CN115819656A - Cycloolefin copolymer, process for producing the same and use thereof - Google Patents
Cycloolefin copolymer, process for producing the same and use thereof Download PDFInfo
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- CN115819656A CN115819656A CN202111086528.1A CN202111086528A CN115819656A CN 115819656 A CN115819656 A CN 115819656A CN 202111086528 A CN202111086528 A CN 202111086528A CN 115819656 A CN115819656 A CN 115819656A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 222
- 238000000034 method Methods 0.000 title claims description 37
- 230000008569 process Effects 0.000 title description 7
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 133
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims abstract description 67
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 30
- 125000004429 atom Chemical group 0.000 claims abstract description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 57
- 239000005977 Ethylene Substances 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 39
- 229910052710 silicon Inorganic materials 0.000 claims description 39
- 239000010703 silicon Substances 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- -1 cyano, amino Chemical group 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 125000004185 ester group Chemical group 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
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- 238000010438 heat treatment Methods 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
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- 125000003277 amino group Chemical group 0.000 claims description 8
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
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- 125000003944 tolyl group Chemical group 0.000 claims description 7
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 6
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- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
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- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
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- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 152
- 230000009477 glass transition Effects 0.000 abstract description 74
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- 150000001925 cycloalkenes Chemical class 0.000 description 42
- 230000000694 effects Effects 0.000 description 39
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 11
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- 238000001914 filtration Methods 0.000 description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 7
- 150000007522 mineralic acids Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- POPHMOPNVVKGRW-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7-octahydronaphthalene Chemical compound C1CCC2CCCCC2=C1 POPHMOPNVVKGRW-UHFFFAOYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- LRMWKHFHNIMDKK-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-yl-9H-fluorene Chemical compound C1(C=CC=C1)C1=CC=CC=2C3=CC=CC=C3CC1=2 LRMWKHFHNIMDKK-UHFFFAOYSA-N 0.000 description 1
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- VKNXYLFKIOFLJG-UHFFFAOYSA-N 4,4-dimethyl-2,3,6,7,8,8a-hexahydro-1H-naphthalene Chemical compound CC1(C)CCCC2CCCC=C12 VKNXYLFKIOFLJG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 1
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- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
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Abstract
The application relates to the technical field of polymer synthesis, and provides a cyclic olefin copolymer, and a preparation method and application thereof. The structural general formula of the cycloolefin copolymer is shown as the following formula (1-1) or formula (1-2):
in the formula (1-1) or the formula (1-2), the values of x, y and z satisfy the following conditions: x/(x + y + z) is more than or equal to 0.57 and less than or equal to 0.67, y/(x + y + z) is more than or equal to 0.32 and less than or equal to 0.39, and z/(x + y + z) is more than or equal to 0.01 and less than or equal to 0.04; a is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time. According to the application, the MDMO monomer is introduced into the cyclic olefin copolymer, so that the glass transition temperature of the cyclic olefin polymer can be increased, and the heat resistance of the cyclic olefin copolymer is improved.
Description
Technical Field
The application belongs to the technical field of polymer synthesis, and particularly relates to a cyclic olefin copolymer, and a preparation method and application thereof.
Background
The cycloolefin copolymer is a thermoplastic engineering plastic with high added value, which is polymerized by cycloolefin and alpha-olefin, and is a very promising optical material. Cycloolefin copolymers have high transparency, excellent heat resistance, chemical stability, melt flowability, dimensional stability and the like, and have been widely used for producing various optical lens prisms, automobile headlamps, optical films for liquid crystal displays, contact lenses and the like. The cycloolefin copolymer is expected to replace polycarbonate and become the best material for producing next-generation high-density DVDs. In addition, the cycloolefin copolymer resin has an extremely low dielectric constant, and is useful for the production of electronic and electric parts, and is also a new medicine, food packaging material, and the like because of its good moisture barrier properties.
There are two methods for synthesizing cycloolefin copolymers: one method is chain polymerization of ethylene with norbornene-type monomers, and the other method is Ring Opening Metathesis Polymerization (ROMP) and hydrogenation of norbornene-type monomers. Currently, mitsui chemical company in Japan and Ticona in the United states have introduced commercial COC under the trade names APEL and TOPAS, respectively.
U.S. Pat. No. 3,989,69812A 1 discloses a process for preparing cycloolefin copolymers, which comprises copolymerizing ethylene and DMON as raw materials, and adding a second cycloolefin monomer (IndNB) for ternary copolymerization, so as to achieve the effect of increasing the glass transition temperature of the copolymer while maintaining the excellent properties of the cycloolefin copolymer. The technology is based on that the mole ratio of ethylene to total cyclic olefin monomers basically does not change, namely the mole ratio of ethylene to total cyclic olefin monomers is about 64, and the high-temperature-resistant cyclic olefin copolymer is prepared, wherein the reaction formula is shown as the following formula 1:
the patent provides performance test data for examples and comparative examples, as in table 1 of the US20200369812A1 application. As can be seen from the data provided in Table 1, the technique produces a cycloolefin copolymer having a glass transition temperature of 143 to 152 deg.C (glass transition temperature of 150 deg.C for the comparative ethylene copolymeric DMON copolymer), a refractive index of 1.55 to 1.56 (refractive index of 1.54 for the comparative ethylene copolymeric DMON copolymer), and an Abbe number of 43 to 49 (Abbe number of 56 for the comparative ethylene copolymeric DMON copolymer) as compared to the comparative example (proportion of ethylene copolymeric with DMON of 65. It can be seen that on the premise of keeping the insertion rate of the total cycloolefin monomer unchanged, the effect of increasing the glass transition temperature of the cycloolefin copolymer by adding the second cycloolefin monomer is not obvious (basically below 150 ℃, the highest 165 ℃) and the regulation trend is disordered (the glass transition temperature of the copolymer does not increase or decrease reversely with the increase of the third monomer, such as P5 and P6), which is related to the selection of the second cycloolefin monomer. Moreover, compared with a cycloolefin copolymer without introducing the second cycloolefin monomer, the introduction of the second cycloolefin monomer has problems that the optical performance (the refractive index is not increased, the abbe number is obviously reduced) of the cycloolefin copolymer is deteriorated, and the like, because the introduction of the benzene ring has a large influence on the norbornene ring existing singly, and the influence is unavoidable.
Disclosure of Invention
The invention aims to provide a cycloolefin copolymer, and a preparation method and application thereof, and aims to solve the problems that the cycloolefin copolymer prepared by the existing method has low glass transition temperature and poor optical performance.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the first aspect of the present application provides a cycloolefin copolymer having a general structural formula as shown in the following formula (1-1) or formula (1-2):
in the formula (1-1) or the formula (1-2), x/(x + y + z) is more than or equal to 0.57 and less than or equal to 0.67, y/(x + y + z) is more than or equal to 0.32 and less than or equal to 0.39, and z/(x + y + z) is more than or equal to 0.01 and less than or equal to 0.04; a is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time.
The cyclic olefin copolymer provided by the application is formed by polymerizing an ethylene monomer (corresponding to a first monomer counted from the left of a structure shown in a formula (1-1) or a formula (1-2)), a DMON monomer (corresponding to a second monomer counted from the left of a structure shown in a formula (1-1) or a formula (1-2)), and a MDMO monomer (corresponding to a third monomer counted from the left of a structure shown in a formula (1-1) or a formula (1-2)). Wherein, the polymer formed by the MDMON monomer self-ring-opening metathesis polymerization and hydrogenation has higher glass transition temperature which can reach more than 230 ℃. The MDMO monomer is introduced into the cycloolefin copolymer to improve the glass transition temperature of the cycloolefin copolymer, so that the heat resistance of the cycloolefin copolymer is improved. Due to the high glass transition temperature of the MDMO-polymer, a small amount (0.01-0.04 of the total molar amount of the polymer) of MDMO monomer can form a cycloolefin copolymer, which can significantly increase the glass transition temperature of the cycloolefin polymer. Meanwhile, the MDMON monomer of the cycloolefin copolymer provided by the application can contain no benzene ring substituent or the benzene ring substituent is far away from a norbornene ring which is a reaction site, so that the adverse effect of the reaction on the optical property of the cycloolefin copolymer can be reduced, and the cycloolefin copolymer can keep good optical performance. In addition, the effect of obviously improving the glass transition temperature of the cycloolefin polymer can be achieved by introducing a small amount of the MDMO monomer, so that the content of the MDMO monomer can be reduced, and the economic efficiency of preparing the cycloolefin polymer is favorably improved.
As one possible implementation of the cycloolefin copolymer according to the present application, a, B are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, a heteroalkyl group, an aryl group, a substituted aryl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group. The MDMO containing A and B is introduced into the cycloolefin copolymer, so that the molecular volume of the polymer is increased, and the volume effect of an MDMO monomer is favorable for improving the glass transition temperature of the cycloolefin copolymer.
As a possible realization of the cycloolefin copolymers according to the present application, the alkyl groups are selected from alkyl groups having a number of carbon atoms of less than or equal to 20. In this case, the alkyl group can increase the volume of the MDMON monomer, which is beneficial to increase the glass transition temperature of the cycloolefin polymer; meanwhile, the carbon number of the alkyl is in a proper range, so that the influence of steric hindrance on the reaction activity of the MDMON monomer can be reduced, and the cyclic olefin copolymer shown in the formula (1-1) or the formula (1-2) can be obtained.
As one possible implementation manner of the cycloolefin copolymer herein, the number of carbon atoms of the substituted alkyl group is less than or equal to 20, and the substituent in the substituted alkyl group is at least one of a hydroxyl group, a carboxyl group, an ester group, a cyano group, an amino group, a thiol group, and a halogen atom. In this case, the substituted alkyl can increase the volume of the MDMO monomer, promote the MDMO monomer to generate a volume effect, and is beneficial to increasing the glass transition temperature of the cycloolefin polymer; meanwhile, the carbon atom number of the substituted alkyl is in a proper range, so that the influence of steric hindrance on the reaction activity of the MDMON monomer can be reduced. Moreover, polar groups such as hydroxyl, carboxyl, ester group, cyano, amino, thiol group and the like are introduced into the A and the B, so that the polarity of the cycloolefin copolymer can be increased, the compatibility between the cycloolefin copolymer and a polar material is improved, the cycloolefin copolymer can be compatible with other polar materials or materials containing the polar materials, and the application range of the cycloolefin copolymer is widened.
As one possible implementation manner of the cycloolefin copolymer herein, the number of carbon atoms in the heteroalkyl group is less than or equal to 20, and the heteroatom in the heteroalkyl group is at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. In this case, the above-mentioned heteroalkyl group can increase the volume of the MDMO monomer, promote the MDMO monomer to generate the volume effect, and is beneficial to increasing the glass transition temperature of the cycloolefin polymer; meanwhile, the carbon atom number of the heteroalkyl is in a proper range, and the influence of steric hindrance on the reaction activity of the MDMON monomer can be reduced. Moreover, the skeleton structure of the cycloolefin copolymer has excellent affinity and hydrophobicity, and after oxygen atoms, nitrogen atoms, sulfur atoms and phosphorus atoms are introduced into the A and the B, the polarity of the cycloolefin copolymer can be increased, so that the compatibility between the cycloolefin copolymer and a polar material is improved, the cycloolefin copolymer can be compatible with other polar materials or materials containing the polar materials, and the application range of the cycloolefin copolymer is widened.
As one possible implementation of the cyclic olefin copolymer herein, the aryl group is selected from phenyl, tolyl, naphthyl, benzyl, or phenethyl. The aryl is introduced into the MDMO monomer structure of the cyclic olefin polymer, so that the volume of the MDMO monomer can be increased, the MDMO monomer is promoted to generate a volume effect, and the glass transition temperature of the cyclic olefin polymer is favorably improved; moreover, the introduction of the benzene ring is beneficial to improving the refractive index of the cycloolefin polymer, thereby improving the optical performance of the cycloolefin polymer.
The aryl in the substituted aryl is selected from phenyl, tolyl, naphthyl, benzyl or phenethyl, and the substituent in the substituted aryl is at least one of alkyl, hydroxyl, carboxyl, ester group, cyano, amino, thiol group and halogen atom. Wherein, the substitution of the aryl in the aryl is beneficial to improving the glass transition temperature and the refractive index of the cycloolefin polymer; and polar groups such as hydroxyl, carboxyl, ester group, cyano, amino, thiol group and the like are beneficial to adjusting the polarity of the cycloolefin polymer, so that the compatibility between the cycloolefin polymer and other polar materials is improved, and the cycloolefin polymer has a wider application prospect.
The heterocyclic group is selected from furan, pyran, pyridine or thiophene. Wherein, the groups have certain aromaticity, which is beneficial to improving the glass transition temperature and the refractive index of the cycloolefin polymer; and the oxygen atom, the nitrogen atom and the sulfur atom are beneficial to adjusting the polarity of the cycloolefin polymer, so that the compatibility between the cycloolefin polymer and other polar materials is improved, and the cycloolefin polymer has a wider application prospect.
As a possible embodiment of the cycloolefin copolymers according to the invention, A, B are each independently selected from the group consisting of hydrogen atoms, halogen atoms, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, -OC n H m 、-OCOC n H m 、-C n H m 、-C 6 H 5 、-C 6 H 4 CH 3 、-C 10 H 7 、-CH 2 C 6 H 5 、-CH 2 CH 2 C 6 H 5 、-C n H m C 6 H 5 (ii) a Wherein n is a positive integer less than or equal to 10, and m is less than or equal to 2n +1. Because A and B are not hydrogen atoms at the same time, the introduction of at least one substituted alkyl group in the formula (1-1) or the formula (1-2) can increase the volume of the MDMO monomer, promote the MDMO monomer to generate a volume effect and is beneficial to improving the glass transition temperature of the cycloolefin polymer; the introduction of aryl is beneficial to improving the glass transition temperature and the refractive index of the cycloolefin polymer; the introduction of the polar group or the polar atom can increase the polarity of the cycloolefin copolymer, thereby improving the compatibility between the cycloolefin copolymer and the polar material, enabling the cycloolefin copolymer to be compatible with other polar materials or materials containing the polar materials, and further widening the application range of the cycloolefin copolymer.
As a possible embodiment of the cycloolefin copolymers according to the invention, the A and B are linked to form a ring. A. B is connected into a ring, the volume of the MDMON monomer is increased, the volume effect is increased, and the glass transition temperature of the cycloolefin polymer is favorably improved.
As one possible implementation manner of the cycloolefin copolymer herein, the ring is an aromatic ring, a cycloalkane, or a ring structure containing both an aromatic ring and a cycloalkane. In this case, the cycloolefin polymer has a relatively high glass transition temperature. When the ring is an aromatic ring or a ring structure containing both an aromatic ring and cycloalkane, the refractive index of the cycloolefin copolymer can be increased without lowering the Abbe number of the cycloolefin copolymer, and the optical properties of the cycloolefin copolymer can be improved to a certain extent.
As one possible implementation manner of the cycloolefin copolymer of the present application, the ring is one of the following ring structures:
when A and B are connected into the ring structure, the glass transition temperature of the cycloolefin polymer can be increased, and the refractive index of the cycloolefin copolymer can be increased on the premise of not reducing the Abbe number, so that the overall optical performance of the cycloolefin copolymer is improved.
As one possible implementation of the cyclic olefin copolymer of the present application, the cyclic olefin copolymer is a copolymer represented by the following structure:
the cycloolefin copolymer has a better glass transition temperature, so that the cycloolefin copolymer has a better high-temperature resistance. In addition, the cycloolefin copolymer contains a benzene ring structure, so that the refractive index of the cycloolefin copolymer can be improved on the premise of not reducing the Abbe number, and the overall optical performance of the cycloolefin copolymer is improved.
As one possible implementation of the cycloolefin copolymer herein, the cycloolefin copolymer has a number average molecular weight of less than or equal to 8 ten thousand and a weight average low molecular weight of less than or equal to 15 ten thousand. In this case, the cycloolefin copolymer has a lower viscosity and a better flowability at a low temperature, thereby being advantageous in improving the processability of the polymer.
In a second aspect, the present application provides a method for preparing a cycloolefin copolymer, comprising the steps of:
heating a solution system containing DMON, MDMON, ethylene, a catalyst and a cocatalyst for reaction to prepare the cyclic olefin copolymer;
wherein the structural general formula of the cycloolefin copolymer is shown as the following formula (1-1) or formula (1-2):
in the formula (1-1) or the formula (1-2), the values of x, y and z satisfy the following conditions: x/(x + y + z) is more than or equal to 0.57 and less than or equal to 0.67, y/(x + y + z) is more than or equal to 0.32 and less than or equal to 0.39, and z/(x + y + z) is more than or equal to 0.01 and less than or equal to 0.04;R 1 is an atom or group of atoms, R 2 Is an atom or a radical of an atom, and R 1 、R 2 Not being hydrogen atoms at the same time;
the catalyst is a metallocene catalyst.
According to the preparation method of the cyclic olefin copolymer, DMON and quaternary cyclic olefin monomer MDMO are selected as cyclic olefin monomers, wherein a polymer formed by the MDMO monomers through ring-opening metathesis polymerization and hydrogenation has a high glass transition temperature which can reach over 230 ℃. Therefore, the glass transition temperature of the three-membered cyclic olefin polymer can be increased by using ethylene, DMON and MDMO monomers as raw materials for polymerization reaction, so that the heat resistance of the cyclic olefin copolymer is improved. Since the glass transition temperature of the MDMO polymer is high, the glass transition temperature of the cyclic olefin polymer can be significantly increased by adding a small amount (0.01 to 0.04 of the total molar amount of the viscous polymer) of MDMO monomer to the bonding reaction. Meanwhile, according to the preparation method of the cyclic olefin copolymer provided by the application, the MDMON monomer does not contain benzene ring substituent groups or the benzene ring substituent groups are far away from a norbornene ring which is a reaction site, so that the negative influence of the reaction on the optical properties of the cyclic olefin copolymer can be reduced, and the cyclic olefin copolymer can keep good optical performance. In addition, the effect of remarkably improving the glass transition temperature of the cycloolefin polymer can be achieved by introducing a small amount of the MDMO monomer, so that the addition amount of the MDMO monomer can be reduced, and the economic efficiency of preparing the cycloolefin polymer is favorably improved.
The general structural formula of the catalyst is shown as the following formula (2):
in the formula (2), M 1 Selected from scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, M 2 、M 3 Each independently selected from carbon, silicon, germanium or tin;
x represents carbon or silicon;
R 1 and R 2 Each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group,Alkenyl, aryl, aryloxy, aralkyl, alkaryl, or aralkenyl;
R 3 and R 4 Each independently selected from a hydrogen atom or a hydrocarbyl group;
R 5 、R 6 、R 7 、R 8 each independently selected from a hydrogen atom, a hydrocarbon group, or a silicon-containing group bonded through a silicon atom to a carbon atom at a corresponding substitution position;
R 10 、R 11 、R 12 、R 15 、R 16 、R 17 each independently selected from alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl, or aralkenyl;
R 9 、R 13 、R 14 、R 18 each independently selected from a hydrogen atom, a hydrocarbyl group or a hydrocarbyloxy group;
wherein, R is 5 、R 6 、R 7 、R 8 At least one of which is a silicon-containing group, and/or said M 2 、M 3 At least one of which is silicon.
The catalyst shown in the formula (2) is beneficial to promoting the polymerization of three polymerization monomers to form the cyclic olefin polymer shown in the formula (1-1) or the formula (1-2).
As a possible mode of realization of the process for the preparation of the cycloolefin copolymers according to the present application, the R group 6 、R 7 At least one of is said silicon-containing group, or said M 2 、M 3 At least one of which is silicon.
In this case, the catalyst shown in formula (2) is favorable for promoting the polymerization activity of the three polymerization monomers, and the substituent group in the heteroatom-containing substituted alkyl group contains a silicon group, which is favorable for controlling the selectivity of the reaction monomers and further controlling the ratio of the three reaction monomers, thereby finally obtaining the cycloolefin polymer having the ratio of each monomer in the structure of formula (1-1) or formula (1-2).
As a possible mode of realization of the process for the preparation of the cycloolefin copolymers according to the present application, the R group 5 、R 6 、R 7 、R 8 Independently selected from hydrocarbyl or silicon-containing groups with the number of carbon atoms less than or equal to 6. In this kind ofUnder the condition, the silicon-containing group can control the selectivity of the reaction monomer through steric effect, and further control the proportion of the three reaction monomers; furthermore, R 5 、R 6 、R 7 、R 8 The catalyst shown in formula (2) containing silicon groups can obtain the cyclic olefin copolymer with low molecular weight (such as the number average molecular weight is less than or equal to 8 ten thousand, and the weight average low molecular weight is less than or equal to 15 ten thousand) without adding additives such as chain transfer agents when catalyzing the polymerization reaction of three reaction monomers.
As a possible embodiment of the process for preparing cycloolefin copolymers according to the application, R 10 、R 11 、R 12 、R 15 、R 16 、R 17 Has a carbon number of 10 or less. In this case, the catalyst has a suitable space size, which is advantageous for improving its catalytic activity.
As one possible implementation manner of the preparation method of the cyclic olefin copolymer, the cocatalyst is at least one of methylaluminoxane, modified methylaluminoxane and organoboron compound. The methylaluminoxane, the modified methylaluminoxane and the organoboron compound can activate the catalyst with the structure shown in the formula (2) and improve the activity of the catalyst. When R in the catalyst 5 、R 6 、R 7 、R 8 The silicon-containing group can also improve the selectivity of the catalyst to the reaction monomer, thereby controlling the reaction monomer proportion of the polymerization reaction.
As a possible implementation manner of the preparation method of the cyclic olefin copolymer, the heating reaction temperature is 50-90 ℃ and the time is 2-60min. Under the condition, the catalyst has better catalytic activity and is beneficial to improving the polymerization reaction efficiency.
In a third aspect of the present application, there is provided a use of a cyclic olefin copolymer as a lens material of a camera, wherein the cyclic olefin copolymer is the cyclic olefin copolymer described in the first aspect or the cyclic olefin copolymer prepared by the method described in the second aspect.
The cycloolefin copolymer provided by the application has higher glass transition temperature, so that the cycloolefin copolymer has better high temperature resistance, keeps better optical performance, can be used as a camera lens material, and endows the camera lens with good high temperature resistance and optical performance.
As a possible implementation manner of the application of the cycloolefin copolymer, the camera lens material is a vehicle-mounted camera lens material and a security camera lens material. Compared with the current commercial cyclic olefin copolymer material, the cyclic olefin copolymer provided by the application is adopted as the vehicle-mounted camera lens material and the security camera lens material, and has better heat resistance on the basis of not influencing the optical performance of the camera lens.
Drawings
FIG. 1 is a scheme showing the preparation of the cycloolefin monomer MDMO 1 H-NMR nuclear magnetic spectrum;
FIG. 2 shows the preparation of a novel cycloolefin monomer MDMO prepared in example 1 of the present application 13 C-NMR nuclear magnetic spectrum;
FIG. 3 is a DSC chart of the cycloolefin copolymer P1 obtained in example 2 of the present application;
FIG. 4 shows the preparation of a cycloolefin copolymer P1 obtained in example 2 of the present application 13 C-NMR nuclear magnetic spectrum;
FIG. 5 is a DSC chart of the cycloolefin copolymer P2 obtained in example 3 of the present application;
FIG. 6 shows the preparation of a cycloolefin copolymer P2 obtained in example 3 of the present application 13 C-NMR nuclear magnetic spectrum;
FIG. 7 is a DSC chart of the cycloolefin copolymer P3 obtained in example 4 of the present application;
FIG. 8 shows a block diagram of a cycloolefin copolymer P3 obtained in example 4 of the present application 13 C-NMR nuclear magnetic spectrum;
FIG. 9 is a DSC chart of the cycloolefin copolymer P4 obtained in example5 of the present application;
FIG. 10 shows the preparation of cycloolefin copolymer P5 from comparative example 1 13 C-NMR nuclear magnetic spectrum;
FIG. 11 is a DSC chart of the cycloolefin copolymer P5 obtained in comparative example 1.
In the DSC graph, the abscissa "Temperature" represents Temperature, and the ordinate "Heat Flow" represents "Heat Flow".
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The term "COC" is an abbreviation for "Cyclic Olefin Copolymer", which means a Cyclic Olefin Copolymer;
the term "DVD" is an abbreviation for "Digital Video Disc", which stands for high-density Digital Video Disc;
the term "ROMP" is an abbreviation for "Ring-Opening Polymerization", which means Ring-Opening Metathesis Polymerization;
the term "DMON" is an abbreviation for "1,2,3, 4a,5,8,8a-octahydro-1,4, 5, 8-dimethylhanapthalene", which represents dimethyloctahydronaphthalene;
the term "MDMON" is an abbreviation for "Modified DMON" and denotes a substituted dimethylbridged octahydronaphthalene, which is the third monomer introduced in the examples of this application;
the term "IndNB" is an abbreviation for "1, 4a, 9a-tetrahydroo-1, 4-methano-fluorene r", meaning indenoinorbomene;
the term "IndDMON" is an abbreviation for "5,5a,6,9,9a,10,10a,11-octahydro-4bH-5,10,6, 9-dimehano-benzor [ b ] fluorner", which stands for indeno-methano-octahydronaphthalene;
the term "MAO" is an abbreviation for "Methylaluminoxane" and refers to Methylaluminoxane.
COC is widely applied due to the excellent performances of high transparency, excellent heat resistance, excellent chemical stability, melt fluidity, excellent dimensional stability and the like, a large amount of COC materials are consumed for manufacturing various commodities in China every year, but the Tg of the COC materials is lower than 140 ℃ at present, the requirement of an application scene with high long-term use temperature is not met, and therefore the development of optical resin materials with better heat resistance is particularly important.
In view of this, embodiments of the present application provide a cyclic olefin copolymer, which is a random copolymer formed by a vinyl monomer and two cyclic olefin monomers, and has a general structural formula as shown in formula (1-1) or formula (1-2):
the structure of formula (1-1) or formula (1-2) shows the molar contents of the three monomers in the cyclic olefin copolymer, but does not indicate the arrangement order of the three monomers in the cyclic olefin copolymer. In the structure of the formula (1-1) or the formula (1-2) in the examples of the present application, three monomers are randomly arranged in a molecular chain to form a random copolymer.
In the examples of the present application, the two olefin monomers are a DMON monomer and a MDMON monomer, respectively, and the structures of the ethylene monomer (corresponding to the first monomer from the left of the structure shown in formula (1-1) or formula (1-2)), the DMON monomer (corresponding to the second monomer from the left of the structure shown in formula (1-1) or formula (1-2)) are shown in the following formulas (1-1) and (1-2), respectively:
the MDMON monomer has a structural difference according to the formula (1-1) or the formula (1-2), including two cases, the structures of which correspond to the third monomer from the left of the structures shown in the formula (1-1) and the formula (1-2), respectively, and the structures of the monomers in the two cases are shown in the following formulas (1-3-1) and the formula (1-3-2), respectively:
wherein, the structure (MDMON monomer) shown in the formula (1-3-1) and the formula (1-3-2) has higher glass transition temperature which can reach more than 230 ℃ after the self ring-opening metathesis polymerization and hydrogenation. Therefore, the embodiments of the present application improve the glass transition temperature of the cyclic olefin polymer by introducing mdron monomer into the cyclic olefin copolymer, thereby improving the heat resistance of the cyclic olefin copolymer.
Moreover, the reaction site norbornene ring in the structures of the formulae (1-3-1) and (1-3-2) may not be connected to a benzene ring, even if a benzene ring structure or a substituent containing a benzene ring structure is introduced into the structures of the formulae (1-3-1) and (1-3-2), the distance between the benzene ring and the norbornene ring is relatively long, so that the negative effect of the polymerization reaction on the optical properties of the cycloolefin copolymer can be reduced by the structure of the formulae (1-3), and the cycloolefin copolymer provided by the embodiment of the present application can maintain good optical performance. The good optical properties include at least that the Abbe number of the cycloolefin copolymer is not reduced.
In the embodiment of the application, due to the high glass transition temperature of the MDMON polymer, the values of x, y and z in the formula (1-1) or the formula (1-2) satisfy: x/(x + y + z) is more than or equal to 0.57 and less than or equal to 0.67, y/(x + y + z) is more than or equal to 0.32 and less than or equal to 0.39, and z/(x + y + z) is more than or equal to 0.01 and less than or equal to 0.04. The small amount of MDMON monomer can significantly increase the glass transition temperature of cycloolefin polymer. In addition, the embodiment of the application can achieve the effect of obviously improving the glass transition temperature of the cycloolefin polymer by introducing a small amount of the MDMO monomer, so that the content of the MDMO monomer can be reduced, and the economic efficiency for preparing the cycloolefin polymer is favorably improved.
The structures of the formula (1-3-1) and the formula (1-3-2), namely A and B in the MDMON monomer, are A and B in cycloolefins shown in the formula (1-1) or the formula (1-2). Wherein A is an atom or an atomic group, B is an atom or an atomic group, and A and B are not hydrogen atoms at the same time. Atoms or atomic groups which are not simultaneously hydrogen are introduced into the formulas (1-3-1) and (1-3-2), and non-hydrogen atoms or atomic groups can increase the volume of the MDMO monomer, promote the MDMO monomer to generate a volume effect, and are favorable for increasing the glass transition temperature of the cycloolefin copolymer. In addition, the skeleton structure of the cycloolefin copolymer provided by the embodiment of the application has excellent affinity and hydrophobicity, and has a better compatibility effect with non-polar or weak-polar materials. The polarity of the cyclic olefin copolymer can be adjusted by introducing polar groups or polar atoms into the A and the B, so that the polar olefin copolymer can be more suitable for the polarity requirements of different application scenes on the cyclic olefin copolymer.
As a possible implementation manner, a and B are each independently selected from a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, a heteroalkyl group, an aryl group, a substituted aryl group, a heteroaryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group. When A and B are not hydrogen atoms simultaneously, MDMON containing A and B is introduced into the cycloolefin copolymer, so that the molecular volume of the polymer is increased, and the volume effect of the MDMON improves the glass transition temperature of the cycloolefin polymer.
As a possible realization, the alkyl group is chosen from alkyl groups having a number of carbon atoms less than or equal to 20. In this case, the above alkyl group can increase the volume effect of the MDMON monomer, which is beneficial for increasing the glass transition temperature of the cycloolefin polymer; meanwhile, the carbon number of the alkyl is in a proper range, so that the influence of steric hindrance on the reaction activity of the MDMON monomer can be reduced, and the cyclic olefin copolymer shown in the formula (1-1) or the formula (1-2) can be obtained. In some embodiments, the number of carbon atoms in the alkyl group is less than or equal to 10. Illustratively, the alkyl group may be the following group having an isomeric structure: -CH 3 、-C 2 H 5 、-C 3 H 7 、-C 4 H 9 、-C 5 H 11 、-C 6 H 13 、-C 7 H 15 、-C 8 H 17 、-C 9 H 19 、-C 10 H 21 。
As one possible implementation manner, the number of carbon atoms of the substituted alkyl group is less than or equal to 20, and the substituent in the substituted alkyl group is at least one of a hydroxyl group, a carboxyl group, an ester group, a cyano group, an amino group, a thiol group, and a halogen atom. In this case, the substituted alkyl can increase the volume of the MDMO monomer, promote the MDMO monomer to generate a volume effect, and is beneficial to increasing the glass transition temperature of the cycloolefin polymer; meanwhile, since the number of carbon atoms of the substituted alkyl group is within a suitable range, the substituted alkyl group may haveTo reduce the effect of steric hindrance on the reactivity of the MDMON monomer. Moreover, polar groups such as hydroxyl, carboxyl, ester group, cyano, amino, thiol group and the like are introduced into the A and the B, so that the polarity of the cycloolefin copolymer can be increased, the compatibility between the cycloolefin copolymer and a polar material is improved, the cycloolefin copolymer can be compatible with other polar materials or materials containing the polar materials, and the application range of the cycloolefin copolymer is widened. In some embodiments, the number of carbon atoms in the substituted alkyl group is less than or equal to 10. Illustratively, the substituted alkyl group may be-CH 2 OH、-C 2 H 4 OH、-C 3 H 6 OH、-C 4 H 8 OH、-C 5 H 10 OH、-C 6 H 12 OH、-C 7 H 14 OH、-C 8 H 16 OH、-C 9 H 18 OH、-C 10 H 20 OH、-CH 2 COOH、-C 2 H 4 COOH、-C 3 H 6 COOH、-C 4 H 8 COOH、-C 5 H 10 COOH、-C 6 H 12 COOH、-C 7 H 14 COOH、-C 8 H 16 COOH、-C 9 H 18 COOH、-OCOCH 3 、-COOCH 3 、-COOC 2 H 5 、-OCOC 2 H 5 、-CH 2 COOCH 3 、-CH 2 OCOCH 3 、-COOC 3 H 7 、-OCOC 3 H 7 、-CH 2 COOC 2 H 5 、-CH 2 OCOC 2 H 5 、-C 2 H 4 COOCH 3 、-C 2 H 4 OCOCH 3 、-COOC 4 H 9 、-OCOC 4 H 9 、-CH 2 COOC 3 H 7 、-CH 2 OCOC 3 H 7 、-C 2 H 4 COOC 2 H 5 、-C 2 H 4 OCOCC 2 H 5 、-C 3 H 6 COOCH 3 、-C 3 H 6 OCOCCH 3 、-COOC 5 H 11 、-OCOC 5 H 11 、-CH 2 COOC 4 H 9 、-CH 2 OCOC 4 H 9 、-C 2 H 4 COOC 3 H 7 、-C 2 H 4 OCOCC 3 H 7 、-C 3 H 6 COOC 2 H 5 、-C 3 H 6 OCOCC 2 H 5 、-C 4 H 7 COOCH 3 、-C 4 H 7 OCOCCH 3 、-COOC 6 H 13 、-OCOC 6 H 13 、-CH 2 COOC 5 H 11 、-CH 2 OCOC 5 H 11 、-C 2 H 4 COOC 4 H 9 、-C 2 H 4 OCOCC 4 H 9 、-C 3 H 6 COOC 3 H 7 、-C 3 H 6 OCOCC 3 H 7 、-C 4 H 8 COOC 2 H 5 、-C 4 H 8 OCOCC 2 H 5 、-C 5 H 10 COOCH 3 、-C 5 H 10 OCOCCH 3 、-COOC 7 H 15 、-OCOC 7 H 15 、-CH 2 COOC 6 H 13 、-CH 2 OCOC 6 H 13 、-C 2 H 4 COOC 5 H 11 、-C 2 H 4 OCOCC 5 H 11 、-C 3 H 6 COOC 4 H 9 、-C 3 H 6 OCOCC 4 H 9 、-C 4 H 8 COOC 3 H 7 、-C 4 H 8 OCOCC 3 H 7 、-C 5 H 10 COOC 2 H 5 、-C 5 H 10 OCOCC 2 H 5 、-C 6 H 12 COOCH 3 、-C 6 H 12 OCOCH 3 、-COOC 8 H 17 、-OCOC 8 H 17 、-CH 2 COOC 7 H 15 、-CH 2 OCOC 7 H 15 、-C 2 H 4 COOC 6 H 13 、-C 2 H 4 OCOCC 6 H 13 、-C 3 H 6 COOC 5 H 11 、-C 3 H 6 OCOCC 5 H 11 、-C 4 H 8 COOC 4 H 9 、-C 4 H 8 OCOCC 4 H 9 、-C 5 H 10 COOC 3 H 7 、-C 5 H 10 OCOCC 3 H 7 、-C 6 H 12 COOC 2 H 5 、-C 6 H 12 OCOC 2 H 5 、-C 7 H 14 COOCH 3 、-C 7 H 14 OCOCH 3 、-CH 2 CN、-C 2 H 4 CN、-C 3 H 6 CN、-C 4 H 8 CN、-C 5 H 10 CN、-C 6 H 12 CN、-C 7 H 14 CN、-C 8 H 16 CN、-C 9 H 18 CN、-C 10 H 20 CN、-CH 2 NH 2 、-C 2 H 4 NH 2 、-C 3 H 6 NH 2 、-C 4 H 8 NH 2 、-C 5 H 10 NH 2 、-C 6 H 12 NH 2 、-C 7 H 14 NH 2 、-C 8 H 16 NH 2 、-C 9 H 18 NH 2 、-C 10 H 20 NH 2 、-CH 2 SH、-C 2 H 4 SH、-C 3 H 6 SH、-C 4 H 8 SH、-C 5 H 10 SH、-C 6 H 12 SH、-C 7 H 14 SH、-C 8 H 16 SH、-C 9 H 18 SH、-C 10 H 20 SH。
As a possible implementation manner, the number of carbon atoms in the heteroalkyl group is less than or equal to 20, and the heteroatom in the heteroalkyl group is at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. In this case, the above-mentioned heteroalkyl can increase the volume of the MDMON monomer, promote the MDMON monomer to produce the volume effect, help to raise the glass transition temperature of the cyclic olefin polymer; meanwhile, the carbon atom number of the heteroalkyl is in a proper range, and the influence of steric hindrance on the reaction activity of the MDMON monomer can be reduced. Moreover, the skeleton structure of the cycloolefin copolymer has excellent affinity and hydrophobicity, and the polarity of the cycloolefin copolymer can be increased by introducing oxygen atoms, nitrogen atoms, sulfur atoms and phosphorus atoms into the A and the B, so that the compatibility between the cycloolefin copolymer and a polar material is improved, the cycloolefin copolymer can be compatible with other polar materials or materials containing the polar materials, and the application range of the cycloolefin copolymer is widened. In some embodiments, the number of carbon atoms in the heteroalkyl group is less than or equal to 10.
As a possible realization, the aryl group is chosen from aryl groups having a number of carbon atoms less than or equal to 30. The aryl group includes an aryl group and an aralkyl group. Illustratively, the aryl group is selected from aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenethyl. The aryl is introduced into the MDMO monomer structure of the cyclic olefin polymer, so that the volume of the MDMO monomer can be increased, the MDMO monomer is promoted to generate a volume effect, and the glass transition temperature of the cyclic olefin polymer is favorably improved; moreover, the introduction of benzene ring is beneficial to improving the refractive index of the cycloolefin polymer, thereby improving the optical performance of the cycloolefin polymer.
As a possible implementation, the number of carbon atoms in the substituted aryl is less than or equal to 30. Exemplary aryl groups in the substituted aryl group are aryl or aralkyl groups selected from phenyl, tolyl, naphthyl, benzyl, phenethyl, and the like. The substituent in the substituted aryl is at least one of alkyl, hydroxyl, carboxyl, ester group, cyano, amino, thiol and halogen atom. Wherein, the substitution of the aryl in the aryl is beneficial to improving the glass transition temperature and the refractive index of the cycloolefin polymer; and polar groups such as hydroxyl, carboxyl, ester group, cyano, amino, thiol group and the like are beneficial to adjusting the polarity of the cycloolefin polymer, so that the compatibility between the cycloolefin polymer and other polar materials is improved, and the cycloolefin polymer has a wider application prospect.
As one possible implementation, the number of carbon atoms in the heterocyclic group is less than or equal to 30. Illustratively, the heteroaryl group is selected from furan, pyran, pyridine, or thiophene. The groups have certain aromaticity, and are beneficial to improving the glass transition temperature and the refractive index of the cycloolefin polymer; and the oxygen atom, the nitrogen atom, the sulfur atom and the phosphorus atom are beneficial to adjusting the polarity of the cycloolefin polymer, so that the compatibility between the cycloolefin polymer and other polar materials is improved, and the cycloolefin polymer has wider application prospect.
As a possible realization mode, A and B are respectively and independently selected from hydrogen atoms, halogen atoms, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups and-OC n H m 、-OCOC n H m 、-C n H m 、-C 6 H 5 、-C 6 H 4 CH 3 、-C 10 H 7 、-CH 2 C 6 H 5 、-CH 2 CH 2 C 6 H 5 、-C n H m C 6 H 5 (ii) a Wherein n is a positive integer less than or equal to 10, m is less than or equal to 2n +1, i.e., m is a positive integer less than or equal to 21. Because A and B are not hydrogen atoms at the same time, the introduction of at least one substituted alkyl group in the formula (1-1) or the formula (1-2) can increase the volume of the MDMO monomer, promote the MDMO monomer to generate a volume effect and is beneficial to improving the glass transition temperature of the cycloolefin polymer; the introduction of aryl is beneficial to improving the glass transition temperature and the refractive index of the cycloolefin polymer; the introduction of the polar group or the polar atom can increase the polarity of the cycloolefin copolymer, thereby improving the compatibility between the cycloolefin copolymer and the polar material, enabling the cycloolefin copolymer to be compatible with other polar materials or materials containing the polar materials, and further widening the application range of the cycloolefin copolymer.
As a possible implementation, a, B are connected in a ring. In the present embodiment, the phrase "A and B are linked to form a ring" means that A and B are bonded so that A and B are in a ring structure. A. After B is connected into a ring, the volume of the MDMON monomer is increased, the volume effect is increased, and the glass transition temperature of the cycloolefin polymer is favorably improved.
As one possible implementation, the ring is an aromatic ring, a cycloalkane, or a ring structure containing both an aromatic ring and a cycloalkane. In this case, the cycloolefin polymer has a relatively high glass transition temperature. When the ring is an aromatic ring or a ring structure containing both aromatic ring and cycloalkane, the refractive index of the cycloolefin copolymer can be increased without lowering the Abbe number of the cycloolefin copolymer, and the optical properties of the cycloolefin copolymer can be improved to a certain extent.
As a possible implementation, the ring is one of the following ring structures:
when A and B are connected into the ring structure, the glass transition temperature of the cycloolefin polymer can be increased, and the refractive index of the cycloolefin copolymer can be increased on the premise of not reducing the Abbe number, so that the overall optical performance of the cycloolefin copolymer is improved.
Illustratively, the MDMON monomer may be, but is not limited to, INDDMON or StDMON.
As a possible implementation, the cyclic olefin copolymer is a polymer represented by the following structure:
the cycloolefin copolymer has a better glass transition temperature, so that the cycloolefin copolymer has a better high-temperature resistance. In addition, when the cycloolefin copolymer contains a benzene ring structure, the refractive index of the cycloolefin copolymer can be increased without lowering the Abbe number, thereby improving the overall optical performance of the cycloolefin copolymer.
In the embodiment of the application, the cyclic olefin copolymers with different molecular weights can be obtained according to the application scene of the cyclic olefin copolymers. As a possible implementation, the cycloolefin copolymer has a number average molecular weight of less than or equal to 8 ten thousand and a weight average low molecular weight of less than or equal to 15 ten thousand. In this case, the cycloolefin copolymer has a lower viscosity and a better flowability at a low temperature, thereby contributing to an improvement in processability of the polymer.
The cycloolefin copolymer provided in the examples of the present application can be prepared by the following method.
Correspondingly, the embodiment of the application provides a preparation method of the cycloolefin copolymer, which comprises the following steps:
heating a solution system containing DMON, MDMO, ethylene, a catalyst and a cocatalyst for reaction to prepare the cyclic olefin copolymer.
In the embodiment of the application, two cycloolefin monomers DMON and MDMON (such as INDDMON or StDMON) and ethylene are used as polymerization monomers, and under the action of a catalyst and a cocatalyst, the three monomers are subjected to random copolymerization to prepare the cycloolefin copolymer shown in the structure of the formula (1-1) or the formula (1-2).
Among them, the cycloolefin monomer, indDMON, is originally a by-product generated during the synthesis of IndNB, and has a very small yield and is hardly used. The structures of the cycloolefin monomers IndDMON refer to example 1, example 2. In one possible implementation, the yield of the cycloolefin monomer, indDMON, is increased by varying the ratio of the two starting materials for the synthesis of IndNB. By this method, indNB and IndDMON, which are important cyclic olefin monomers, are mainly synthesized and can be more effectively used.
The embodiment of the application can achieve the effect of greatly improving the glass transition temperature of the cycloolefin copolymer by introducing a very small amount of the cycloolefin monomer MDSON, and maintain the prepared cycloolefin copolymer with excellent optical properties and high heat resistance in the aspect of the cycloolefin copolymer.
In the examples of the present application, when the three reactive monomers are randomly polymerized, the activity of MDMO is slightly reduced, and therefore, the amount of the reactive monomers to be fed is appropriately adjusted according to the molar ratio of the three monomers in the copolymer to be obtained. In one possible embodiment, the cycloolefin polymer is prepared with a molar ratio of the ethylene to DMON to MDMON fed in (0.57 to 0.67): (0.32-0.39): (0.01-0.04). In this case, the three components can participate in the reaction in a proper proportion to prepare the cycloolefin copolymer represented by the formula (1-1) or the formula (1-2).
In the embodiment of the present application, when adding DMON, MDMON, and ethylene into the reaction apparatus, the DMON and MDMON may be first added into the reaction apparatus, and then the ethylene is connected into the reaction apparatus through a pipeline. The method can control the content of ethylene monomer and adjust the reaction efficiency by controlling the ethylene pressure during pumping.
In the examples of the present application, a metallocene catalyst is used to catalyze DMON, MDMON, and ethylene to undergo random polymerization to form a cyclic olefin copolymer having a structure represented by formula (1-1) or formula (1-2). In one possible implementation, the general structural formula of the catalyst is as follows (2):
in the formula (2), M 1 Selected from scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, M 2 、M 3 Each independently selected from carbon, silicon, germanium or tin;
x represents carbon or silicon;
R 1 and R 2 Each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an alkaryl group or an aralkenyl group;
R 3 and R 4 Each independently selected from a hydrogen atom or a hydrocarbyl group;
R 5 、R 6 、R 7 、R 8 each independently selected from a hydrogen atom, a hydrocarbyl group, or a silicon-containing group bonded to the carbon atom at the corresponding substitution position through a silicon atom;
R 10 、R 11 、R 12 、R 15 、R 16 、R 17 each independently selected from alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl, or aralkenyl;
R 9 、R 13 、R 14 、R 18 each independently selected from a hydrogen atom, a hydrocarbyl group or a hydrocarbyloxy group;
wherein, R is 5 、R 6 、R 7 、R 8 At least one of which is a silicon-containing group, and/or said M 2 、M 3 At least one of which is silicon.
The catalyst shown in the formula (2) is a cyclopentadienyl fluorene bridged transition metal catalyst, a silicon-containing heteroatom group is introduced on cyclopentadienyl or fluorenyl of the catalyst, and a metal center M of the catalyst is subjected to ternary polymerization 1 The modified cyclic olefin copolymer has a synergistic effect with silicon atoms introduced on cyclopentadienyl or fluorenyl, can promote chain transfer in the polymerization process, and improve the insertion rate of cyclic olefin monomers, so that the cyclic olefin copolymer with low molecular weight (the weight average molecular weight is less than or equal to 15 ten thousand) and moderate glass transition temperature can be obtained in a chain addition copolymerization mode under the condition of not additionally introducing molecular weight regulators such as hydrogen or propylene. The obtained cycloolefin copolymer has a low melt flow index due to low molecular weight, and good processability, so that the cycloolefin copolymer is suitable for various application scenes. In addition, the silicon-containing group can control the selectivity of the reaction monomers through steric effect, thereby controlling the proportion of the three reaction monomers.
As one possible implementation, R 5 、R 6 、R 7 、R 8 At least one of which is a silicon-containing group, M 2 、M 3 Independently selected from carbon, germanium or tin. In other embodiments of the present application, R 5 、R 6 、R 7 、R 8 Independently selected from a hydrogen atom or a hydrocarbon group, M 2 、M 3 At least one of which is silicon. In other embodiments of the present application, R 5 、R 6 、R 7 、R 8 At least one of them being a silicon-containing group, while M 2 、M 3 At least one of which is silicon. The silicon-containing group is beneficial to controlling the selectivity of the reaction monomer, and further controlling the proportion of the three reaction monomers, and finally obtaining the cycloolefin polymer with the proportion of each monomer in the structure of the formula (1-1) or the formula (1-2).
In some embodiments of the present application, R 5 、R 6 、R 7 、R 8 Independently selected from hydrocarbyl or silicon-containing groups with the number of carbon atoms less than or equal to 6. Illustratively, the silicon-containing group may be selected from trimethylsilyl, triethylsilyl, triphenylsilyl, but is not limited thereto.
In some embodiments of the present application, R 6 、R 7 At least one of them being a silicon-containing group, or M 2 、M 3 At least one of which is silicon. The silicon-containing group being in the 3-and 4-positions of the cyclopentadiene compared with the 2-and 5-positions from the metal center M 1 Furthermore, silicon-containing groups are introduced into the 3-position and the 4-position of the cyclopentadiene, so that the metal center M can be contacted 1 Weak coordination is formed to promote chain transfer, the molecular weight of the polymer is reduced, and the influence on the polymerization reaction activity of the catalyst due to strong coordination action can be avoided.
In some embodiments of the present application, the R 10 、R 11 、R 12 、R 15 、R 16 、R 17 Has a carbon number of 10 or less. In this case, the catalyst has a suitable space size, which is advantageous for improving its catalytic activity.
In the embodiment of the present application, the catalyst for preparing cyclic olefin copolymer further comprises a cocatalyst, which includes but is not limited to at least one of methylaluminoxane, modified methylaluminoxane, and organoboron compound. In some embodiments herein, the organoboron compound comprises one or more of tris (pentafluorophenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Methyl aluminoxane, modified methyl aluminoxane and organic boron compound are used as cocatalyst, which is beneficial to ensuring the copolymerization reaction activity of the preparation of the cycloolefin copolymer.
As a possible implementation mode, the molar ratio of the catalyst shown in the formula (2) to the cocatalyst is 1 (10-10000). The molar weight of the two is in the range, which is beneficial to the activating performance of the cocatalyst on the catalyst. Exemplary, the molar ratio of the catalyst represented by formula (1-1) or formula (1-2) is 1, 1.
In the examples of the present application, the solvent for dispersing the raw material and the catalyst in the solution system containing DMON, MDMON, ethylene, the catalyst and the co-catalyst is an inert solvent. In a possible implementation manner, the solvent is a nonpolar solvent, has better dispersibility to DMON, MDMON and ethylene, and has reaction inertia, and the reaction effect of the polymerization reaction is not influenced. In some embodiments, the solvent is a linear alkane, cyclic hydrocarbon, or aromatic hydrocarbon. Illustratively, the solvent is toluene, but is not limited thereto.
In the examples of the present application, the polymerization reaction is carried out in an inert environment. The inert environment can be a nitrogen atmosphere or an inert atmosphere. In some embodiments, the gas environment in the reaction environment is replaced with an inert environment prior to the reaction. Illustratively, the reaction ambient gas is replaced with nitrogen.
In the examples of the present application, the polymerization reaction was carried out under heating. As a possible realization mode, the heating reaction temperature is 50-90 ℃ and the time is 2-60min. Under the condition, the catalyst has better catalytic activity and is beneficial to improving the polymerization reaction efficiency. Illustratively, the temperature of the heating reaction is 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and other specific temperatures, and the heating time can be 2min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min and other specific times. Generally, the higher the heating temperature, the shorter the heating time. In some embodiments, the temperature of the heating reaction is from 2 to 20min.
In one possible implementation, the solution system containing DMON, MDMON, ethylene, catalyst and promoter is heated to react under a pressure of 1 to 3 atmospheres. The reaction can be promoted by appropriately applying pressure. However, when the pressure is too high, the requirement for the safety performance of the equipment is higher, which is not beneficial to improving the safety performance.
After the polymerization, an aqueous solution of an inorganic acid is added to the resulting solution system to remove the catalyst and the cocatalyst in the solution system, particularly for removing the cocatalyst which is present in a large amount in the solution system. Specifically, the catalyst and the cocatalyst are dissolved in an inorganic acid aqueous solution, and the catalyst and the cocatalyst dissolved in the inorganic acid aqueous solution are removed by collecting an organic phase after the inorganic acid aqueous solution and the prepared cycloolefin polymer are layered. In some embodiments, the aqueous solution of inorganic acid has a weight percentage of inorganic acid of 2 to 10%. Illustratively, the inorganic acid is preferably hydrochloric acid which is inexpensive and does not cause side reactions. The oxidizing properties of nitric acid and the reactivity of sulfuric acid may initiate other miscellaneous side reactions.
After the organic phase is collected, the organic phase is washed with water to further remove residual water-soluble impurities. And purifying the organic phase by using acetone and/or ethanol, drying, and collecting the white cyclic olefin copolymer. When the organic phase is purified using acetone and ethanol, the acetone and ethanol may be mixed in any ratio to form a mixed solution. The organic phase is purified by adopting acetone and/or ethanol, so that unreacted monomers in the organic phase can be removed, and the purity of the cycloolefin polymer is improved.
In some embodiments, the method for purifying the organic phase with acetone is: fully stirring the obtained organic layer with acetone and/or ethanol, standing for settling, and filtering; adding acetone and/or ethanol into the solution collected by filtration, refluxing, filtering, and washing again. In some embodiments, the manner of drying treatment is vacuum drying.
In the examples of the present application, the general structural formula of the prepared cycloolefin copolymer is shown as the following formula (1-1) or formula (1-2):
in the formula (1-1) or the formula (1-2), the values of x, y and z satisfy the following conditions: x/(x + y + z) is more than or equal to 0.57 and less than or equal to 0.67, y/(x + y + z) is more than or equal to 0.32 and less than or equal to 0.39, and z/(x + y + z) is more than or equal to 0.01 and less than or equal to 0.04; r 1 Is an atom or group of atoms, R 2 Is an atom or a radical of an atom, and R 1 、R 2 Not simultaneously hydrogen atoms. In the case of the cycloolefin polymer having the structure represented by the formula (1-1) or the formula (1-2), as described above, the structure of the cycloolefin polymer will not be described here for the sake of brevity.
According to the preparation method of the cyclic olefin copolymer provided by the embodiment of the application, the DMON and the quadricyclic cyclic olefin monomer MDMO are selected as cyclic olefin monomers, wherein a polymer formed by the MDMO monomer through ring opening metathesis polymerization and hydrogenation has a higher glass transition temperature, and can reach more than 230 ℃. Therefore, the embodiments of the present application can improve the glass transition temperature of the three-membered cyclic olefin polymer by polymerizing ethylene, DMON and MDMON monomers as raw materials, thereby improving the heat resistance of the cyclic olefin copolymer. Since the glass transition temperature of the MDMO polymer is high, the glass transition temperature of the cyclic olefin polymer can be significantly increased by adding a small amount (0.01 to 0.04 of the total molar amount of the viscous polymer) of MDMO monomer to the bonding reaction. Meanwhile, according to the preparation method of the cyclic olefin copolymer provided by the application, the MDMON monomer does not contain benzene ring substituent groups or the benzene ring substituent groups are far away from a norbornene ring which is a reaction site, so that the negative influence of the reaction on the optical properties of the cyclic olefin copolymer can be reduced, and good optical performance is kept. In addition, the embodiment of the application can achieve the effect of obviously improving the glass transition temperature of the cyclic olefin polymer by introducing a small amount of MDMO monomer, and is beneficial to improving the economic efficiency of preparing the cyclic olefin polymer.
In a third aspect of the embodiments of the present application, there is provided a use of a cyclic olefin copolymer as a lens material of a camera, where the cyclic olefin copolymer is the cyclic olefin copolymer of the first aspect or the cyclic olefin copolymer prepared by the method of the second aspect.
The cycloolefin copolymer provided by the embodiment of the application has higher glass transition temperature, so that the cycloolefin copolymer has better high temperature resistance, keeps better optical performance, can be used as a camera lens material, and endows the camera lens with good high temperature resistance and optical performance.
As a possible implementation manner of the application of the cyclic olefin copolymer, the camera lens material is a vehicle-mounted camera lens material or a security camera lens material. Compared with the commercial cycloolefin copolymer material at present, the cycloolefin copolymer provided by the application is adopted as the vehicle-mounted camera lens material and the security camera lens material, and the cycloolefin copolymer has better heat resistance on the basis of not influencing the optical performance of the camera lens.
The following description will be given with reference to specific examples.
Example 1
A method for preparing a cyclic olefin monomer, indDMON, comprising:
in a stainless steel autoclave, 58g of cyclopentadiene, 33g of indene and 0.5g of butynedioic acid were charged and reacted at 190 ℃ for 15 hours. The crude product of 22g of IndNB and 10g of IndDMON was obtained by distillation under reduced pressure after temperature reduction. The crude product was dissolved in hexane and recrystallized in a refrigerator to give 8g of a white solid after filtration.
The 1H-NMR spectrum of the cycloolefin monomer IndDMON obtained in example 1 is shown in FIG. 1, and the 13C-NMR spectrum of the cycloolefin monomer IndDMON obtained is shown in FIG. 2.
Example 2
A method of preparing a cycloolefin copolymer, comprising:
a glass reaction vessel containing 2.5g of cycloolefin monomer DMON,0.25g of cycloolefin monomer IndDMON,2.5mL of MAO (1.5 mol/L) and 45mL of toluene was placed in an ethylene line, the gas in the ethylene line was replaced with nitrogen for three times, and after the replacement, the ethylene gas was purged, and the toluene solution in the glass vessel was stirred to saturate ethylene. The polymerization temperature was adjusted to 90 ℃ and 2.0mg of a toluene solution of catalyst A having the following structure was added under the condition of passing ethylene, and the pressure of ethylene was adjusted to one atmosphere and the polymerization was carried out for 5 minutes. After the polymerization is finished, pouring the obtained reaction solution into a 10% hydrochloric acid aqueous solution by mass percent, fully stirring, separating the solution, collecting an organic layer, and washing twice with water; the obtained organic layer was precipitated with acetone under sufficient stirring, an appropriate amount of acetone was added after filtration and refluxed for 2 hours, the collected polymer was filtered and washed with acetone three times, and the product was placed in a vacuum drying oven and dried at 130 ℃ for 18 hours to obtain a white cycloolefin copolymer P1.
The glass transition temperature of the cycloolefin copolymer obtained in example 2 was measured by Differential Scanning Calorimetry (DSC), and the results are shown in FIG. 3. The results of FIG. 3 show that the glass transition temperature of the cycloolefin copolymer prepared in example 2 was 142.81 ℃.
FIG. 4 shows the results of high-temperature nuclear magnetic carbon spectrum detection of the cycloolefin copolymer obtained in example 2. FIG. 4 shows that the insertion rates of the cycloolefin monomers DMON and IndDMON of the cycloolefin copolymer prepared in example 2 were 32% and 1%, respectively.
The cycloolefin copolymer obtained in example 2 was weighed out to a mass of 3.42g and a reactivity of 2.05X 10 7 g mol -1 h -1 The cycloolefin copolymer obtained in example 2 was found to have a number average molecular weight of 47kg/mol and a molecular weight distribution index of 1.73 by high temperature gel chromatography.
The cycloolefin copolymer prepared in example 2 was prepared as a cycloolefin copolymer film by a solution film laying method, and the cycloolefin copolymer film was tested by an optical instrument, and it was found that the cycloolefin copolymer P1 had a refractive index of 1.54, an abbe number of 55.1 and a transmittance of 90.7%.
Example 3
A method of preparing a cycloolefin copolymer, comprising:
a glass reactor containing 2.5g of cycloolefin monomer DMON,0.5g of cycloolefin monomer IndDMON,2.5mL of MAO (1.5 mol/L) and 45mL of toluene was placed in an ethylene line, the ethylene line was purged with nitrogen three times, the ethylene gas was purged, and the toluene solution in the glass reactor was saturated with ethylene by stirring. The polymerization temperature was adjusted to 90 ℃ and 2.0mg of a toluene solution of catalyst A (same as in example 1) in 2mL was added thereto under feeding ethylene, and the pressure of ethylene was adjusted to one atmospheric pressure and the polymerization was carried out for 5 minutes. After the polymerization is finished, pouring the obtained reaction solution into a 10% hydrochloric acid aqueous solution by mass percent, fully stirring, separating the solution, collecting an organic layer, and washing twice with water; the obtained organic layer was precipitated with acetone under sufficient stirring, an appropriate amount of acetone was added after filtration to reflux for 2 hours, the collected polymer was filtered and washed with acetone three times, and the product was placed in a vacuum drying oven and dried at 130 ℃ for 18 hours to obtain a white cycloolefin copolymer P2.
The glass transition temperature of the cycloolefin copolymer obtained in example 3 was measured by Differential Scanning Calorimetry (DSC), and the results are shown in FIG. 5. The results of FIG. 5 show that the glass transition temperature of the cycloolefin copolymer prepared in example 3 was 150.58 ℃.
FIG. 6 shows the results of high-temperature nuclear magnetic carbon spectrum detection of the cycloolefin copolymer obtained in example 3. FIG. 6 shows that the insertion rates of the cycloolefin monomers DMON and IndDMON of the cycloolefin copolymer prepared in example 3 were 35.4% and 1.6%, respectively.
The cycloolefin copolymer obtained in example 3 was weighed out to a mass of 2.82g and a reactivity of 1.69X 10 7 g mol -1 h -1 The cycloolefin copolymer obtained in example 3 was determined by high-temperature gel chromatography to have a number average molecular weight of 37kg/mol and a molecular weight distribution index of 1.78.
The cycloolefin copolymer prepared in example 3 was prepared as a cycloolefin copolymer film by a solution film-laying method, and the cycloolefin copolymer film was tested by an optical instrument, whereby it was found that the cycloolefin copolymer P2 had a refractive index of 1.54, an abbe number of 53.2 and a transmittance of 90.6%.
Example 4
A method of preparing a cycloolefin copolymer, comprising:
a glass reaction kettle filled with 2.5g of cycloolefin monomer DMON,1g of cycloolefin monomer IndDMON,2.5mL of MAO (1.5 mol/L) and 45mL of toluene was placed in an ethylene pipeline, the gas in the ethylene pipeline was replaced with nitrogen for three times, then the ethylene gas was introduced, and the glass kettle was stirred to saturate the toluene solution with ethylene. The polymerization temperature was adjusted to 90 ℃ and 1.5mg of a toluene solution of the catalyst B having the following structure in 2mL was added thereto under feeding ethylene, and the pressure of ethylene was adjusted to one atmosphere and the polymerization was carried out for 5 minutes. After the polymerization is finished, pouring the obtained reaction solution into a 10% hydrochloric acid aqueous solution by mass percent, fully stirring, separating the solution, collecting an organic layer, and washing twice with water; the obtained organic layer was precipitated with acetone under sufficient stirring, an appropriate amount of acetone was added after filtration and refluxed for 2 hours, the collected polymer was filtered and washed with acetone three times, and the product was placed in a vacuum drying oven and dried at 130 ℃ for 18 hours to obtain a white cycloolefin copolymer P3.
The glass transition temperature of the cycloolefin copolymer obtained in example 4 was measured by Differential Scanning Calorimetry (DSC), and the results are shown in FIG. 7. The results of FIG. 7 show that the glass transition temperature of the cycloolefin copolymer prepared in example 4 was 164.89 ℃.
FIG. 8 shows the results of high-temperature nuclear magnetic carbon spectrum detection of the cycloolefin copolymer obtained in example 4. FIG. 8 shows that the insertion rates of the cycloolefin monomers DMON and IndDMON of the cycloolefin copolymer prepared in example 4 were 39% and 4%, respectively.
The cycloolefin copolymer obtained in example 4 was weighed out to a mass of 1.78g and a reactivity of 1.07X 10 7 g mol -1 h -1 The cycloolefin copolymer obtained in example 4 was determined by high-temperature gel chromatography to have a number average molecular weight of 38kg/mol and a molecular weight distribution index of 1.77.
The cycloolefin copolymer prepared in example 4 was prepared as a cycloolefin copolymer film by a solution film-laying method, and the cycloolefin copolymer film was tested by an optical instrument, whereby it was found that the cycloolefin copolymer P3 had a refractive index of 1.55, an abbe number of 53.5 and a transmittance of 91.4%.
Example5
A method of preparing a cycloolefin copolymer, comprising:
a glass reaction vessel containing 2.5g of cycloolefin monomer DMON,0.5g of cycloolefin monomer StDMON,2.5mL of MAO (1.5 mol/L) and 45mL of toluene was placed in an ethylene line, the gas in the ethylene line was replaced with nitrogen gas three times, and after the replacement, the ethylene gas was purged, and the toluene solution in the glass reaction vessel was stirred to saturate ethylene. The polymerization temperature was adjusted to 90 ℃ and 1.5mg of the structural catalyst B (same as in example 4) in 2mL of toluene was added thereto under feeding ethylene, and the pressure of ethylene was adjusted and maintained at one atmospheric pressure for 5 minutes of polymerization. After the polymerization is finished, pouring the obtained reaction solution into a 10% hydrochloric acid aqueous solution by mass percent, fully stirring, separating the solution, collecting an organic layer, and washing twice with water; the obtained organic layer was precipitated with acetone under sufficient stirring, an appropriate amount of acetone was added after filtration and refluxed for 2 hours, the collected polymer was filtered and washed with acetone three times, and the product was placed in a vacuum drying oven and dried at 130 ℃ for 18 hours to obtain a white cycloolefin copolymer P4.
The glass transition temperature of the cycloolefin copolymer obtained in example 2 was measured by Differential Scanning Calorimetry (DSC), and the results are shown in FIG. 9. The results of FIG. 9 show that the glass transition temperature of the cycloolefin copolymer prepared in example5 was 157 ℃.
When the cycloolefin copolymer obtained in example5 was subjected to high temperature nuclear magnetic carbon spectrum detection, the insertion rates of the cycloolefin monomers DMON and StDMON of the cycloolefin copolymer were 35.8% and 2%, respectively.
The cycloolefin copolymer obtained in example5 was weighed out to a mass of 2.66g and had an activity of 1.60X 10 7 g mol -1 h -1 The cycloolefin copolymer obtained in example5 was found to have a number average molecular weight of 36kg/mol and a molecular weight distribution index of 1.78 by high temperature gel chromatography.
The cycloolefin copolymer prepared in example5 was prepared as a cycloolefin copolymer film by a solution film-laying method, and the cycloolefin copolymer film was tested by an optical instrument to find that the cycloolefin copolymer P4 had a refractive index of 1.55, an abbe number of 53.2, and a transmittance of 90.1%.
Comparative example 1
A method of preparing a cycloolefin copolymer, comprising:
a glass reactor containing 2.5g of cycloolefin monomer DMON,2.5mL of MAO (1.5 mol/L) and 45mL of toluene was placed in an ethylene line, the gas in the ethylene line was replaced with nitrogen gas three times, and then ethylene gas was introduced into the ethylene line, followed by stirring to saturate the toluene solution in the glass reactor with ethylene. The polymerization temperature was adjusted to 90 ℃ and 1.2mg of a metallocene catalyst B (the same as in example 4) in 2mL of toluene was added thereto under feeding ethylene, and the pressure of ethylene was adjusted to one atmospheric pressure and the polymerization was carried out for 5 minutes. After the polymerization is completed, pouring the obtained reaction solution into a hydrochloric acid aqueous solution with the mass percent of 10%, fully stirring, separating liquid, collecting an organic layer, and washing twice with water; the obtained organic layer was precipitated with acetone under sufficient stirring, an appropriate amount of acetone was added after filtration and refluxed for 2 hours, the collected polymer was filtered and washed with acetone three times, and the product was placed in a vacuum drying oven and dried at 130 ℃ for 18 hours to obtain a white cycloolefin copolymer P5.
The glass transition temperature of the cycloolefin copolymer obtained in comparative example 1 was measured by Differential Scanning Calorimetry (DSC), and the results are shown in FIG. 10. The results of FIG. 10 show that the glass transition temperature of the cycloolefin copolymer prepared in comparative example 1 was 128 ℃.
The results of high temperature nuclear magnetic carbon spectrum detection of the cycloolefin copolymer obtained in comparative example 1 are shown in FIG. 11. The results of FIG. 11 show that the insertion rate of the cycloolefin monomer DMON was 30% in the cycloolefin copolymer prepared in the comparative example.
The cycloolefin copolymer obtained in comparative example 1 was weighed out to a mass of 3.72g and had an activity of 2.23X 10 7 g mol -1 h -1 The cycloolefin copolymer obtained in comparative example 1 was determined by high-temperature gel chromatography to have a relative number-average molecular weight of 54kg/mol and a molecular weight distribution index of 1.62.
The cycloolefin copolymer prepared in comparative example 1 was prepared into a cycloolefin copolymer film by a solution-spreading method, and the cycloolefin copolymer film was tested by an optical instrument, whereby it was found that the cycloolefin copolymer P5 had a refractive index of 1.54, an Abbe number of 59.1 and a transmittance of 91.0%.
Comparative example 2
The cycloolefin copolymer P6 prepared by Table3 Example5 in patent US20200369812A1 had a glass transition temperature of 154 ℃ and the cycloolefin copolymer P6 prepared in comparative Example 2 had insertion rates of the cycloolefin monomers DMON and IndNB of 21.3% and 15.4%, respectively, and refractive indices and Abbe numbers of 1.56 and 47, respectively.
In the preparation methods of examples 2 to 4 and comparative examples 1 to 2, the selection of the cycloolefin monomers DMON and IndNB and the amounts thereof, the reaction activities, the numbers of the prepared cycloolefin copolymers, the insertion amounts of the ethylene monomers, the cycloolefin monomers DMON and IndNB, mn, the glass transition temperature, the abbe number, and the transmittance were statistically shown in table 1 below.
TABLE 1
As can be seen from table 1, compared to comparative example 1, the abbe number and transmittance of the examples are not significantly reduced after introducing the cycloolefin monomers IndDMON and StDMON, but the glass transition temperature is increased, and it can be seen that the cycloolefin copolymer prepared in the examples has improved heat resistance while maintaining good optical properties.
Compared with the comparative example 2, after the examples of the present application adopt a very small amount of IndDMON and StDMON as the cycloolefin monomers, the abbe number of the prepared cycloolefin copolymer is increased, the refractive index can be maintained to be better, and the glass transition temperature is 143 ℃ to 165 ℃, so that the cycloolefin copolymer prepared by the examples of the present application has better optical performance and heat resistance, that is, the cycloolefin copolymer provided by the examples of the present application does not increase the glass transition temperature at the expense of optical performance. In particular, the cycloolefin copolymer prepared in example 4, in which the insertion amount of the cycloolefin monomer IndDMON was only about one fourth of that of comparative example 2, was higher than that of the cycloolefin copolymer provided in comparative example 2 in Abbe number and the glass transition temperature was higher than that of the cycloolefin copolymer provided in comparative example 2 because the cycloolefin monomer IndDMON had a polycyclic structure and a benzene ring structure affecting the Abbe number was far from the polymerization site.
The test methods of the examples and comparative examples of the present application are as follows:
the refractive index test method is according to ASTM D542;
the transmittance was measured according to ASTM D1003;
the insertion rate refers to the molar ratio of the cycloolefin monomer in the polymer, and the calculation method through high-temperature nuclear magnetism is as follows: insertion = a/(a + b + c) · 100%, where a is the molar amount of cycloolefin monomer in the polymer, b is the molar amount of other cycloolefin monomers in the polymer, and c is the molar amount of polyethylene in the polymer;
mn refers to the number average molecular weight of the polymer, the value of which is directly measured by high temperature GPC.
The present application is intended to cover various modifications, equivalent arrangements, and adaptations of the present application without departing from the spirit and scope of the present application.
Claims (19)
1. A cycloolefin copolymer is characterized in that the structural general formula of the cycloolefin copolymer is shown as the following formula (1-1) or formula (1-2):
in the formula (1-1) or the formula (1-2), the values of x, y and z satisfy the following conditions: x/(x + y + z) is more than or equal to 0.57 and less than or equal to 0.67, y/(x + y + z) is more than or equal to 0.32 and less than or equal to 0.39, and z/(x + y + z) is more than or equal to 0.01 and less than or equal to 0.04; a is an atom or an atomic group, B is an atom or an atomic group, and A and B are not simultaneously hydrogen atoms.
2. The cycloolefin copolymer according to claim 1, wherein A and B are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, a heteroalkyl group, an aryl group, a substituted aryl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group.
3. The cycloolefin copolymer according to claim 2, characterized in that the alkyl groups are selected from the group consisting of alkyl groups having a number of carbon atoms of less than or equal to 20;
the carbon atom number of the substituted alkyl is less than or equal to 20, and the substituent in the substituted alkyl is at least one of hydroxyl, carboxyl, ester group, cyano-group, amino, thiol group and halogen atom;
the number of carbon atoms in the heteroalkyl group is less than or equal to 20, and the heteroatom in the heteroalkyl group is at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
4. The cyclic olefin copolymer of claim 2, wherein the aryl group is selected from phenyl, tolyl, naphthyl, benzyl, or phenethyl;
the aryl in the substituted aryl is selected from phenyl, tolyl, naphthyl, benzyl or phenethyl, and the substituent in the substituted aryl is at least one of alkyl, hydroxyl, carboxyl, ester group, cyano, amino, thiol group and halogen atom;
the heterocyclic group is selected from furan, pyran, pyridine or thiophene.
5. The cycloolefin copolymer according to any one of claims 1 to 4, characterized in that A, B are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, -OC n H m 、-OCOC n H m 、-C n H m 、-C 6 H 5 、-C 6 H 4 CH 3 、-C 10 H 7 、-CH 2 C 6 H 5 、-CH 2 CH 2 C 6 H 5 、-C n H m C 6 H 5 (ii) a Wherein n is a positive integer less than or equal to 10, m is a positive integer less than or equal to 21, and m is less than or equal to 2n +1.
6. The cycloolefin copolymer according to claim 1, characterized in that A and B are joined to form a ring.
7. The cycloolefin copolymer according to claim 6, characterized in that the ring is an aromatic ring, a cycloalkane, or a ring structure containing both an aromatic ring and a cycloalkane.
8. The cyclic olefin copolymer of claim 7, wherein the ring is one of the following ring structures:
9. cycloolefin copolymer according to one of claims 1 to 8, characterized in that the cycloolefin copolymer is a copolymer of the following structure:
10. the cycloolefin copolymer according to any of claims 1 to 9, characterized in that the number average molecular weight of the cycloolefin copolymer is less than or equal to 8 ten thousand and the weight average low molecular weight is less than or equal to 15 ten thousand.
11. A method for preparing a cycloolefin copolymer, characterized by comprising the steps of:
heating a solution system containing DMON, MDMO, ethylene, a catalyst and a cocatalyst for reaction to prepare the cyclic olefin copolymer;
wherein the structural general formula of the cycloolefin copolymer is shown as the following formula (1-1) or formula (1-2):
in the formula (1-1) or the formula (1-2), the values of x, y and z satisfy the following conditions: x/(x + y + z) is more than or equal to 0.57 and less than or equal to 0.67, y/(x + y + z) is more than or equal to 0.32 and less than or equal to 0.39, and z/(x + y + z) is more than or equal to 0.01 and less than or equal to 0.04; a is atom or atom group, B is atom or atom group, and A, B are not hydrogen atom at the same time;
the catalyst is a metallocene catalyst.
12. The method of preparing a cyclic olefin copolymer according to claim 11, wherein the general structural formula of the catalyst is represented by the following formula (2):
in the formula (2), M 1 Selected from scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, M 2 、M 3 Each independently selected from carbon, silicon, germanium or tin;
x represents carbon or silicon;
R 1 and R 2 Each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an alkaryl group or an aralkenyl group;
R 3 and R 4 Each independently selected from a hydrogen atom or a hydrocarbyl group;
R 5 、R 6 、R 7 、R 8 each independently selected from a hydrogen atom, a hydrocarbyl group, or a silicon-containing group bonded to the carbon atom at the corresponding substitution position through a silicon atom;
R 10 、R 11 、R 12 、R 15 、R 16 、R 17 each independently selected from alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl, or aralkenyl;
R 9 、R 13 、R 14 、R 18 each independently selected from a hydrogen atom, a hydrocarbyl group or a hydrocarbyloxy group;
wherein, R is 5 、R 6 、R 7 、R 8 At least one of which is a silicon-containing group, and/or said M 2 、M 3 At least one of which is silicon.
13. The method for preparing cycloolefin copolymer according to claim 12, wherein R is 6 、R 7 At least one of is said silicon-containing group, or said M 2 、M 3 At least one of which is silicon.
14. The method for preparing cycloolefin copolymer according to claim 12 or 13, wherein R is 5 、R 6 、R 7 、R 8 Independently selected from hydrocarbyl or silicon-containing groups with the number of carbon atoms less than or equal to 6.
15. The method for preparing cycloolefin copolymer according to any one of claims 12 to 14, characterized in that R is 10 、R 11 、R 12 、R 15 、R 16 、R 17 Has a carbon number of 10 or less.
16. The method of preparing a cyclic olefin copolymer according to any one of claims 11 to 15, wherein the cocatalyst is at least one of methylaluminoxane, modified methylaluminoxane, and organoboron compound.
17. The process for preparing a cycloolefin copolymer according to any one of claims 11 to 16, characterized in that the temperature of the heating reaction is 50 to 90 ℃ for 2 to 60min.
18. Use of a cyclic olefin copolymer as a lens material for a camera, wherein the cyclic olefin copolymer is a cyclic olefin copolymer according to any one of claims 1 to 10 or a cyclic olefin copolymer prepared by the method according to any one of claims 11 to 17.
19. The use of claim 18, wherein the camera lens material is a vehicle camera lens material, a security camera lens material.
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