CN111718580A - Phthalonitrile resin composite material and preparation method thereof - Google Patents
Phthalonitrile resin composite material and preparation method thereof Download PDFInfo
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- CN111718580A CN111718580A CN202010734296.5A CN202010734296A CN111718580A CN 111718580 A CN111718580 A CN 111718580A CN 202010734296 A CN202010734296 A CN 202010734296A CN 111718580 A CN111718580 A CN 111718580A
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- phthalonitrile resin
- phthalonitrile
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- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 45
- 239000000805 composite resin Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 239000000945 filler Substances 0.000 claims abstract description 34
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000011417 postcuring Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 28
- 239000007788 liquid Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 26
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- WTSJLYWSCIPJNI-UHFFFAOYSA-N 3-(4-aminophenoxy)benzene-1,2-dicarbonitrile Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(C#N)=C1C#N WTSJLYWSCIPJNI-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WCVHUIPWSPEOIG-UHFFFAOYSA-N n,n-dimethylheptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN(C)C WCVHUIPWSPEOIG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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)
- 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 provides a phthalonitrile resin composite material and a preparation method thereof, wherein the composite material is prepared from zero-dimensional nano TiO2And one-dimensional halloysite nano filler and phthalonitrile resin. Compared with the discrete composite material prepared by the traditional mixing method, the novel composite material prepared by the invention contains zero-dimensional nano TiO2The one-dimensional halloysite and the one-dimensional halloysite are reasonably distributed in a phthalonitrile resin matrix and are cooperatively matched, so that the two reinforced polymer matrixes are effectively integratedThe advantages of the composite material make up the disadvantages of the composite material, greatly improve the properties of the novel composite material, and can be used in various special complex environments.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a phthalonitrile resin composite material and a preparation method thereof.
Background
The phthalonitrile resin material has excellent high temperature resistance, outstanding thermal-oxidative stability, excellent mechanical property, dielectric property and chemical stability, and good flame retardant property. The halloysite has a hollow tubular structure with a complete form, does not end-cap, has no curling fracture or sleeving phenomenon, is a natural one-dimensional nano material, has a larger length-diameter ratio, and has strong action with a matrix. The modulus, thermal stability, fire resistance and other properties of the composite material can be effectively improved by adding a small amount of halloysite. But do notHalloysite is not ideal, and sometimes even decreases, in increasing the strength of the composite. Thus, the existing halloysite/phthalonitrile resin composites have not been able to be used to manufacture critical structural components with special requirements under complex environmental conditions. Zero-dimensional nano TiO2The ball is another important reinforcing agent, has high hardness and high strength, can obviously improve the strength of the phthalonitrile resin composite material, and has reports in some literatures that the thermal stability of the composite material is reduced. The two nano materials are independently compounded with phthalonitrile resin, so that the problems that one part of service performance is improved and the other part of service performance is reduced exist.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a phthalonitrile resin composite material and a preparation method thereof, two nano materials are simultaneously compounded with phthalonitrile resin, and zero-dimensional nano TiO is utilized2And the advantages of the one-dimensional halloysite are complemented with the advantages of the one-dimensional halloysite, a synergistic enhancement effect is generated, and the overall performance of the composite material is greatly improved in many aspects.
In order to achieve the purpose, the scheme of the invention is as follows:
in a first aspect, the present invention provides a phthalonitrile resin composite material, characterized in that: the phthalonitrile resin composite material is prepared from zero-dimensional nano TiO2And one-dimensional halloysite are used for synergy to prepare: the phthalonitrile resin composite material contains zero-dimensional nano TiO2And a one-dimensional halloysite two-dimensional nanoparticle filler.
As a preferred scheme, the phthalonitrile resin is a high-performance thermosetting resin which is terminated by a phthalonitrile structure and serves as a crosslinking group;
further, the filler particles have a size in at least one dimension of 1nm to 100 nm; the zero-dimensional nano TiO2The diameter of the filler particles is 1 nm-100 nm; the pipe diameter of the one-dimensional halloysite filler particles is 1 nm-100 nm.
Furthermore, the volume percentage of the filler particles is 0.5-30% based on 100% of the total volume of the phthalonitrile resin composite material.
In a second aspect, the present invention provides a method for preparing the above phthalonitrile resin composite material, which is characterized in that: the method comprises the following steps:
(1) mixing zero-dimensional nano TiO2And one-dimensional halloysite filler particles and a surfactant are stirred and dispersed after being ultrasonically dispersed in a dispersing agent;
(2) uniformly stirring and mixing the nano filler particles and the coupling agent in the step (1), performing ultrasonic dispersion for 0.5-2h, and drying;
(3) stirring and mixing the mixed nanoparticle filler obtained in the step (2) with a phthalonitrile prepolymer, a curing agent and an accelerator uniformly at a melting temperature, and performing ultrasonic dispersion for 0.5-2 h;
(4) keeping the mixture obtained in the step (3) in vacuum for 0.5-1 h, and removing bubbles in the system to obtain a uniform and transparent mixed system;
(5) and (4) injecting the mixed system in the step (4) into a mold coated with a release agent, curing step by step at a curing temperature, post-curing, and demolding to obtain the phthalonitrile resin composite material.
Preferably, the surfactant includes any one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyethylene glycol, polyethylene oxide, hexadecyl trimethyl amine bromide, polyvinylpyrrolidone or sodium carboxymethyl cellulose.
Further, in the step (1), the zero-dimensional nano TiO2And the one-dimensional halloysite nanometer filler particles are in a mass ratio of 1: 1-1: 9.
In the step (2), the dried composite nanoparticle filler is obtained by using a freeze drying or low-temperature vacuum drying method.
In the step (3), the mass ratio of the curing agent to the phthalonitrile prepolymer is (5-120): 100, respectively; the mass ratio of the accelerator to the phthalonitrile prepolymer is (0.005-3) to 100.
In the step (5), the curing time is 8-36 h; the post-curing time is 4-6 h.
The invention has the following advantages and beneficial effects:
the invention relates to zero-dimensional nano TiO2And the one-dimensional halloysite is reasonably distributed in a phthalonitrile resin matrix and is in cooperative fit, the advantages of the two reinforced polymer matrixes are effectively integrated, respective disadvantages are made up, the problem of insufficient performance improvement caused by interface effect in the traditional composite material is solved, the novel composite material is greatly and comprehensively improved in multiple performances, and the novel composite material can be used in multiple special complex environments.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
the preparation method comprises the following steps: 0.3g of zero-dimensional nano TiO with the average particle size of 30nm is taken2Dispersing in 50mL of absolute ethyl alcohol, taking out after ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid A; 0.7g of one-dimensional organic halloysite with the average pipe diameter of 40nm is dispersed in 50mL of absolute ethyl alcohol, taken out after ultrasonic dispersion for 30min, and magnetically stirred at 5000rpm for 30min to obtain uniform dispersion liquid B. And mixing the dispersion liquid A and the dispersion liquid B, performing ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid C. And (3) under the catalytic action of ammonia water, modifying the composite nano filler in the dispersion liquid C by using a silane coupling agent hexadecyl trimethoxy silane, carrying out magnetic stirring reaction at room temperature, and obtaining a dispersion liquid D after full reaction. And (3) carrying out freeze drying for 48 hours at the temperature of minus 40 ℃ to obtain the composite nanoparticle filler with various dimensions. 40g of m-benzene type benzonitrile monomer (MBD-CN), 4-aminophenoxy phthalonitrile (4-NH) was taken2-CN) 4g and the multi-dimensional composite nanoparticle filler are mixed at room temperature and ultrasonically dispersed for 0.5h, so that all parts are uniformly mixed to obtain a uniform and transparent system. And keeping the vacuum state for 0.5h to remove bubbles in the system. Injecting the system into a mold, curing in 7 steps, step 1: heating to 200 ℃, and keeping the temperature for 2 hours; step 2: heating to 220 ℃, and keeping the temperature for 4 hours; and 3, step 3: heating to 240 ℃, and preserving heat for 4 hours; and 4, step 4: heating to 260 deg.C, and keeping the temperature4 h; and 5, step 5: heating to 280 ℃, and preserving heat for 4 hours; and 6, step 6: heating to 300 ℃, and preserving heat for 4 hours; and 7, step 7: heating to 320 ℃, post-curing, and keeping the temperature for 6 h. And (5) demolding to obtain the high-performance composite material sample strip.
And (4) analyzing results: compared with the filler-free phthalonitrile resin prepared under the same condition, the modulus of the prepared high-performance composite material is improved by 77.7 percent, the strength is improved by 33.5 percent, the notch impact strength is improved by 27.2 percent, the glass transition temperature is improved by 8.8 ℃, and the thermal decomposition temperature is improved by 11.2 ℃.
Example 2:
the preparation method comprises the following steps: 0.6g of zero-dimensional nano TiO with the average particle size of 30nm is taken2Dispersing in 50mL of absolute ethyl alcohol, taking out after ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid A; 0.4g of one-dimensional organic halloysite DK1 with the average pipe diameter of 40nm is dispersed in 50mL of absolute ethyl alcohol, taken out after ultrasonic dispersion for 30min, and magnetically stirred at 5000rpm for 30min to obtain uniform dispersion liquid B. And mixing the dispersion liquid A and the dispersion liquid B, performing ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid C. And (3) under the catalytic action of ammonia water, modifying the composite nano filler in the dispersion liquid C by using a silane coupling agent hexadecyl trimethoxy silane, carrying out magnetic stirring reaction at room temperature, and obtaining a dispersion liquid D after full reaction. And (3) carrying out freeze drying for 48 hours at the temperature of minus 40 ℃ to obtain the composite nanoparticle filler with various dimensions. 40g of bisphenol A type benzonitrile monomer (BPACN), 4-aminophenoxy phthalonitrile (4-NH) was taken2-CN) 4g and the multi-dimensional composite nanoparticle filler are mixed at room temperature and ultrasonically dispersed for 0.5h, so that all parts are uniformly mixed to obtain a uniform and transparent system. And keeping the vacuum state for 0.5h to remove bubbles in the system. Injecting the system into a mold, curing in 7 steps, step 1: heating to 200 ℃, and keeping the temperature for 2 hours; step 2: heating to 220 ℃, and keeping the temperature for 4 hours; and 3, step 3: heating to 240 ℃, and preserving heat for 4 hours; and 4, step 4: heating to 260 ℃, and keeping the temperature for 4 hours; and 5, step 5: heating to 280 ℃, and preserving heat for 4 hours; and 6, step 6: heating to 300 ℃, and preserving heat for 4 hours; and 7, step 7: heating to 320 ℃, post-curing, and keeping the temperature for 6 h. And (5) demolding to obtain the high-performance composite material sample strip.
And (4) analyzing results: compared with the filler-free phthalonitrile resin prepared under the same condition, the modulus of the prepared high-performance composite material is improved by 74.1 percent, the strength is improved by 31.5 percent, the notch impact strength is improved by 26.1 percent, the glass transition temperature is improved by 8.2 ℃, and the thermal decomposition temperature is improved by 9.7 ℃.
Example 3:
the preparation method comprises the following steps: 0.4g of zero-dimensional nano TiO with the average particle size of 30nm is taken2Dispersing in 50mL of absolute ethyl alcohol, taking out after ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid A; 0.6g of one-dimensional organic halloysite DK1 with the average pipe diameter of 40nm is dispersed in 50mL of absolute ethyl alcohol, taken out after ultrasonic dispersion for 30min, and magnetically stirred at 5000rpm for 30min to obtain uniform dispersion liquid B. And mixing the dispersion liquid A and the dispersion liquid B, performing ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid C. And (3) under the catalytic action of ammonia water, modifying the composite nano filler in the dispersion liquid C by using a silane coupling agent hexadecyl trimethoxy silane, carrying out magnetic stirring reaction at room temperature, and obtaining a dispersion liquid D after full reaction. And (3) carrying out freeze drying for 48 hours at the temperature of minus 40 ℃ to obtain the composite nanoparticle filler with various dimensions. 40g of biphenyl type benzonitrile monomer (DABP-CN), 4-aminophenoxy phthalonitrile (4-NH) was taken2-CN) 4g and the multi-dimensional composite nanoparticle filler are mixed at room temperature and ultrasonically dispersed for 0.5h, so that all parts are uniformly mixed to obtain a uniform and transparent system. And keeping the vacuum state for 0.5h to remove bubbles in the system. Injecting the system into a mold, curing in 9 steps, and carrying out the step 1: heating to 200 ℃, and keeping the temperature for 2 hours; step 2: heating to 240 ℃, and preserving heat for 4 hours; and 3, step 3: heating to 260 ℃, and keeping the temperature for 4 hours; and 4, step 4: heating to 280 ℃, and preserving heat for 4 hours; and 5, step 5: heating to 300 ℃, and preserving heat for 4 hours; and 6, step 6: heating to 320 ℃, and preserving heat for 4 hours; and 7, step 7: heating to 340 ℃, and keeping the temperature for 4 hours; and 8, step 8: heating to 360 ℃, and preserving heat for 4 hours; step 9: heating to 380 deg.C, post-curing, and keeping the temperature for 6 h. And (5) demolding to obtain the high-performance composite material sample strip.
And (4) analyzing results: compared with the filler-free phthalonitrile resin prepared under the same condition, the modulus of the prepared high-performance composite material is improved by 71.5 percent, the strength is improved by 35.2 percent, the notch impact strength is improved by 27.2 percent, the glass transition temperature is improved by 9.4 ℃, the thermal decomposition temperature is improved by 10.1 ℃, and the thermal conductivity coefficient is improved by 11.4 percent.
Example 4:
the preparation method comprises the following steps: 0.5g of zero-dimensional nano TiO with the average particle size of 30nm is taken2Dispersing in 50mL of absolute ethyl alcohol, taking out after ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid A; 0.5g of one-dimensional organic halloysite DK1 with the average pipe diameter of 40nm is dispersed in 50mL of absolute ethyl alcohol, taken out after ultrasonic dispersion for 30min, and magnetically stirred at 5000rpm for 30min to obtain uniform dispersion liquid B. And mixing the dispersion liquid A and the dispersion liquid B, performing ultrasonic dispersion for 30min, and magnetically stirring at 5000rpm for 30min to obtain a uniform dispersion liquid C. And (3) under the catalytic action of ammonia water, modifying the composite nano filler in the dispersion liquid C by using a silane coupling agent hexadecyl trimethoxy silane, carrying out magnetic stirring reaction at room temperature, and obtaining a dispersion liquid D after full reaction. And (3) carrying out freeze drying for 48 hours at the temperature of minus 40 ℃ to obtain the composite nanoparticle filler with various dimensions. Mixing phthalonitrile monomer 40g, 4, 4' -diaminodiphenyl ether (ODA)4g and multi-dimensional composite nanoparticle filler at room temperature, and performing ultrasonic dispersion for 0.5h to uniformly mix the components to obtain a uniform and transparent system. And keeping the vacuum state for 0.5h to remove bubbles in the system. Injecting the system into a mould, curing in 3 steps, and carrying out the step 1: heating to 275 deg.c and maintaining for 4 hr; step 2: heating to 300 ℃, and preserving heat for 5 hours; and 3, step 3: heating to 340 ℃, post-curing, and keeping the temperature for 5 h. And (5) demolding to obtain the high-performance composite material sample strip.
And (4) analyzing results: compared with the filler-free phthalonitrile resin prepared under the same condition, the modulus of the prepared high-performance composite material is improved by 84.7 percent, the strength is improved by 56.3 percent, the notch impact strength is improved by 27.7 percent, the glass transition temperature is improved by 11.8 ℃, the thermal decomposition temperature is improved by 16.5 ℃, and the limiting oxygen index is improved by 15.3 percent.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It is obvious to those skilled in the art that any modification of the present invention, equivalent substitution of each raw material and addition of auxiliary components to the product of the present invention, and changes in the specific mode, etc., fall within the scope of protection and disclosure of the present invention.
Claims (8)
1. A phthalonitrile resin composite material is characterized in that: the phthalonitrile resin composite material is prepared from zero-dimensional nano TiO2And one-dimensional halloysite are used for synergy to prepare: the phthalonitrile resin composite material contains zero-dimensional nano TiO2And a one-dimensional halloysite two-dimensional nanoparticle filler.
2. The phthalonitrile resin composite as claimed in claim 1, wherein: the phthalonitrile resin is high-performance thermosetting resin which is terminated by a phthalonitrile structure and is used as a crosslinking group.
3. The phthalonitrile resin composite according to claim 1 or 2, characterized in that: the filler particles have a size in at least one dimension of 1nm to 100 nm; the zero-dimensional nano TiO2The diameter of the filler particles is 1 nm-100 nm; the pipe diameter of the one-dimensional halloysite filler particles is 1 nm-100 nm.
4. The phthalonitrile resin composite according to claim 1 or 2, characterized in that: the volume percentage of the filler particles is 0.5-30% based on the total volume of the phthalonitrile resin composite material as 100%.
5. The phthalonitrile resin composite according to claim 3, wherein: the volume percentage of the filler particles is 0.5-30% based on the total volume of the phthalonitrile resin composite material as 100%.
6. A method for preparing the phthalonitrile resin composite as claimed in claim 1 or 2 or 5, characterized in that: the method comprises the following steps:
(1) mixing zero-dimensional nano TiO2And one-dimensional halloysiteUltrasonically dispersing filler particles and a surfactant in a dispersing agent, and stirring for dispersing;
(2) uniformly stirring and mixing the nano filler particles and the coupling agent in the step (1), performing ultrasonic dispersion for 0.5-2h, and drying;
(3) stirring and mixing the mixed nanoparticle filler obtained in the step (2) with a phthalonitrile prepolymer, a curing agent and an accelerator uniformly at a melting temperature, and performing ultrasonic dispersion for 0.5-2 h;
(4) keeping the mixture obtained in the step (3) in vacuum for 0.5-1 h, and removing bubbles in the system to obtain a uniform and transparent mixed system;
(5) and (4) injecting the mixed system in the step (4) into a mold coated with a release agent, curing step by step at a curing temperature, post-curing, and demolding to obtain the phthalonitrile resin composite material.
7. The method of phthalonitrile resin composite according to claim 5, characterized in that: the surfactant comprises any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyethylene glycol, polyethylene oxide, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone or sodium carboxymethyl cellulose.
8. The method of phthalonitrile resin composite according to claim 5, characterized in that: in the step (1), the zero-dimensional nano TiO2And the one-dimensional halloysite nanometer filler particles are in a mass ratio of 1: 1-1: 9.
In the step (2), the dried composite nanoparticle filler is obtained by using a freeze drying or low-temperature vacuum drying method.
In the step (3), the mass ratio of the curing agent to the phthalonitrile prepolymer is (5-120): 100, respectively; the mass ratio of the accelerator to the phthalonitrile prepolymer is (0.005-3) to 100.
In the step (5), the curing time is 8-36 h; the post-curing time is 4-6 h.
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| US20080176987A1 (en) * | 2007-01-22 | 2008-07-24 | Trevet Fred W | System and methods for modified resin and composite material |
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