CN117866387B - High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof - Google Patents
High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof Download PDFInfo
- Publication number
- CN117866387B CN117866387B CN202410282527.1A CN202410282527A CN117866387B CN 117866387 B CN117866387 B CN 117866387B CN 202410282527 A CN202410282527 A CN 202410282527A CN 117866387 B CN117866387 B CN 117866387B
- Authority
- CN
- China
- Prior art keywords
- norbornene
- cover plate
- mofs
- amino
- resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000003756 stirring Methods 0.000 claims abstract description 59
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 47
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 38
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 29
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 13
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims abstract description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 11
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000004917 carbon fiber Substances 0.000 claims abstract description 11
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims abstract description 11
- 239000011986 second-generation catalyst Substances 0.000 claims abstract description 11
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims abstract description 9
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004744 fabric Substances 0.000 claims abstract description 6
- 230000006835 compression Effects 0.000 claims abstract description 4
- 238000007906 compression Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 25
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 13
- 150000001718 carbodiimides Chemical class 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 238000005352 clarification Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001153 Polydicyclopentadiene Polymers 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000945 filler Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 2
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-L 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polydipentadienyl cover plates and discloses a high-pressure-resistance polydipentadienyl cover plate and a preparation method thereof; the polydicyclopentadiene material comprises the following components: ethylidene norbornene, dicyclopentadiene, norbornene-based silica, norbornene-based MOFs, amino MOFs, poly (1, 4-butadiene) -polyethylene oxide diblock copolymers, bisphenol A diglycidyl ether, methylnadic anhydride, 2,4, 6-tris (dimethylaminomethyl) phenol, grubbs' second generation catalyst, tributyl phosphite, cyclohexylbenzene; the preparation method comprises the following steps: placing the cut carbon fiber fabric in a mold, uniformly stirring the polydicyclopentadiene material, removing bubbles, pouring the mixture into the mold, and curing to obtain the polydicyclopentenyl cover plate with high compression resistance.
Description
Technical Field
The invention relates to the technical field of polydipentadienyl cover plates, in particular to a polydipentadienyl cover plate with high compression resistance and a preparation method thereof.
Background
Dicyclopentadiene is an important by-product of the petroleum industry. After exothermic ring-opening double decomposition polymerization, the novel engineering plastic with excellent impact resistance, chemical corrosion resistance and thermal stability can be formed, and the comprehensive performance of the engineering plastic is better than that of polymers such as polyurethane, nylon and the like, and the engineering plastic is widely applied to various industries.
Pure polydicyclopentadiene, while having excellent mechanical properties, is still not satisfactory for engineering applications in certain specific engineering fields. For this reason, researchers have focused on meeting the increasing demands on polydicyclopentadiene material properties by adding fillers and copolymerizing other polymers. Most fillers are a major bottleneck for large scale practical applications due to their poor compatibility and dispersibility.
Therefore, the invention provides the high-pressure-resistance polydicyclopentenyl cover plate and the preparation method thereof have important significance.
Disclosure of Invention
The invention aims to provide a high-pressure-resistance polydicyclopentenyl cover plate and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate comprises the following steps:
S1: adding ethylidene norbornene into dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding norbornene-based silicon dioxide, norbornene-based MOFs and amino MOFs into dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
S2: adding the poly (1, 4-butadiene) -polyethylene oxide diblock copolymer and bisphenol A diglycidyl ether into methylene dichloride, uniformly stirring, and vacuum drying at room temperature to remove the methylene dichloride to obtain a substance B; adding the substance B, methyl nadic anhydride and 2,4, 6-tris (dimethylaminomethyl) phenol into the substance A, and uniformly stirring to obtain a substance C;
s3: uniformly mixing the Grubbs second-generation catalyst, tributyl phosphite and cyclohexylbenzene according to a proportion, sealing and heating the mixture to 45-50 ℃ for dissolution, and cooling after clarification to obtain the catalyst;
S4: placing the cut carbon fiber fabric in a mould, adding a catalyst into the substance C, uniformly stirring, removing bubbles, pouring the mixture into the mould, and curing to obtain the high-pressure-resistance polydicyclopentenyl cover plate.
Further, the preparation method of the norbornene-based silica comprises the following steps:
Adding 3-aminopropyl trimethoxy silane into deionized water, stirring uniformly, adding ammonium hydroxide, heating to 50-55 ℃ and stirring for 4-4.5h, centrifuging, washing, and vacuum drying to obtain amino-functionalized silica; adding amino functionalized silica and 5-norbornene-2-carboxylic acid into dichloromethane, adding carbodiimide and 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene-based silica.
Further, 3-aminopropyl trimethoxysilane: the mass ratio of the ammonium hydroxide is 1 (2-3); amino-functionalized silica: the mass ratio of the 5-norbornene-2-carboxylic acid is 1 (1-2).
Further, the preparation method of the norbornene-based MOFs comprises the following steps:
Adding zirconium chloride into a hydrochloric acid solution of N, N-dimethylformamide, uniformly stirring, adding the N, N-dimethylformamide solution of 2-amino terephthalic acid, heating to 80-85 ℃ for reacting for 12-14h, centrifuging, washing and drying to obtain amino MOFs; adding amino MOFs and 5-norbornene-2-carboxylic acid into dichloromethane, adding carbodiimide and 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene MOFs.
Further, in the hydrochloric acid solution of the N, N-dimethylformamide, the molar ratio of the N, N-dimethylformamide to the hydrochloric acid is 5:1.
Further, the zirconium chloride: the mass ratio of the 2-amino terephthalic acid is 1 (1.05-1.2); amino MOFs: the mass ratio of the 5-norbornene-2-carboxylic acid is 1 (0.5-0.6).
Further, in the step S1, the addition amount of the ethylidene norbornene is 5-6wt% of the dicyclopentadiene; the addition amount of the norbornene-based silicon dioxide, the norbornene-based MOFs and the amino MOFs is 0.05-0.3wt%, 0.2-1.0wt% and 0.2-1.0wt% of the dicyclopentadiene monomer.
Further, in the step S2, bisphenol a diglycidyl ether: the mass ratio of dicyclopentadiene monomer is (3-7) to (5-5); the addition amount of the poly (1, 4-butadiene) -polyethylene oxide diblock copolymer is 5-8wt% of the total mass of bisphenol A diglycidyl ether and dicyclopentadiene monomer; bisphenol a diglycidyl ether: methyl nadic anhydride: the mass ratio of the 2,4, 6-tris (dimethylaminomethyl) phenol is 10 (8.5-9.5) to 0.1-0.12.
Further, in the step S3, grubbs second generation catalyst: tributyl phosphite: the mass ratio of the cyclohexylbenzene is 1:0.5 (10-15).
Further, in the step S4, dicyclopentadiene monomer: the mass ratio of the catalyst is 1 (4.5 multiplied by 10 -4-5×10-4)
Further, in the preparation process of the norbornene-based silica and norbornene-based MOFs, carbodiimide: the mass ratio of the 1-hydroxybenzotriazole is 1:1; the addition amount of the carbodiimide and 1-hydroxybenzotriazole mixture is 0.1-0.5wt% of the total mass of the amino-functionalized silica and the 5-norbornene-2-carboxylic acid.
Further, the curing treatment temperature is 35-45 ℃ for 0.5-1h,60-70 ℃ for 0.5-2h,90-100 ℃ for 0.5-2h,120-160 ℃ for 2-4h and 180-200 ℃ for 2-3h.
Compared with the prior art, the invention has the following beneficial effects:
The application aims to overcome the additional problem that the filler has poor compatibility and dispersibility in dicyclopentadiene due to the self-properties; 3-aminopropyl trimethoxy silane is selected as a monomer, and nano silicon dioxide particles with amino active functional groups on the surfaces are prepared through a sol-gel process; under the catalysis of carbodiimide and 1-hydroxybenzotriazole, amino functionalized silica reacts with 5-norbornene-2-carboxylic acid, and norbornene groups are successfully grafted on the surface of the silica, so that norbornene-based silica is prepared; similarly, the application prepares the zirconium-based MOFs with excellent mechanical property and thermal stability and containing amino on the surface by taking 2-amino terephthalic acid and zirconium chloride as raw materials, and further reacts with 5-norbornene-2-carboxylic acid under the action of a catalyst, and introduces norbornene groups into the zirconium-based MOFs structure to prepare the norbornene-based MOFs; on the one hand, the rigid structure provided by the norbornene-based silicon dioxide and the norbornene-based MOFs is difficult to deform, when the stress reaches a certain value, interface debonding occurs between rigid silicon dioxide particles and a (polydicyclopentadiene) PDCPD matrix, so that a large number of micropores are formed around the particles in a direction parallel to the stress application direction, and the load state is changed from a plane strain state to a plane stress state due to the formation of the micropores and the continuous growth of the micropores, so that weak shear bands are formed in matrix ligaments among the particles, and shear yield occurs. These processes absorb a large amount of energy, thereby improving toughness; on the other hand, the groups coated on the surfaces of the norbornene-based silicon dioxide and the norbornene-based MOFs enhance the dispersion performance and the compatibility of the filler in the matrix, and meanwhile, the two fillers can form cross-linking with a plurality of PDCPD polymer chains of the PDCPD under the weak interaction of hydrogen bonds, van der Waals force and the like, so that the mechanical property of the material is improved; and participate in the polymerization of PDCPD in the presence of Grubbs' catalyst, form strong chemical bond connection between base member and reinforcing agent to realize better load transmission, when one or more PDCPD polymer chains is destroyed by external tensile stress, other polymer chains act as the connection filler, further improve the mechanical properties of material.
The invention selects a poly (1, 4-butadiene) -polyethylene oxide diblock copolymer, and utilizes the strong affinity of 1, 4-polybutadiene in the diblock copolymer to polydicyclopentadiene, the strong affinity of polyethylene oxide to epoxy resin, and the polyethylene oxide and amino MOFs act together to improve the interfacial compatibility of polydicyclopentadiene and epoxy resin, thus achieving the function of compatibilizer in the polydicyclopentadiene and the epoxy resin; the problem that the bonding capability between the traditional polydicyclopentadiene and the carbon fiber is weak, and the resin is easily stripped from the surface of the carbon fiber, so that the load cannot be transmitted to the stress is solved; greatly improves the bonding performance between the polydicyclopentadiene and the carbon fiber, and further improves the mechanical property of the polydipentadienyl cover plate.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, 3-aminopropyl trimethoxysilane was purchased from Shanghai Ala Biotechnology Co., ltd; 5-norbornene-2-carboxylic acid was purchased from Shanghai Meilin Biochemical technologies Co., ltd; 2-amino terephthalic acid was purchased from Shanghai Meilin Biochemical technologies Co., ltd; dicyclopentadiene was purchased from Shanghai Meilin Biochemical technologies Co., ltd; poly (1, 4-butadiene) -polyethylene oxide diblock copolymers were purchased from sienna ziyue biotechnology limited; bisphenol a diglycidyl ether was purchased from dow chemical company under the model of dow epoxy DRE331 (fraction of DGEBA molecules pre-polymerized and having additional hydroxyl-containing intermediate groups, n=0.15); the nano silicon dioxide has the particle size of 20nm and is purchased from Shanghai Ji nano materials science and technology Co., ltd; carbon fiber plain weave (T300, 3K, areal density 200g/m 2) was purchased from Toli, japan; the rest raw materials are all sold in the market.
Example 1: a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate, which comprises the following steps: s1: adding 10g of 3-aminopropyl trimethoxysilane into 50g of deionized water, uniformly stirring, adding 20g of ammonium hydroxide, heating to 50 ℃, stirring for 4 hours, centrifuging, washing, and vacuum drying at 50 ℃ for 12 hours to obtain amino-functionalized silica; adding 10g of amino-functionalized silica and 10g of 5-norbornene-2-carboxylic acid into 50mL of dichloromethane, adding 0.02g of carbodiimide and 0.02g of 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene-based silica;
S2: adding 10g of zirconium chloride into a hydrochloric acid solution of N, N-dimethylformamide, uniformly stirring, adding 10.5g of an N, N-dimethylformamide solution of 2-amino terephthalic acid, heating to 80 ℃ for reaction for 12 hours, centrifuging, washing, and drying at 120 ℃ for 12 hours to obtain amino MOFs; adding 10g of amino MOFs and 5g of 5-norbornene-2-carboxylic acid into dichloromethane, adding 0.015g of carbodiimide and 0.015g of 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene MOFs;
S3: adding 5g of ethylidene norbornene into 100g of dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding 0.05g of norbornene-based silicon dioxide, 0.2g of norbornene-based MOFs and 0.2g of amino MOFs into 100g of dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
S4: adding 5g of poly (1, 4-butadiene) -polyethylene oxide diblock copolymer and 100g of bisphenol A diglycidyl ether into methylene dichloride, uniformly stirring, and drying the mixture at room temperature in vacuum to remove the methylene dichloride to obtain a substance B; adding the substance B, 85g of methyl nadic anhydride and 1g of 2,4, 6-tris (dimethylaminomethyl) phenol into the substance A, and uniformly stirring to obtain a substance C;
s5: uniformly mixing the Grubbs second-generation catalyst, tributyl phosphite and cyclohexylbenzene according to a proportion, sealing and heating the mixture to 45 ℃ for dissolution, and cooling after clarification to obtain the catalyst; wherein Grubbs second generation catalyst: tributyl phosphite: the mass ratio of the cyclohexylbenzene is 1:0.5:10;
S6: placing the cut carbon fiber fabric in a mold, adding 0.05g of catalyst into the substance C, uniformly stirring, removing bubbles, pouring into the mold, curing at 40 ℃ for 0.5h,60 ℃ for 0.5h,90 ℃ for 2h,140 ℃ for 2h, and 200 ℃ for 2h to obtain the high-pressure-resistance polydicyclopentadienyl cover plate.
Example 2: a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate, which comprises the following steps: s1: adding 10g of 3-aminopropyl trimethoxysilane into 50g of deionized water, uniformly stirring, adding 20g of ammonium hydroxide, heating to 50 ℃, stirring for 4 hours, centrifuging, washing, and vacuum drying at 50 ℃ for 12 hours to obtain amino-functionalized silica; adding 10g of amino-functionalized silica and 10g of 5-norbornene-2-carboxylic acid into 50mL of dichloromethane, adding 0.02g of carbodiimide and 0.02g of 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene-based silica;
S2: adding 10g of zirconium chloride into a hydrochloric acid solution of N, N-dimethylformamide, uniformly stirring, adding 10.5g of an N, N-dimethylformamide solution of 2-amino terephthalic acid, heating to 80 ℃ for reaction for 12 hours, centrifuging, washing, and drying at 120 ℃ for 12 hours to obtain amino MOFs; adding 10g of amino MOFs and 5g of 5-norbornene-2-carboxylic acid into dichloromethane, adding 0.015g of carbodiimide and 0.015g of 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene MOFs;
S3: adding 5g of ethylidene norbornene into 100g of dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding 0.2g of norbornene-based silicon dioxide, 0.5g of norbornene-based MOFs and 0.5g of amino MOFs into 100g of dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
S4: adding 5g of poly (1, 4-butadiene) -polyethylene oxide diblock copolymer and 100g of bisphenol A diglycidyl ether into methylene dichloride, uniformly stirring, and drying the mixture at room temperature in vacuum to remove the methylene dichloride to obtain a substance B; adding the substance B, 85g of methyl nadic anhydride and 1g of 2,4, 6-tris (dimethylaminomethyl) phenol into the substance A, and uniformly stirring to obtain a substance C;
s5: uniformly mixing the Grubbs second-generation catalyst, tributyl phosphite and cyclohexylbenzene according to a proportion, sealing and heating the mixture to 45 ℃ for dissolution, and cooling after clarification to obtain the catalyst; wherein Grubbs second generation catalyst: tributyl phosphite: the mass ratio of the cyclohexylbenzene is 1:0.5:10;
S6: placing the cut carbon fiber fabric in a mold, adding 0.05g of catalyst into the substance C, uniformly stirring, removing bubbles, pouring into the mold, curing at 40 ℃ for 0.5h,60 ℃ for 0.5h,90 ℃ for 2h,140 ℃ for 2h, and 200 ℃ for 2h to obtain the high-pressure-resistance polydicyclopentadienyl cover plate.
Example 3: a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate, which comprises the following steps: s1: adding 10g of 3-aminopropyl trimethoxysilane into 50g of deionized water, uniformly stirring, adding 20g of ammonium hydroxide, heating to 50 ℃, stirring for 4 hours, centrifuging, washing, and vacuum drying at 50 ℃ for 12 hours to obtain amino-functionalized silica; adding 10g of amino-functionalized silica and 10g of 5-norbornene-2-carboxylic acid into 50mL of dichloromethane, adding 0.02g of carbodiimide and 0.02g of 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene-based silica;
S2: adding 10g of zirconium chloride into a hydrochloric acid solution of N, N-dimethylformamide, uniformly stirring, adding 10.5g of an N, N-dimethylformamide solution of 2-amino terephthalic acid, heating to 80 ℃ for reaction for 12 hours, centrifuging, washing, and drying at 120 ℃ for 12 hours to obtain amino MOFs; adding 10g of amino MOFs and 5g of 5-norbornene-2-carboxylic acid into dichloromethane, adding 0.015g of carbodiimide and 0.015g of 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene MOFs;
S3: adding 5g of ethylidene norbornene into 100g of dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding 0.3g of norbornene-based silicon dioxide, 1.0g of norbornene-based MOFs and 1.0g of amino MOFs into 100g of dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
S4: adding 5g of poly (1, 4-butadiene) -polyethylene oxide diblock copolymer and 100g of bisphenol A diglycidyl ether into methylene dichloride, uniformly stirring, and drying the mixture at room temperature in vacuum to remove the methylene dichloride to obtain a substance B; adding the substance B, 85g of methyl nadic anhydride and 1g of 2,4, 6-tris (dimethylaminomethyl) phenol into the substance A, and uniformly stirring to obtain a substance C;
s5: uniformly mixing the Grubbs second-generation catalyst, tributyl phosphite and cyclohexylbenzene according to a proportion, sealing and heating the mixture to 45 ℃ for dissolution, and cooling after clarification to obtain the catalyst; wherein Grubbs second generation catalyst: tributyl phosphite: the mass ratio of the cyclohexylbenzene is 1:0.5:10;
S6: placing the cut carbon fiber fabric in a mold, adding 0.05g of catalyst into the substance C, uniformly stirring, removing bubbles, pouring into the mold, curing at 40 ℃ for 0.5h,60 ℃ for 0.5h,90 ℃ for 2h,140 ℃ for 2h, and 200 ℃ for 2h to obtain the high-pressure-resistance polydicyclopentadienyl cover plate.
Comparative example 1: a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate, which comprises the following steps: s3: adding 5g of ethylidene norbornene into 100g of dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding 0.5g of norbornene-based silicon dioxide, 0.2g of norbornene-based MOFs and 0.2g of amino MOFs into 100g of dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
the remaining steps were the same as in example 1.
Comparative example 2: a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate, which comprises the following steps: s3: adding 5g of ethylidene norbornene into 100g of dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding 0.05g of norbornene-based silicon dioxide, 1.2g of norbornene-based MOFs and 0.2g of amino MOFs into 100g of dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
the remaining steps were the same as in example 1.
Comparative example 3: a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate, which comprises the following steps: s3: adding 5g of ethylidene norbornene into 100g of dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding 0.05g of nano silicon dioxide, 0.2g of norbornene-based MOFs and 0.2g of amino MOFs into 100g of dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
the remaining steps were the same as in example 1.
Comparative example 4: a preparation method of a high-pressure-resistance polydicyclopentadienyl cover plate, which comprises the following steps: s4: adding 100g of bisphenol A diglycidyl ether into dichloromethane, uniformly stirring, and vacuum drying at room temperature to remove dichloromethane to obtain a substance B; adding the substance B, 85g of methyl nadic anhydride and 1g of 2,4, 6-tris (dimethylaminomethyl) phenol into the substance A, and uniformly stirring to obtain a substance C;
the remaining steps were the same as in example 1.
And (3) testing: mechanical property test: tensile yield strength was tested according to ISO 527 standard; flexural strength was tested according to GB/T9341-2008 standard; impact strength was measured according to ISO 179/1eU standard.
TABLE 1 Poly-dicyclopentadienyl cover plate test data sheet
Conclusion: the polydipentadienyl cover plate prepared by the method has excellent high compression resistance. The addition of excess norbornene-based silica in comparative example 1 resulted in agglomeration, decreased dispersion properties, and inability to effectively transfer loads; in comparative example 2, agglomeration caused by adding excessive norbornene-based MOFs occurs, the dispersion performance is reduced, and the load cannot be effectively transmitted; comparative example 3 using ordinary commercially available nanosilicon dioxide instead of norbornene-based silica, the dispersibility in the matrix was reduced and the load could not be transferred effectively; the absence of the poly (1, 4-butadiene) -polyethylene oxide diblock copolymer in comparative example 4 resulted in reduced compatibility between the polydicyclopentadiene and the epoxy resin, reduced interfacial bonding with the carbon fibers, and reduced mechanical properties.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-pressure-resistance polydipentadienyl cover plate is characterized by comprising the following steps: comprises the following steps:
S1: adding ethylidene norbornene into dicyclopentadiene, and uniformly stirring to obtain dicyclopentadiene monomer; adding norbornene-based silicon dioxide, norbornene-based MOFs and amino MOFs into dicyclopentadiene monomer, and uniformly stirring to obtain a substance A;
S2: adding the poly (1, 4-butadiene) -polyethylene oxide diblock copolymer and bisphenol A diglycidyl ether into methylene dichloride, uniformly stirring, and vacuum drying at room temperature to remove the methylene dichloride to obtain a substance B; adding the substance B, methyl nadic anhydride and 2,4, 6-tris (dimethylaminomethyl) phenol into the substance A, and uniformly stirring to obtain a substance C;
s3: uniformly mixing the Grubbs second-generation catalyst, tributyl phosphite and cyclohexylbenzene according to a proportion, sealing and heating the mixture to 45-50 ℃ for dissolution, and cooling after clarification to obtain the catalyst;
s4: placing the cut carbon fiber fabric in a mould, adding a catalyst into the substance C, uniformly stirring, removing bubbles, pouring the mixture into the mould, and curing to obtain the high-pressure-resistance polydicyclopentenyl cover plate;
the preparation method of the norbornene-based silicon dioxide comprises the following steps:
Adding 3-aminopropyl trimethoxy silane into deionized water, stirring uniformly, adding ammonium hydroxide, heating to 50-55 ℃ and stirring for 4-4.5h, centrifuging, washing, and vacuum drying to obtain amino-functionalized silica; adding amino functionalized silica and 5-norbornene-2-carboxylic acid into dichloromethane, adding carbodiimide and 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene-based silica;
the preparation method of the norbornene-based MOFs comprises the following steps:
Adding zirconium chloride into a hydrochloric acid solution of N, N-dimethylformamide, uniformly stirring, adding the N, N-dimethylformamide solution of 2-amino terephthalic acid, heating to 80-85 ℃ for reacting for 12-14h, centrifuging, washing and drying to obtain amino MOFs; adding amino MOFs and 5-norbornene-2-carboxylic acid into dichloromethane, adding carbodiimide and 1-hydroxybenzotriazole, and stirring for reaction to obtain norbornene MOFs.
2. The method for preparing the high-pressure-resistance polydicyclopentenyl cover plate according to claim 1, wherein the method comprises the following steps: 3-aminopropyl trimethoxysilane: the mass ratio of the ammonium hydroxide is 1 (2-3); amino-functionalized silica: the mass ratio of the 5-norbornene-2-carboxylic acid is 1 (1-2).
3. The method for preparing the high-pressure-resistance polydicyclopentenyl cover plate according to claim 1, wherein the method comprises the following steps: zirconium chloride: the mass ratio of the 2-amino terephthalic acid is 1 (1.05-1.2); amino MOFs: the mass ratio of the 5-norbornene-2-carboxylic acid is 1 (0.5-0.6).
4. The method for preparing the high-pressure-resistance polydicyclopentenyl cover plate according to claim 1, wherein the method comprises the following steps: in the step S1, the addition amount of ethylidene norbornene is 5-6wt% of the dicyclopentadiene; the addition amount of the norbornene-based silicon dioxide, the norbornene-based MOFs and the amino MOFs is 0.05-0.3wt%, 0.2-1.0wt% and 0.2-1.0wt% of the dicyclopentadiene monomer.
5. The method for preparing the high-pressure-resistance polydicyclopentenyl cover plate according to claim 1, wherein the method comprises the following steps: in the step S2, bisphenol a diglycidyl ether: the mass ratio of dicyclopentadiene monomer is (3-7) to (5-5); the addition amount of the poly (1, 4-butadiene) -polyethylene oxide diblock copolymer is 5-8wt% of the total mass of bisphenol A diglycidyl ether and dicyclopentadiene monomer; bisphenol a diglycidyl ether: methyl nadic anhydride: the mass ratio of the 2,4, 6-tris (dimethylaminomethyl) phenol is 10 (8.5-9.5) to 0.1-0.12.
6. The method for preparing the high-pressure-resistance polydicyclopentenyl cover plate according to claim 1, wherein the method comprises the following steps: in the step S3, grubbs second generation catalyst: tributyl phosphite: the mass ratio of the cyclohexylbenzene is 1:0.5 (10-15).
7. The method for preparing the high-pressure-resistance polydicyclopentenyl cover plate according to claim 1, wherein the method comprises the following steps: in the step S4, dicyclopentadiene monomer: the mass ratio of the catalyst is 1 (4.5X10 -4-5×10-4).
8. The polydipentadienyl cover plate prepared by the method for preparing the polydipentadienyl cover plate with high compression resistance according to any one of claims 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410282527.1A CN117866387B (en) | 2024-03-13 | 2024-03-13 | High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410282527.1A CN117866387B (en) | 2024-03-13 | 2024-03-13 | High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117866387A CN117866387A (en) | 2024-04-12 |
| CN117866387B true CN117866387B (en) | 2024-05-28 |
Family
ID=90581458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410282527.1A Active CN117866387B (en) | 2024-03-13 | 2024-03-13 | High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117866387B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150051787A (en) * | 2013-11-05 | 2015-05-13 | 롯데케미칼 주식회사 | Polydicyclopentadiene inorganic complex |
| CN108285465A (en) * | 2017-01-09 | 2018-07-17 | 南开大学 | Metal-organic framework material, preparation method, modification metal-organic framework material and preparation method thereof |
| CN112759709A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Dicyclopentadiene-ethylidene norbornene copolymer and preparation method thereof |
| CN115160590A (en) * | 2022-08-22 | 2022-10-11 | 北京航空航天大学 | Preparation method of surface enhanced Raman spectrum substrate with bimetallic metal organic framework |
-
2024
- 2024-03-13 CN CN202410282527.1A patent/CN117866387B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150051787A (en) * | 2013-11-05 | 2015-05-13 | 롯데케미칼 주식회사 | Polydicyclopentadiene inorganic complex |
| CN108285465A (en) * | 2017-01-09 | 2018-07-17 | 南开大学 | Metal-organic framework material, preparation method, modification metal-organic framework material and preparation method thereof |
| CN112759709A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Dicyclopentadiene-ethylidene norbornene copolymer and preparation method thereof |
| CN115160590A (en) * | 2022-08-22 | 2022-10-11 | 北京航空航天大学 | Preparation method of surface enhanced Raman spectrum substrate with bimetallic metal organic framework |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117866387A (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112795142B (en) | Epoxy resin-carbon nanotube flame-retardant composite material and preparation method thereof | |
| CN109265922B (en) | High-toughness autocatalytic epoxy resin and preparation method thereof | |
| CN102190858B (en) | Epoxy resin material toughened by nanometer silica and preparation method thereof | |
| CN113201207B (en) | Preparation method of high-toughness and high-strength carbon nanotube/epoxy resin composite material | |
| CN117866387B (en) | High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof | |
| CN1020618C (en) | Method for preparation of toughened epoxy resin | |
| CN111995861A (en) | GO/TPU composite powder for selective laser sintering of heat-resistant workpieces and preparation method thereof | |
| CN115746404B (en) | Surface modified hexagonal boron nitride nanosheet, modification method thereof and epoxy composite material | |
| CN114874496B (en) | High-strength low-curing shrinkage silicone rubber and preparation method thereof | |
| CN114891249A (en) | Preparation method of glass fiber reinforced epoxy resin composite material | |
| CN114437539B (en) | Reinforced nylon material and preparation method and application thereof | |
| CN114316870A (en) | Injection type bar planting glue and preparation method thereof | |
| Xu et al. | Synchronously improving mechanical and thermal performances of cured epoxy resins by epoxidized polyether sulphones as modifiers | |
| CN111500041A (en) | Low-density halogen-free flame-retardant BMC material and preparation method thereof | |
| CN107513135B (en) | High-shear-resistance carbon nanotube-containing unsaturated resin for pultrusion and preparation method thereof | |
| CN102504489B (en) | Thermosetting resin composition, preparation method thereof and laminate | |
| CN111205461A (en) | Preparation method of phenyl methyl vinyl organosilicon powder material | |
| CN1239558C (en) | Process for preparing nano-particle modified epoxy resin | |
| CN114479445B (en) | High-flexural modulus and low-water-absorption carbon fiber-graphene/nylon composite material and preparation method thereof | |
| CN1290884C (en) | Modified ethenoid resin | |
| CN113801458B (en) | Hydrophobic wear-resistant PC/PET composite material and preparation method thereof | |
| CN116333549B (en) | Polymer cement anti-corrosion paint based on functional MXene and preparation method thereof | |
| CN116162318B (en) | Polyvinyl alcohol/modified glass fiber composite material and preparation method thereof | |
| CN115074065B (en) | Epoxy adhesive for chip packaging and preparation process thereof | |
| CN117328266A (en) | Carbon fiber sizing agent, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |