CN112980129A - Montmorillonite modified polytriecyclopentadiene PTCPD composite material and preparation method thereof - Google Patents
Montmorillonite modified polytriecyclopentadiene PTCPD composite material and preparation method thereof Download PDFInfo
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- CN112980129A CN112980129A CN202110185161.2A CN202110185161A CN112980129A CN 112980129 A CN112980129 A CN 112980129A CN 202110185161 A CN202110185161 A CN 202110185161A CN 112980129 A CN112980129 A CN 112980129A
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- montmorillonite
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- polytrieopentadiene
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 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 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000007781 pre-processing Methods 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 235000011837 pasties Nutrition 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- UCQHUEOREKHIBP-UHFFFAOYSA-N heptacyclo[9.6.1.14,7.113,16.02,10.03,8.012,17]icosa-5,14-diene Chemical compound C1C(C23)C4C(C=C5)CC5C4C1C3CC1C2C2C=CC1C2 UCQHUEOREKHIBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000011417 postcuring Methods 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001153 Polydicyclopentadiene Polymers 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 9
- -1 tungsten halide Chemical class 0.000 description 8
- 238000005452 bending Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910003091 WCl6 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a montmorillonite modified polytrieopentadiene PTCPD composite material and a preparation method thereof. Because the molecular weight of the tricyclopentadiene TCPD is large, the rigidity is large, and simultaneously because of the modification of the montmorillonite, the flexural modulus of the prepared montmorillonite-modified polytrieopentadiene PTCPD composite material can reach 4020-4460 MPa, thereby solving the technical problem of insufficient rigidity of the polydicyclopentadiene PDCPD material in the prior art. The montmorillonite modified poly-tricyclopentadiene composite material has the excellent characteristics of high strength, high energy storage modulus, good thermal stability and barrier property, acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, capacity increase, cost reduction and the like, and has wide application range.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a montmorillonite modified polytriecyclopentadiene PTCPD composite material and a preparation method thereof.
Background
The polydicyclopentadiene PDCPD polymer material is homopolymer or copolymer of dicyclopentadiene DCPD, and is a cross-linked three-dimensional network structure engineering plastic. The polydicyclopentadiene PDCPD is a material with the characteristics of good heat resistance, creep resistance, dimensional stability, shape memory, corrosion resistance, light weight and the like, and can be used for manufacturing various high-performance, high-added-value and high-grade fine products. Such as: automobile bumpers, guard plates, side plates, buffer plates, instrument panels, mud guards, engine covers, body shells and the like in the transportation industry; housings for large-sized electrical devices such as motors and air conditioners in electrical devices; parts of snowmobiles, surfboards, golf carts, etc. in sports equipment, agricultural machinery, civil engineering and construction materials, etc.
However, in the process of implementing the technical solution of the invention in the embodiments of the present application, the inventors of the present application find that the above-mentioned technology has at least the following technical problems:
although polydicyclopentadiene PDCPD has good comprehensive performance, the strength of the polydicyclopentadiene PDCPD cannot meet the higher requirements in certain specific engineering fields. The bending modulus of the polydicyclopentadiene PDCPD high polymer material is about 1790-2070 MPa, and the material rigidity of the polydicyclopentadiene PDCPD can not meet the requirement on the working condition with higher requirement on the bending modulus. In addition, the storage modulus, thermal stability and barrier property of the polydicyclopentadiene PDCPD high molecular material are also required to be further improved.
Disclosure of Invention
The embodiment of the application provides a montmorillonite modified polytrieopentadiene PTCPD composite material and a preparation method thereof, solves the technical problem that the material rigidity and the storage modulus of polydicyclopentadiene PDCPD in the prior art are insufficient, and the montmorillonite modified polytrieopentadiene PTCPD composite material has the advantages of large bending modulus, high storage modulus, good thermal stability and barrier property, excellent properties of acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance and the like, and wide application range.
The embodiment of the application provides a montmorillonite-modified polytrieopentadiene PTCPD composite material, which comprises montmorillonite and a polytrieopentadiene resin system, wherein the montmorillonite is uniformly dispersed in the polytrieopentadiene resin system.
Preferably, the polytriacyclopentadiene resin system is prepared from the following components:
tricyclopentadiene TCPD;
a catalyst;
the weight percentage of the tricyclopentadiene TCPD in the polytrieopentadiene resin system is more than or equal to 50% and less than 100%.
More preferably, the component of the polytrieopentadiene resin system further comprises one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
Preferably, the catalyst is one or more of a tungsten catalyst, a molybdenum catalyst, a ruthenium catalyst, a titanium catalyst and a rhenium catalyst.
The catalyst also comprises one or more of metal organic compounds of aluminum, magnesium, tin, zinc and silicon. Such as triethylaluminum, tributylaluminum, diethylaluminum monochloride, triisobutylaluminum, etc.
The catalyst also comprises alcohol, phenol and BF3One or more of them.
The tungsten catalyst comprises one or more of tungsten simple substance, tungsten oxide, tungsten halide (such as tungsten sulfide and tungsten chloride), tungsten hydroxyl compound and heteropolytungstic acid;
the molybdenum catalyst comprises one or more of molybdenum simple substance, molybdenum oxide, molybdenum halide, molybdenum hydroxyl compound, phosphomolybdic acid and ammonium molybdate;
the ruthenium catalyst is one or more of ruthenium metal and ruthenium compounds; such as a ruthenium carbene catalyst.
The titanium catalyst is one or more of metal titanium, titanium oxide, titanium halide and titanium hydroxyl compound;
the rhenium catalyst is one or more of metal rhenium, rhenium oxide, rhenium halide and rhenium hydroxyl compound.
The embodiment of the application also provides a preparation method of the montmorillonite modified polytrieopentadiene PTCPD composite material, which comprises the following steps:
step S1: preprocessing montmorillonite to form paste montmorillonite;
step S2: heating the tricyclopentadiene TCPD to change the TCPD into a liquid state, adding the paste montmorillonite into the liquid TCPD to uniformly disperse the paste montmorillonite in the TCPD to form a mixed solution;
step S3: heating the mould, mixing the mixed solution and the catalyst, and injecting the mixed system into a closed mould cavity; polymerizing the mixed solution and the catalyst, and crosslinking, curing and molding;
step S4: opening the mold, and demolding to obtain a sample;
step S5: and (3) placing the sample in an oven for post-curing to form the montmorillonite modified polytrieopentadiene PTCPD composite material.
Preferably, the specific process of step S1 is: modifying the surface of montmorillonite with coupling agent, mixing the modified montmorillonite with liquid TCPD, and grinding the mixture to obtain paste montmorillonite;
in the paste montmorillonite, the mass percentage of montmorillonite to liquid TCPD is 1: 2-1: 5.
Preferably, in step S2, the mass fraction of the paste montmorillonite in TCPD is less than or equal to 80%.
Preferably, in the step S2, the paste montmorillonite is uniformly dispersed in the TCPD by mechanical stirring, and the time of the mechanical stirring is 40min to 60 min.
Preferably, in the step S3, the mold is preheated to 50-80 ℃.
Preferably, in the step S5, the sample is placed in an oven at 80-100 ℃ for post-curing for 4-6 h.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. the component of the material contains a high proportion of tricyclopentadiene TCPD, the tricyclopentadiene TCPD has a large molecular weight and high rigidity, and meanwhile, due to the modification of montmorillonite, the flexural modulus of the prepared polytrietadiene/montmorillonite composite material can reach 4020-4460 MPa, so that the technical problem of insufficient rigidity of the material of polydicyclopentadiene PDCPD in the prior art is solved.
2. In the montmorillonite-modified polytrieopentadiene PTCPD composite material provided by the application, when the content of montmorillonite is less than 5%, the thermal degradation temperature of a polytrieopentadiene/montmorillonite composite material product is gradually increased along with the increase of the mass fraction of the montmorillonite, and because the montmorillonite is uniformly dispersed in a polytrieopentadiene matrix, the thermal stability and the barrier property of the polytrieopentadiene matrix are improved and are far higher than that of a polytrieopentadiene PDCPD product in the prior art. When the content of the montmorillonite is more than or equal to 5 percent, the montmorillonite is used as a filler, and the beneficial effects of capacity increase and cost reduction are achieved.
3. The storage modulus of the montmorillonite-modified polytrieopentadiene PTCPD composite material is 1.63-1.88 GPa, which is far higher than that of a polydicyclopentadiene PDCPD product (about 0.813GPa) in the prior art.
4. The montmorillonite modified polytriecyclopentadiene PTCPD composite material provided by the application also has excellent characteristics of acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance and the like, and has a wide application range.
Detailed Description
The embodiment of the application solves the technical problem of insufficient rigidity of polydicyclopentadiene PDCPD materials in the prior art by providing the montmorillonite modified polytriacyclopentadiene PTCPD composite material.
In order to solve the problem of crosstalk, the technical scheme in the embodiment of the present application has the following general idea:
montmorillonite MMT is a layered silicate, which has a natural nanosheet structure in nanocomposite technology. Modifying the polytriale cyclopentadiene PTCPD by using montmorillonite, stripping the montmorillonite into nano-sheet layers, and uniformly dispersing the nano-sheet layers in a polytriale cyclopentadiene PTCPD matrix to prepare the polytriale cyclopentadiene/montmorillonite composite material.
Because the molecular weight of the tricyclopentadiene TCPD is large, the rigidity of the tricyclopentadiene TCPD is large, and simultaneously, because of the modification of the montmorillonite, the flexural modulus of the prepared polytrietadiene/montmorillonite composite material can reach 4020-4460 MPa, and the storage modulus is 1.63-1.88 GPa.
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments.
Example one
The embodiment of the application provides a montmorillonite modified polytrieopentadiene PTCPD composite material which comprises the following components:
50% of tricyclopentadiene;
4.99 percent of dicyclopentadiene;
WCl60.127 percent by weight;
AlEt2cl, 0.382% by weight;
C6H2Cl4o, 0.001 percent by weight;
montmorillonite with the weight percentage of 41 percent.
In this embodiment, the preparation method of the montmorillonite-modified polytrieopentadiene PTCPD composite material comprises the following steps:
step S1: preprocessing montmorillonite to form paste montmorillonite;
the specific process is as follows: heating a small amount of tricyclopentadiene TCPD to change the TCPD into a liquid state; modifying the surface of montmorillonite with coupling agent, mixing the modified montmorillonite with liquid TCPD, and grinding the mixture to obtain paste montmorillonite; in the paste montmorillonite, the mass percentage of montmorillonite to liquid TCPD is 1: 2.
Step S2: heating a large amount of tricyclopentadiene TCPD to change the TCPD into a liquid state, and adding the paste montmorillonite into the liquid TCPD, wherein the paste montmorillonite accounts for 80% of the mass of the TCPD. The pasty montmorillonite is uniformly dispersed in TCPD by mechanical stirring to form a mixed solution, and the mechanical stirring time is 40 min.
Step S3: preheating a mould to 50 ℃, mixing the mixed solution and the catalyst, and injecting the mixed system into a closed mould cavity; polymerizing the mixed solution and the catalyst, and crosslinking, curing and molding;
step S4: opening the mold, and demolding to obtain a sample;
step S5: and (3) putting the sample in an oven at 80 ℃ and then curing for 6h to form the montmorillonite modified polytriecyclopentadiene PTCPD composite material.
The prepared polytrieopentadiene/montmorillonite composite material product has the flexural modulus of 4020MPa and the storage modulus of 1.63GPa through measurement.
Example two
The embodiment of the application provides a montmorillonite modified polytrieopentadiene PTCPD composite material which comprises the following components:
tricyclopentadiene TCPD, 70% by weight;
5% of dicyclopentadiene by weight;
2.65 percent of tetracyclopentadiene;
ReCls, 0.085% by weight;
(CH3)4sn, 0.265% by weight;
montmorillonite with the weight percentage of 22 percent.
In this embodiment, the preparation method of the montmorillonite-modified polytrieopentadiene PTCPD composite material comprises the following steps:
step S1: preprocessing montmorillonite to form paste montmorillonite;
the specific process is as follows: heating a small amount of tricyclopentadiene TCPD to change the TCPD into a liquid state; modifying the surface of montmorillonite with coupling agent, mixing the modified montmorillonite with liquid TCPD, and grinding the mixture to obtain paste montmorillonite; in the paste montmorillonite, the mass percentage of montmorillonite to liquid TCPD is 1: 3.
Step S2: heating a large amount of tricyclopentadiene TCPD to change the TCPD into a liquid state, and adding the paste montmorillonite into the liquid TCPD, wherein the paste montmorillonite accounts for 30% of the mass of the TCPD. The pasty montmorillonite is uniformly dispersed in TCPD by mechanical stirring to form a mixed solution, and the mechanical stirring time is 40 min.
Step S3: preheating a mould to 60 ℃, mixing the mixed solution and the catalyst, and injecting the mixed system into a closed mould cavity; polymerizing the mixed solution and the catalyst, and crosslinking, curing and molding;
step S4: opening the mold, and demolding to obtain a sample;
step S5: and (3) putting the sample in an oven at 90 ℃ and then curing for 5h to form the montmorillonite modified polytriecyclopentadiene PTCPD composite material.
The prepared polytrieyclopentadiene/montmorillonite composite material product has the flexural modulus of 4214MPa and the storage modulus of 1.68GPa through measurement.
EXAMPLE III
The embodiment of the application provides a montmorillonite modified polytrieopentadiene PTCPD composite material which comprises the following components:
tricyclopentadiene TCPD, weight percent 83%;
4.7 percent of dicyclopentadiene;
pentacyclopentadiene, weight percent 2.7%;
CpTiCl20.145 percent by weight;
CH3MgI, 0.435 percent by weight.
Montmorillonite 9 wt%.
In this embodiment, the preparation method of the montmorillonite-modified polytrieopentadiene PTCPD composite material comprises the following steps:
step S1: preprocessing montmorillonite to form paste montmorillonite;
the specific process is as follows: heating a small amount of tricyclopentadiene TCPD to change the TCPD into a liquid state; modifying the surface of montmorillonite with coupling agent, mixing the modified montmorillonite with liquid TCPD, and grinding the mixture to obtain paste montmorillonite; in the paste montmorillonite, the mass percentage of montmorillonite to liquid TCPD is 1: 4.
Step S2: heating a large amount of tricyclopentadiene TCPD to change the TCPD into a liquid state, and adding the paste montmorillonite into the liquid TCPD, wherein the paste montmorillonite accounts for 10% of the mass of the TCPD. The pasty montmorillonite is uniformly dispersed in TCPD by mechanical stirring to form a mixed solution, and the mechanical stirring time is 50 min.
Step S3: preheating a mould to 70 ℃, mixing the mixed solution and the catalyst, and injecting the mixed system into a closed mould cavity; polymerizing the mixed solution and the catalyst, and crosslinking, curing and molding;
step S4: opening the mold, and demolding to obtain a sample;
step S5: and (3) putting the sample in an oven at 90 ℃ and then curing for 5h to form the montmorillonite modified polytriecyclopentadiene PTCPD composite material.
The measurement shows that the flexural modulus of the prepared polytrieyclopentadiene/montmorillonite composite material product is 4320MPa, and the storage modulus is 1.74 GPa.
Example four
The embodiment of the application provides a montmorillonite modified polytrieopentadiene PTCPD composite material which comprises the following components:
tricyclopentadiene TCPD, 99% by weight;
0.501 percent of tetracyclopentadiene;
ruthenium carbene catalyst, weight percent 0.099%;
montmorillonite, 0.4% by weight.
In this embodiment, the preparation method of the montmorillonite-modified polytrieopentadiene PTCPD composite material comprises the following steps:
step S1: preprocessing montmorillonite to form paste montmorillonite;
the specific process is as follows: heating a small amount of tricyclopentadiene TCPD to change the TCPD into a liquid state; modifying the surface of montmorillonite with coupling agent, mixing the modified montmorillonite with liquid TCPD, and grinding the mixture to obtain paste montmorillonite; in the paste montmorillonite, the mass percentage of montmorillonite to liquid TCPD is 1: 5.
Step S2: heating a large amount of tricyclopentadiene TCPD to change the TCPD into a liquid state, and adding the paste montmorillonite into the liquid TCPD, wherein the paste montmorillonite accounts for 0.02 percent of the mass of the TCPD. The pasty montmorillonite is uniformly dispersed in TCPD by mechanical stirring to form a mixed solution, and the mechanical stirring time is 60 min.
Step S3: preheating a mould to 80 ℃, mixing the mixed solution and the catalyst, and injecting the mixed system into a closed mould cavity; polymerizing the mixed solution and the catalyst, and crosslinking, curing and molding;
step S4: opening the mold, and demolding to obtain a sample;
step S5: and (3) putting the sample in an oven at 100 ℃ and then curing for 4h to form the montmorillonite modified polytriecyclopentadiene PTCPD composite material.
The prepared polytrieyclopentadiene/montmorillonite composite material product has the flexural modulus of 4460MPa and the storage modulus of 1.88 GPa.
While the foregoing is directed to the preferred embodiment of the present application, and not to the limiting thereof in any way and any way, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. Those skilled in the art can make various changes, modifications and equivalent arrangements to those skilled in the art without departing from the spirit and scope of the present application; moreover, any equivalent alterations, modifications and variations of the above-described embodiments according to the spirit and techniques of this application are intended to be within the scope of the claims of this application.
Claims (10)
1. The montmorillonite-modified polytrieopentadiene PTCPD composite material is characterized by comprising montmorillonite and a polytrieopentadiene resin system, wherein the montmorillonite is uniformly dispersed in the polytrieopentadiene resin system.
2. The montmorillonite-modified polytrieopentadiene PTCPD composite of claim 1, wherein the polytrieopentadiene resin system is made from:
tricyclopentadiene TCPD;
a catalyst;
the weight percentage of the tricyclopentadiene TCPD in the polytrieopentadiene resin system is more than or equal to 50% and less than 100%.
3. The montmorillonite-modified polytrieopentadiene PTCPD composite material of claim 2, wherein the component of the polytrieopentadiene resin system further comprises one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene, pentacyclopentadiene.
4. The montmorillonite-modified polytrieopentadiene PTCPD composite material as claimed in claim 2, wherein the catalyst is one or more of tungsten catalyst, molybdenum catalyst, ruthenium catalyst, titanium catalyst and rhenium catalyst.
5. A preparation method of a montmorillonite modified polytrieopentadiene PTCPD composite material is characterized by comprising the following steps:
step S1: preprocessing montmorillonite to form paste montmorillonite;
step S2: heating the tricyclopentadiene TCPD to change the TCPD into a liquid state, adding the paste montmorillonite into the liquid TCPD to uniformly disperse the paste montmorillonite in the TCPD to form a mixed solution;
step S3: heating the mould, mixing the mixed solution and the catalyst, and injecting the mixed system into a closed mould cavity; polymerizing the mixed solution under the action of a catalyst, and crosslinking, curing and molding;
step S4: opening the mold, and demolding to obtain a sample;
step S5: and (3) placing the sample in an oven for post-curing to form the montmorillonite modified polytrieopentadiene PTCPD composite material.
6. The method for preparing the montmorillonite-modified polytrieopentadiene PTCPD composite material as claimed in claim 5, wherein the specific process of the step S1 is as follows: modifying the surface of montmorillonite with coupling agent, mixing the modified montmorillonite with liquid TCPD, and grinding the mixture to obtain paste montmorillonite;
in the paste montmorillonite, the mass percentage of montmorillonite to liquid TCPD is 1: 2-1: 5.
7. The method for preparing the montmorillonite-modified polytrieopentadiene PTCPD composite material according to claim 5, wherein in the step S2, the mass fraction of paste montmorillonite in TCPD is less than or equal to 80%.
8. The method for preparing the montmorillonite-modified polytrieopentadiene PTCPD composite material according to claim 5, wherein in the step S2, the pasty montmorillonite is uniformly dispersed in TCPD by mechanical stirring, and the mechanical stirring time is 40-60 min.
9. The method for preparing the montmorillonite-modified polytrieopentadiene PTCPD composite material according to claim 3, wherein in the step S3, the mold is preheated to 50-80 ℃.
10. The preparation method of the montmorillonite-modified polytrieopentadiene PTCPD composite material as claimed in claim 3, wherein in the step S5, the sample is placed in an oven at 80-100 ℃ and then is subjected to post-curing for 4-6 h.
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Application publication date: 20210618 |