping the reaction by injecting 10mL of ethanol acidified by hydrochloric acid, washing and suction filtering the product, and then drying the product in vacuum at 60 ℃ for 8h, wherein the obtained cycloolefin copolymer is marked as 1.
Example 2 the reactor was evacuated three times with high purity nitrogen to vent air, polar monomer A
11.17g (0.05 mol) and a cyclic olefin B +>
14.52g (0.05 mol) of the mixture was added to 190mL of dehydrated toluene, the mixture was poured into a reactor under nitrogen atmosphere, ethylene was introduced to a pressure of 0.15MPa, the temperature was raised to 80℃and the content (Ind) was added 2 ZrCl 2 1.57mg (4. Mu. Mol) of MAO 464.12mg (containing Al 8 mmol) of toluene solution (10 mL) and after 40min of reaction, the heating was stopped, 10mL of ethanol acidified by hydrochloric acid was injected to terminate the reaction, and the product was washed and suction-filtered and dried in vacuo at 60℃for 8 hours to give cycloolefin copolymer designated 2. Example 3 the reactor was evacuated three times with high purity nitrogen to vent air, polar monomer A
11.97g（0.05mol）And a cyclic olefin B->
14.52g (0.05 mol) of dehydrated toluene (190 mL) was added and mixed well, and the mixture was poured into a reaction vessel under nitrogen atmosphere, ethylene was introduced to a pressure of 0.15MPa, the temperature was raised to 80℃and a mixture containing rac- [ Et (Ind) 2 ]ZrCl 2 2.51mg (6. Mu. Mol) of MAO696.18mg (containing Al 12 mmol) of toluene solution (10 mL) were reacted for 60 minutes, then the heating was stopped, 10mL of ethanol acidified by hydrochloric acid was injected to terminate the reaction, and the product was washed and suction-filtered and then vacuum-dried at 60℃for 8 hours, and the obtained cycloolefin copolymer was designated 3. Example 4 the experimental procedure of this example 4 differs from that of example 3 in that a solution containing rac- [ Et (Ind) was added 2 ]ZrCl 2 1.67mg (4. Mu. Mol) of MAO 464.12mg (containing Al 8 mmol) of toluene solution in 10mL, the other conditions were kept the same, and the resulting cycloolefin copolymer was designated 4. Comparative example 1 reaction vessel was evacuated three times with high purity nitrogen to vent air, polar monomer +.>
11.97g (0.05 mol) and cyclic olefins +>
4.71g (0.05 mol) of the mixture is added into 95mL of dehydrated toluene, the mixture is evenly mixed, and is injected into a reaction kettle under nitrogen atmosphere, ethylene is introduced until the pressure is 0.1MPa, the temperature is raised to 70 ℃, and Cp-containing catalyst is added 2 ZrCl 2 0.57mg (2. Mu. Mol) of MAO 232.06mg (containing Al 4 mmol) of toluene solution 5mL, stopping heating after reacting for 30min, injecting 10mL of ethanol acidified by hydrochloric acid to terminate the reaction, washing and suction filtering the product, and drying the product in vacuum at 60 ℃ for 8h, wherein the obtained cycloolefin copolymer is marked as 5. Comparative example 2 reaction vessel was evacuated three times with high purity nitrogen to vent air, cyclic olefin +.>
29.04g (0.1 mol) of the mixture is added into 190mL of dehydrated toluene, the mixture is evenly mixed, and is injected into a reaction kettle under nitrogen atmosphere, ethylene is introduced until the pressure is 0.15MPa, the temperature is raised to 70 ℃, and Cp-containing catalyst is added 2 ZrCl 2 1.14mg (4. Mu. Mol) of MAO 464.12mg (containing Al 8 mmol) of toluene solution (10 mL) and after 30min of reaction, the heating was stopped, 10mL of ethanol acidified by hydrochloric acid was injected to terminate the reaction, and the product was washed and filtered by suction and dried in vacuo at 60℃for 8 hours to give a cycloolefin copolymer designated 6. The cycloolefin copolymer obtained has a monomer insertion rate, a glass transition temperature (Tg), a weight average molecular weight (M w ) Refractive index (n) D ) The Abbe number and elongation at break are shown in Table 1. TABLE 1
As can be seen from table 1, the refractive index of example 1 was 1.592, abbe number was 32, and elongation at break was 6.2%; the refractive index of example 2 was 1.606, abbe number was 29, elongation at break was 5.8%; example 3 has a refractive index of 1.633, an Abbe number of 24, and an elongation at break of 8.7%; the refractive index of example 4 was 1.630, abbe number was 25, and elongation at break was 8.4%. It can be seen that the cycloolefin copolymers prepared in examples 1 to 4 have a high refractive index, a low Abbe number and a high elongation at break, i.e. optical properties and mechanical properties.
In contrast, comparative example 1 had a refractive index of 1.566, an abbe number of 42, and an elongation at break of 3.9%; comparative example 2 had a refractive index of 1.545, an Abbe number of 47 and an elongation at break of 1.4%. It can be seen that the cycloolefin copolymers obtained in comparative example 1 and comparative example 2 have a lower refractive index, a higher Abbe number and a lower elongation at break.
It can be seen that the products of examples 1 to 4 all have a high refractive index, a low abbe number and an improved elongation at break compared to comparative examples 1 and 2. That is, as can be seen from Table 1, the cycloolefin copolymer according to the examples of the present invention has a very high refractive index and a correspondingly low Abbe number as compared with other cycloolefin copolymers, and at the same time, the elongation at break is improved and the toughness is remarkably improved.
That is, as can be seen from Table 1, the cycloolefin copolymer according to the present invention has a very high refractive index and a correspondingly low Abbe number, and at the same time, the elongation at break is improved and the toughness is remarkably improved, as compared with other cycloolefin copolymers.
In summary, the polar monomer A of the cycloolefin copolymer according to the embodiment of the present invention contains (CH 3 ) 2 The ring-shaped olefin B contains benzene rings, so that the prepared cycloolefin polymer has the properties of high refractive index and low Abbe number and has good optical properties.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (12)
1. A cycloolefin copolymer comprising a polar monomer A and a cyclic olefin B, wherein the polar monomer A contains (CH 3 ) 2 -N-and-N-CO-groups, said cyclic olefin B containing a benzene ring.
2. The cycloolefin copolymer according to claim 1, characterized in that the polar monomer A contains a freely rotatable carbon-carbon single bond.
3. The cyclic olefin copolymer according to claim 2, wherein the polar monomer a has the formula:
wherein k is 1, 2, 3, 4 or 5, R 1 Is hydrogen or alkyl or cycloalkyl with 1-20 carbon atoms.
4. A cyclic olefin copolymer according to any one of claims 1 to 3, characterized in that the cyclic olefin B has the formula:
5. the cyclic olefin copolymer according to claim 4, wherein the comonomer of the cyclic olefin copolymer further comprises an alpha-olefin having 20 or less carbon atoms.
6. The cycloolefin copolymer according to claim 5, characterized in that the insertion rate of the α -olefin is 1 to 99%, the insertion rate of the polar monomer A is 1 to 70%, and the insertion rate of the cyclic olefin B is 1 to 70%.
7. The cycloolefin copolymer according to claim 5, characterized in that the cycloolefin copolymer has a weight average molecular weight of 100000 ～ 800000.
8. The cycloolefin copolymer according to claim 5, characterized in that the glass transition temperature of the cycloolefin copolymer is in the range of 110℃to 220 ℃.
9. The cycloolefin copolymer according to claim 5, characterized in that the cycloolefin copolymer has a refractive index of 1.54 to 1.70 at a wavelength of 589nm and an Abbe number of 16 to 42 in a state that it is injection molded into a flat plate having a size of 100 mm. Times.50 mm. Times.3 mm.
10. The cycloolefin copolymer according to claim 5, characterized in that the elongation at break of the cycloolefin copolymer is 1% to 25% in the state of being injection molded into a flat plate having a size of 100mm×10mm×1 mm.
11. An optical article, characterized in that it is prepared from the cycloolefin copolymer according to any one of claims 1 to 10.
12. An electronic device comprising the optical article of claim 11.
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