CN112812487A - Carbon nano tube modified polytriacyclopentadiene PTCPD composite material and preparation method thereof - Google Patents
Carbon nano tube modified polytriacyclopentadiene PTCPD composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 114
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 150000001263 acyl chlorides Chemical class 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 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 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 9
- 238000004821 distillation Methods 0.000 claims 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000009477 glass transition Effects 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
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 20
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910006124 SOCl2 Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
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- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (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 discloses a carbon nano tube modified polytriacyclopentadiene PTCPD composite material and a preparation method thereof. When in preparation, the carbon nano tube is pretreated; then modifying the pretreated carbon nano tube by norbornene; and finally, adding the norbornene-modified carbon nano tube into liquid tricyclopentadiene TCPD, adding a catalyst, uniformly mixing, and curing to obtain the polytrieopentadiene/carbon nano tube nanocomposite. The carbon nanotube modified polytrieclopentadiene PTCPD composite material provided by the invention has the advantages of large bending modulus, good fracture toughness, high glass transition temperature, excellent characteristics of acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, high storage modulus and the like, and has a wide application range.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a carbon nano tube 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, polydicyclopentadiene PDCPD has brittle fracture characteristics, and the toughness of the material is not enough.
Disclosure of Invention
The embodiment of the application provides a carbon nanotube modified polytrieopentadiene PTCPD composite material and a preparation method thereof, so that the technical problems of insufficient material rigidity and insufficient toughness of polydicyclopentadiene PDCPD in the prior art are solved, the carbon nanotube modified polytrieopentadiene PTCPD composite material is large in flexural modulus and good in fracture toughness, and has excellent characteristics of acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, high storage modulus and the like, and the application range is wide.
The embodiment of the application provides a carbon nanotube modified polytriecyclopentadiene PTCPD composite material, which comprises:
a polytrialene resin system;
a carbon nanotube;
the carbon nano-tubes are uniformly dispersed in the polytriacyclopentadiene resin system to form the polytriacyclopentadiene/carbon nano-tube nano-composite material.
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%.
Preferably, the component of the polytrieopentadiene resin system further comprises one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
Preferably, the carbon nanotube is a carbon nanotube with a surface modified by norbornene.
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 embodiment of the application also provides a preparation method of the carbon nanotube modified polytriecyclopentadiene PTCPD composite material, which is characterized by comprising the following steps:
step S1: pretreating the carbon nano tube;
step S2: modifying the pretreated carbon nano tube by norbornene;
step S3: adding the carbon nano tube modified by the norbornene into liquid tricyclopentadiene TCPD, adding a catalyst, uniformly mixing, and curing to obtain the polytrieopentadiene/carbon nano tube nanocomposite.
Preferably, in the step S1, the step of pretreating the carbon nanotubes includes the following steps:
step S101: adding the carbon nano tube into nitric acid, performing ultrasonic dispersion and reflux reaction, performing suction filtration and washing on a product to be neutral, and performing vacuum drying to obtain an acid oxidized carbon nano tube;
step S102: adding the carbon nanotube oxide acid into a container containing thionyl chloride and a cocatalyst, reacting in a nitrogen atmosphere, and after the reaction is finished, distilling the product under reduced pressure to remove SOCl2Then obtaining the carbon nano tube modified by acyl chloride;
step S103: adding the carbon nano tube modified by acyl chloride into a reaction vessel containing glycol and pyridine for reflux reaction, and after the reaction is finished, purifying, cleaning and vacuum-drying a product.
Further, in step S102, the cocatalyst is N, N' -dimethylformamide.
Further, in step S103, the product is purified and then washed with tetrahydrofuran and acetone, respectively.
Preferably, the specific steps of step S2 are: and adding the pretreated carbon nano tube into a norbornene solution at 65-75 ℃, performing reflux reaction, performing suction filtration and washing on a product, and performing vacuum drying to obtain the norbornene-modified carbon nano tube.
Preferably, in step S3, the catalyst is one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst.
Preferably, in the step S3, the carbon nanotubes account for 0.1 to 0.5 mass percent of the tricyclopentadiene;
preferably, in step S3, the curing process is divided into two stages: firstly, curing for 110-130 min at 65-75 ℃, and then curing for 80-100 min at 165-170 ℃.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. the application provides a carbon nanotube modified polytrieopentadiene PTCPD composite material, the material component contains a high proportion of tricyclopentadiene TCPD, the large molecular weight of the tricyclopentadiene TCPD is large, the rigidity is large, meanwhile, due to the modification of the carbon nanotube, the bending modulus of the prepared polytrieopentadiene/carbon nanotube nano composite material is large, and the technical problem of insufficient rigidity of the material of the polytrieopentadiene PDCPD in the prior art is solved. And the flexural modulus of the polytriacyclopentadiene/carbon nanotube nano composite material is gradually increased along with the increase of the mass fraction of the carbon nanotubes in the tricyclopentadiene.
2. In the carbon nanotube modified polytrieopentadiene PTCPD composite material provided by the application, along with the increase of the mass fraction of the carbon nanotubes in the tricyclopentadiene, the elongation at break of the polytrieopentadiene/carbon nanotube nano composite material is gradually increased, and the fracture toughness is greatly increased. This is because the carbon nanotubes, when the polytrialene polymer matrix starts to fracture, toughen the composite nanoparticles by the effect of bridging the voids by forming a large number of subcritical microcracks and micropores, and delaying the formation of critical cracks by defects, and promoting the crack bridging effect and the subsequent inter-particle matrix ties, thereby improving the fracture toughness of the polytrialene/carbon nanotube nanocomposites.
3. In the carbon nanotube modified polytriacyclopentadiene PTCPD composite material provided by the application, along with the increase of the mass fraction of the carbon nanotubes in the tricyclopentadiene, the vitrification temperature of the polytriacyclopentadiene/carbon nanotube nanocomposite material is gradually increased, the storage modulus is gradually increased, the carbon nanotubes and the polytriacyclopentadiene generate covalent bonds in the polymerization process, and the movement of polytriacyclopentadiene molecular chains is reduced.
4. The carbon nanotube 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 is wide in application range.
Detailed Description
The embodiment of the application provides a preparation method of a carbon nanotube modified polytrieopentadiene PTCPD composite material, and solves the technical problems of insufficient material rigidity and insufficient toughness of polydicyclopentadiene PDCPD in the prior art.
In order to solve the problem of crosstalk, the technical scheme in the embodiment of the present application has the following general idea:
the carbon nanotube CNT has a cage-like structure in which one or more carbon atoms in a graphite layer are curled, and has a hollow interior and an outer diameter of several to several tens of nanometers. Carbon nanotubes are ideally seamless, hollow tubes rolled from graphene sheets formed of carbon atoms, and are lightweight, with a density of 1/6 for steel and a strength of exactly 100 times that of steel.
And modifying the polytriacyclopentadiene PTCPD by using the carbon nano tube to ensure that the carbon nano tube is stably dispersed in the polytriacyclopentadiene PTCPD matrix to prepare the polytriacyclopentadiene/carbon nano tube nano 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 carbon nano tube, the prepared polytrietadiene/carbon nano tube nano composite material has large bending modulus, large fracture toughness strength and high glass transition temperature.
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 preparation method of a carbon nanotube modified polytriecyclopentadiene PTCPD composite material, which comprises the following steps:
step S1: pretreating the carbon nano tube;
step S101: adding 0.8g of carbon nano tube into 480ml of nitric acid with the concentration of 50%, performing ultrasonic dispersion for 8 minutes, performing reflux reaction for 6 hours at 110 ℃, performing suction filtration and washing on a product to be neutral, and drying in a vacuum oven at 100 ℃ for 24 hours to obtain an acid oxidized carbon nano tube;
step S102: adding the carbon nanotube oxide acid into a container containing thionyl chloride and a cocatalyst, reacting in a nitrogen atmosphere, and after the reaction is finished, distilling the product under reduced pressure to remove SOCl2Then obtaining the carbon nano tube modified by acyl chloride;
step S103: adding the carbon nano tube modified by acyl chloride into a reaction vessel containing glycol and pyridine for reflux reaction, and after the reaction is finished, purifying, cleaning and vacuum-drying a product.
Step S2: modifying the pretreated carbon nano tube by norbornene;
step S3: adding the carbon nano tube modified by the norbornene into liquid tricyclopentadiene TCPD, wherein the mass fraction of the carbon nano tube in the tricyclopentadiene TCPD is 0.1%, adding a tungsten catalyst, uniformly mixing, curing at 65 ℃ for 110min, and then curing at 165 ℃ for 80min to obtain the polytrieopentadiene/carbon nano tube nanocomposite.
Example two
The embodiment of the application provides a preparation method of a carbon nanotube modified polytriecyclopentadiene PTCPD composite material, which comprises the following steps:
step S1: pretreating the carbon nano tube;
step S101: adding 1g of carbon nano tube into 600ml of 50% nitric acid, performing ultrasonic dispersion for 10 minutes, performing reflux reaction at 120 ℃ for 7 hours, performing suction filtration and washing on a product to be neutral, and drying in a vacuum oven at 100 ℃ for 24 hours to obtain an acid oxidized carbon nano tube;
step S102: adding the carbon nanotube oxide acid into a container containing thionyl chloride and a cocatalyst, reacting in a nitrogen atmosphere, and after the reaction is finished, distilling the product under reduced pressure to remove SOCl2Then obtaining the carbon nano tube modified by acyl chloride;
step S103: adding the carbon nano tube modified by acyl chloride into a reaction vessel containing glycol and pyridine for reflux reaction, and after the reaction is finished, purifying, cleaning and vacuum-drying a product.
Step S2: modifying the pretreated carbon nano tube by norbornene;
step S3: adding the carbon nano tube modified by the norbornene into a liquid mixture of tricyclopentadiene TCPD and dicyclopentadiene DCPD (the weight percentage of TCPD in the mixture is 51%), wherein the mass fraction of the carbon nano tube in the tricyclopentadiene is 0.25%, adding a molybdenum catalyst, uniformly mixing, curing at 70 ℃ for 120min, and then curing at 170 ℃ for 90min to obtain the polytriepentadiene/carbon nano tube nanocomposite.
EXAMPLE III
The embodiment of the application provides a preparation method of a carbon nanotube modified polytriecyclopentadiene PTCPD composite material, which comprises the following steps:
step S1: pretreating the carbon nano tube;
step S101: adding 1.2g of carbon nano tube into 720ml of nitric acid with the concentration of 50%, performing ultrasonic dispersion for 12 minutes, performing reflux reaction for 8 hours at 125 ℃, performing suction filtration and washing on a product to be neutral, and drying for 24 hours in a vacuum oven at 100 ℃ to obtain an acid oxidized carbon nano tube;
step S102: adding the carbon nanotube oxide acid into a container containing thionyl chloride and a cocatalyst, reacting in a nitrogen atmosphere, and after the reaction is finished, distilling the product under reduced pressure to remove SOCl2Then obtaining the carbon nano tube modified by acyl chloride;
step S103: adding the carbon nano tube modified by acyl chloride into a reaction vessel containing glycol and pyridine for reflux reaction, and after the reaction is finished, purifying, cleaning and vacuum-drying a product.
Step S2: modifying the pretreated carbon nano tube by norbornene;
step S3: adding the carbon nano tube modified by the norbornene into a mixture of liquid tricyclopentadiene TCPD, dicyclopentadiene DCPD and tetracyclopentadiene (the weight percentage of TCPD in the mixture is 75%), wherein the mass fraction of the carbon nano tube in the tricyclopentadiene is 0.5%, adding a ruthenium catalyst, uniformly mixing, curing at 75 ℃ for 130min, and then curing at 168 ℃ for 100min to obtain the polytriaclopentadiene/carbon nano tube nanocomposite.
The performance of the polytrieopentadiene/carbon nanotube nanocomposite prepared in the first to third embodiments is detected, and the results are as follows:
from the above table, it can be seen that:
with the increase of the mass fraction of the carbon nano tube in the tricyclopentadiene, the flexural modulus of the polytrieopentadiene/carbon nano tube nano composite material is gradually increased, and the flexural modulus of the polytrieopentadiene/carbon nano tube nano composite material is far greater than that of the existing polydicyclopentadiene high polymer material.
With the increase of the mass fraction of the carbon nano tube in the tricyclopentadiene, the elongation at break of the polytrieopentadiene/carbon nano tube nano composite material is gradually increased, and the fracture toughness is greatly increased. This is because the carbon nanotubes, when the polytrialene polymer matrix starts to fracture, toughen the composite nanoparticles by the effect of bridging the voids by forming a large number of subcritical microcracks and micropores, and delaying the formation of critical cracks by defects, and promoting the crack bridging effect and the subsequent inter-particle matrix ties, thereby improving the fracture toughness of the polytrialene/carbon nanotube nanocomposites.
Along with the increase of the mass fraction of the carbon nano tubes in the tricyclopentadiene, the glass transition temperature of the polytrieopentadiene/carbon nano tube nano composite material is gradually increased, the storage modulus is gradually increased, the carbon nano tubes and the polytrieopentadiene generate covalent bonds in the polymerization process, and the movement of the polytrieopentadiene molecular chains is reduced.
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. A carbon nanotube-modified polytrieopentadiene PTCPD composite, comprising:
a polytrialene resin system;
a carbon nanotube;
the carbon nano-tubes are uniformly dispersed in the polytriacyclopentadiene resin system to form the polytriacyclopentadiene/carbon nano-tube nano-composite material.
2. The carbon nanotube-modified polytrieopentadiene PTCPD composite of claim 1, wherein the polytrieopentadiene resin system is made comprising:
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 carbon nanotube-modified polytrieopentadiene PTCPD composite material of claim 2, wherein the components of the polytrieopentadiene resin system further comprise one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene, pentacyclopentadiene.
4. The carbon nanotube-modified polytrieopentadiene PTCPD composite material of claim 1, wherein the carbon nanotubes are carbon nanotubes having surfaces modified with norbornene.
5. The carbon nanotube-modified polytrieopentadiene PTCPD composite material according to claim 1, wherein the catalyst is one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst.
6. A preparation method of a carbon nanotube modified polytrieopentadiene PTCPD composite material is characterized by comprising the following steps:
step S1: pretreating the carbon nano tube;
step S2: modifying the pretreated carbon nano tube by norbornene;
step S3: adding the carbon nano tube modified by the norbornene into liquid tricyclopentadiene TCPD, adding a catalyst, uniformly mixing, and curing to obtain the polytrieopentadiene/carbon nano tube nanocomposite.
7. The method of preparing the carbon nanotube-modified polytrieopentadiene PTCPD composite material according to claim 6, wherein the step S1 of pretreating the carbon nanotubes comprises the steps of:
step S101: adding the carbon nano tube into nitric acid, performing ultrasonic dispersion and reflux reaction, performing suction filtration and washing on a product to be neutral, and performing vacuum drying to obtain an acid oxidized carbon nano tube;
step S102: adding the carbon nanotube oxide acid into a container containing thionyl chloride and a cocatalyst, reacting in a nitrogen atmosphere, and reducing the product after the reaction is finishedRemoval of SOCl by pressure distillation2Then obtaining the carbon nano tube modified by acyl chloride;
step S103: adding the carbon nano tube modified by acyl chloride into a reaction vessel containing glycol and pyridine for reflux reaction, and after the reaction is finished, purifying, cleaning and vacuum-drying a product.
8. The method for preparing the carbon nanotube-modified polytrieopentadiene PTCPD composite material according to claim 6, wherein in the step S102, the cocatalyst is N, N' -dimethylformamide;
in step S103, the product is purified and then washed with tetrahydrofuran and acetone, respectively.
9. The method for preparing the carbon nanotube-modified polytrieopentadiene PTCPD composite material according to claim 6, wherein the step S2 comprises the following steps: and adding the pretreated carbon nano tube into a norbornene solution at 65-75 ℃, performing reflux reaction, performing suction filtration and washing on a product, and performing vacuum drying to obtain the norbornene-modified carbon nano tube.
10. The method for preparing the carbon nanotube-modified polytrieopentadiene PTCPD composite material according to claim 6, wherein in the step S3, the mass fraction of the carbon nanotubes in the tricyclopentadiene is 0.1-0.5%;
in step S3, the curing process is divided into two stages: firstly, curing for 110-130 min at 65-75 ℃, and then curing for 80-100 min at 165-170 ℃.
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