CN109306150A - A kind of preparation method of room temperature curing epoxy composite material - Google Patents
A kind of preparation method of room temperature curing epoxy composite material Download PDFInfo
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- CN109306150A CN109306150A CN201811205928.8A CN201811205928A CN109306150A CN 109306150 A CN109306150 A CN 109306150A CN 201811205928 A CN201811205928 A CN 201811205928A CN 109306150 A CN109306150 A CN 109306150A
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of preparation methods of room temperature curing epoxy composite material, are related to epoxy resin field of new materials, comprising the following steps: (1) the dry processing of inorganic particulate；(2) surface of inorganic particulate is modified；(3) centrifuge washing of inorganic particulate；(3) preparation of functional material；(5) mixing of functional material and epoxy resin；(6) material mixes；(6) it pours, room temperature curing molding；It is modified that the method for the present invention uses silane coupling agent to carry out surface to inorganic particulate first, then modified functional material is compounded with curing agent, diluent, oxidant and epoxy resin, by the associated effect in preparation method between technological parameter and component raw material, the epoxy resin composite material of preparation has good mechanical property and thermal stability.
Description
Technical field
The present invention relates to epoxy resin field of new materials, and in particular to a kind of system of room temperature curing epoxy composite material
Preparation Method.
Background technique
Epoxy resin has excellent mechanical property, electrical insulating property, chemical stability and shrinking percentage is low, machine-shaping is held
Easily, the advantages that low in cost, be widely used at present, the fibre reinforced composites basis material of superior performance.
Room temperature curing epoxy can solidify at room temperature, and the time used is several minutes to a few hours, and is placed at room temperature for 7 days
Use intensity can further improve afterwards, while it is small with thermal stress, and low energy consumption, simple operation and other advantages, transmit mould in resin
It is widely applied in the fields such as modeling technique, fibre reinforced plastics, epoxy layer compression moulding.But epoxy resin there are matter crisp, impact strength
The disadvantage of difference is widely applied to limit it.
Chinese patent CN101602926B discloses a kind of room temperature curing epoxy adhesive, it includes component A and group
Part B, the component A is made of the raw material of following weight part ratio: 80-100 parts of epoxy resin, 10-30 parts of filler, and White Carbon black 1-
5 parts, 2-10 parts of plasticizer；The component B is made of the raw material of following weight part ratio: long-chain fat modified amine curing agent 24-
50 parts, 18-35 parts of filler, 1-2 parts of White Carbon black, 1-3 parts of plasticizer, 2-4 parts of coupling agent, in which: the weight of component A and component B
Than being 2: 0.8-1.3.Preparation method is simple, can effectively improve the flexibility of epoxy resin, reduces curing time.
Chinese patent CN102796349B discloses a kind of membranaceous room temperature curing epoxy composite material gasket and its system
Preparation Method is made of epoxy resin, amine curing agent, toughener, inorganic filler and chopped strand.The preparation method is as follows: one, press
Parts by weight stir evenly epoxy resin, toughener and inorganic filler, obtain hybrid resin；Two, hybrid resin and amine are consolidated
After agent is sufficiently mixed uniformly, chopped strand stirring is added, obtains mixture；Three, by mixture by molding or in adhesive film machine
Upper roll-forming to get.Membranaceous ambient temperature curable epoxy resin composite material gasket adhesive property with higher of the invention
It is but inorganic filler and chopped strand is direct without any processing with excellent compressive strength, impact strength and tensile strength
It is mixed with epoxy resin, dispersibility and compatibility in the epoxy still has the space of promotion.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of systems of room temperature curing epoxy composite material
Preparation Method, the method for the present invention uses silane coupling agent modified to inorganic particulate progress surface first, then by modified function
Can material compounded with curing agent, diluent, oxidant and epoxy resin, by preparation method between technological parameter and component raw material
Associated effect, the epoxy resin composite material of preparation has good mechanical property and thermal stability.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A kind of preparation method of room temperature curing epoxy composite material, comprising the following steps:
(1) according to parts by weight weigh 1-2 parts of nano-titanium dioxide, 1-2 parts of nano zine oxide, 0.4-0.8 parts of white carbon black and
3-5 parts of nano silica, nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are individually positioned in
It is 12 hours dry in 150-170 degrees Celsius of baking oven；
(2) nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are mixed and is added in calcining furnace
It after being calcined 1-2 hours under 300-400 degrees Celsius, is added in ethanol water, is uniformly mixed, be added suitable silane coupled
Agent, heating water bath is to 68-75 degrees Celsius, with 600-800 revs/min of speed, after constant temperature stirs 2 hours；
(3) mixed liquor made from step (2) is added in centrifuge tube with 5000-6000 revs/min of speed, is centrifuged
Layering 5-10 minutes removes supernatant liquid, lower layer's solid particle is added to absolute ethanol, at 500-600W, 8-12KHz,
Ultrasonic cleaning 15-20 minutes is carried out, filtering after filtrate is rinsed 3-5 times with deionized water, under 60-70 degrees Celsius, is dried in vacuo
20-25 hours；
(4) filtrate made from step (3) is put into ball mill, controls drum's speed of rotation at 600-1000 revs/min, grinds
Mill 10 hours, obtains functional material；
(5) the solid-liquid ratio adding into acetone according to 1g:2 milliliters, 500-800W is added in functional stuffing made from step (4)
Under, mixing acetone soln is added in epoxy resin, after 8-15 minutes with 1600-2000 revs/min of speed by ultrasonic treatment
After stirring 20-28 minutes, 70-80 degrees Celsius is warming up to after lower ultrasonic disperse 2-4 hours, and temperature control is to 70 degrees Celsius, heating water bath
10-12 hours, extra acetone is removed, obtains epoxy resin-functional material mixed liquor；
(6) it is even that diluent, antioxidant and silane are added into epoxy resin made from step (5)-functional material mixed liquor
Join agent, after being stirred 20-25 minutes with 1200-1800 revs/min of speed, vacuumize, deaerates 30-50 minutes；
(7) curing agent is added in the mixture in step (6), is stirred with 2000-2500 revs/min of speed
It after even, injects in Teflon mould, places solidification 5-7 days at room temperature to get the room temperature curing epoxy composite wood
Material.
Preferably, the ethanol water is that dehydrated alcohol and deionized water are formed according to volume ratio 4:1 mixed preparing.
Preferably, the additional amount of silane coupling agent is nano-titanium dioxide, nano zine oxide, hard charcoal in the step (2)
Black and nano silica total weight 4-7%.
Preferably, it is 120-200KHz, power 7-15KW that ultrasonic disperse condition, which is ultrasonic power, in the step (5).
Preferably, the room temperature curing epoxy composite material includes the raw material of following parts by weight meter: epoxy resin 90-
100 parts, 3-8 parts of functional material, 10-20 parts of diluent, 30-40 parts of curing agent, 1.2-2.5 parts of antioxidant and silane coupling agent 1-
4 parts.
Preferably, the room temperature curing epoxy composite material includes the raw material of following parts by weight meter: epoxy resin 96
Part, 5 parts of functional material, 14 parts of diluent, 35 parts of curing agent, 1.8 parts of antioxidant and 2.2 parts of silane coupling agent.
Preferably, the silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl front three
One or more of oxysilane and γ-(methacryloxy) propyl trimethoxy silicane combine.
Preferably, the diluent is allyl alkyl glycidol ether, phenyl glycidyl ether, benzyl glycidol
One or more of ether, octyl glycidyl ether and resorcinolformaldehyde resin combine.
Preferably, the antioxidant be β-((3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, three (2,
4- dibutyl phenyl ester) one of phosphite, triphenyl phosphite and pentaerythritol bis-phosphite two (octadecyl alcolol) ester or
Several combinations.
Preferably, the curing agent is diethylenetriamine, triethylene tetramine, tetraethylenepentamine, hexamethylene diamine, methylol second two
One or more of amine, methylol diethylenetriamine and beta-hydroxyethyl ethylenediamine combine.
The present invention have it is following the utility model has the advantages that
(1) the method for the present invention uses silane coupling agent modified to inorganic filler progress surface first, then will be modified
Functional material compounded with curing agent, diluent, oxidant and epoxy resin, it is former to pass through technological parameter in preparation method and component
Associated effect between material, the epoxy resin composite material of preparation have good mechanical property and thermal stability.
(2) contain nano-titanium dioxide, nano zine oxide and nano silica, nanoparticle in functional material of the present invention
Toughening have particle specific surface area it is big, high surface activity, particle surface dangling bonds abundant easily with epoxy resin-base formationization
Learn key the features such as, can effectively reinforced epoxy toughness, but nanoparticle there are surface energy height, one reunite lack
Point, therefore, to reduce reunion, improving particle dispersibility, the present invention uses silane coupling agent to carry out inorganic nano-particle first
Surface is modified, can effectively reduce the reunion of particle, while enhancing the compatibility of inorganic particulate and epoxy resin.
(3) it joined suitable silane coupling agent again when material of the present invention in step (6) mixes, not only can be improved
Compatibility between organic phase and inorganic phase, while the flexible segment that silane coupling agent itself contains, can be enhanced, composite material
Impact strength.
(4) preparation method raw material sources of the present invention are extensive, and preparation method is simple, unharmful substance discharge, safety and environmental protection.
Specific embodiment
Below with reference to embodiment, further description of the specific embodiments of the present invention, and following embodiment is only used for more
Technical solution of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
Embodiment 1
A kind of preparation method of room temperature curing epoxy composite material, comprising the following steps:
(1) 1 part of nano-titanium dioxide, 1 part of nano zine oxide, 0.4 part of white carbon black and nano-silica are weighed according to parts by weight
3 parts of SiClx, nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are individually positioned in 150 degrees Celsius of baking
It is 12 hours dry in case；
(2) nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are mixed and is added in calcining furnace
After being calcined 1 hour under 300 degrees Celsius, it is added in ethanol water, is uniformly mixed, suitable silane coupling agent, water is added
Bath is heated to 68 degrees Celsius, with 600 revs/min of speed, after constant temperature stirs 2 hours；
(3) mixed liquor made from step (2) is added in centrifuge tube with 5000 revs/min of speed, carries out centrifugation layering 5
Minute, supernatant liquid is removed, lower layer's solid particle is added to absolute ethanol, at 500W, 8KHz, carries out 15 points of ultrasonic cleaning
Clock, filtering after filtrate is rinsed 3 times with deionized water, at 60 c, are dried in vacuo 20 hours；
(4) filtrate made from step (3) is put into ball mill, controls drum's speed of rotation at 600 revs/min, grinds 10
Hour, obtain functional material；
(5) functional stuffing made from step (4) is added according to 1g:2 milliliters of solid-liquid ratio adding into acetone, under 500W,
Mixing acetone soln was added in epoxy resin, is stirred 20 minutes with 1600 revs/min of speed after 8 minutes by ultrasonic treatment
Afterwards, 70 degrees Celsius of lower ultrasonic disperses are warming up to after 2 hours, temperature control is to 70 degrees Celsius, heating water bath 10 hours, removal extra third
Ketone obtains epoxy resin-functional material mixed liquor；
(6) it is even that diluent, antioxidant and silane are added into epoxy resin made from step (5)-functional material mixed liquor
Join agent, after twenty minutes with 1200 revs/min of speed stirring, vacuumizes, deaerate 30 minutes；
(7) curing agent is added in the mixture in step (6), after being uniformly mixed with 2000 revs/min of speed,
It injects in Teflon mould, places solidification 5 days at room temperature to get the room temperature curing epoxy composite material.
Ethanol water is that dehydrated alcohol and deionized water are formed according to volume ratio 4:1 mixed preparing.
The additional amount of silane coupling agent is nano-titanium dioxide, nano zine oxide, white carbon black and nano-silica in step (2)
The 4% of SiClx total weight.
It is 120KHz, power 7KW that ultrasonic disperse condition, which is ultrasonic power, in step (5).
Room temperature curing epoxy composite material includes the raw material of following parts by weight meter: 90 parts of epoxy resin, functional material 3
Part, 10 parts of diluent, 30 parts of curing agent, 1.2 parts of antioxidant and 1 part of silane coupling agent.
Silane coupling agent is gamma-aminopropyl-triethoxy-silane.
Diluent is allyl alkyl glycidol ether.
Antioxidant is β-((3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
Curing agent is diethylenetriamine.
Embodiment 2
A kind of preparation method of room temperature curing epoxy composite material, comprising the following steps:
(1) 2 parts of nano-titanium dioxide, 2 parts of nano zine oxide, 0.8 part of white carbon black and nano-silica are weighed according to parts by weight
5 parts of SiClx, nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are individually positioned in 170 degrees Celsius of baking
It is 12 hours dry in case；
(2) nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are mixed and is added in calcining furnace
After being calcined 2 hours under 400 degrees Celsius, it is added in ethanol water, is uniformly mixed, suitable silane coupling agent, water is added
Bath is heated to 75 degrees Celsius, with 800 revs/min of speed, after constant temperature stirs 2 hours；
(3) mixed liquor made from step (2) is added in centrifuge tube with 6000 revs/min of speed, carries out centrifugation layering
10 minutes, supernatant liquid is removed, lower layer's solid particle is added to absolute ethanol, at 600W, 12KHz, is cleaned by ultrasonic
20 minutes, filtering after filtrate is rinsed 5 times with deionized water, under 70 degrees Celsius, was dried in vacuo 25 hours；
(4) filtrate made from step (3) is put into ball mill, controls drum's speed of rotation at 1000 revs/min, grinds 10
Hour, obtain functional material；
(5) functional stuffing made from step (4) is added according to 1g:2 milliliters of solid-liquid ratio adding into acetone, under 800W,
Mixing acetone soln was added in epoxy resin, is stirred 28 minutes with 2000 revs/min of speed after 15 minutes by ultrasonic treatment
Afterwards, 80 degrees Celsius of lower ultrasonic disperses are warming up to after 4 hours, temperature control is to 70 degrees Celsius, heating water bath 12 hours, removal extra third
Ketone obtains epoxy resin-functional material mixed liquor；
(6) it is even that diluent, antioxidant and silane are added into epoxy resin made from step (5)-functional material mixed liquor
Join agent, after being stirred 25 minutes with 1800 revs/min of speed, vacuumize, deaerates 50 minutes；
(7) curing agent is added in the mixture in step (6), after being uniformly mixed with 2500 revs/min of speed,
It injects in Teflon mould, places solidification 7 days at room temperature to get the room temperature curing epoxy composite material.
Ethanol water is that dehydrated alcohol and deionized water are formed according to volume ratio 4:1 mixed preparing.
The additional amount of silane coupling agent is nano-titanium dioxide, nano zine oxide, white carbon black and nano-silica in step (2)
The 7% of SiClx total weight.
It is 200KHz, power 15KW that ultrasonic disperse condition, which is ultrasonic power, in step (5).
Room temperature curing epoxy composite material includes the raw material of following parts by weight meter: 100 parts of epoxy resin, functional material
8 parts, 20 parts of diluent, 40 parts of curing agent, 2.5 parts of antioxidant and 4 parts of silane coupling agent.
Silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
Diluent is phenyl glycidyl ether.
Antioxidant is three (2,4- dibutyl phenyl ester) phosphites.
Curing agent is triethylene tetramine.
Embodiment 3
A kind of preparation method of room temperature curing epoxy composite material, comprising the following steps:
(1) according to parts by weight weigh 1.2 parts of nano-titanium dioxide, 1.6 parts of nano zine oxide, 0.6 part of white carbon black and nanometer
3.8 parts of silica, it is Celsius that nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are individually positioned in 156
It is 12 hours dry in the baking oven of degree；
(2) nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are mixed and is added in calcining furnace
After being calcined 1.7 hours under 360 degrees Celsius, it is added in ethanol water, is uniformly mixed, suitable silane coupling agent is added,
Heating water bath is to 72 degrees Celsius, with 650 revs/min of speed, after constant temperature stirs 2 hours；
(3) mixed liquor made from step (2) is added in centrifuge tube with 5500 revs/min of speed, carries out centrifugation layering 8
Minute, supernatant liquid is removed, lower layer's solid particle is added to absolute ethanol, at 560W, 10KHz, carries out ultrasonic cleaning 18
Minute, filtering after filtrate is rinsed 4 times with deionized water, under 68 degrees Celsius, is dried in vacuo 23 hours；
(4) filtrate made from step (3) is put into ball mill, controls drum's speed of rotation at 800 revs/min, grinds 10
Hour, obtain functional material；
(5) functional stuffing made from step (4) is added according to 1g:2 milliliters of solid-liquid ratio adding into acetone, under 600W,
Mixing acetone soln was added in epoxy resin, is stirred 25 minutes with 1800 revs/min of speed after 12 minutes by ultrasonic treatment
Afterwards, 78 degrees Celsius of lower ultrasonic disperses are warming up to after 3 hours, temperature control is to 70 degrees Celsius, heating water bath 11 hours, removal extra third
Ketone obtains epoxy resin-functional material mixed liquor；
(6) it is even that diluent, antioxidant and silane are added into epoxy resin made from step (5)-functional material mixed liquor
Join agent, after being stirred 24 minutes with 1500 revs/min of speed, vacuumize, deaerates 40 minutes；
(7) curing agent is added in the mixture in step (6), after being uniformly mixed with 2200 revs/min of speed,
It injects in Teflon mould, places solidification 6 days at room temperature to get the room temperature curing epoxy composite material.
Ethanol water is that dehydrated alcohol and deionized water are formed according to volume ratio 4:1 mixed preparing.
The additional amount of silane coupling agent is nano-titanium dioxide, nano zine oxide, white carbon black and nano-silica in step (2)
The 6% of SiClx total weight.
It is 180KHz, power 12KW that ultrasonic disperse condition, which is ultrasonic power, in step (5).
Room temperature curing epoxy composite material includes the raw material of following parts by weight meter: 92 parts of epoxy resin, functional material 7
Part, 18 parts of diluent, 38 parts of curing agent, 2.1 parts of antioxidant and 2.8 parts of silane coupling agent.
Silane coupling agent is γ-(methacryloxy) propyl trimethoxy silicane.
Diluent is benzyl glycidyl ether.
Antioxidant is triphenyl phosphite.
Curing agent is dihydroxymethyl ethylenediamine.
Embodiment 4
A kind of preparation method of room temperature curing epoxy composite material, comprising the following steps:
(1) according to parts by weight weigh 1.8 parts of nano-titanium dioxide, 1.5 parts of nano zine oxide, 0.6 part of white carbon black and nanometer
4.5 parts of silica, it is Celsius that nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are individually positioned in 165
It is 12 hours dry in the baking oven of degree；
(2) nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are mixed and is added in calcining furnace
After being calcined 1.4 hours under 360 degrees Celsius, it is added in ethanol water, is uniformly mixed, suitable silane coupling agent is added,
Heating water bath is to 72 degrees Celsius, with 740 revs/min of speed, after constant temperature stirs 2 hours；
(3) mixed liquor made from step (2) is added in centrifuge tube with 5800 revs/min of speed, carries out centrifugation layering 8
Minute, supernatant liquid is removed, lower layer's solid particle is added to absolute ethanol, at 570W, 9KHz, carries out 17 points of ultrasonic cleaning
Clock, filtering after filtrate is rinsed 3 times with deionized water, under 64 degrees Celsius, are dried in vacuo 23 hours；
(4) filtrate made from step (3) is put into ball mill, controls drum's speed of rotation at 800 revs/min, grinds 10
Hour, obtain functional material；
(5) functional stuffing made from step (4) is added according to 1g:2 milliliters of solid-liquid ratio adding into acetone, under 680W,
Mixing acetone soln was added in epoxy resin, is stirred 27 minutes with 1800 revs/min of speed after 12 minutes by ultrasonic treatment
Afterwards, 78 degrees Celsius of lower ultrasonic disperses are warming up to after 3.5 hours, temperature control is to 70 degrees Celsius, heating water bath 11 hours, removal extra third
Ketone obtains epoxy resin-functional material mixed liquor；
(6) it is even that diluent, antioxidant and silane are added into epoxy resin made from step (5)-functional material mixed liquor
Join agent, after being stirred 24 minutes with 1500 revs/min of speed, vacuumize, deaerates 38 minutes；
(7) curing agent is added in the mixture in step (6), after being uniformly mixed with 2300 revs/min of speed,
It injects in Teflon mould, places solidification 5-7 days at room temperature to get the room temperature curing epoxy composite material.
Ethanol water is that dehydrated alcohol and deionized water are formed according to volume ratio 4:1 mixed preparing.
The additional amount of silane coupling agent is nano-titanium dioxide, nano zine oxide, white carbon black and nano-silica in step (2)
The 4-7% of SiClx total weight.
It is 120-200KHz, power 7-15KW that ultrasonic disperse condition, which is ultrasonic power, in step (5).
Room temperature curing epoxy composite material includes the raw material of following parts by weight meter: 97 parts of epoxy resin, functional material 6
Part, 17 parts of diluent, 36 parts of curing agent, 1.9 parts of antioxidant and 3 parts of silane coupling agent.
Silane coupling agent is γ-(methacryloxy) propyl trimethoxy silicane.
Diluent is octyl glycidyl ether.
Antioxidant is pentaerythritol bis-phosphite two (octadecyl alcolol) ester.
Curing agent is beta-hydroxyethyl ethylenediamine.
Embodiment 5
A kind of preparation method of room temperature curing epoxy composite material, comprising the following steps:
(1) according to parts by weight weigh 1.6 parts of nano-titanium dioxide, 1.8 parts of nano zine oxide, 0.6 part of white carbon black and nanometer
4.2 parts of silica, it is Celsius that nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are individually positioned in 164
It is 12 hours dry in the baking oven of degree；
(2) nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are mixed and is added in calcining furnace
After being calcined 1.6 hours under 360 degrees Celsius, it is added in ethanol water, is uniformly mixed, suitable silane coupling agent is added,
Heating water bath is to 72 degrees Celsius, with 680 revs/min of speed, after constant temperature stirs 2 hours；
(3) mixed liquor made from step (2) is added in centrifuge tube with 5700 revs/min of speed, carries out centrifugation layering 8
Minute, supernatant liquid is removed, lower layer's solid particle is added to absolute ethanol, at 540W, 10KHz, carries out ultrasonic cleaning 18
Minute, filtering after filtrate is rinsed 4 times with deionized water, under 68 degrees Celsius, is dried in vacuo 23 hours；
(4) filtrate made from step (3) is put into ball mill, controls drum's speed of rotation at 800 revs/min, grinds 10
Hour, obtain functional material；
(5) functional stuffing made from step (4) is added according to 1g:2 milliliters of solid-liquid ratio adding into acetone, under 700W,
Mixing acetone soln was added in epoxy resin, is stirred 26 minutes with 1900 revs/min of speed after 13 minutes by ultrasonic treatment
Afterwards, 78 degrees Celsius of lower ultrasonic disperses are warming up to after 3 hours, temperature control is to 70 degrees Celsius, heating water bath 11 hours, removal extra third
Ketone obtains epoxy resin-functional material mixed liquor；
(6) it is even that diluent, antioxidant and silane are added into epoxy resin made from step (5)-functional material mixed liquor
Join agent, after being stirred 24 minutes with 1600 revs/min of speed, vacuumize, deaerates 46 minutes；
(7) curing agent is added in the mixture in step (6), after being uniformly mixed with 2400 revs/min of speed,
It injects in Teflon mould, places solidification 7 days at room temperature to get the room temperature curing epoxy composite material.
Ethanol water is that dehydrated alcohol and deionized water are formed according to volume ratio 4:1 mixed preparing.
The additional amount of silane coupling agent is nano-titanium dioxide, nano zine oxide, white carbon black and nano-silica in step (2)
The 6.1% of SiClx total weight.
It is 170KHz, power 13KW that ultrasonic disperse condition, which is ultrasonic power, in step (5).
Room temperature curing epoxy composite material includes the raw material of following parts by weight meter: 96 parts of epoxy resin, functional material 5
Part, 14 parts of diluent, 35 parts of curing agent, 1.8 parts of antioxidant and 2.2 parts of silane coupling agent.
Silane coupling agent is gamma-aminopropyl-triethoxy-silane.
Diluent is resorcinolformaldehyde resin.
Antioxidant is β-((3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
Curing agent is methylol diethylenetriamine.
Comparative example 1: except any functional material is not added with, remaining raw material and preparation method are same as Example 1；
Comparative example 2: the step of functional material surface is modified in removing step (2), step (3) and step (4),
It is remaining to prepare raw material and preparation method is same as Example 1；
By room temperature curing ring made from room temperature curing epoxy composite material made from embodiment 1-5 and comparative example 1-2
Epoxy resin composite material is tested for the property, as a result such as the following table 1:
Table 1:
| Test group | Impact strength (kJ/m2) | Tensile strength (MPa) | Bending strength (MPa) |
| Embodiment 1 | 55.6 | 52.9 | 94.1 |
| Embodiment 2 | 54.8 | 51.3 | 91.2 |
| Embodiment 3 | 56.1 | 53.8 | 96.1 |
| Embodiment 4 | 56.9 | 54.2 | 97.5 |
| Embodiment 5 | 57.4 | 55.6 | 97.8 |
| Comparative example 1 | 28.4 | 26.8 | 74.1 |
| Comparative example 2 | 35.7 | 33.4 | 78.6 |
Analyze above-mentioned 1 data of table:
The data of comparative example 1 and comparative example 1, embodiment 1 are improved relative to the impact strength of comparative example 1
95.8%, tensile strength improves 97.4%, and bending strength improves 27.0%, therefore it can be concluded that adds functional material to room
The available significant raising of the comprehensive mechanical property of warm cured epoxy resin composite material.
The data of comparative example 1 and comparative example 2, embodiment 1 are improved relative to the impact strength of comparative example 2
55.7%, tensile strength improves 58.4%, and bending strength improves 19.7%, therefore, it can be deduced that by calcining and silane
Inorganic particulate after coupling agent integrated treatment is substantially better than any processing of surface free to the improvement of the mechanical property of epoxy resin
Effect of the inorganic particulate to epoxy resin.
In conclusion the invention has the following advantages that
(1) the method for the present invention uses silane coupling agent modified to inorganic filler progress surface first, then will be modified
Functional material compounded with curing agent, diluent, oxidant and epoxy resin, it is former to pass through technological parameter in preparation method and component
Associated effect between material, the epoxy resin composite material of preparation have good mechanical property and thermal stability.
(2) contain nano-titanium dioxide, nano zine oxide and nano silica, nanoparticle in functional material of the present invention
Toughening have particle specific surface area it is big, high surface activity, particle surface dangling bonds abundant easily with epoxy resin-base formationization
Learn key the features such as, can effectively reinforced epoxy toughness, but nanoparticle there are surface energy height, one reunite lack
Point, therefore, to reduce reunion, improving particle dispersibility, the present invention uses silane coupling agent to carry out inorganic nano-particle first
Surface is modified, can effectively reduce the reunion of particle, while enhancing the compatibility of inorganic particulate and epoxy resin.
(3) it joined suitable silane coupling agent again when material of the present invention in step (6) mixes, not only can be improved
Compatibility between organic phase and inorganic phase, while the flexible segment that silane coupling agent itself contains, can be enhanced, composite material
Impact strength.
(4) preparation method raw material sources of the present invention are extensive, and preparation method is simple, unharmful substance discharge, safety and environmental protection.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of room temperature curing epoxy composite material, which comprises the following steps:
(1) 1-2 parts of nano-titanium dioxide, 1-2 parts of nano zine oxide, 0.4-0.8 parts of white carbon black and nanometer are weighed according to parts by weight
3-5 parts of silica, nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are individually positioned in 150-170
Degree Celsius baking oven in, dry 12 hours；
(2) nano-titanium dioxide, nano zine oxide, white carbon black and nano silica are mixed and is added in calcining furnace in 300-
After being calcined 1-2 hours under 400 degrees Celsius, it is added in ethanol water, is uniformly mixed, suitable silane coupling agent is added,
Heating water bath is to 68-75 degrees Celsius, with 600-800 revs/min of speed, after constant temperature stirs 2 hours；
(3) mixed liquor made from step (2) is added in centrifuge tube with 5000-6000 revs/min of speed, carries out centrifugation layering
5-10 minutes, supernatant liquid is removed, lower layer's solid particle is added to absolute ethanol, at 500-600W, 8-12KHz, carried out
Ultrasonic cleaning 15-20 minutes, filtering after filtrate is rinsed 3-5 times with deionized water, under 60-70 degrees Celsius, are dried in vacuo 20-
25 hours；
(4) filtrate made from step (3) is put into ball mill, controls drum's speed of rotation at 600-1000 revs/min, grinds 10
Hour, obtain functional material；
(5) functional stuffing made from step (4) is added according to 1g:2 milliliters of solid-liquid ratio adding into acetone, under 500-800W,
Mixing acetone soln was added in epoxy resin, is stirred with 1600-2000 revs/min of speed after 8-15 minutes by ultrasonic treatment
After mixing 20-28 minutes, 70-80 degrees Celsius is warming up to after lower ultrasonic disperse 2-4 hours, and temperature control is to 70 degrees Celsius, heating water bath 10-
12 hours, extra acetone is removed, obtains epoxy resin-functional material mixed liquor；
(6) diluent, antioxidant and silane coupling agent are added into epoxy resin made from step (5)-functional material mixed liquor,
It after being stirred 20-25 minutes with 1200-1800 revs/min of speed, vacuumizes, deaerates 30-50 minutes；
(7) curing agent is added in the mixture in step (6), is uniformly mixed with 2000-2500 revs/min of speed
Afterwards, it injects in Teflon mould, places solidification 5-7 days at room temperature to get the room temperature curing epoxy composite material.
2. the preparation method of room temperature curing epoxy composite material according to claim 1, which is characterized in that the second
Alcohol solution is that dehydrated alcohol and deionized water are formed according to volume ratio 4:1 mixed preparing.
3. the preparation method of room temperature curing epoxy composite material according to claim 1, which is characterized in that the step
Suddenly the additional amount of silane coupling agent is nano-titanium dioxide, nano zine oxide, white carbon black and nano silica total weight in (2)
4-7%.
4. the preparation method of room temperature curing epoxy composite material according to claim 1, which is characterized in that the step
Suddenly it is 120-200KHz, power 7-15KW that ultrasonic disperse condition, which is ultrasonic power, in (5).
5. the preparation method of room temperature curing epoxy composite material according to claim 1, which is characterized in that the room
Warm cured epoxy resin composite material includes the raw material of following parts by weight meter: 90-100 parts of epoxy resin, 3-8 parts of functional material,
10-20 parts of diluent, 30-40 parts of curing agent, 1.2-2.5 parts of antioxidant and 1-4 parts of silane coupling agent.
6. the preparation method of room temperature curing epoxy composite material according to claim 5, which is characterized in that the room
Warm cured epoxy resin composite material includes the raw material of following parts by weight meter: 96 parts of epoxy resin, 5 parts of functional material, diluent
14 parts, 35 parts of curing agent, 1.8 parts of antioxidant and 2.2 parts of silane coupling agent.
7. the preparation method of room temperature curing epoxy composite material according to claim 3 or 5, which is characterized in that institute
Stating silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-(methyl
Acryloxy) one or more of propyl trimethoxy silicane combines.
8. the preparation method of room temperature curing epoxy composite material according to claim 5, which is characterized in that described dilute
Releasing agent is allyl alkyl glycidol ether, phenyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether and isophthalic
One or more of diphenol diglycidyl ether combines.
9. the preparation method of room temperature curing epoxy composite material according to claim 5, which is characterized in that described anti-
Oxygen agent be β-((3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, three (2,4- dibutyl phenyl ester) phosphites,
One or more of triphenyl phosphite and pentaerythritol bis-phosphite two (octadecyl alcolol) ester combine.
10. the preparation method of room temperature curing epoxy composite material according to claim 5, which is characterized in that described
Curing agent is diethylenetriamine, triethylene tetramine, tetraethylenepentamine, hexamethylene diamine, methylol ethylenediamine, methylol diethylenetriamine
It is combined with one or more of beta-hydroxyethyl ethylenediamine.
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| CN111701831A (en) * | 2020-07-03 | 2020-09-25 | 合肥学院 | Preparation method of hydrophobic silica nanoparticle modified epoxy resin anticorrosive film coated on carbon steel |
| CN112063109A (en) * | 2020-09-11 | 2020-12-11 | 石家庄元鼎新材料有限公司 | Nano zinc oxide/artemisia yellow-wormwood volatile oil/epoxy resin high-performance antibacterial material and preparation method thereof |
| CN113088038A (en) * | 2021-04-23 | 2021-07-09 | 钟华明 | Synthetic resin with high hardness and corrosion resistance and preparation method thereof |
| CN114106512A (en) * | 2021-09-09 | 2022-03-01 | 周琬彤 | Preparation method of epoxy resin-based composite material for curved surface and flow channel of hydraulic element |
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| CN113088038A (en) * | 2021-04-23 | 2021-07-09 | 钟华明 | Synthetic resin with high hardness and corrosion resistance and preparation method thereof |
| CN114106512A (en) * | 2021-09-09 | 2022-03-01 | 周琬彤 | Preparation method of epoxy resin-based composite material for curved surface and flow channel of hydraulic element |
| CN114513099A (en) * | 2022-03-02 | 2022-05-17 | 卓尔博（宁波）精密机电股份有限公司 | Preparation process of soft magnetic composite material stator |
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Application publication date: 20190205 |