CN113372478B - Aldehyde group functionalized cycloolefin-ethylene copolymer and preparation method thereof - Google Patents
Aldehyde group functionalized cycloolefin-ethylene copolymer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 125000003172 aldehyde group Chemical group 0.000 title abstract description 17
- 229920001038 ethylene copolymer Polymers 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- 239000011733 molybdenum Substances 0.000 claims abstract description 21
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 107
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- -1 hydroxy norbornene Chemical compound 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 9
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 7
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 7
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 claims description 6
- BXKVMQAJHSXYHX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-en-4-ol Chemical compound C1CC2C=CC1(O)C2 BXKVMQAJHSXYHX-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- ASLHVQCNFUOEEN-UHFFFAOYSA-N dioxomolybdenum;dihydrochloride Chemical compound Cl.Cl.O=[Mo]=O ASLHVQCNFUOEEN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- CZYVCAJKUNEWLC-UHFFFAOYSA-N 2-(5-bicyclo[2.2.1]hept-2-enyl)ethanol Chemical compound C1C2C(CCO)CC1C=C2 CZYVCAJKUNEWLC-UHFFFAOYSA-N 0.000 claims description 4
- RRQIBICVEGYMKJ-UHFFFAOYSA-N 3-(5-bicyclo[2.2.1]hept-2-enyl)propan-1-ol Chemical compound C1C2C(CCCO)CC1C=C2 RRQIBICVEGYMKJ-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940117389 dichlorobenzene Drugs 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- PFBDSPCRSGIFPN-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2](CC)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2](CC)C1C2=CC=CC=C2C=C1 PFBDSPCRSGIFPN-UHFFFAOYSA-L 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- WLCBPITVIPSVKN-UHFFFAOYSA-N 4-(5-bicyclo[2.2.1]hept-2-enyl)butan-1-ol Chemical compound C1C2C(CCCCO)CC1C=C2 WLCBPITVIPSVKN-UHFFFAOYSA-N 0.000 claims description 2
- NVZOLHDRKMPIRA-UHFFFAOYSA-L C[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 NVZOLHDRKMPIRA-UHFFFAOYSA-L 0.000 claims description 2
- QLABXPWIGKDWFY-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=2C3=CC=CC=C3CC12)[Zr+2].C1(=CC=CC=C1)C(C1=CC=CC=C1)=C1C=CC=C1 Chemical compound [Cl-].[Cl-].C1(=CC=CC=2C3=CC=CC=C3CC12)[Zr+2].C1(=CC=CC=C1)C(C1=CC=CC=C1)=C1C=CC=C1 QLABXPWIGKDWFY-UHFFFAOYSA-L 0.000 claims description 2
- QQNVVKOCWIAFDB-UHFFFAOYSA-L [Cl-].[Cl-].CC(C)[Zr++](C1C=Cc2ccccc12)C1C=Cc2ccccc12 Chemical compound [Cl-].[Cl-].CC(C)[Zr++](C1C=Cc2ccccc12)C1C=Cc2ccccc12 QQNVVKOCWIAFDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000012968 metallocene catalyst Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000003780 insertion Methods 0.000 abstract description 20
- 230000037431 insertion Effects 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 16
- 230000009477 glass transition Effects 0.000 abstract description 14
- 229920001577 copolymer Polymers 0.000 abstract description 9
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000009566 Mao-to Substances 0.000 description 1
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 description 1
- FZQRDAAZGWFJQD-UHFFFAOYSA-L [Cl-].[Cl-].C1=Cc2ccccc2C1[Zr++](C(c1ccccc1)c1ccccc1)C1C=Cc2ccccc12 Chemical compound [Cl-].[Cl-].C1=Cc2ccccc2C1[Zr++](C(c1ccccc1)c1ccccc1)C1C=Cc2ccccc12 FZQRDAAZGWFJQD-UHFFFAOYSA-L 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SFFFIHNOEGSAIH-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene;ethene Chemical group C=C.C1C2CCC1C=C2 SFFFIHNOEGSAIH-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an aldehyde functional cycloolefin-ethylene copolymer and a preparation method thereof, the copolymer structure comprises two copolymerization units, one is ethylene, the other is aldehyde functional norbornene, and the specific structure is shown as follows:
Description
Technical Field
The invention belongs to the field of polymerization of cycloolefin, and relates to an aldehyde-group functionalized norbornene-ethylene copolymer and a preparation method thereof.
Background
Cycloolefin copolymer (COC) is a high value-added thermoplastic engineering plastic prepared by copolymerizing Norbornene (NB) and ethylene (E). The COC has extremely high light transmittance, low scattering and birefringence, excellent heat resistance, chemical resistance and ray resistance due to an amorphous structure with a rigid ring in a main chain, and has good dimensional stability in different temperature and humidity environments due to a hydrocarbon nonpolar structure. At present, COC is widely applied to the fields of optical lenses, optical gratings, medical packaging, food packaging, communication and the like. The introduction of polar groups into the COC structure can improve the refractive index, hydrophilicity, compatibility with other materials and the like of the material, and can greatly widen the application field of the COC. However, due to the poisoning effect of polar functional groups on metal catalysts, the preparation of polarized COCs by copolymerization of polarized norbornene with ethylene is very challenging and a hotspot for industrial and academic research.
Since late transition metals have weak electrophilicity and strong resistance to polar groups, various polarized COCs are successfully prepared by the academia through the catalysts, and examples of the polarized COCs prepared by the late transition metal catalysts successfully triggering the copolymerization of norbornene hydrocarbons with various polar groups such as hydroxyl, carboxyl, carbonyl, ester groups and the like with ethylene are reported in documents (macromolecules.2003,36,9731, j.am.chem.soc.2009,131,5902, j.polym.sci.a. chem.2002,40,2842 and the like). However, the post-transition metal catalyst has low activity, and the COC obtained by polymerization has low molecular weight, low insertion rate of polar groups and poor structure controllability, so that no related commercial product exists. The COC is industrially produced by adopting a pre-transition metal catalyst which has strong electrophilicity and is easy to be poisoned by polar groups, so that the catalyst is not suitable for catalyzing polar COC polymerization, and only a few patents report hydroxyl-functionalized COC, but no other COC with polar groups is reported.
Disclosure of Invention
The invention aims to provide a polarized COC which has good hydrophilicity and optical characteristics, and compared with the traditional COC, the polymer has higher glass transition temperature and refractive index at the same insertion rate, so that the polarized COC is quite suitable for being used as optical materials such as lenses.
The invention firstly prepares hydroxyl functional COC by an alkyl aluminum protection method, then removes a protective group by hydrochloric acid, and finally dehydrogenates the hydroxyl by a molybdenum catalyst to obtain aldehyde functional COC.
The polymer structure provided by the invention comprises two copolymerization units, wherein one is ethylene, and the other is aldehyde group functionalized norbornene, and the specific structure is represented as follows:
wherein m is an integer of 1-10000, preferably 100-2000, n is an integer of 10-10000, preferably 100-2000, and x is 0-10, preferably 1-3; preferably, the aldehyde-functionalized COC has Mw of 1000-.
The aldehyde functional COC is prepared by dehydrogenating hydroxylated COC:
adding hydroxyl functionalized COC, a molybdenum catalyst and a solvent into a reaction flask, raising the temperature of the reaction flask to T1 to mark the reaction as the beginning, filtering reaction liquid to remove the catalyst after T1 of reaction, and then pumping the solvent to dry to obtain aldehyde functionalized COC;
in the preparation method, the reaction temperature T1 is 0-250 ℃, preferably 100-150 ℃;
the reaction time t1 is 0.5 to 50 hours, preferably 2 to 10 hours;
the solvent is one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide, chlorobenzene (DMSO) and dichlorobenzene, and the mass ratio of the solvent to the hydroxyl-functionalized COC can be 100: 1 to 1: 1;
the mass ratio of molybdenum catalyst to hydroxyl-functionalized COC may be 1:10 to 1: 100000.
in the preparation method, the preparation method of the molybdenum catalyst comprises the following steps:
adding molybdenum dichloride dioxide, carbon black and a solvent into a reaction bottle, stirring for 2-50 hours at 80-250 ℃, evaporating the solvent after the reaction is finished, performing reflux extraction on the solvent, and drying the extracted solid to obtain a molybdenum catalyst;
wherein the mass ratio of the added molybdenum dichloride dioxide to the carbon black is 1: 2 to 100: 1; the solvent is one or more of DMF, DMSO and dichlorobenzene; the mass ratio of the solvent to the molybdenum dichloride dioxide can be 1:1 to 100: 1.
in the preparation method of the invention, the hydroxyl-functionalized COC is prepared by cationic polymerization:
adding a certain amount of hydroxy norbornene monomer into a nonpolar solvent to prepare a solution, then adding an equimolar amount of alkyl aluminum solid into the solution, uniformly stirring, heating to 50-120 ℃, stirring for 1-20 hours, then introducing ethylene gas into the solution to control the pressure in a reaction kettle to be 0.1-3MPa, then adding Methylaluminoxane (MAO) and a catalyst solid into the reaction solution through a catalyst feeding bin, continuing to react for 1-30 minutes, adding an excessive hydrochloric acid and ethanol mixed solution after the reaction is finished, quenching and precipitating, separating and drying the precipitated solid to obtain the hydroxyl functionalized COC.
In the preparation method of the hydroxylated COC, the nonpolar solvent is one or more of toluene, cyclohexane, methylcyclohexane and hexane, and toluene is preferred.
In the preparation method of the hydroxylated COC, the alkyl aluminum is one of trimethyl aluminum, triisobutyl aluminum and triethyl aluminum, and the preferred is trimethyl aluminum.
In the preparation method of the hydroxylated COC, the structure of the hydroxyl norbornene is as follows:
x is 0 to 10, preferably 1 to 3, such as 5-norbornene-2-methanol, 5-norbornene-2-ethanol, 5-norbornene-2-propanol, 5-norbornene-2-butanol and the like, preferably 5-norbornene-2-ethanol, 5-norbornene-2-propanol.
In the method of preparing a hydroxylated COC according to the invention, the concentration of the solution of hydroxynorbornene may be from 0.01 to 10mol/L, preferably from 0.1 to 2 mol/L.
In the preparation method of the hydroxylated COC, the molar ratio of MAO to hydroxynorbornene is 1:10 to 1:10000, preferably 1:100 to 1: 1000;
in the preparation method of the hydroxylated COC, the catalyst is a general bridged metallocene catalyst, such as rac-dimethylsilylbisindene zirconium dichloride, ethylbisindenyl zirconium dichloride, isopropylbisindenyl zirconium dichloride, diphenylmethyl bisindenyl zirconium dichloride, diphenylmethylene (cyclopentadiene) fluorenyl zirconium dichloride, dimethylsilyl (cyclopentadiene) fluorenyl zirconium dichloride, methyl biscyclopentadienyl zirconium dichloride and the like, preferably rac-dimethylsilylbisindene zirconium dichloride and ethylbisindenyl zirconium dichloride, and the molar ratio of the catalyst to the hydroxyl norbornene is 1:1000 to 1:1000000, preferably 1:10000 to 1: 100000.
The invention has the beneficial effects that:
compared with the traditional COC, the polymer has higher glass transition temperature and refractive index when the insertion rate of polar groups is lower, the refractive index of the completely formylated COC reaches 1.58 which is far higher than 1.54 of the commercial COC, and the preparation method is quite suitable for being used as optical materials such as lenses and the like, is simple and easy to implement, has few side reactions, can be suitable for the existing solution method polyolefin process, and has good industrial prospect.
Detailed Description
The following examples are intended to further illustrate the process of the present invention but should not be construed as limiting thereof.
The performance test method is as follows:
molecular weight and molecular weight distribution (PDI): molecular weight and molecular weight distribution index HT-GPC (Agilent PL-220) was determined by high temperature gel permeation chromatography.
Polymer insertion Rate Structure is determined by Inova-500500 MHz liquid phase Nuclear magnetic assay13C NMR analysis was carried out at 120 ℃ in 1,1,2, 2-tetrachloroethane-d 2 for a relaxation time of 10 s.
Contact angle: tested by a german krusei DSA100E contact angle determinator.
Glass transition temperature: measured by differential scanning calorimetry (TA DSC Q200).
Refractive index: measured by a Mettler-Torrimulti refractometer, the test method is ISO 489.
Example 1
Preparation of ethylene, 5-norbornene-2-methanol copolymer:
respectively adding 3.7g (0.03mol) of 5-norbornene-2-methanol and 100ml of refined toluene into a 500ml reaction kettle, then adding 2.1g (0.03mol) of trimethylaluminum into the reaction solution, stirring uniformly, heating the reaction solution to 70 ℃, continuing to stir for 10 hours, introducing high-purity ethylene into the reaction kettle after the reaction is finished until the pressure in the kettle is 0.5MPa, adding 74mg (1mmol) of MAO and 4.5mg (10umol) of rac-dimethylsilyl bisindene zirconium dichloride into the kettle through a feeding bin after the pressure is balanced to initiate polymerization, opening a discharge valve at the bottom of the reaction kettle after the reaction is carried out for 5 minutes, and directly adding the reaction solutionAnd injecting the solution into 500ml of mixed solution of hydrochloric acid and ethanol for quenching precipitation, wherein the volume ratio of 30 wt% hydrochloric acid to ethanol in the mixed solution is 1:10 (the mixed solution in the following examples is identical to example 1), 2.2g of hydroxyl-functionalized COC-1 are obtained after separation of the precipitated solid, the catalyst activity being 2640kg/(mol. Zr. h). Mw of the obtained COC-1 was 4.4X 104g/mol, PDI 2.8, hydroxyl norbornene insertion rate 51 mol%, contact angle 88 DEG, glass transition temperature 175 ℃, refractive index 1.55.
Preparing a molybdenum catalyst:
and sequentially adding 10g of molybdenum dichloride, 10g of carbon black and 100ml of N, N-Dimethylformamide (DMF) into a reaction bottle, stirring for 24 hours at 120 ℃, evaporating the solvent after the reaction is finished, performing reflux extraction on the solvent through the DMF, and drying the extracted solid to obtain 15g of molybdenum catalyst.
Preparation of aldehyde-functionalized COC:
sequentially adding 0.5g of hydroxylated COC-1, 10mg of molybdenum catalyst and 10ml of DMF (dimethyl formamide) into a reaction bottle, raising the temperature of the reaction bottle to 50 ℃, reacting for 2 hours, and filtering and draining reaction liquid after the reaction is finished to obtain 0.49g of aldehyde group functionalized COC-2, wherein the hydroxyl insertion rate is 6 mol%, the aldehyde group insertion rate is 45 mol%, the hydroxyl conversion rate is 88.2%, and the molecular weight is 4.3 multiplied by 104g/mol, PDI 2.8, contact angle 88 deg., glass transition temperature 179 deg.C, refractive index 1.56.
Example 2
Preparation of ethylene, 5-norbornene-2-methanol copolymer:
respectively adding 14.88g (0.12mol) of 5-norbornene-2-methanol and 100ml of refined toluene into a 500ml reaction kettle, then adding 8.3g (0.12mol) of trimethylaluminum into the reaction solution, uniformly stirring, heating the reaction solution to 100 ℃, then continuously stirring for 3 hours, introducing high-purity ethylene into the reaction kettle after the reaction is finished until the pressure in the kettle is 1MPa, adding 74mg (1mmol) of MAO and 4.5mg (10umol) of rac-dimethylsilyl bis-indene zirconium dichloride into the kettle through a feeding bin after the pressure is balanced to initiate polymerization, opening a discharge valve at the bottom of the reaction kettle after the reaction is carried out for 15 minutes, directly injecting the reaction solution into 500ml of a mixed solution of hydrochloric acid and ethanol to carry out quenching precipitation, separating and precipitating solids to obtain 2.3g of hydroxyl functionalized COC-3, wherein the catalyst activity is 2760kg/(mol. Zr.h).
Preparation of aldehyde-functionalized COC:
0.5g of hydroxylated COC-3, 5mg of molybdenum catalyst (prepared in example 1) and 10ml of DMF are sequentially added into a reaction bottle, the temperature of the reaction bottle is raised to 110 ℃, the reaction is carried out for 5 hours, and after the reaction is finished, reaction liquid is filtered and drained to obtain 0.47g of aldehyde group functionalized COC-4, wherein the hydroxyl insertion rate is 1mol percent, the aldehyde group insertion rate is 61mol percent, the hydroxyl conversion rate is 98.4 percent, and the molecular weight is 4.6 multiplied by 104g/mol, PDI 2.6, contact angle 81 deg., glass transition temperature 199 deg.C, refractive index 1.59.
Example 3
Preparation of ethylene, 5-norbornene-2-methanol copolymer:
respectively adding 3.7g (0.03mol) of 5-norbornene-2-methanol and 100ml of refined toluene into a 500ml reaction kettle, then adding 2.1g (0.03mol) of trimethylaluminum into the reaction solution, stirring uniformly, heating the reaction solution to 65 ℃, then continuing to stir for 20 hours, introducing high-purity ethylene into the reaction kettle after the reaction is finished until the pressure in the kettle is 2MPa, adding 74mg (1mmol) of MAO and 8.4mg (20umol) of vinylbisindane zirconium dichloride into the kettle through a feeding bin after the pressure is balanced to initiate polymerization, opening a discharge valve at the bottom of the reaction kettle after 5 minutes of reaction, directly injecting the reaction solution into 500ml of mixed solution of hydrochloric acid and ethanol for quenching and precipitation, separating and precipitating solids to obtain 2.1g of hydroxyl functionalized COC-5, wherein the catalyst activity is 0kg/(mol. Zr. h).
Preparation of aldehyde-functionalized COC:
0.5g of hydroxylated COC-5, 15mg of molybdenum catalyst (prepared in example 1) and 10ml of DMF are sequentially added into a reaction bottle, the temperature of the reaction bottle is raised to 180 ℃, the reaction is carried out for 20 hours, and after the reaction is finished, reaction liquid is filtered and drained to obtain 0.47g of aldehyde group functionalized COC-6, wherein the hydroxyl insertion rate is 1 mol%, the aldehyde group insertion rate is 46 mol%, the hydroxyl conversion rate is 97.9%, and the molecular weight is 4.1 multiplied by 104g/mol, PDI 2.8, contact angle 88 deg., glass transition temperature 175 deg.C, refractive index 1.58.
Example 4
Preparation of an ethylene, 5-norbornene-2-methanol copolymer:
adding 1.24g (0.01mol) of 5-norbornene-2-methanol and 100ml of refined methylcyclohexane into a 500ml reaction kettle respectively, then adding 1.98g (0.01mol) of triisobutylaluminum into the reaction solution, stirring uniformly, heating the reaction solution to 90 ℃, then stirring for 10 hours, introducing high-purity ethylene into the reaction kettle after the reaction is finished until the pressure in the kettle is 1MPa, adding MAO22mg (0.3mmol) and rac-dimethylsilyl bis-indene zirconium dichloride 1.3mg (3umol) into the kettle through a feeding bin after the pressure is balanced to initiate polymerization, opening a discharge valve at the bottom of the reaction kettle after the reaction is 8 minutes, directly injecting the reaction solution into 500ml of hydrochloric acid and ethanol mixed solution for quenching and precipitation, separating and precipitating solids to obtain 1.2g of hydroxyl functionalized COC-7, and obtaining 4800kg/(mol. Zr. h) of catalyst activity.
Preparation of aldehyde-functionalized COC:
0.6g of hydroxylated COC-7, 18mg of molybdenum catalyst (prepared in example 1) and 15ml of DMF are sequentially added into a reaction bottle, the temperature of the reaction bottle is raised to 160 ℃, the reaction is carried out for 10 hours, and after the reaction is finished, reaction liquid is filtered and drained to obtain 0.58g of aldehyde group functionalized COC-8, wherein the hydroxyl insertion rate is 2mol percent, the aldehyde group insertion rate is 47mol percent, the hydroxyl conversion rate is 95.9 percent, and the molecular weight is 4.2 multiplied by 104g/mol, PDI 2.5, contact angle 84 deg., glass transition temperature 185 deg., refractive index 1.58.
Example 5
Preparation of ethylene, 5-norbornene-2-ethanol copolymer:
respectively adding 4.14g (0.03mol) of 5-norbornene-2-ethanol and 150ml of refined cyclohexane into a 500ml reaction kettle, then adding 2.1g (0.03mol) of trimethylaluminum into the reaction solution, stirring uniformly, heating the reaction solution to 110 ℃, then continuing to stir for 5 hours, introducing high-purity ethylene into the reaction kettle after the reaction is finished until the pressure in the kettle is 0.9MPa, adding 44mg (0.6mmol) of MAO and 2.7mg (6umol) of rac-dimethylsilyl bis-indene zirconium dichloride into the kettle through a feeding bin after the pressure is balanced to initiate polymerization, opening a discharge valve at the bottom of the reaction kettle after 12 minutes of reaction, directly injecting the reaction solution into 500ml of a mixed solution of hydrochloric acid and ethanol to quench and precipitate, separating and precipitating solids to obtain 3.2g of hydroxyl functionalized COC-9, wherein the activity of the catalyst is 3840kg/(mol. Zr.h).
Preparation of aldehyde-functionalized COC:
sequentially adding 1.5g of hydroxylated COC-9, 30mg of molybdenum catalyst (prepared in example 1) and 20ml of DMF (dimethyl formamide) into a reaction bottle, raising the temperature of the reaction bottle to 140 ℃, reacting for 18 hours, filtering and draining reaction liquid after the reaction is finished to obtain 1.49g of aldehyde-functionalized COC-10, wherein the hydroxyl insertion rate is 1 mol%, the aldehyde insertion rate is 49 mol%, the hydroxyl conversion rate is 98%, and the molecular weight is 4.4 multiplied by 104g/mol, PDI 2.4, contact angle 83 degrees, glass transition temperature 185 degrees, refractive index 1.58.
Example 6
Preparation of an ethylene, 5-norbornene-2-propanol copolymer:
respectively adding 3.1g (0.02mol) of 5-norbornene-2-propanol and 90ml of refined toluene into a 500ml reaction kettle, then adding 1.4g (0.02mol) of trimethylaluminum into the reaction solution, stirring uniformly, heating the reaction solution to 60 ℃, then stirring for 20 hours, introducing high-purity ethylene into the reaction kettle after the reaction is finished until the pressure in the kettle is 0.7MPa, adding 22mg (0.3mmol) of MAO and 1.3mg (3umol) of rac-dimethylsilyl bisindenyl zirconium dichloride into the kettle through a feeding bin after the pressure is balanced to initiate 880 polymerization, opening a discharge valve at the bottom of the reaction kettle after the reaction is carried out for 6 minutes, directly injecting the reaction solution into 500ml of hydrochloric acid and ethanol mixed solution for quenching precipitation, separating precipitated solid to obtain 2.2g of hydroxyl functionalized COC-11, and obtaining 0kg/(mol. Zr. h) of catalyst activity.
Preparing a molybdenum catalyst: 20g of molybdenum dichloride, 10g of carbon black and 100ml of N, N-Dimethylformamide (DMF) are sequentially added into a reaction bottle, stirred for 24 hours at 120 ℃, the solvent is evaporated after the reaction is finished, then reflux extraction is carried out through the DMF, and the extracted solid is dried to obtain 18g of molybdenum catalyst.
Preparation of aldehyde-functionalized COC:
sequentially adding 1.2g of hydroxylated COC-11, 8mg of molybdenum catalyst and 20ml of DMF (dimethyl formamide) into a reaction bottle, raising the temperature of the reaction bottle to 140 ℃, reacting for 18 hours, filtering and draining reaction liquid after the reaction is finished to obtain 1.18g of aldehyde-functionalized COC-12, wherein the hydroxyl insertion rate is 0.5 mol%, the aldehyde insertion rate is 49 mol%, the hydroxyl conversion rate is 99%, and the molecular weight is 4.7 multiplied by 104g/mol，PDI 2.3, contact angle 84 °, glass transition temperature 186 ℃, refractive index 1.58.
Comparative example 1
Preparation of ethylene and norbornene copolymer.
Respectively adding 2.82g (0.03mol) of norbornene and 100ml of refined toluene into a 500ml reaction kettle, heating the reaction kettle to 70 ℃, introducing high-purity ethylene into the reaction kettle to 0.5MPa in the kettle, after pressure balance, adding 74mg (1mmol) of MAO and 4.5mg (10umol) of rac-dimethyl silicon-based bisindenyl zirconium dichloride into the kettle through a feeding bin to initiate polymerization, opening a discharge valve at the bottom of the reaction kettle after 5 minutes of reaction, directly injecting a reaction solution into 500ml of a mixed solution of hydrochloric acid and ethanol to quench and precipitate, and separating precipitated solids to obtain 2.7g of COC-11 and catalyst activity of 3240kg/(mol. Zr.h). Mw of the obtained COC-11 was 5.1X 104g/mol, PDI 2.8, norbornene insertion rate 52 mol%, contact angle 106 °, glass transition temperature 165 ℃, refractive index 1.53.
It can be seen from the analysis of examples 1-6 that hydroxyl-functionalized COCs can be successfully prepared by the aluminum alkyl protection method, while the molybdenum metal catalyst can catalyze the dehydrogenation of hydroxyl groups to aldehyde groups. Analysis of the test results of the samples in examples 1 to 6 and comparative example 1 shows that the introduction of the polar groups of hydroxyl and aldehyde groups into the COC material can greatly increase the glass transition temperature of the material and reduce the contact angle of the material, which indicates that the introduction of the polar groups increases the hydrophilicity of the material and increases the binding force between polymer molecular chains. On the other hand, the refractive index of the material after the polarization is obviously improved, the refractive index of COC without polar groups is 1.53, the refractive index of hydroxylated COC-1 in the example 1 is improved to 1.55, and the refractive index can be further improved by converting hydroxyl into aldehyde group through a molybdenum metal catalyst, wherein the refractive index is as high as 1.59 (example 2), and is far higher than the refractive index of COC products sold in the market at present, which is 1.54. The tests show that the aldehydized COC sample is not only very suitable for being used as a lens material, but also suitable for the fields of other medical treatment, packaging material modification and the like, and the application range of COC can be greatly expanded.
In conclusion, compared with the traditional COC material, the aldehyde-functionalized COC prepared by the method has higher glass transition temperature and refractive index under the condition of the same insertion rate, has good hydrophilicity and is suitable for being used as optical materials such as lenses and the like.
Claims (18)
1. An aldehyde-functionalized COC, the structure of which is represented as follows:
wherein m is an integer of 1 to 10000, n is an integer of 10 to 10000, and x is 0 to 10.
2. The aldehyde-functionalized COC according to claim 1, wherein m is an integer of 100-2000, n is an integer of 100-2000, and x is 1-3.
3. The aldehyde-functionalized COC according to claim 1 or 2, wherein the aldehyde-functionalized COC Mw is 1000-.
4. A method of preparing aldehyde functionalized COC according to any one of claims 1 to 3, comprising: adding hydroxyl-functionalized COC, a molybdenum catalyst and a solvent into a reaction flask, raising the temperature of the reaction flask to T1 to mark the beginning of the reaction, filtering the reaction solution to remove the catalyst after T1 of the reaction, and then pumping the solvent to dry to obtain aldehyde-functionalized COC.
5. The process according to claim 4, wherein the reaction temperature T1 is 0 to 250 ℃ and the reaction time T1 is 0.5 to 50 hours.
6. The preparation method as claimed in claim 5, wherein the reaction temperature T1 is 100-150 ℃ and the reaction time T1 is 2-10 hours.
7. The method according to claim 4, wherein the solvent is one or more of N, N-dimethylformamide, dimethylsulfoxide, chlorobenzene, and dichlorobenzene,
the mass ratio of solvent to hydroxyl-functionalized COC is 100: 1 to 1: 1.
8. the method of claim 4, wherein the mass ratio of molybdenum catalyst to hydroxyl-functionalized COC is from 1:10 to 1: 100000.
9. the production method according to any one of claims 4 to 8, wherein the molybdenum catalyst production method comprises: adding molybdenum dichloride dioxide, carbon black and a solvent into a reaction bottle, stirring for 2-50 hours at 80-250 ℃, evaporating the solvent after the reaction is finished, performing reflux extraction on the solvent, and drying the extracted solid to obtain the molybdenum catalyst.
10. The production method according to claim 9, wherein the mass ratio of the added molybdenum dichloride to the carbon black is 1: 2 to 100: 1; the solvent is one or more of DMF, DMSO and dichlorobenzene; the mass ratio of the solvent to the molybdenum dichloride dioxide is 1:1 to 100: 1.
11. the method of claim 4, wherein the hydroxyl-functionalized COC is prepared by a process comprising:
adding a certain amount of hydroxy norbornene monomer into a solvent to prepare a solution, then adding an alkyl aluminum solid into the solution, uniformly stirring, heating to 50-120 ℃, then stirring for 1-20 hours, then introducing ethylene gas into the solution to control the pressure in a reaction kettle to be 0.1-3MPa, then adding methylaluminoxane and a catalyst solid into the reaction solution, continuing to react for 1-30 minutes, adding an excessive hydrochloric acid and ethanol mixed solution after the reaction is finished, quenching and precipitating, separating and drying the precipitated solid to obtain the hydroxyl functionalized COC.
12. The method of claim 11, wherein the alkyl aluminum is selected from the group consisting of trimethylaluminum, triisobutylaluminum, and triethylaluminum.
13. The production method according to claim 12, wherein the molar amount of the aluminum alkyl is the same as that of the hydroxy norbornene monomer.
14. The method of claim 11, wherein the hydroxy norbornene has the following structure:
wherein x is 0 to 10.
15. The production method according to claim 14, wherein the hydroxynorbornene is selected from the group consisting of 5-norbornene-2-methanol, 5-norbornene-2-ethanol, 5-norbornene-2-propanol, and 5-norbornene-2-butanol.
16. The production method according to any one of claims 11 to 15, wherein the molar ratio of methylaluminoxane to hydroxynorbornene is 1:10 to 1: 10000; and/or:
the catalyst is a general bridged double metallocene catalyst.
17. The method according to claim 16, wherein the molar ratio of methylaluminoxane to hydroxynorbornene is 1:100 to 1: 1000; and/or:
the catalyst is selected from rac-dimethylsilylbisindene zirconium dichloride, ethylbisindenyl zirconium dichloride, isopropylbisindenyl zirconium dichloride, diphenylmethyldisindene zirconium dichloride, diphenylmethylene (cyclopentadiene) fluorenyl zirconium dichloride, dimethylsilyl (cyclopentadiene) fluorenyl zirconium dichloride and methyldicyclopentadienyl zirconium dichloride.
18. The production method according to claim 16, wherein the molar ratio of the catalyst to the hydroxynorbornene is 1:1000 to 1: 1000000.
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