CN115947892B - high-Tg high-temperature-resistant COC material and preparation method thereof - Google Patents
high-Tg high-temperature-resistant COC material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- KNDQHSIWLOJIGP-RNGGSSJXSA-N (3ar,4r,7s,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound C1[C@@H]2[C@@H]3C(=O)OC(=O)[C@@H]3[C@H]1C=C2 KNDQHSIWLOJIGP-RNGGSSJXSA-N 0.000 claims abstract description 10
- ZUSSTQCWRDLYJA-UHFFFAOYSA-N n-hydroxy-5-norbornene-2,3-dicarboximide Chemical compound C1=CC2CC1C1C2C(=O)N(O)C1=O ZUSSTQCWRDLYJA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 claims abstract 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 241
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- SHCVFTPKMMFSEE-UHFFFAOYSA-N C1(=CC=CC=C1)C.B(OC1=C(C(=C(C(=C1F)F)F)F)F)(O)O Chemical compound C1(=CC=CC=C1)C.B(OC1=C(C(=C(C(=C1F)F)F)F)F)(O)O SHCVFTPKMMFSEE-UHFFFAOYSA-N 0.000 claims description 21
- -1 fluorenyl amino dimethyl titanium Chemical compound 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 19
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- KRJJDXSTPKETCM-UHFFFAOYSA-N (1-methylcyclopentyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1C(=O)OC1(C)CCCC1 KRJJDXSTPKETCM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 103
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 46
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 44
- 238000003756 stirring Methods 0.000 description 22
- 150000002848 norbornenes Chemical class 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 150000001925 cycloalkenes Chemical class 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- QTYSEROKLOZXDX-UHFFFAOYSA-N 2-(hydroxycarbamoyl)bicyclo[2.2.1]hept-5-ene-3-carboxylic acid Chemical compound C1C2C=CC1C(C(O)=NO)C2C(O)=O QTYSEROKLOZXDX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The application relates to a high Tg high temperature resistant COC material and a preparation method thereof, belonging to the technical field of high polymer materials; the method comprises the following steps: mixing norbornene derivative, cocatalyst, triisobutyl aluminum and main catalyst in solvent to obtain the first mixture to be reacted; carrying out polymerization reaction on the first mixture to be reacted and ethylene to obtain a COC material; wherein the norbornene derivative comprises at least one of 5-norbornene-2-carboxylic acid (1' -methylcyclopentyl) ester, N-hydroxy-5-norbornene-2, 3-dicarboximide and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride; by selecting norbornene derivatives with larger volume steric hindrance as reaction substrates, the asymmetry of a polymer main chain can be improved, the Tg of the polymer is further improved, the Tg is improved from 187 ℃ to 248 ℃, and the Td is improved from 325 ℃ to 395 ℃, so that the problem of poor heat resistance of the conventional COC material is solved.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a high-Tg high-temperature-resistant COC material and a preparation method thereof.
Background
Cycloolefin copolymers, COC for short, are amorphous thermoplastic polymers of the type formed by copolymerization of alpha-olefins with cycloolefins, of which norbornene and ethylene are most typical. COC materials have a very large number of advantages: the specific gravity is light and is about 1; low water absorption of about 0.01%; high transparency, and light transmittance reaching 92%; the thermal decomposition temperature is higher, and the heat resistance is good; extremely low dielectric constants and dielectric losses; has good chemical resistance, corrosion resistance and biocompatibility. With these advantages, COC materials have wide application in the optical material, food medicine, and semiconductor electronics industries.
Norbornene, cyclopentene and dimethyloctahydronaphthalene are monomers of common cycloolefin copolymerization reaction, and are subjected to addition polymerization or ring-opening metathesis polymerization under the catalysis of a transition metal catalyst, most Tg of COC materials prepared by the prior art is less than 200 ℃, the heat resistance of the materials is further improved, and the COC materials still have certain limitation on application in environments with higher temperature.
Disclosure of Invention
The application provides a high-Tg high-temperature-resistant COC material and a preparation method thereof, so as to solve the problem of poor heat resistance of the current COC material.
In a first aspect, the present application provides a method for preparing a high Tg high temperature resistant COC material, the method comprising:
mixing norbornene derivative, cocatalyst, triisobutyl aluminum and main catalyst in solvent to obtain the first mixture to be reacted;
carrying out polymerization reaction on the first mixture to be reacted and ethylene to obtain a COC material;
wherein the norbornene derivative comprises at least one of 5-norbornene-2-carboxylic acid (1' -methylcyclopentyl) ester, N-hydroxy-5-norbornene-2, 3-dicarboximide and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride.
As an alternative embodiment, the molar ratio of the norbornene derivative to the ethylene is (1-10): 1.
As an alternative embodiment, the cocatalyst comprises pentafluorophenyl borate; and/or
The main catalyst comprises Cs-symmetrical fluorenyl amino dimethyl titanium complex.
As an alternative embodiment, the method for preparing the catalyst comprises the steps of mixing a norbornene derivative, a cocatalyst, triisobutylaluminum and a main catalyst in a solvent to obtain a first mixture to be reacted, specifically comprising:
mixing a norbornene derivative toluene solution, a pentafluorophenyl borate toluene solution and a triisobutyl aluminum toluene solution in toluene to obtain a second mixture to be reacted;
and mixing the second mixture to be reacted with a toluene solution of the Cs-symmetrical fluorenyl amino dimethyl titanium complex to obtain a first mixture to be reacted.
As an alternative embodiment, the norbornene derivative toluene solution has a molar concentration of 0.0002 to 0.002mol/mL and the norbornene derivative toluene solution is added in an amount of 40 to 60mL; and/or
The molar concentration of the pentafluorophenyl borate toluene solution is 20-40 mu mol/mL, and the addition amount of the pentafluorophenyl borate toluene solution is 1-10mL; and/or
The molar concentration of the triisobutylaluminum toluene solution is 10-20 mu mol/mL, and the adding amount of the triisobutylaluminum toluene solution is 50-75mL.
As an alternative embodiment, the norbornene derivative toluene solution has a molar concentration of 0.0008 to 0.0015mol/mL and the norbornene derivative toluene solution is added in an amount of 45 to 55mL; and/or
The molar concentration of the pentafluorophenyl borate toluene solution is 25-35 mu mol/mL, and the addition amount of the pentafluorophenyl borate toluene solution is 3-7mL; and/or
The molar concentration of the triisobutylaluminum toluene solution is 12-17 mu mol/mL, and the addition amount of the triisobutylaluminum toluene solution is 58-69mL.
As an alternative embodiment, the molar concentration of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 5-10 mu mol/mL, and the addition amount of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 10-20mL.
As an alternative embodiment, the molar concentration of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 7 to 8 mu mol/mL, and the addition amount of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 13 to 17mL.
As an alternative embodiment, the temperature of the polymerization reaction is 40-70 ℃ and the time of the polymerization reaction is 10-30min.
In a second aspect, the present application provides a high Tg high temperature resistant COC material made by the method of making the high Tg high temperature resistant COC material of the first aspect.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the method provided by the embodiment of the application, the norbornene derivatives with larger steric hindrance are selected: (5-norbornene-2-carboxylic acid (1' -methylcyclopentyl) ester, N-hydroxy-5-norbornene-2, 3-dicarboximide and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride) are used as reaction substrates, so that asymmetry of a polymer main chain can be improved, tg of the polymer is further improved, tg is improved from 187 ℃ to 248 ℃, td is improved from 325 ℃ to 395 ℃, and the problem that the heat resistance of the conventional COC material is poor is solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a flowchart of a method provided in an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
Norbornene, cyclopentene and dimethyloctahydronaphthalene are commonly used monomers for cycloolefin copolymerization, and the addition polymerization or ring-opening metathesis polymerization is carried out under the catalysis of a transition metal catalyst, and the specific polymerization mode needs to consider the performance of the catalyst, the type of the monomers and the polymerization environment. In the prior art, chinese patent application No. CN 113372478A discloses an aldehyde group functionalized cycloolefin-ethylene copolymer and a preparation method thereof, wherein the copolymer structure comprises two copolymerization units, namely ethylene and aldehyde group functionalized norbornene, and the preparation method of the material needs to prepare hydroxyl group functionalized COC in advance and then convert hydroxyl group into aldehyde group through a molybdenum catalyst. Chinese patent application CN 115073664A discloses a cyclic olefin polymer film with optical anisotropy, which comprises the following steps: (1): dissolving a catalyst, a catalyst modifier and a cocatalyst in a solvent in a high-purity nitrogen atmosphere to obtain a stable catalyst solution; (2): adding the catalyst solution prepared in the step (1) into a solvent, respectively adding different cycloolefin monomers at a feed rate of 1-30 mL/min, and reacting at 60-70 ℃ for 1.5-2.5 hours to obtain the cycloolefin polymer.
The copolymerization of ethylene and norbornene under the condition of catalyst is the most commonly used and classical method for preparing COC material at present, the main catalyst is a transition metal inorganic compound, and the cocatalyst is a main group metal organic compound. However, most Tg of the COC material prepared by the prior art is less than 200 ℃, the heat resistance of the material has room for further improvement, and the COC material has certain limitation on application in the environment with higher temperature.
According to the preparation method, norbornene derivative monomers (large in volume and large in steric hindrance) with different structures are selected, the proper main catalyst and cocatalyst and concentration ratio of the main catalyst and the cocatalyst are adopted, the mole ratio of the norbornene derivative monomers to the ethylene monomers is controlled, and finally, the proper polymerization reaction temperature is controlled, so that the thermal decomposition temperature of the COC material is improved by improving Tg and increasing the molecular weight, and then the heat resistance of the COC material is improved, and the preparation process is simple and convenient.
As shown in fig. 1, an embodiment of the present application provides a method for preparing a high Tg high temperature resistant COC material, including:
s1, mixing a norbornene derivative, a cocatalyst, triisobutyl aluminum and a main catalyst in a solvent to obtain a first mixture to be reacted; wherein the norbornene derivative comprises at least one of 5-norbornene-2-carboxylic acid (1' -methylcyclopentyl) ester, N-hydroxy-5-norbornene-2, 3-dicarboximide and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride.
In some embodiments, the mixing of the norbornene derivative, the cocatalyst, the triisobutylaluminum and the procatalyst in a solvent results in a first mixture to be reacted, specifically comprising:
s1.1, mixing a norbornene derivative toluene solution, a pentafluorophenyl borate toluene solution and a triisobutyl aluminum toluene solution into toluene to obtain a second mixture to be reacted;
specifically, in this embodiment, the polymerization reaction bottle is dried and then subjected to nitrogen gas introduction for a plurality of times; then 50ml of toluene, a proper amount of norbornene derivative toluene solution, a cocatalyst of pentafluorophenyl borate toluene solution and a triisobutyl aluminum toluene solution are added into a reaction bottle, and the mixed solution is stirred for 10min at the temperature of 40 ℃ and the stirring speed of 300rpm/min, so as to obtain a second mixture to be reacted.
In some embodiments, the norbornene derivative type toluene solution has a molar concentration of 0.0002 to 0.002mol/mL and is added in an amount of 40 to 60mL; the molar concentration of the pentafluorophenyl borate toluene solution is 20-40 mu mol/mL, and the addition amount of the pentafluorophenyl borate toluene solution is 1-10mL; the molar concentration of the triisobutylaluminum toluene solution is 10-20 mu mol/mL, and the adding amount of the triisobutylaluminum toluene solution is 50-75mL. Preferably, the molar concentration of the norbornene derivative toluene solution is 0.0008-0.0015mol/mL, and the addition amount of the norbornene derivative toluene solution is 45-55mL; the molar concentration of the pentafluorophenyl borate toluene solution is 25-35 mu mol/mL, and the addition amount of the pentafluorophenyl borate toluene solution is 3-7mL; the molar concentration of the triisobutylaluminum toluene solution is 12-17 mu mol/mL, and the addition amount of the triisobutylaluminum toluene solution is 58-69mL.
S1.2, mixing the second mixture to be reacted with a toluene solution of Cs-symmetrical fluorenyl amino dimethyl titanium complex to obtain a first mixture to be reacted.
Specifically, in this example, a proper amount of toluene solution of the procatalyst Cs-symmetrical fluorenyl amino dimethyl titanium complex was then added to the second mixture to be reacted to obtain a first mixture to be reacted.
In some embodiments, the molar concentration of the Cs-symmetric fluorenylaminomethyl titanium complex toluene solution is from 5 to 10. Mu. Mol/mL and the Cs-symmetric fluorenylaminomethyl titanium complex toluene solution is added in an amount of from 10 to 20mL. Preferably, the molar concentration of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 7-8 mu mol/mL, and the addition amount of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 13-17mL.
S2, carrying out polymerization reaction on the first mixture to be reacted and ethylene to obtain a COC material;
specifically, in this example, ethylene gas was introduced into the first mixture to be reacted at 40 to 70℃for solution polymerization for 10 to 60 minutes. And finally, stopping the reaction by using a hydrochloric acid/ethanol solution after the reaction is finished, transferring the reaction solution into a beaker, washing the reaction solution by using ethanol for three times, soaking and stirring the reaction solution in acetone, and carrying out suction filtration and drying to obtain the COC material.
In some embodiments, the polymerization reaction is at a temperature of 40-70 ℃ and the polymerization reaction is for a time of 10-30 minutes. The termination of the polymerization reaction is performed by using a hydrochloric acid/ethanol solution, and specifically, the hydrochloric acid/ethanol termination solution is prepared by adding 1ml of 99% concentrated hydrochloric acid into 40-60ml of ethanol solution.
With the above design, by selecting norbornene-type derivatives with greater steric hindrance: (5-norbornene-2-carboxylic acid (1' -methylcyclopentyl) ester, N-hydroxy-5-norbornene-2, 3-dicarboximide, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride) can increase asymmetry of a polymer main chain and increase Tg of a polymer when polymerized with ethylene. The molecular weight of the polymer is increased by controlling the mole ratio of norbornene monomer to ethylene monomer, the dosage of the catalyst and the polymerization temperature and time, and the Tg is further increased.
Based on one general inventive concept, the embodiment of the present application also provides a high Tg high temperature resistant COC material, which is prepared by the preparation method of the high Tg high temperature resistant COC material of the first aspect.
The high Tg high temperature resistant COC material is obtained based on the preparation method of the high Tg high temperature resistant COC material, and specific steps of the preparation method of the high Tg high temperature resistant COC material can refer to the above embodiment.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A preparation method of a high Tg high temperature resistant COC material comprises the following steps:
firstly, drying a polymerization reaction bottle and then carrying out nitrogen gas introduction treatment for a plurality of times; 0.02mol of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride was dissolved in 50ml of toluene solution. The pentafluorophenyl borate was dissolved in toluene at a concentration of 20. Mu. Mol/mL. Triisobutylaluminum was dissolved in toluene solution at a concentration of 10. Mu. Mol/mL. Then stirring 50mL of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride toluene solution, 5mL of pentafluorophenyl borate toluene solution with the concentration of 20 mu mol/mL, 50mL of triisobutyl aluminum toluene solution with the concentration of 10 mu mol/mL and 50mL of toluene solution at the temperature of 40 ℃ at the stirring speed of 300rpm/min for 10min to uniformly stir the mixed solution; then 10mL of Cs-symmetrical fluorenylaminomethyl titanium complex toluene solution at a concentration of 5. Mu. Mol/mL was added. And (3) starting to introduce ethylene gas at 40 ℃ for solution polymerization, wherein the polymerization is carried out for 10min, and the ethylene gas introducing amount is controlled to be 0.02mol. And finally, adding 1ml of concentrated hydrochloric acid with the concentration of 99% into 40ml of ethanol solution to prepare hydrochloric acid/ethanol solution to terminate the reaction after the reaction, transferring the reaction solution into a beaker, washing with ethanol for three times, soaking with acetone, stirring, and carrying out suction filtration and drying to obtain the COC material.
Example 2
A preparation method of a high Tg high temperature resistant COC material comprises the following steps:
firstly, drying a polymerization reaction bottle and then carrying out nitrogen gas introduction treatment for a plurality of times; 0.05mol of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride was dissolved in 50ml of toluene solution. The pentafluorophenyl borate was dissolved in toluene at a concentration of 20. Mu. Mol/mL. Triisobutylaluminum was dissolved in toluene solution at a concentration of 10. Mu. Mol/mL. Then stirring 50mL of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride toluene solution, 10mL of pentafluorophenyl borate toluene solution with the concentration of 20 mu mol/mL, 50mL of triisobutyl aluminum toluene solution with the concentration of 10 mu mol/mL and 50mL of toluene solution at the temperature of 40 ℃ at the stirring speed of 300rpm/min for 10min to uniformly stir the mixed solution; 15mL of a toluene solution of Cs-symmetrical fluorenylaminomethyl titanium complex with a concentration of 5. Mu. Mol/mL was then added. And (3) starting to introduce ethylene gas at 40 ℃ for solution polymerization, wherein the polymerization is carried out for 10min, and the ethylene gas introducing amount is controlled to be 0.02mol. And finally, adding 1ml of concentrated hydrochloric acid with the concentration of 99% into 40ml of ethanol solution to prepare hydrochloric acid/ethanol solution to terminate the reaction after the reaction, transferring the reaction solution into a beaker, washing with ethanol for three times, soaking with acetone, stirring, and carrying out suction filtration and drying to obtain the COC material.
Example 3
A preparation method of a high Tg high temperature resistant COC material comprises the following steps:
firstly, drying a polymerization reaction bottle and then carrying out nitrogen gas introduction treatment for a plurality of times; 0.02mol of N-hydroxy-5-norbornene-2, 3-dicarboxylic monoimide are dissolved in 50ml of toluene. The pentafluorophenyl borate was dissolved in toluene at a concentration of 20. Mu. Mol/mL. Triisobutylaluminum was dissolved in toluene solution at a concentration of 10. Mu. Mol/mL. Then stirring 50mL of N-hydroxy-5-norbornene-2, 3-dicarboximide toluene solution, 5mL of pentafluorophenyl borate toluene solution with the concentration of 20 mu mol/mL, 50mL of triisobutyl aluminum toluene solution with the concentration of 10 mu mol/mL and 50mL of toluene solution at the temperature of 40 ℃ at the stirring speed of 300rpm/min for 10min to uniformly stir the mixed solution; then 10mL of Cs-symmetrical fluorenylaminomethyl titanium complex toluene solution at a concentration of 5. Mu. Mol/mL was added. And (3) starting to introduce ethylene gas at 40 ℃ for solution polymerization, wherein the polymerization is carried out for 20min, and the ethylene gas introducing amount is controlled to be 0.02mol. And finally, adding 1ml of concentrated hydrochloric acid with the concentration of 99% into 50ml of ethanol solution to prepare hydrochloric acid/ethanol solution to terminate the reaction after the reaction, transferring the reaction solution into a beaker, washing with ethanol for three times, soaking with acetone, stirring, and carrying out suction filtration and drying to obtain the COC material.
Example 4
A preparation method of a high Tg high temperature resistant COC material comprises the following steps:
firstly, drying a polymerization reaction bottle and then carrying out nitrogen gas introduction treatment for a plurality of times; 0.1mol of N-hydroxy-5-norbornene-2, 3-dicarboxylic monoimide is dissolved in 50ml of toluene. The pentafluorophenyl borate was dissolved in toluene at a concentration of 30. Mu. Mol/mL. Triisobutylaluminum was dissolved in toluene solution at a concentration of 15. Mu. Mol/mL. Then stirring 50mL of N-hydroxy-5-norbornene-2, 3-dicarboximide toluene solution, 5mL of pentafluorophenyl borate toluene solution with the concentration of 30 mu mol/mL, 50mL of triisobutyl aluminum toluene solution with the concentration of 15 mu mol/mL and 50mL of toluene solution at the temperature of 40 ℃ at the stirring speed of 300rpm/min for 10min to uniformly stir the mixed solution; then 10mL of Cs-symmetrical fluorenylaminomethyl titanium complex toluene solution at a concentration of 10. Mu. Mol/mL was added. And (3) starting to introduce ethylene gas at 60 ℃ for solution polymerization, wherein the polymerization is carried out for 20min, and the ethylene gas introducing amount is controlled to be 0.02mol. And finally, adding 1ml of concentrated hydrochloric acid with the concentration of 99% into 50ml of ethanol solution to prepare hydrochloric acid/ethanol solution to terminate the reaction after the reaction, transferring the reaction solution into a beaker, washing with ethanol for three times, soaking with acetone, stirring, and carrying out suction filtration and drying to obtain the COC material.
Example 5
A preparation method of a high Tg high temperature resistant COC material comprises the following steps:
firstly, drying a polymerization reaction bottle and then carrying out nitrogen gas introduction treatment for a plurality of times; 0.08mol of 5-norbornene-2-carboxylic acid (1' -methylcyclopentyl) ester was dissolved in 50ml of a toluene solution. The pentafluorophenyl borate was dissolved in toluene at a concentration of 30. Mu. Mol/mL. Triisobutylaluminum was dissolved in toluene solution at a concentration of 15. Mu. Mol/mL. Then stirring 50mL of 5-norbornene-2-carboxylic acid (1' -methylcyclopentyl) ester toluene solution, 5mL of pentafluorophenyl borate toluene solution with a concentration of 30 mu mol/mL, 50mL of triisobutylaluminum toluene solution with a concentration of 15 mu mol/mL, and 50mL of toluene solution at 40 ℃ at a stirring speed of 300rpm for 10min to stir the mixed solution uniformly; then 10mL of Cs-symmetrical fluorenylaminomethyl titanium complex toluene solution at a concentration of 10. Mu. Mol/mL was added. And (3) starting to introduce ethylene gas at 60 ℃ for solution polymerization, wherein the polymerization is carried out for 10min, and the ethylene gas introducing amount is controlled to be 0.03mol. And finally, adding 1ml of concentrated hydrochloric acid with the concentration of 99% into 60ml of ethanol solution to prepare hydrochloric acid/ethanol solution to terminate the reaction after the reaction is finished, transferring the reaction solution into a beaker, washing with ethanol for three times, soaking with acetone, stirring, and carrying out suction filtration and drying to obtain the COC material.
Comparative example 1
COC materials are commercially available.
The COC (cyclic olefin copolymer) materials provided in examples 1 to 5 and comparative example 1 were tested for glass transition temperature Tg and thermal decomposition temperature Td and weight average molecular weight Mw, and the results are shown in the following table:
as can be seen from the above table, using the methods provided in the examples of the present application to prepare COC materials, the Tg of the COC materials can be raised from 187 ℃ to 248 ℃ and Td from 325 ℃ to 395 ℃ of the commercially available (norbornene copolymerized) COC materials.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2,3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of 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, c may be single or multiple, respectively.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. The preparation method of the high Tg high temperature resistant COC material is characterized by comprising the following steps:
mixing a norbornene derivative toluene solution, a pentafluorophenyl borate toluene solution and a triisobutyl aluminum toluene solution in toluene to obtain a second mixture to be reacted;
mixing the second mixture to be reacted with a toluene solution of Cs-symmetrical fluorenyl amino dimethyl titanium complex to obtain a first mixture to be reacted;
carrying out polymerization reaction on the first mixture to be reacted and ethylene, and stopping the reaction by using hydrochloric acid/ethanol solution after the reaction is finished to obtain a COC material;
wherein the norbornene derivative comprises at least one of N-hydroxy-5-norbornene-2, 3-dicarboximide and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride; the temperature of the polymerization reaction is 40-70 ℃, and the time of the polymerization reaction is 10-30min;
the mol ratio of the norbornene derivative to the ethylene is (1-10) 1, the mol concentration of the norbornene derivative toluene solution is 0.0002-0.002mol/mL, and the addition amount of the norbornene derivative toluene solution is 40-60mL; the molar concentration of the pentafluorophenyl borate toluene solution is 20-40 mu mol/mL, and the addition amount of the pentafluorophenyl borate toluene solution is 1-10mL; the molar concentration of the triisobutylaluminum toluene solution is 10-20 mu mol/mL, the adding amount of the triisobutylaluminum toluene solution is 50-75mL, the molar concentration of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 5-10 mu mol/mL, and the adding amount of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 10-20mL.
2. The method for producing a high Tg resistant COC material according to claim 1, wherein the norbornene derivative type toluene solution has a molar concentration of 0.0008 to 0.0015mol/mL, and the norbornene derivative type toluene solution is added in an amount of 45 to 55mL; and/or
The molar concentration of the pentafluorophenyl borate toluene solution is 25-35 mu mol/mL, and the addition amount of the pentafluorophenyl borate toluene solution is 3-7mL; and/or
The molar concentration of the triisobutylaluminum toluene solution is 12-17 mu mol/mL, and the addition amount of the triisobutylaluminum toluene solution is 58-69mL.
3. The method for preparing the high-Tg and high-temperature resistant COC material according to claim 1, wherein the molar concentration of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 7-8 mu mol/mL, and the addition amount of the Cs-symmetrical fluorenyl amino dimethyl titanium complex toluene solution is 13-17mL.
4. A high Tg high temperature resistant COC material, characterized in that said COC material is produced by the production method of the high Tg high temperature resistant COC material according to any one of claims 1 to 3.
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