CN102675802A - Modified carbon nanotube-reinforced polydicyclopentadiene compound material and method for preparing same - Google Patents
Modified carbon nanotube-reinforced polydicyclopentadiene compound material and method for preparing same Download PDFInfo
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Abstract
The invention discloses a modified carbon nanotube-reinforced polydicyclopentadiene compound material. The compound material is made by mixing and polymerizing the following main materials in part by weight: 95 to 99.9 percent of dicyclopentadiene and 0.1 to 5 percent of modified carbon nanotube; and acrylic acid units are connected to the surface of the modified carbon nanotube. The modified carbon nanotube has good dispersion and interfacial adhesion, can fully show the reinforced characteristics of the high-perfo0rmance carbon nanotube and provides a novel channel for the industrialized production of high-performance carbon nanotube-reinforced polydicyclopentadiene nano compound material. Compared with the polydicyclopentadiene material not reinforced by the modified carbon nanotubes, the modified carbon nanotube-reinforced polydicyclopentadiene compound material has the advantages that the impact strength of the compound material is raised from original 100J/m up to 160 to 300J/m, and the tensile strength is raised from original 25MPa up to 28 to 32MPa.
Description
Technical field
The present invention relates to a kind of modified carbon nano-tube and strengthen the polydicyclopentadiene matrix material, relate to a kind of preparation method of this matrix material simultaneously.
Background technology
Polydicyclopentadiene (Polydicyclopentadiene; Be called for short PDCPD) be a kind of by NSC 7352 (dicyclopentadiene; DCPD) polymkeric substance with certain degree of crosslinking that forms through the organo-metallic catalyzed polymerization, catalyzer adopts bicomponent catalyst.Present employed catalyst system comprises the carbone catalyst of aryl or aryloxy tungsten, molybdenum match or molybdenum, ruthenium and osmium.Wherein aryloxy tungsten, molybdenum match catalyzer must have aluminum alkyls or zinc alkyl(s) promotor could effectively make NSC 7352 generation polymerization, belong to the two-pack coordination catalyst system, because of its cost is lower, be use at present more a kind of.In view of the character of DCPD itself, reaction injection moulding (Reaction Injection Maudling is called for short RIM) is the best method of producing PDCPD.This technology has advantages such as moulding is fast, the cycle is short, cost is low, good product quality.The polydicyclopentadiene of preparing is called the PDCPD-RIM material, and its cost is than general injection moulding low about 70%.
PDCPD has high-modulus, impact and high creep resistance simultaneously, demonstrates good comprehensive machine city performance, is particularly suitable for reaction injection moulding and makes large-scale and baroque member.Application Areas has: the housing of (2) large electric equipment such as (1) vehicle bumper and bodyshell; (3) member of snowmobile, surfboard, golf cart etc.; (4) satellite communication parabolic antenna; (5) substitute timber, the in light weight and crash-proof freight container of steel manufacturing.Though polydicyclopentadiene has better comprehensive performance, its intensity and toughness can't satisfy the high requirement in some special engineering field.
(carbon nanotubes CNT) has high specific surface area and mechanical property (theoretic axial modulus of elasticity of carbon nanotube and tensile strength are respectively 1-2TPa and 200Gpa) to carbon nanotube.These characteristics of carbon nanotube make it become the ideal filler in field of compound material.But the length-to-diameter ratio of carbon nanotube is big, and surface energy is high, reunites easily, makes it in polymkeric substance, be difficult to homodisperse.
Summary of the invention
The purpose of this invention is to provide a kind of modified carbon nano-tube and strengthen the polydicyclopentadiene matrix material, improve the toughness and the intensity of matrix material, and this preparation methods.
In order to realize above purpose; The technical scheme that the present invention adopted is: a kind of modified carbon nano-tube strengthens the polydicyclopentadiene matrix material; Be that main raw material blending polymerization by following weight part forms: NSC 7352 95～99.9%, modified carbon nano-tube 0.1～5%; Said modified carbon nano-tube is connected with the modified carbon nano-tube of acrylic acid units for the surface.
Acrylic acid units adopts formula I structure:
R is selected from from hydrogen, methyl or cyanic acid among the formula I.
The present invention introduces acrylic acid units in carbon nano tube surface, obtains the graft type carbon nanotube that the surface has a large amount of two keys, and it has schematic construction shown in Figure 1.
Because carbon nano tube surface has a large amount of nonpolar organic groups, in NSC 7352, has good dispersiveness, has improved the workability of carbon nanotube greatly; Participate in the ring opening metathesis polymerization of NSC 7352 under the effect of the great amount of heat energy that a large amount of two keys in surface can be emitted when NSC 7352 generation ring-opening metathesis polymerization; Make and generate covalent bond structure between carbon nanotube and polymeric matrix; Increase the boundary strength between matrix resin and the carbon nanotube on the one hand, strengthened resin matrix on the other hand.Modified carbon nano-tube of the present invention has good dispersion and bonding interface, can give full play of the enhanced characteristic of high-performance carbon nanotube, for the industriallization of producing high performance carbon nanotube enhancing polydicyclopentadiene nano composite material provides new approach.Matrix material of the present invention is not compared with adopting modified carbon nano-tube enhanced dicyclopentadiene material, and its shock strength is brought up to 160～300J/m by original 100J/m, and tensile strength is brought up to 28～32MPa by original 25MPa.
Modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene composite material by adopting and is prepared as follows method:
1) modification of carbon nanotube: carbon nanotube is joined in the nitration mixture of sulfuric acid and nitric acid in 100～200 ℃ of stirring and refluxing reactions 0.5～10 hour, the microfiltration membrane suction filtration, to neutral, oven dry obtains oxide/carbon nanometer tube with filter cake washing; Oxide/carbon nanometer tube is joined in the liquid formula III compound (acrylic acid modified reagent)
formula III, R is selected from hydrogen, methyl or cyanic acid.
Add oxidizing substance as catalyzer in 40～120 ℃ of stirring reactions 1～12 hour, the microfiltration membrane suction filtration obtains modified carbon nano-tube;
2) polymerization of NSC 7352: the step 1) modified carbon nano-tube of 0.1～5 part of weight part is dispersed in 95～99.9 parts of liquid NSC 7352s, obtains mixed dispersion liquid; Mixed dispersion liquid is divided into two portions, wherein adds tungsten catalyst according to 1/1000～1/3000 of NSC 7352 total mole number in the part and obtain A liquid, the aluminum alkyl catalyst that adds 25～45 times of tungsten catalyst mole numbers in another part obtains B liquid; Under protection of inert gas, under 40～90 ℃ of conditions, A liquid and the blend of B liquid are injected in the mould, the insulation moulding obtains modified carbon nano-tube and strengthens the polydicyclopentadiene matrix material.
Wherein the volume percent of nitric acid is 15～40% in the nitration mixture, and the sulfuric acid volume percent is 60～85%, and nitration mixture can excessively add, and guarantees that carbon nanotube fully disperses, and wherein the concentration of nitric acid is 5～10mol/L, and said vitriolic concentration is 8～13mol/L.Wherein the said oxidizing substance of step 1) is nitric acid, sulfuric acid or potassium permanganate; Oxidizing substance is as catalyzer, the reaction of catalyzing propone acid modifying agent and oxide/carbon nanometer tube, and its add-on is a small amount of; Consider cost factor, general selection accounts for 0.01～0.3 of oxide/carbon nanometer tube weight; The R substituting group is selected from hydrogen (H), methyl (CH in the wherein acrylic acid modified reagent
3) or cyanic acid (CN), acrylic acid modified reagent can excessively add, and guarantees the abundant dispersion of oxide/carbon nanometer tube.Wherein said carbon nanotube is SWCN or multi-walled carbon nano-tubes.
A kind of modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene matrix material; Earlier modified carbon nano-tube is dispersed in through ultrasonic concussion and obtains homogeneous solution in the NSC 7352; Under the acting in conjunction of tungsten catalyst and aluminum alkyls, make the NSC 7352 solution polymerization; Wherein selecting for use of tungsten catalyst and aluminum alkyls is prior art, 2,6 di-tert-butyls of specifically selecting for use among the present invention-4-methylphenoxy) tungsten tetrachloride and aluminium diethyl monochloride.The modified carbon nano tube tube-surface contains under the effect of the great amount of heat energy that a large amount of two keys that react are emitted when NSC 7352 generation ring-opening metathesis polymerization and participates in the ring opening metathesis polymerization of NSC 7352, realizes simultaneously that at the NSC 7352 polymeric carbon nanotube strengthens the purpose of polydicyclopentadiene.Modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene nano composite material and has high toughness and intensity, and the preparation method is simple, and is easy to operate, and preparation efficiency is high.
Description of drawings
Fig. 1 has the schematic configuration diagram of the graft type carbon nanotube of a large amount of two keys for surface of the present invention.
Embodiment
It is bright specifically below in conjunction with specific embodiment modified carbon nano-tube of the present invention to be strengthened polydicyclopentadiene nano composite material and preparation method thereof work, but does not limit technical scheme of the present invention.The raw material NSC 7352 that wherein relates to, vinylformic acid or β substitutional crylic acid, acid, tungsten catalyst, aluminum alkyls are commercially available product.
Embodiment 1
It is that main raw material blending polymerization by following weight part forms: 99.5 parts of NSC 7352s and 0.5 part of modified carbon nano-tube that the modified carbon nano-tube of present embodiment strengthens the polydicyclopentadiene nano composite material.
The preparation method that modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene nano composite material may further comprise the steps:
(1) SWCN of 1 gram and the nitric acid of 100mL are mixed (nitric acid 30mL, sulfuric acid 70mL) with vitriolic mixing acid; Be heated to 120 ℃ then; Stir and back flow reaction 3 hours, with the microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7; 80 ℃ of following vacuum-dryings 20 hours, obtain oxide/carbon nanometer tube;
(2) 1 gram oxide/carbon nanometer tube is joined in the 30 gram vinylformic acid (being that R is a hydrogen in the formula III), add the 0.3 gram vitriol oil (18.4mol/L), stirring reaction is 8 hours under 60 ℃ of conditions, and reaction can obtain modified carbon nano-tube with the microfiltration membrane suction filtration after finishing;
(3) under 45 ℃ condition; It is in 99.5 parts the NSC 7352 that 0.5 part of modified carbon nano-tube of weight part is dispersed in mass percent through ultrasonic concussion; Obtain the homodisperse NSC 7352 mixed solution of modified carbon nano-tube, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(4) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of modified carbon nano-tube respectively respectively; In the A jar, add then 0.125 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.75 kilograms the NSC 7352 mole number 1/2100); In the B jar, add 0.486 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 25 times);
(5) temperature of charge in injection reaction shaper A, the B jar is remained on 45 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects the mould of 45 ℃ of preheatings after the mixed at high speed in filling gun, keep die sinking after 25 minutes, promptly obtains modified carbon nano-tube and strengthens the polydicyclopentadiene nano composite material.
Embodiment 2
It is that main raw material blending polymerization by following weight part forms: 97 parts of NSC 7352s and 3 parts of modified carbon nano-tubes that the modified carbon nano-tube of present embodiment strengthens the polydicyclopentadiene nano composite material.
The preparation method that modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene nano composite material may further comprise the steps:
(1) multi-walled carbon nano-tubes of 1 gram and the nitric acid of 100mL are mixed (nitric acid 25mL, sulfuric acid 75mL) with vitriolic mixing acid; Be heated to 110 ℃ then; Stir and back flow reaction 4 hours, with the microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7; 80 ℃ of following vacuum-dryings 20 hours, obtain oxide/carbon nanometer tube;
(2) 1 gram oxide/carbon nanometer tube is joined in the 30 gram methylacrylic acids (being that R is a hydrogen in the formula III), add the 0.1 gram vitriol oil, stirring reaction is 7 hours under 65 ℃ of conditions, and reaction can obtain modified carbon nano-tube with the microfiltration membrane suction filtration after finishing;
(3) under 45 ℃ condition; It is in 97 parts the NSC 7352 that the modified carbon nano-tube of 3 parts of weight parts is dispersed in mass percent through ultrasonic concussion; Obtain the homodisperse NSC 7352 mixed solution of modified carbon nano-tube, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(4) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of modified carbon nano-tube respectively; In the A jar, add then 0.122 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 48.5 kilograms the NSC 7352 mole number 1/2100); In the B jar, add 0.569 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 30 times);
(5) temperature of charge in injection reaction shaper A, the B jar is remained on 45 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects the mould of 50 ℃ of preheatings after the mixed at high speed in filling gun, keep die sinking after 25 minutes, promptly obtains modified carbon nano-tube and strengthens the polydicyclopentadiene nano composite material.
Embodiment 3
It is that main raw material blending polymerization by following weight part forms: 95 parts of NSC 7352s and 5 parts of modified carbon nano-tubes that the modified carbon nano-tube of present embodiment strengthens the polydicyclopentadiene nano composite material.
The preparation method that modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene nano composite material may further comprise the steps:
(1) SWCN of 1 gram and the nitric acid of 100mL are mixed (nitric acid 40mL, sulfuric acid 60mL) with vitriolic mixing acid; Be heated to 130 ℃ then; Stir and back flow reaction 3 hours, with the microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7; 80 ℃ of following vacuum-dryings 20 hours, obtain oxide/carbon nanometer tube;
(2) 1 gram oxide/carbon nanometer tube is joined in the 30 gram beta-cyano vinylformic acid (being that R is a cyanic acid in the formula III), add the 0.05 gram vitriol oil, stirring reaction is 6 hours under 70 ℃ of conditions, and reaction can obtain modified carbon nano-tube with the microfiltration membrane suction filtration after finishing;
(3) under 45 ℃ condition; It is in 95 parts the NSC 7352 that the modified carbon nano-tube of 5 parts of weight parts is dispersed in mass percent through ultrasonic concussion; Obtain the homodisperse NSC 7352 mixed solution of modified carbon nano-tube, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(4) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of modified carbon nano-tube respectively; In the A jar, add then 0.119 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 47.5 kilograms the NSC 7352 mole number 1/2100); In the B jar, add 0.650 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 35 times);
(5) temperature of charge in injection reaction shaper A, the B jar is remained on 45 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects the mould of 55 ℃ of preheatings after the mixed at high speed in filling gun, keep die sinking after 25 minutes, promptly obtains modified carbon nano-tube and strengthens the polydicyclopentadiene nano composite material.
Embodiment 4
Modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material and preparation method thereof with embodiment 2, and difference is that the acrylic acid modified reagent that adopts is beta-cyano vinylformic acid (being that R is a cyanic acid in the formula III).
Embodiment 5
Modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material and preparation method thereof with embodiment 3, and difference is that the acrylic acid modified reagent that adopts is vinylformic acid (being that R is a hydrogen in the formula III).
Embodiment 6
Modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material and preparation method thereof with embodiment 1, and difference is that the acrylic acid modified reagent that adopts is Beta-methyl vinylformic acid (being that R is a methyl in the formula III).
Embodiment 7
It is that main raw material blending polymerization by following weight part forms: 98 parts of NSC 7352s and 2 parts of modified carbon nano-tubes that the modified carbon nano-tube of present embodiment strengthens the polydicyclopentadiene nano composite material.
The preparation method that modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene nano composite material may further comprise the steps:
(1) multi-walled carbon nano-tubes of 1 gram and the nitric acid of 100mL are mixed (nitric acid 35mL, sulfuric acid 65mL) with vitriolic mixing acid; Be heated to 100 ℃ then; Stir and back flow reaction 10 hours, with the microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7; 80 ℃ of following vacuum-dryings 20 hours, obtain oxide/carbon nanometer tube;
(2) 1 gram oxide/carbon nanometer tube is joined in the 30 gram vinylformic acid (being that R is a hydrogen in the formula III), add the 0.01 gram vitriol oil, stirring reaction is 12 hours under 40 ℃ of conditions, and reaction can obtain modified carbon nano-tube with the microfiltration membrane suction filtration after finishing;
(3) under 45 ℃ condition; It is in 98 parts the NSC 7352 that the modified carbon nano-tube of 2 parts of weight parts is dispersed in mass percent through ultrasonic concussion; Obtain the homodisperse NSC 7352 mixed solution of modified carbon nano-tube, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(4) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of modified carbon nano-tube respectively; In the A jar, add then 0.256 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49 kilograms the NSC 7352 mole number 1/1000); In the B jar, add 1.208 kilograms of aluminium diethyl monochlorides (be in the A jar tungsten catalyst mole number 30 times);
(5) temperature of charge in injection reaction shaper A, the B jar is remained on 45 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects the mould of 50 ℃ of preheatings after the mixed at high speed in filling gun, keep die sinking after 25 minutes, promptly obtains modified carbon nano-tube and strengthens the polydicyclopentadiene nano composite material.
Embodiment 8
It is that main raw material blending polymerization by following weight part forms: 96 parts of NSC 7352s and 4 parts of modified carbon nano-tubes that the modified carbon nano-tube of present embodiment strengthens the polydicyclopentadiene nano composite material.
The preparation method that modified carbon nano-tube of the present invention strengthens the polydicyclopentadiene nano composite material may further comprise the steps:
(1) multi-walled carbon nano-tubes of 1 gram and the nitric acid of 100mL are mixed (nitric acid 35mL, sulfuric acid 65mL) with vitriolic mixing acid; Be heated to 200 ℃ then; Stir and back flow reaction 0.5 hour, with the microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7; 80 ℃ of following vacuum-dryings 20 hours, obtain oxide/carbon nanometer tube;
(2) 1 gram oxide/carbon nanometer tube is joined in the 30 gram methylacrylic acids (being that R is a methyl in the formula III), add 0.09 gram potassium permanganate, stirring reaction is 1 hour under 120 ℃ of conditions, and reaction can obtain modified carbon nano-tube with the microfiltration membrane suction filtration after finishing;
(3) under 45 ℃ condition; To be 4% modified carbon nano-tube with mass percent be dispersed in mass percent through ultrasonic concussion is in 98% the NSC 7352; Obtain the homodisperse NSC 7352 mixed solution of modified carbon nano-tube, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(4) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of modified carbon nano-tube respectively; In the A jar, add then 0.084 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 48 kilograms the NSC 7352 mole number 1/3000); In the B jar, add 0.394 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 30 times);
(5) temperature of charge in injection reaction shaper A, the B jar is remained on 45 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects the mould of 45 ℃ of preheatings after the mixed at high speed in filling gun, keep die sinking after 25 minutes, promptly obtains modified carbon nano-tube and strengthens the polydicyclopentadiene nano composite material.
Embodiment 9
It is that main raw material blending polymerization by following weight part forms: 99.9 parts of NSC 7352s and 0.1 part of modified carbon nano-tube that the modified carbon nano-tube of present embodiment strengthens the polydicyclopentadiene nano composite material.
The preparation method that modification SWCN of the present invention strengthens the polydicyclopentadiene nano composite material may further comprise the steps:
(1) carbon nanotube of 1 gram and the nitric acid of 100mL are mixed (nitric acid 40mL, sulfuric acid 60mL) with vitriolic mixing acid; Be heated to 130 ℃ then; Stir and back flow reaction 3 hours, with the microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7; 80 ℃ of following vacuum-dryings 20 hours, obtain oxide/carbon nanometer tube;
(2) 1 gram oxide/carbon nanometer tube is joined in the 30 gram beta-cyano vinylformic acid (being that R is a cyanic acid in the formula III), add the 0.1 gram vitriol oil, stirring reaction is 6 hours under 70 ℃ of conditions, and reaction can obtain modified carbon nano-tube with the microfiltration membrane suction filtration after finishing;
(3) under 45 ℃ condition; It is in 99.9 parts the NSC 7352 that the modified carbon nano-tube of 0.1 part of weight part is dispersed in mass percent through ultrasonic concussion; Obtain the homodisperse NSC 7352 mixed solution of modified carbon nano-tube, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(4) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of modified carbon nano-tube respectively; In the A jar, add then 0.126 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.95 kilograms the NSC 7352 mole number 1/2100); In the B jar, add 0.684 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 35 times);
(5) temperature of charge in injection reaction shaper A, the B jar is remained on 45 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects the mould of 55 ℃ of preheatings after the mixed at high speed in filling gun, keep die sinking after 25 minutes, promptly obtains modified carbon nano-tube and strengthens the polydicyclopentadiene nano composite material.
Experimental example
Modified carbon nano-tube in the foregoing description 1～9 is strengthened the polydicyclopentadiene nano composite material carry out tensile strength and impact strength test, the test-results that obtains is as shown in table 1:
Table 1 modified carbon nano-tube strengthens the tensile strength and the impact strength test result of polydicyclopentadiene matrix material
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Shock strength (J/m) | 273 | 268 | 215 | 275 | 203 | 292 | 189 | 164 | 224 |
| Tensile strength (MPa) | 31.2 | 30.3 | 29.6 | 30.8 | 29.4 | 31.7 | 28.5 | 27.3 | 28.7 |
Claims (7)
1. a modified carbon nano-tube strengthens the polydicyclopentadiene matrix material, it is characterized in that: be that main raw material blending polymerization by following weight part forms: NSC 7352 95～99.9%, modified carbon nano-tube 0.1～5%; Said modified carbon nano-tube is connected with the modified carbon nano-tube of acrylic acid units for the surface.
2. modified carbon nano-tube according to claim 1 strengthens the polydicyclopentadiene matrix material, it is characterized in that: said acrylic acid units adopts formula I structure:
R is selected from from hydrogen, methyl or cyanic acid among the formula I.
One kind according to claim 1 modified carbon nano-tube strengthen the preparation method of polydicyclopentadiene matrix material, it is characterized in that: its step is following:
1) modification of carbon nanotube: carbon nanotube is joined in the nitration mixture of sulfuric acid and nitric acid in 100～200 ℃ of stirring and refluxing reactions 0.5～10 hour, the microfiltration membrane suction filtration, to neutral, oven dry obtains oxide/carbon nanometer tube with filter cake washing; Oxide/carbon nanometer tube is joined liquid as in the formula III compound
formula III, R is selected from hydrogen, methyl or cyanic acid.
Add oxidizing substance as catalyzer in 40～120 ℃ of stirring reactions 1～12 hour, the microfiltration membrane suction filtration obtains modified carbon nano-tube;
2) polymerization of NSC 7352: the step 1) modified carbon nano-tube of 0.1～5 part of weight part is dispersed in 95～99.9 parts of liquid NSC 7352s, obtains mixed dispersion liquid; Mixed dispersion liquid is divided into two portions, wherein adds tungsten catalyst according to 1/1000～1/3000 of NSC 7352 total mole number in the part and obtain A liquid, the aluminum alkyl catalyst that adds 25～45 times of tungsten catalyst mole numbers in another part obtains B liquid; Under protection of inert gas, under 40～90 ℃ of conditions, A liquid and the blend of B liquid are injected in the mould, the insulation moulding obtains modified carbon nano-tube and strengthens the polydicyclopentadiene matrix material.
4. modified carbon nano-tube according to claim 3 strengthens the preparation method of polydicyclopentadiene matrix material, and it is characterized in that: the volume percent of nitric acid is 15～40% in the said nitration mixture, and the sulfuric acid volume percent is 60～85%.
5. according to the preparation method of claim 3 or 4 described modified carbon nano-tubes enhancing polydicyclopentadiene matrix materials, it is characterized in that: the concentration of said nitric acid is 5～10mol/L, and said vitriolic concentration is 8～13mol/L.
6. modified carbon nano-tube according to claim 3 strengthens the preparation method of polydicyclopentadiene matrix material, and it is characterized in that: the said oxidizing substance of step 1) is nitric acid, sulfuric acid or potassium permanganate.
7. modified carbon nano-tube according to claim 3 strengthens the preparation method of polydicyclopentadiene matrix material, and it is characterized in that: described carbon nanotube is SWCN or multi-walled carbon nano-tubes.
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| CN105111344A (en) * | 2015-09-11 | 2015-12-02 | 江南大学 | Carbon nano tube/polyisoprene composite material and preparation method thereof |
| CN105236381A (en) * | 2014-06-26 | 2016-01-13 | 山东大展纳米材料有限公司 | Gas-solid-phase quick preparation method for cyclopentadiene modified carbon nano tube |
| CN112812487A (en) * | 2021-02-10 | 2021-05-18 | 浙江沪通模具有限公司 | Carbon nano tube modified polytriacyclopentadiene PTCPD composite material and preparation method thereof |
| CN117343286A (en) * | 2023-11-09 | 2024-01-05 | 常州德能新材料有限公司 | Carbon nano tube/PDCPD composite material and preparation method thereof |
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| CN1546545A (en) * | 2003-12-04 | 2004-11-17 | 上海交通大学 | Multi-carboxyl polymer grafted water-soluble carbon nanometer tube and preparation method thereof |
| CN101343378A (en) * | 2007-07-10 | 2009-01-14 | 同济大学 | Carbon nano-tube unsaturated polyester resin solidifying agent and preparation thereof |
| CN101407622A (en) * | 2007-10-11 | 2009-04-15 | 同济大学 | Carbon nano-tube / unsaturated polyester composite material and preparation thereof |
| CN101475697A (en) * | 2009-01-23 | 2009-07-08 | 浙江工业大学 | Low dimension conductive composite material and preparation thereof |
| CN102604383A (en) * | 2012-02-16 | 2012-07-25 | 苏州大学 | Carbon nano tube/thermosetting resin composite material and preparation method thereof |
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| CN1546545A (en) * | 2003-12-04 | 2004-11-17 | 上海交通大学 | Multi-carboxyl polymer grafted water-soluble carbon nanometer tube and preparation method thereof |
| CN101343378A (en) * | 2007-07-10 | 2009-01-14 | 同济大学 | Carbon nano-tube unsaturated polyester resin solidifying agent and preparation thereof |
| CN101407622A (en) * | 2007-10-11 | 2009-04-15 | 同济大学 | Carbon nano-tube / unsaturated polyester composite material and preparation thereof |
| CN101475697A (en) * | 2009-01-23 | 2009-07-08 | 浙江工业大学 | Low dimension conductive composite material and preparation thereof |
| CN102604383A (en) * | 2012-02-16 | 2012-07-25 | 苏州大学 | Carbon nano tube/thermosetting resin composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236381A (en) * | 2014-06-26 | 2016-01-13 | 山东大展纳米材料有限公司 | Gas-solid-phase quick preparation method for cyclopentadiene modified carbon nano tube |
| CN105111344A (en) * | 2015-09-11 | 2015-12-02 | 江南大学 | Carbon nano tube/polyisoprene composite material and preparation method thereof |
| CN112812487A (en) * | 2021-02-10 | 2021-05-18 | 浙江沪通模具有限公司 | Carbon nano tube modified polytriacyclopentadiene PTCPD composite material and preparation method thereof |
| CN117343286A (en) * | 2023-11-09 | 2024-01-05 | 常州德能新材料有限公司 | Carbon nano tube/PDCPD composite material and preparation method thereof |
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