阅读说明：本技术 碳纳米管改性聚三环戊二烯ptcpd复合材料及其制备方法 (Carbon nano tube modified polytriacyclopentadiene PTCPD composite material and preparation method thereof ) 是由 陈喆 于 2021-02-10 设计创作，主要内容包括：本发明公开了一种碳纳米管改性聚三环戊二烯PTCPD复合材料及其制备方法,所述复合材料包括碳纳米管和三环戊二烯,所述碳纳米管分散在三环戊二烯基体中,在催化剂的作用下,聚合成聚三环戊二烯/碳纳米管纳米复合材料。制备时,首先对碳纳米管进行预处理；然后将预处理后的碳纳米管通过降冰片烯修饰；最后将降冰片烯修饰后的碳纳米管加入液态的三环戊二烯TCPD中,加入催化剂,混合均匀,固化,得到聚三环戊二烯/碳纳米管纳米复合材料。本发明提供的碳纳米管改性聚三环戊二烯PTCPD复合材料的弯曲模量大、断裂韧性好、玻璃化温度高,还具有耐酸、耐碱、耐盐水腐蚀、耐卤素气体腐蚀、耐疲劳、储能模量高等优异特性,应用范围广泛。(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.)

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 ℃.

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.