CN106519570A - Nano zinc oxide modified epoxy resin composite material and preparation method thereof - Google Patents
Nano zinc oxide modified epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN106519570A CN106519570A CN201610970571.7A CN201610970571A CN106519570A CN 106519570 A CN106519570 A CN 106519570A CN 201610970571 A CN201610970571 A CN 201610970571A CN 106519570 A CN106519570 A CN 106519570A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
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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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a nano zinc oxide modified epoxy resin composite material, which is composed of the following components by weight: 100 parts of epoxy resin, 0.25-0.75 part of a coupling agent, 50-150 parts of a water-acetone solution, 10-20 parts of nano zinc oxide, 70-120 parts of a curing agent, 0.6-3 parts of a promoter, and 2-12 parts of a toughening agent. The preparation method includes: adding modified nano zinc oxide into epoxy resin, conducting stirring under a water bath condition and performing ultrasonic treatment; then adding the curing agent, the promoter and the toughening agent, further performing stirring and ultrasonic treatment; and then carrying out vacuum defoaming and curing, thus obtaining the composite material. The composite material provided by the invention has excellent electrical characteristics, especially under a vacuum condition, in an electric field with extremely uneven needle-plate electrode, the composite material has excellent partial discharge resistance, partial discharge initial voltage increased by 29.2% than that of pure epoxy resin, thus providing the basis for improving the electrical resistance level of the material in a non-uniform electric field. Also the preparation method of the composite material provided by the invention is low in cost.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of nano zinc oxide modified epoxy resin composite wood
Material, the invention further relates to a kind of preparation method of the composite.
Background technology
In numerous polymeric dielectrics, epoxy resin is due to good electrical insulation capability, being widely used as electricity
The insulating materials of Force system electrical equipment.But, often there is short fatigue life, heat resistance, easily in the epoxy resin after solidification
The shortcomings of stress cracking and toughness difference.Research finds, by adding nano-particle, the mechanical performance and electricity of epoxy resin
Gas performance is all improved to some extent.Nano zine oxide is with the Non-linear pressure sensitive more more excellent than other nano materials
Matter, the composite with nano zine oxide as filler have excellent nonlinear characteristic, can be in the improvement of non-uniform electric field
Play a significant role.And be directly appended in epoxy resin to tie because easy reunion, bad dispersibility with base-material by nano zine oxide
The shortcomings of weak with joint efforts, causes boundary defect, declines material property.So, it was necessary to nano oxygen before composite is prepared
Change zinc carries out surface and is modified, and improves the adhesion and organic base-material between, so as to improve material property and loading to greatest extent,
Reduce cost of material.
The content of the invention
It is an object of the invention to provide a kind of nano zinc oxide modified epoxy resin composite material, the composite has good
Good non-linear electric character and excellent resistance to office puts characteristic.
It is a further object to provide a kind of preparation method of nano zinc oxide modified epoxy resin composite material.
The technical solution adopted in the present invention is, a kind of nano zinc oxide modified epoxy resin composite material, by following heavy
The component composition of amount part：100 parts of epoxy resin, coupling agent 0.25-0.75 parts, boiling solution 50-150 parts, nano zine oxide
10-20 parts, curing agent 70-120 parts, accelerator 0.6-3 parts, toughener 2-12 parts.
The characteristics of of the invention, also resides in,
Epoxy resin is bisphenol A type epoxy resin E-51；The average grain diameter of nano zine oxide is 50nm, and specific surface area is
20-60m2/g。
Coupling agent is γ-(methacryloxy) propyl trimethoxy silicane (KH570), and curing agent is methyl tetrahydrochysene benzene
Acid anhydride, accelerator are 2,4,6- tri- (dimethylamino methyl) phenol (DMP-30), and toughener is DH410.
Second technical scheme of the present invention be, a kind of system of nano zinc oxide modified epoxy resin composite material
Preparation Method, specifically implements according to following steps：
Step 1, weighs following components by weight respectively：100 parts of epoxy resin, coupling agent 0.25-0.75 parts, water-the third
Ketone solution 50-150 parts, nano zine oxide 10-20 parts, curing agent 70-120 parts, accelerator 0.6-3 parts, toughener 2-12 parts；
Step 2, under room temperature, will use salt acid for adjusting pH to acidity after coupling agent and the mixing of boiling solution, is hydrolyzed anti-
Should；Nano zine oxide is subsequently adding, filtration under diminished pressure after water bath with thermostatic control stirring is washed with deionized to without chlorion, product Jing
Post activation is dried, modified nano zinc oxide is obtained；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in epoxy resin, is stirred simultaneously under water bath condition
It is ultrasonically treated；
Step 4, adds curing agent, accelerator and toughener in the mixed liquor of step 3, continues to stir and ultrasonically treated；
Step 5, carries out curing process after the mixed liquor vacuum defoamation that step 4 is obtained, obtains nano zinc oxide modified ring
Epoxy resin composite material.
The characteristics of of the invention, also resides in,
In step 1, coupling agent is γ-(methacryloxy) propyl trimethoxy silicane (KH570), and curing agent is first
Base THPA, accelerator are 2,4,6- tri- (dimethylamino methyl) phenol (DMP-30), and toughener is DH410.
In step 2 at room temperature, using salt acid for adjusting pH to 4-6, hydrolysis time is 3-4h；Water bath with thermostatic control temperature is 50-
80 DEG C, speed of agitator is 1200-2000r/min, and mixing time is 30-60min；Activation temperature is 110-140 DEG C, soak time
For 8-10h.
In step 3, bath temperature is 50-80 DEG C, and speed of agitator is 1200-2000r/min, and when ultrasonically treated, power is
200-1000W, frequency 20-40kHz, process time are 30-60min.
In step 4, bath temperature is 50-80 DEG C, and speed of agitator is 1200-2000r/min, and when ultrasonically treated, power is
200-1000W, frequency 20-40kHz, process time are 15-30min.
Vacuum defoamation in step 5 is that mixed liquor after step 4 is processed is put into vacuum extractor, relative vacuum for-
0.09--0.1Mpa, vacuumizes 15-60min, is subsequently heated to 30-50 DEG C and is incubated 30-60min and slough the gas in mixed liquor
Bubble.
In step 5, curing process is to pour the mixed liquor after vacuum defoamation in the mould of Jing releasing agents JD909 process into,
90-105 DEG C is heated in baking oven and 1-1.5h is incubated, is then proceeded to be heated to 110-120 DEG C and is incubated 1-1.5h, be further continued for adding
Heat is to 140-150 DEG C and is incubated 2-3h.
The invention has the beneficial effects as follows, composite of the present invention has excellent non-linear electric character, and in vacuum
Under the conditions of, in needle plate electrode severe non-uniform electric field, characteristic is put in its excellent resistance to office, and starting voltage is put than pure epoxy resin raising in office
More than 16.2%, foundation can be provided to improve resistance to electric level of the material under non-uniform electric field, and composite of the present invention
Preparation method is with low cost.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of nano zinc oxide modified epoxy resin composite material of the invention；
Fig. 2 is the conductance property figure of nano zinc oxide modified epoxy resin composite material of the invention；
Fig. 3 is nano zinc oxide modified epoxy resin composite material dielectric property figure of the invention；
Fig. 4 is that resistance characteristics figure is put in the office of nano zinc oxide modified epoxy resin composite material of the invention.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of nano zinc oxide modified epoxy resin composite material of the present invention, is made up of the component of following weight portion：Epoxy
100 parts of resin, coupling agent 0.25-0.75 parts, boiling solution 50-150 parts, nano zine oxide 10-20 parts, curing agent 70-
120 parts, accelerator 0.6-3 parts, toughener 2-12 parts.
Epoxy resin is bisphenol A type epoxy resin E-51；The average grain diameter of nano zine oxide is 50nm, and specific surface area is
20-60m2/g。
Coupling agent is γ-(methacryloxy) propyl trimethoxy silicane (KH570), and curing agent is methyl tetrahydrochysene benzene
Acid anhydride, accelerator are 2,4,6- tri- (dimethylamino methyl) phenol (DMP-30), and toughener is DH410.
The preparation method of above-mentioned nano zinc oxide modified epoxy resin composite material, specifically implements according to following steps：
Step 1, weighs following components by weight respectively：100 parts of epoxy resin, coupling agent 0.25-0.75 parts, water-the third
Ketone solution 50-150 parts, nano zine oxide 10-20 parts, curing agent 70-120 parts, accelerator 0.6-3 parts, toughener 2-12 parts；
Step 2, under room temperature, will use salt acid for adjusting pH to 4-6 after coupling agent and the mixing of boiling solution, is hydrolyzed anti-
Answer 3-4h；Be subsequently adding nano zine oxide, under 50-80 DEG C of water bath with thermostatic control, rotating speed be 1200-2000r/min, stir 30-60min
Filtration under diminished pressure, is washed with deionized to without chlorion afterwards, and product activates 8-10h after drying at 110-140 DEG C, is changed
Property nano zine oxide；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in epoxy resin, under 50-80 DEG C of water bath condition
Rotating speed be 1200-2000r/min under stirring and it is ultrasonically treated, when ultrasonically treated power be 200-1000W, frequency 20-40kHz,
Process time is 30-60min；
Step 4, adds curing agent, accelerator and toughener in the mixed liquor of step 3, continues in 50-80 DEG C of water-bath bar
Under part, rotating speed is to stir and ultrasonically treated under 1200-2000r/min, and when ultrasonically treated, power is 200-1000W, frequency 20-
40kHz, process time are 15-30min；
Step 5, the mixed liquor after step 4 is processed are put into vacuum extractor, and relative vacuum is -0.09--0.1Mpa, is taken out
Vacuum 15-60min, is subsequently heated to 30-50 DEG C and is incubated 30-60min and slough the bubble in mixed liquor；
Step 6, the mixed liquor after step 5 vacuum defoamation is poured in the mould of Jing releasing agents JD909 process, in an oven
It is heated to 90-105 DEG C and is incubated 1-1.5h, then proceedes to be heated to 110-120 DEG C and be incubated 1-1.5h, be further continued for being heated to
140-150 DEG C and 2-3h is incubated, is obtained final product.
Accompanying drawing 1 show the profile scanning electron microscope of the epoxy resin matrix nano-zinc oxide composite material of present invention preparation,
Particle is in nanoscale distribution substantially as can be seen from Figure 1, and disperses more uniform without obvious agglomeration.
Conductance property curve containing the nano-ZnO/EP composites for different ratio shown in accompanying drawing 2, pure EP and 10% sample
The conductance property of product all do not show it is non-linear, but, with the increase of nano-ZnO content, nonlinear factor maximum αmax
Gradually rise, when doping is more than l0%, the J-E curves of composite sample present apparent nonlinear characteristic.
The dielectric property curve of the different nano-ZnO of doping shown in accompanying drawing 3/EP composites, after addition nano-ZnO,
The relative dielectric constant of material is improved, and with the increase of ZnO content, the relative dielectric constant of composite increases,
Maximum is reached during 30% content.
Starting voltage is put in the office of the ZnO/EP composites measured under vacuum condition shown in accompanying drawing 4, as nano-particle is mixed
The increase of miscellaneous amount, the office of ZnO/EP composites are put starting voltage and maximum are occurred in that at 15%, decline afterwards, 15% current political situation
Portion's discharge inception voltage improves 16.2% than pure epoxy resin.
Embodiment 1
Step 1, weighs following components by weight respectively：Bisphenol A type epoxy resin E-51100 parts, 0.25 part of KH570,
150 parts of boiling solution, 15 parts of nano zine oxide, 100 parts of methyl tetrahydro phthalic anhydride, 0.6 part of DMP-30,10 parts of DH410；
Step 2, under room temperature, will use salt acid for adjusting pH to 6 after KH570 and the mixing of boiling solution, and be hydrolyzed reaction
3h；Be subsequently adding nano zine oxide, under 60 DEG C of waters bath with thermostatic control, rotating speed be 1200r/min, stirring 60min after filtration under diminished pressure, spend
To without chlorion, product activates 9h at 120 DEG C to ion water washing after drying, obtains modified nano zinc oxide；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in bisphenol A type epoxy resin E-51, in 50 DEG C of water
Under the conditions of bath, rotating speed is to stir and ultrasonically treated under 1200r/min, and when ultrasonically treated, power is 200W, frequency 40kHz, during process
Between be 40min；
Step 4, adds methyl tetrahydro phthalic anhydride, DMP-30 and DH410 in the mixed liquor of step 3, continues in 50 DEG C of water-baths
Under the conditions of rotating speed be 1200r/min under stirring and it is ultrasonically treated, when ultrasonically treated power be 200W, frequency 40kHz, process time
For 15min；
Step 5, the mixed liquor after step 4 is processed are put into vacuum extractor, and relative vacuum is -0.09Mpa, is vacuumized
60min, is subsequently heated to 40 DEG C and is incubated 40min and slough the bubble in mixed liquor；
Step 6, the mixed liquor after step 5 vacuum defoamation is poured in the mould of Jing releasing agents JD909 process, in an oven
It is heated to 90 DEG C and is incubated 1.2h, then proceed to be heated to 110 DEG C and be incubated 1.3h, is further continued for being heated to 140 DEG C and is incubated 2h,
Obtain final product.
Embodiment 2
Step 1, weighs following components by weight respectively：Bisphenol A type epoxy resin E-51100 parts, 0.35 part of KH570,
100 parts of boiling solution, 10 parts of nano zine oxide, 70 parts of methyl tetrahydro phthalic anhydride, 1 part of DMP-30,12 parts of DH410；
Step 2, under room temperature, will use salt acid for adjusting pH to 5 after KH570 and the mixing of boiling solution, and be hydrolyzed reaction
3.5h；Be subsequently adding nano zine oxide, under 70 DEG C of waters bath with thermostatic control, rotating speed be 1500r/min, stirring 50min after filtration under diminished pressure, use
Deionized water is washed to without chlorion, and product activates 8h after drying at 140 DEG C, obtains modified nano zinc oxide；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in bisphenol A type epoxy resin E-51, in 60 DEG C of water
Under the conditions of bath, rotating speed is to stir and ultrasonically treated under 1500r/min, and when ultrasonically treated, power is 800W, frequency 30kHz, during process
Between be 30min；
Step 4, adds methyl tetrahydro phthalic anhydride, DMP-30 and DH410 in the mixed liquor of step 3, continues in 60 DEG C of water-baths
Under the conditions of rotating speed be 1500r/min under stirring and it is ultrasonically treated, when ultrasonically treated power be 800W, frequency 30kHz, process time
For 20min；
Step 5, the mixed liquor after step 4 is processed are put into vacuum extractor, and relative vacuum is -0.1Mpa, is vacuumized
50min, is subsequently heated to 30 DEG C and is incubated 60min and slough the bubble in mixed liquor；
Step 6, the mixed liquor after step 5 vacuum defoamation is poured in the mould of Jing releasing agents JD909 process, in an oven
It is heated to 100 DEG C and is incubated 1h, then proceed to be heated to 120 DEG C and be incubated 1.4h, is further continued for being heated to 150 DEG C and is incubated 3h,
Obtain final product.
Embodiment 3
Step 1, weighs following components by weight respectively：Bisphenol A type epoxy resin E-51100 parts, 0.45 part of KH570,
50 parts of boiling solution, 20 parts of nano zine oxide, 90 parts of methyl tetrahydro phthalic anhydride, 2 parts of DMP-30,8 parts of DH410；
Step 2, under room temperature, will use salt acid for adjusting pH to 4 after KH570 and the mixing of boiling solution, and be hydrolyzed reaction
4h；Be subsequently adding nano zine oxide, under 80 DEG C of waters bath with thermostatic control, rotating speed be 1800r/min, stirring 40min after filtration under diminished pressure, spend
To without chlorion, product activates 9h at 110 DEG C to ion water washing after drying, obtains modified nano zinc oxide；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in bisphenol A type epoxy resin E-51, in 70 DEG C of water
Under the conditions of bath, rotating speed is to stir and ultrasonically treated under 1800r/min, and when ultrasonically treated, power is 400W, frequency 20kHz, during process
Between be 50min；
Step 4, adds methyl tetrahydro phthalic anhydride, DMP-30 and DH410 in the mixed liquor of step 3, continues in 70 DEG C of water-baths
Under the conditions of rotating speed be 1800r/min under stirring and it is ultrasonically treated, when ultrasonically treated power be 400W, frequency 20kHz, process time
For 25min；
Step 5, the mixed liquor after step 4 is processed are put into vacuum extractor, and relative vacuum is -0.1Mpa, is vacuumized
40min, is subsequently heated to 50 DEG C and is incubated 30min and slough the bubble in mixed liquor；
Step 6, the mixed liquor after step 5 vacuum defoamation is poured in the mould of Jing releasing agents JD909 process, in an oven
It is heated to 95 DEG C and is incubated 1.3h, then proceed to be heated to 115 DEG C and be incubated 1.5h, is further continued for being heated to 145 DEG C and being incubated
2.5h, obtains final product.
Embodiment 4
Step 1, weighs following components by weight respectively：Bisphenol A type epoxy resin E-51100 parts, 0.55 part of KH570,
75 parts of boiling solution, 18 parts of nano zine oxide, 120 parts of methyl tetrahydro phthalic anhydride, 3 parts of DMP-30,6 parts of DH410；
Step 2, under room temperature, will use salt acid for adjusting pH to 4.5 after KH570 and the mixing of boiling solution, and be hydrolyzed reaction
4h；Be subsequently adding nano zine oxide, under 50 DEG C of waters bath with thermostatic control, rotating speed be 2000r/min, stirring 30min after filtration under diminished pressure, spend
To without chlorion, product activates 10h at 130 DEG C to ion water washing after drying, obtains modified nano zinc oxide；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in bisphenol A type epoxy resin E-51, in 80 DEG C of water
Under the conditions of bath, rotating speed is to stir and ultrasonically treated under 2000r/min, and when ultrasonically treated, power is 600W, frequency 25kHz, during process
Between be 30min；
Step 4, adds methyl tetrahydro phthalic anhydride, DMP-30 and DH410 in the mixed liquor of step 3, continues in 80 DEG C of water-baths
Under the conditions of rotating speed be 2000r/min under stirring and it is ultrasonically treated, when ultrasonically treated power be 600W, frequency 25kHz, process time
For 30min；
Step 5, the mixed liquor after step 4 is processed are put into vacuum extractor, and relative vacuum is -0.09Mpa, is vacuumized
30min, is subsequently heated to 30 DEG C and is incubated 50min and slough the bubble in mixed liquor；
Step 6, the mixed liquor after step 5 vacuum defoamation is poured in the mould of Jing releasing agents JD909 process, in an oven
It is heated to 105 DEG C and is incubated 1.4h, then proceed to be heated to 118 DEG C and be incubated 1h, is further continued for being heated to 150 DEG C and being incubated
2.8h, obtains final product.
Embodiment 5
Step 1, weighs following components by weight respectively：Bisphenol A type epoxy resin E-51100 parts, 0.75 part of KH570,
125 parts of boiling solution, 12 parts of nano zine oxide, 80 parts of methyl tetrahydro phthalic anhydride, 1.5 parts of DMP-30,2 parts of DH410；
Step 2, under room temperature, will use salt acid for adjusting pH to 5.5 after KH570 and the mixing of boiling solution, and be hydrolyzed reaction
3.5h；Be subsequently adding nano zine oxide, under 65 DEG C of waters bath with thermostatic control, rotating speed be 1600r/min, stirring 40min after filtration under diminished pressure, use
Deionized water is washed to without chlorion, and product activates 8h after drying at 115 DEG C, obtains modified nano zinc oxide；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in bisphenol A type epoxy resin E-51, in 50 DEG C of water
Under the conditions of bath, rotating speed is to stir and ultrasonically treated under 1600r/min, and when ultrasonically treated, power is 1000W, frequency 35kHz, is processed
Time is 60min；
Step 4, adds methyl tetrahydro phthalic anhydride, DMP-30 and DH410 in the mixed liquor of step 3, continues in 50 DEG C of water-baths
Under the conditions of rotating speed be 1600r/min under stirring and it is ultrasonically treated, when ultrasonically treated power be 1000W, frequency 35kHz, during process
Between be 20min；
Step 5, the mixed liquor after step 4 is processed are put into vacuum extractor, and relative vacuum is -0.1Mpa, is vacuumized
15min, is subsequently heated to 40 DEG C and is incubated 45min and slough the bubble in mixed liquor；
Step 6, the mixed liquor after step 5 vacuum defoamation is poured in the mould of Jing releasing agents JD909 process, in an oven
It is heated to 100 DEG C and is incubated 1.5h, then proceed to be heated to 110 DEG C and be incubated 1.2h, is further continued for being heated to 140 DEG C and being incubated
2h, obtains final product.
Claims (10)
1. a kind of nano zinc oxide modified epoxy resin composite material, it is characterised in that be made up of the component of following weight portion：Ring
100 parts of oxygen tree fat, coupling agent 0.25-0.75 parts, boiling solution 50-150 parts, nano zine oxide 10-20 parts, curing agent 70-
120 parts, accelerator 0.6-3 parts, toughener 2-12 parts.
2. nano zinc oxide modified epoxy resin composite material according to claim 1, it is characterised in that epoxy resin is
Bisphenol A type epoxy resin E-51；The average grain diameter of nano zine oxide is 50nm, and specific surface area is 20-60m2/g。
3. nano zinc oxide modified epoxy resin composite material according to claim 1 and 2, it is characterised in that coupling agent
For γ-(methacryloxy) propyl trimethoxy silicane, curing agent is methyl tetrahydro phthalic anhydride, and accelerator is 2,4,6- tri-
(dimethylamino methyl) phenol, toughener is DH410.
4. a kind of preparation method of nano zinc oxide modified epoxy resin composite material, it is characterised in that specifically according to following step
It is rapid to implement：
Step 1, weighs following components by weight respectively：100 parts of epoxy resin, coupling agent 0.25-0.75 parts, boiling are molten
Liquid 50-150 parts, nano zine oxide 10-20 parts, curing agent 70-120 parts, accelerator 0.6-3 parts, toughener 2-12 parts；
Step 2, under room temperature, will use salt acid for adjusting pH to acidity after coupling agent and the mixing of boiling solution, and be hydrolyzed reaction；
Nano zine oxide is subsequently adding, filtration under diminished pressure after water bath with thermostatic control stirring is washed with deionized to without chlorion, product drying
Post activation, obtains modified nano zinc oxide；
Step 3, the modified nano zinc oxide that step 2 is obtained is added in epoxy resin, stirring ultrasound under water bath condition
Process；
Step 4, adds curing agent, accelerator and toughener in the mixed liquor of step 3, continues to stir and ultrasonically treated；
Step 5, carries out curing process after the mixed liquor vacuum defoamation that step 4 is obtained, obtains nano zinc oxide modified asphalt mixtures modified by epoxy resin
Resin composite material.
5. the preparation method of nano zinc oxide modified epoxy resin composite material according to claim 4, it is characterised in that
In step 1, coupling agent is γ-(methacryloxy) propyl trimethoxy silicane, and curing agent is methyl tetrahydro phthalic anhydride, is promoted
Agent is 2,4,6- tri- (dimethylamino methyl) phenol, and toughener is DH410.
6. the preparation method of nano zinc oxide modified epoxy resin composite material according to claim 4, it is characterised in that
In step 2 at room temperature, using salt acid for adjusting pH to 4-6, hydrolysis time is 3-4h；Water bath with thermostatic control temperature is 50-80 DEG C, stirring
Rotating speed is 1200-2000r/min, and mixing time is 30-60min；Activation temperature is 110-140 DEG C, and soak time is 8-10h.
7. the preparation method of nano zinc oxide modified epoxy resin composite material according to claim 4, it is characterised in that
In step 3 bath temperature be 50-80 DEG C, speed of agitator is 1200-2000r/min, when ultrasonically treated power be 200-1000W,
Frequency 20-40kHz, process time are 30-60min.
8. the preparation method of nano zinc oxide modified epoxy resin composite material according to claim 4, it is characterised in that
In step 4 bath temperature be 50-80 DEG C, speed of agitator is 1200-2000r/min, when ultrasonically treated power be 200-1000W,
Frequency 20-40kHz, process time are 15-30min.
9. the preparation method of nano zinc oxide modified epoxy resin composite material according to claim 4, it is characterised in that
Vacuum defoamation in step 5 is that mixed liquor after step 4 is processed is put into vacuum extractor, and relative vacuum is -0.09--0.1Mpa,
15-60min is vacuumized, is subsequently heated to 30-50 DEG C and is incubated 30-60min and slough the bubble in mixed liquor.
10. the preparation method of nano zinc oxide modified epoxy resin composite material according to claim 4, its feature exist
In in step 5, curing process is to pour the mixed liquor after vacuum defoamation in the mould of Jing releasing agents JD909 process, in baking oven into
In be heated to 90-105 DEG C and be incubated 1-1.5h, then proceed to be heated to 110-120 DEG C and be incubated 1-1.5h, be further continued for being heated to
140-150 DEG C and it is incubated 2-3h.
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| CN201610970571.7A CN106519570A (en) | 2016-10-28 | 2016-10-28 | Nano zinc oxide modified epoxy resin composite material and preparation method thereof |
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| CN201610970571.7A CN106519570A (en) | 2016-10-28 | 2016-10-28 | Nano zinc oxide modified epoxy resin composite material and preparation method thereof |
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| CN201610970571.7A Pending CN106519570A (en) | 2016-10-28 | 2016-10-28 | Nano zinc oxide modified epoxy resin composite material and preparation method thereof |
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| CN114940807A (en) * | 2022-05-12 | 2022-08-26 | 郯城博化化工科技有限公司 | Modified zinc oxide and mercaptan synergistically toughened high-impact-resistance epoxy resin composite material and preparation method thereof |
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| CN114940807B (en) * | 2022-05-12 | 2024-01-16 | 郯城博化化工科技有限公司 | Modified zinc oxide and mercaptan synergistic toughened high impact resistance epoxy resin composite material and preparation method thereof |
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