CN102675802B - 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 Polydicyclopentadiencomposite composite 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 dicyclopentadiene (dicyclopentadiene, DCPD) polymkeric substance with certain degree of crosslinking forming through organo-metallic catalyzed polymerization, catalyzer adopts bicomponent catalyst.The catalyst system using at present 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 dicyclopentadiene generation polymerization, belong to two-pack coordination catalyst system, because its cost is lower, are to use at present more one.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 technique has the advantages such as moulding is fast, the cycle is short, cost is low, good product quality.The polydicyclopentadiene of preparing is called PDCPD-RIM material, and its cost is than low 70% left and right of general injection moulding.
PDCPD has high-modulus, impact and high creep resistance simultaneously, demonstrates good integrated machine city performance, is particularly suitable for reaction injection moulding and manufactures large-scale and baroque member.Application Areas has: the housing of (2) the 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 lightweight and crash-proof freight container of steel manufacture.Although polydicyclopentadiene has good over-all properties, its intensity and toughness can't meet the high requirement in some specific engineering field.
Carbon nanotube (carbon nanotubes, CNT) has high specific surface area and mechanical property (the theoretic axial modulus of elasticity of carbon nanotube and tensile strength are respectively 1-2TPa and 200Gpa).These characteristics of carbon nanotube make it in field of compound material, become desirable filler.But the length-to-diameter ratio of carbon nanotube is large, surface can be high, easily reunites, and it is difficult in polymkeric substance dispersed.
Summary of the invention
The object of this invention is to provide a kind of modified carbon nano-tube and strengthen Polydicyclopentadiencomposite composite material, improve toughness and the intensity of matrix material, and the preparation method of this material.
In order to realize above object, the technical solution adopted in the present invention is: a kind of modified carbon nano-tube strengthens Polydicyclopentadiencomposite composite material, to be formed by the main raw material blending polymerization of following weight part: dicyclopentadiene 95～99.9%, modified carbon nano-tube 0.1～5%; Described modified carbon nano-tube is the modified carbon nano-tube that surface is connected with acrylic acid units.
Acrylic acid units adopts formula I structure:
In formula I, R is selected from from hydrogen, methyl or cyano group.
The present invention introduces acrylic acid units in carbon nano tube surface, obtains surface and has the graft type carbon nanotube of pair keys in a large number, and it has the schematic construction shown in Fig. 1.
Because carbon nano tube surface is with a large amount of nonpolar organic groups, in dicyclopentadiene, there is good dispersiveness, greatly improved the workability of carbon nanotube; Under the effect of a large amount of heat energy that a large amount of two keys in surface can be emitted when dicyclopentadiene generation ring-opening metathesis polymerization, participate in the ring opening metathesis polymerization of dicyclopentadiene, make to generate covalent bond structure between carbon nanotube and polymeric matrix, increase the boundary strength between matrix resin and carbon nanotube on the one hand, strengthened on the other hand resin matrix.Modified carbon nano-tube of the present invention has good dispersion and bonding interface, can give full play of the enhancing characteristic of high-performance carbon nanotube, and the industrialization that strengthens polydicyclopentadiene nano composite material for producing high performance carbon nanotube provides new approach.Matrix material of the present invention is compared with the dicyclopentadiene material that does not adopt modified carbon nano-tube to strengthen, 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 Polydicyclopentadiencomposite composite material and adopts the method that is prepared as follows:
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, microfiltration membrane suction filtration, to neutral, dry filter cake washing to obtain oxide/carbon nanometer tube; Oxide/carbon nanometer tube is joined in liquid formula III compound (acrylic acid modified reagent)
formula III, R is selected from hydrogen, methyl or cyano group.
Add oxidizing substance as catalyzer in 40～120 ℃ of stirring reactions 1～12 hour, microfiltration membrane suction filtration obtains modified carbon nano-tube;
2) polymerization of dicyclopentadiene: by the step 1 of 0.1～5 part of weight part) modified carbon nano-tube is dispersed in 95～99.9 parts of liquid dicyclopentadiene, obtains mixed dispersion liquid; Mixed dispersion liquid is divided into two portions, wherein in a part, according to 1/1000～1/3000 of dicyclopentadiene total mole number, adds tungsten catalyst to obtain A liquid, in another part, add the aluminum alkyl catalyst of 25～45 times of tungsten catalyst mole numbers to obtain B liquid; Under protection of inert gas, under 40～90 ℃ of conditions, A liquid and the blend of B liquid are injected in mould, insulation moulding obtains modified carbon nano-tube and strengthens Polydicyclopentadiencomposite composite material.
Wherein in nitration mixture, the volume percent of nitric acid is 15～40%, and 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 the concentration of described sulfuric acid is 8～13mol/L.Wherein step 1) described oxidizing substance is nitric acid, sulfuric acid or potassium permanganate, oxidizing substance is as catalyzer, and catalyzing propone acid modifying agent reacts with 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; Wherein in acrylic acid modified reagent, R substituting group is selected from hydrogen (H), methyl (CH
3) or cyano group (CN), acrylic acid modified reagent can excessively add, and guarantees the abundant dispersion of oxide/carbon nanometer tube.Wherein said carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
A kind of modified carbon nano-tube of the present invention strengthens Polydicyclopentadiencomposite composite material, first modified carbon nano-tube is dispersed in and in dicyclopentadiene, obtains homogeneous solution through ultrasonic concussion, under the acting in conjunction of tungsten catalyst and aluminum alkyls, make dicyclopentadiene solution polymerization, wherein tungsten catalyst and aluminum alkyls selects as prior art, 2,6 di-tert-butyls-4-methylphenoxy of specifically selecting in the present invention) tungsten tetrachloride and aluminium diethyl monochloride.Under the effect that modified carbon nano tube tube-surface contains a large amount of heat energy that a large amount of two keys that react emit when dicyclopentadiene generation ring-opening metathesis polymerization, participate in the ring opening metathesis polymerization of dicyclopentadiene, in dicyclopentadiene polymerization, realize carbon nanotube and strengthen the object of polydicyclopentadiene.Modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material and has higher toughness and intensity, and preparation method is simple, and easy to operate, preparation efficiency is high.
Accompanying drawing explanation
Fig. 1 is the schematic configuration diagram that surface of the present invention has the graft type carbon nanotube of a large amount of two keys.
Embodiment
Below in conjunction with specific embodiment, modified carbon nano-tube of the present invention is strengthened to polydicyclopentadiene nano composite material and preparation method thereof and make specific description, but do not limit technical scheme of the present invention.Raw material dicyclopentadiene, vinylformic acid or the β substitutional crylic acid, acid, tungsten catalyst, the aluminum alkyls that wherein relate to are commercially available product.
Embodiment 1
It is to be formed by the main raw material blending polymerization of following weight part that the modified carbon nano-tube of the present embodiment strengthens polydicyclopentadiene nano composite material: 99.5 parts of dicyclopentadiene and 0.5 part of modified carbon nano-tube.
The preparation method that modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material comprises the following steps:
(1) nitric acid of the Single Walled Carbon Nanotube of 1 gram and 100mL is mixed to (nitric acid 30mL, sulfuric acid 70mL) with the mixing acid of sulfuric acid, then be heated to 120 ℃, stirring back flow reaction 3 hours, with microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7, at 80 ℃, vacuum-drying 20 hours, obtains oxide/carbon nanometer tube;
(2) 1 gram of oxide/carbon nanometer tube is joined in 30 grams of vinylformic acid (being that in formula III, R is hydrogen), add 0.3 gram of vitriol oil (18.4mol/L), stirring reaction 8 hours under 60 ℃ of conditions, after reaction finishes, can obtain modified carbon nano-tube with microfiltration membrane suction filtration;
(3) under the condition of 45 ℃, it is in the dicyclopentadiene of 99.5 parts that 0.5 part of modified carbon nano-tube of weight part is dispersed in to mass percent through ultrasonic concussion, obtain the homodisperse dicyclopentadiene mixed solution of modified carbon nano-tube, after the degassed 25min of vacuum pump, inflated with nitrogen protection is stand-by;
(4) under nitrogen protection, in the A tank of reaction injection molding machine and B tank, add respectively 25 kilograms of homodisperse dicyclopentadiene mixed solutions of modified carbon nano-tube respectively; Then in A tank, add 0.125 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.75 kilograms dicyclopentadiene mole number 1/2100); In B tank, add 0.486 kilogram of aluminium diethyl monochloride (for 25 times of tungsten catalyst mole number in A tank);
(5) temperature of charge in injection reaction forming machine A, B tank is remained on to 45 ℃, open two Matter Transfer pumps of reaction injection molding machine simultaneously, the injection head of reaction injection molding machine is docked and is opened filling gun with die orifice, material in A, B batch can injects the mould of 45 ℃ of preheatings in filling gun after high-speed mixing, keep die sinking after 25 minutes, obtain modified carbon nano-tube and strengthen polydicyclopentadiene nano composite material.
Embodiment 2
It is to be formed by the main raw material blending polymerization of following weight part that the modified carbon nano-tube of the present embodiment strengthens polydicyclopentadiene nano composite material: 97 parts of dicyclopentadiene and 3 parts of modified carbon nano-tubes.
The preparation method that modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material comprises the following steps:
(1) nitric acid of the multi-walled carbon nano-tubes of 1 gram and 100mL is mixed to (nitric acid 25mL, sulfuric acid 75mL) with the mixing acid of sulfuric acid, then be heated to 110 ℃, stirring back flow reaction 4 hours, with microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7, at 80 ℃, vacuum-drying 20 hours, obtains oxide/carbon nanometer tube;
(2) 1 gram of oxide/carbon nanometer tube is joined in 30 grams of methacrylic acids (being that in formula III, R is hydrogen), add 0.1 gram of vitriol oil, stirring reaction 7 hours under 65 ℃ of conditions, after reaction finishes, can obtain modified carbon nano-tube with microfiltration membrane suction filtration;
(3) under the condition of 45 ℃, it is in the dicyclopentadiene of 97 parts that the modified carbon nano-tube of 3 parts of weight parts is dispersed in to mass percent through ultrasonic concussion, obtain the homodisperse dicyclopentadiene mixed solution of modified carbon nano-tube, after the degassed 25min of vacuum pump, inflated with nitrogen protection is stand-by;
(4) under nitrogen protection, in the A tank of reaction injection molding machine and B tank, add 25 kilograms of homodisperse dicyclopentadiene mixed solutions of modified carbon nano-tube respectively; Then in A tank, add 0.122 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 48.5 kilograms dicyclopentadiene mole number 1/2100); In B tank, add 0.569 kilogram of aluminium diethyl monochloride (for 30 times of tungsten catalyst mole number in A tank);
(5) temperature of charge in injection reaction forming machine A, B tank is remained on to 45 ℃, open two Matter Transfer pumps of reaction injection molding machine simultaneously, the injection head of reaction injection molding machine is docked and is opened filling gun with die orifice, material in A, B batch can injects the mould of 50 ℃ of preheatings in filling gun after high-speed mixing, keep die sinking after 25 minutes, obtain modified carbon nano-tube and strengthen polydicyclopentadiene nano composite material.
Embodiment 3
It is to be formed by the main raw material blending polymerization of following weight part that the modified carbon nano-tube of the present embodiment strengthens polydicyclopentadiene nano composite material: 95 parts of dicyclopentadiene and 5 parts of modified carbon nano-tubes.
The preparation method that modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material comprises the following steps:
(1) nitric acid of the Single Walled Carbon Nanotube of 1 gram and 100mL is mixed to (nitric acid 40mL, sulfuric acid 60mL) with the mixing acid of sulfuric acid, then be heated to 130 ℃, stirring back flow reaction 3 hours, with microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7, at 80 ℃, vacuum-drying 20 hours, obtains oxide/carbon nanometer tube;
(2) 1 gram of oxide/carbon nanometer tube is joined in 30 grams of beta-cyano vinylformic acid (being that in formula III, R is cyano group), add 0.05 gram of vitriol oil, stirring reaction 6 hours under 70 ℃ of conditions, after reaction finishes, can obtain modified carbon nano-tube with microfiltration membrane suction filtration;
(3) under the condition of 45 ℃, it is in the dicyclopentadiene of 95 parts that the modified carbon nano-tube of 5 parts of weight parts is dispersed in to mass percent through ultrasonic concussion, obtain the homodisperse dicyclopentadiene mixed solution of modified carbon nano-tube, after the degassed 25min of vacuum pump, inflated with nitrogen protection is stand-by;
(4) under nitrogen protection, in the A tank of reaction injection molding machine and B tank, add 25 kilograms of homodisperse dicyclopentadiene mixed solutions of modified carbon nano-tube respectively; Then in A tank, add 0.119 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 47.5 kilograms dicyclopentadiene mole number 1/2100); In B tank, add 0.650 kilogram of aluminium diethyl monochloride (for 35 times of tungsten catalyst mole number in A tank);
(5) temperature of charge in injection reaction forming machine A, B tank is remained on to 45 ℃, open two Matter Transfer pumps of reaction injection molding machine simultaneously, the injection head of reaction injection molding machine is docked and is opened filling gun with die orifice, material in A, B batch can injects the mould of 55 ℃ of preheatings in filling gun after high-speed mixing, keep die sinking after 25 minutes, obtain modified carbon nano-tube and strengthen 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 adopting is beta-cyano vinylformic acid (being that in formula III, R is cyano group).
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 adopting is vinylformic acid (being that in formula III, R is hydrogen).
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 adopting is Beta-methyl vinylformic acid (being that in formula III, R is methyl).
Embodiment 7
It is to be formed by the main raw material blending polymerization of following weight part that the modified carbon nano-tube of the present embodiment strengthens polydicyclopentadiene nano composite material: 98 parts of dicyclopentadiene and 2 parts of modified carbon nano-tubes.
The preparation method that modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material comprises the following steps:
(1) nitric acid of the multi-walled carbon nano-tubes of 1 gram and 100mL is mixed to (nitric acid 35mL, sulfuric acid 65mL) with the mixing acid of sulfuric acid, then be heated to 100 ℃, stirring back flow reaction 10 hours, with microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7, at 80 ℃, vacuum-drying 20 hours, obtains oxide/carbon nanometer tube;
(2) 1 gram of oxide/carbon nanometer tube is joined in 30 grams of vinylformic acid (being that in formula III, R is hydrogen), add 0.01 gram of vitriol oil, stirring reaction 12 hours under 40 ℃ of conditions, after reaction finishes, can obtain modified carbon nano-tube with microfiltration membrane suction filtration;
(3) under the condition of 45 ℃, it is in the dicyclopentadiene of 98 parts that the modified carbon nano-tube of 2 parts of weight parts is dispersed in to mass percent through ultrasonic concussion, obtain the homodisperse dicyclopentadiene mixed solution of modified carbon nano-tube, after the degassed 25min of vacuum pump, inflated with nitrogen protection is stand-by;
(4) under nitrogen protection, in the A tank of reaction injection molding machine and B tank, add 25 kilograms of homodisperse dicyclopentadiene mixed solutions of modified carbon nano-tube respectively; Then in A tank, add 0.256 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49 kilograms dicyclopentadiene mole number 1/1000); In B tank, add 1.208 kilograms of aluminium diethyl monochlorides (for 30 times of tungsten catalyst mole number in A tank);
(5) temperature of charge in injection reaction forming machine A, B tank is remained on to 45 ℃, open two Matter Transfer pumps of reaction injection molding machine simultaneously, the injection head of reaction injection molding machine is docked and is opened filling gun with die orifice, material in A, B batch can injects the mould of 50 ℃ of preheatings in filling gun after high-speed mixing, keep die sinking after 25 minutes, obtain modified carbon nano-tube and strengthen polydicyclopentadiene nano composite material.
Embodiment 8
It is to be formed by the main raw material blending polymerization of following weight part that the modified carbon nano-tube of the present embodiment strengthens polydicyclopentadiene nano composite material: 96 parts of dicyclopentadiene and 4 parts of modified carbon nano-tubes.
The preparation method that modified carbon nano-tube of the present invention strengthens polydicyclopentadiene nano composite material comprises the following steps:
(1) nitric acid of the multi-walled carbon nano-tubes of 1 gram and 100mL is mixed to (nitric acid 35mL, sulfuric acid 65mL) with the mixing acid of sulfuric acid, then be heated to 200 ℃, stirring back flow reaction 0.5 hour, with microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7, at 80 ℃, vacuum-drying 20 hours, obtains oxide/carbon nanometer tube;
(2) 1 gram of oxide/carbon nanometer tube is joined in 30 grams of methacrylic acids (being that in formula III, R is methyl), add 0.09 gram of potassium permanganate, stirring reaction 1 hour under 120 ℃ of conditions, after reaction finishes, can obtain modified carbon nano-tube with microfiltration membrane suction filtration;
(3) under the condition of 45 ℃, it is in 98% dicyclopentadiene that the modified carbon nano-tube that is 4% by mass percent is dispersed in mass percent through ultrasonic concussion, obtain the homodisperse dicyclopentadiene mixed solution of modified carbon nano-tube, after the degassed 25min of vacuum pump, inflated with nitrogen protection is stand-by;
(4) under nitrogen protection, in the A tank of reaction injection molding machine and B tank, add 25 kilograms of homodisperse dicyclopentadiene mixed solutions of modified carbon nano-tube respectively; Then in A tank, add 0.084 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 48 kilograms dicyclopentadiene mole number 1/3000); In B tank, add 0.394 kilogram of aluminium diethyl monochloride (for 30 times of tungsten catalyst mole number in A tank);
(5) temperature of charge in injection reaction forming machine A, B tank is remained on to 45 ℃, open two Matter Transfer pumps of reaction injection molding machine simultaneously, the injection head of reaction injection molding machine is docked and is opened filling gun with die orifice, material in A, B batch can injects the mould of 45 ℃ of preheatings in filling gun after high-speed mixing, keep die sinking after 25 minutes, obtain modified carbon nano-tube and strengthen polydicyclopentadiene nano composite material.
Embodiment 9
It is to be formed by the main raw material blending polymerization of following weight part that the modified carbon nano-tube of the present embodiment strengthens polydicyclopentadiene nano composite material: 99.9 parts of dicyclopentadiene and 0.1 part of modified carbon nano-tube.
The preparation method that modification Single Walled Carbon Nanotube of the present invention strengthens polydicyclopentadiene nano composite material comprises the following steps:
(1) nitric acid of the carbon nanotube of 1 gram and 100mL is mixed to (nitric acid 40mL, sulfuric acid 60mL) with the mixing acid of sulfuric acid, then be heated to 130 ℃, stirring back flow reaction 3 hours, with microfiltration membrane suction filtration, repetitive scrubbing repeatedly to pH value of solution be 7, at 80 ℃, vacuum-drying 20 hours, obtains oxide/carbon nanometer tube;
(2) 1 gram of oxide/carbon nanometer tube is joined in 30 grams of beta-cyano vinylformic acid (being that in formula III, R is cyano group), add 0.1 gram of vitriol oil, stirring reaction 6 hours under 70 ℃ of conditions, after reaction finishes, can obtain modified carbon nano-tube with microfiltration membrane suction filtration;
(3) under the condition of 45 ℃, it is in the dicyclopentadiene of 99.9 parts that the modified carbon nano-tube of 0.1 part of weight part is dispersed in to mass percent through ultrasonic concussion, obtain the homodisperse dicyclopentadiene mixed solution of modified carbon nano-tube, after the degassed 25min of vacuum pump, inflated with nitrogen protection is stand-by;
(4) under nitrogen protection, in the A tank of reaction injection molding machine and B tank, add 25 kilograms of homodisperse dicyclopentadiene mixed solutions of modified carbon nano-tube respectively; Then in A tank, add 0.126 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.95 kilograms dicyclopentadiene mole number 1/2100); In B tank, add 0.684 kilogram of aluminium diethyl monochloride (for 35 times of tungsten catalyst mole number in A tank);
(5) temperature of charge in injection reaction forming machine A, B tank is remained on to 45 ℃, open two Matter Transfer pumps of reaction injection molding machine simultaneously, the injection head of reaction injection molding machine is docked and is opened filling gun with die orifice, material in A, B batch can injects the mould of 55 ℃ of preheatings in filling gun after high-speed mixing, keep die sinking after 25 minutes, obtain modified carbon nano-tube and strengthen polydicyclopentadiene nano composite material.
Experimental example
Modified carbon nano-tube in above-described embodiment 1～9 is strengthened to polydicyclopentadiene nano composite material and carry out tensile strength and impact strength test, the test-results obtaining is as shown in table 1:
Table 1 modified carbon nano-tube strengthens tensile strength and the impact strength test result of Polydicyclopentadiencomposite composite 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. modified carbon nano-tube strengthens a Polydicyclopentadiencomposite composite material, it is characterized in that: be to be formed by the main raw material blending polymerization of following weight part: dicyclopentadiene 95～99.9%, modified carbon nano-tube 0.1～5%; Described modified carbon nano-tube is the modified carbon nano-tube that surface is connected with acrylic acid units;
Described modified carbon nano-tube strengthens Polydicyclopentadiencomposite composite material and adopts following steps preparation:
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, microfiltration membrane suction filtration, to neutral, dry filter cake washing to obtain oxide/carbon nanometer tube; Oxide/carbon nanometer tube is joined liquid as in formula III compound
Add oxidizing substance as catalyzer in 40～120 ℃ of stirring reactions 1～12 hour, microfiltration membrane suction filtration obtains modified carbon nano-tube;
2) polymerization of dicyclopentadiene: the step 1) modified carbon nano-tube of 0.1～5 part of weight part is dispersed in 95～99.9 parts of liquid dicyclopentadiene, obtains mixed dispersion liquid; Mixed dispersion liquid is divided into two portions, wherein in a part, according to 1/1000～1/3000 of dicyclopentadiene total mole number, adds tungsten catalyst to obtain A liquid, in another part, add the aluminum alkyl catalyst of 25～45 times of tungsten catalyst mole numbers to obtain B liquid; Under protection of inert gas, under 40～90 ℃ of conditions, A liquid and the blend of B liquid are injected in mould, insulation moulding obtains modified carbon nano-tube and strengthens Polydicyclopentadiencomposite composite material.
2. modified carbon nano-tube according to claim 1 strengthens Polydicyclopentadiencomposite composite material, it is characterized in that: described acrylic acid units adopts formula I structure:
In formula I, R is selected from from hydrogen, methyl or cyano group.
3. modified carbon nano-tube strengthens the preparation method of Polydicyclopentadiencomposite composite material as claimed in claim 1, it is characterized in that: its step is as follows:
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, microfiltration membrane suction filtration, to neutral, dry filter cake washing to obtain oxide/carbon nanometer tube; Oxide/carbon nanometer tube is joined liquid as in formula III compound
formula III, R is selected from hydrogen, methyl or cyano group;
Add oxidizing substance as catalyzer in 40～120 ℃ of stirring reactions 1～12 hour, microfiltration membrane suction filtration obtains modified carbon nano-tube;
2) polymerization of dicyclopentadiene: the step 1) modified carbon nano-tube of 0.1～5 part of weight part is dispersed in 95～99.9 parts of liquid dicyclopentadiene, obtains mixed dispersion liquid; Mixed dispersion liquid is divided into two portions, wherein in a part, according to 1/1000～1/3000 of dicyclopentadiene total mole number, adds tungsten catalyst to obtain A liquid, in another part, add the aluminum alkyl catalyst of 25～45 times of tungsten catalyst mole numbers to obtain B liquid; Under protection of inert gas, under 40～90 ℃ of conditions, A liquid and the blend of B liquid are injected in mould, insulation moulding obtains modified carbon nano-tube and strengthens Polydicyclopentadiencomposite composite material.
4. modified carbon nano-tube according to claim 3 strengthens the preparation method of Polydicyclopentadiencomposite composite material, it is characterized in that: in described nitration mixture, the volume percent of nitric acid is 15～40%, and sulfuric acid volume percent is 60～85%.
5. the preparation method who strengthens Polydicyclopentadiencomposite composite material according to the modified carbon nano-tube described in claim 3 or 4, is characterized in that: the concentration of described nitric acid is 5～10mol/L, the concentration of described sulfuric acid is 8～13mol/L.
6. modified carbon nano-tube according to claim 3 strengthens the preparation method of Polydicyclopentadiencomposite composite material, it is characterized in that: described in step 1), oxidizing substance is nitric acid, sulfuric acid or potassium permanganate.
7. modified carbon nano-tube according to claim 3 strengthens the preparation method of Polydicyclopentadiencomposite composite material, it is characterized in that: described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
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| 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 |
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