CN102516714A - Preparation method of nano epoxy resin composite material - Google Patents
Preparation method of nano epoxy resin composite material Download PDFInfo
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- CN102516714A CN102516714A CN2011103865442A CN201110386544A CN102516714A CN 102516714 A CN102516714 A CN 102516714A CN 2011103865442 A CN2011103865442 A CN 2011103865442A CN 201110386544 A CN201110386544 A CN 201110386544A CN 102516714 A CN102516714 A CN 102516714A
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Abstract
The invention relates to a preparation method of a nano epoxy resin composite material. The preparation method of the nano epoxy resin composite material is characterized by comprising the following steps of: 1) pre-processing raw materials; 2) extracting a starch nano-crystal under an effect of a sulfuric acid solution so as to obtain white cotton-shaped starch nano-crystal; 3) melting and blending pre-processed liquid epoxy resin and the starch nano-crystal, so as to obtain an epoxy resin/starch nano-crystal composite; 4) adding a curing agent into the epoxy resin/starch nano-crystal composite so as to obtain an epoxy resin/starch nano-crystal prepolymer; and 5) curing and forming the epoxy resin/starch nano-crystal prepolymer, and pouring the epoxy resin/starch nano-crystal prepolymer into a die to form, so as to obtain the nanometer epoxy resin composite material. The preparation method disclosed by the invention has the advantages of simple process, low cost and environmental friendless.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy resin nano composites, belong to technical field of novel materials.
Background technology
Nanometer starch crystal is the important a member of gathering in the polysaccharide nano-crystalline, size between tens to more than 100 nanometers, mainly by crystal form preferably pulullan form, can make through the method for hydrolyzed starch grain.Under acid, alkali or ultransonic effect; Unbodied pulullan at first is hydrolyzed in the starch small grain; Retain molecular arrangement more neatly, crystal form pulullan zone is desired laminated structure nanometer starch crystal closely, and hydrolysis method is the topmost method of current preparation nanometer starch crystal.The nanometer starch crystal good biocompatibility, biological renewable and degraded, intensity is big, and modulus is high, and density is little, and the source is abundant, and cost is low, on a large scale high quality of production; The equivalent material that is used as traditional inorganic nano-particle with the specificity of its excellent performance and relative inorganic nano-particle; Have much and be widely used in the various synthetic trend that reach in the natural polymer based nano composite material; In research and development biodegradable nano composite material, become the focus of nano material and biological material field crossing research.
Nanometer starch crystal is applied in the nano composite material; Can promote the optimization utilization and the high value of biological material to transform; Environment deposition drawback when avoiding inorganic nano-particle to use has given matrix material certain biodegradability simultaneously, meets the strategy of sustainable development.The conventional epoxies based nano composite material mostly adopts inorganic nano-particle, though some performances are improved, matrix material exists degraded difficulty, density to reach the high deficiency of cost more greatly.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of epoxy resin nano composites, this method technology is simple, environmental protection.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is: a kind of preparation method of epoxy resin nano composites is characterized in that it comprises following steps:
1) pre-treatment of raw material: liquid-state epoxy resin vacuum-drying under 50～100 ℃ condition dewaters, up to liquid-state epoxy resin become clarification and do not have bubble and emerge till, obtain pretreated liquid-state epoxy resin;
Before using, solidifying agent, makes the purity >=95wt% of solidifying agent through the underpressure distillation purification process;
2) through the extraction of the nanometer starch crystal of sulphuric acid soln effect: press H
2SO
4The proportioning of solution, starch, deionized water is 250mL: 36.00g: 100mL, chooses 3.16mol/L H
2SO
4Solution, starch and deionized water, subsequent use;
Under stirring condition, starch joined 3.16mol/L H is housed
2SO
4In the container of solution; Container is placed 40 ℃ oil bath pan, and mechanical stirring 5d under the speed of 100rpm obtains white suspension liquid A;
Suspension liquid A is centrifuge washing extremely approaching neutral (pH is 6～8) again, and goes upper strata suspension-s and sedimentary upper part (half deposition), obtains the more closely knit white solid B of bottom settlings;
White solid B is mixed with deionized water, the back dialysis 1d that stirs (my god), rapid freezing and vacuum lyophilization after packing obtains the flower-shaped nanometer starch crystal of white cotton again;
3) the melt blending process of pretreated liquid-state epoxy resin and nanometer starch crystal: by pretreated liquid-state epoxy resin quality: the quality of nanometer starch crystal is that 100: 0.01～95 proportioning joins raw material in the container (like round-bottomed flask); And container placed 60～90 ℃ oil bath pan; 100～1000rpm stirs 15～60min down; Ultrasonic again 15～60min, ultrasonic postcooling get epoxy resin/nanometer starch crystal mixture to room temperature;
4) the solidifying agent adition process of epoxy resin/nanometer starch crystal mixture: epoxy resin/nanometer starch crystal mixture is inserted in the mixing vessel; At room temperature add with step 3) in the solidifying agent of the corresponding stoichiometric ratio of pretreated liquid-state epoxy resin quality (quality according to liquid-state epoxy resin in the step 3) is confirmed); Stir 5～30min and make it thorough mixing, obtain prepolymer; Prepolymer at room temperature vacuumize degassing 5～30min (vacuum tightness is-0.1MPa),, obtain epoxy resin/nanometer starch crystal prepolymer to remove air and a small amount of steam in the prepolymer;
5) the curing molding process of epoxy resin/nanometer starch crystal prepolymer: with mould and die preheating to 20～40 ℃; Subsequently epoxy resin/nanometer starch crystal prepolymer is poured in the mould; Mould is together vacuumized the 5～30min that outgases again [vacuum tightness is-0.1MPa ("-" expression≤)] together with epoxy resin/nanometer starch crystal prepolymer; Solidify 2～5d under the prepolymer room temperature after the degassing, 90～120 ℃ of after fixing 2～8h obtain epoxy resin nano composites (product) again.
Described liquid-state epoxy resin is that any one or they in liquid-state epoxy resin E54, E51, E44, E42, E35, E31, the E20 epoxy resin that equals to be in a liquid state under 50～100 ℃ of heating conditions are by the mixture of any proportioning.
Solidifying agent can be diethylenetriamine, triethylene tetramine, TEPA or diethylin in the aliphatic polyamines such as propylamine any.
Described starch is any one in pea starch, yam starch, green starch, tapioca(flour), sweet potato starch, sweet potato starch, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch, the W-Gum etc.
Described ultrasonic frequency is 40KHz, and power is 100W.
Epoxy resin nano composites of the present invention adopts the nanometer starch crystal wild phase of melt blending technology and biomass simultaneously; The phenomenons such as environment deposition of not only having avoided environment that the small molecules volatile organic solvent of traditional use causes and human harm and inorganic nano-particle to cause; And stir and ultrasonic control of process condition such as auxiliary through heating and melting; Reached the homodisperse of nanometer starch crystal in epoxy matrix material; Thereby the collaborative reinforced effects of the optimization of microfacies structure and each component macroscopic property in the realization matrix material has significantly improved flexural strength and has ruptured crooked deformation.Expectation replaces traditional inorganic nano-particle will give epoxy resin nano composites significant more lighting nanometer starch crystal; Particularly be applied to the vehicles and the space flight equipment can be than the reduction overall weight of limits when this matrix material; Energy efficient is than less contamination; Epoxy resin nano composites after this modification be except being competent in engineering plastics, expectation can also wide popularization and application in fields such as sizing agent and coating.
The present invention adopts the wild phase of nanometer starch crystal as epoxy resin, and the difference of starch material kind is not only given the variety and the alternative of its nano-scale, has also given the designability of matrix material microfacies structure; The high-specific surface area of nanometer starch crystal, high surface, HS and high firmness also give matrix material excellent mechanical property and dimensional stability; Simultaneously because characteristic such as biodegradable, the density of nanometer starch crystal is little also can be given certain degradation property of matrix material and lighter quality.
The nanometer wild phase of resulting epoxy resin nano composites is biological renewable and degraded; Light weight; Low toxicity, pollution-free and standing stock are abundant, and because of the difference in nanometer starch crystal source; Character such as nanometer starch crystal size, pattern and specific surface area that extraction obtains are various, and this provides very big selectivity for the selection of nanometer starch crystal.
The present invention adopts the technology of heating and melting blend, reduces or avoided the use of small molecules volatile solvent; Ultrasonic auxiliary in heated and stirred, can promote the further dispersion of nanometer starch crystal in epoxy matrix material, realized the collaborative reinforced effects of each component of epoxy resin nano composites, still be the strong guarantee of constant product quality property simultaneously.
The present invention can utilize starch material bio-regeneration and degraded, characteristics that standing stock are abundant, nontoxic fully, and theories such as the green of performance technology, environmental protection, meets sustainable development view; The extensive application of nanometer starch crystal in epoxy resin modification also can improve additional value of farm products, increases national income.Estimate that the prepared epoxy resin nano composites of this invention can be widely used in engineering plastics, and be applied to fields such as sizing agent and coating.
The invention has the beneficial effects as follows: this method technology is simple, low-cost, environmental protection.
Description of drawings
Fig. 1 is the nanocrystalline transmission electron microscope picture of pea starch.
Fig. 2 is the photo of the three-point bending batten of epoxy resin nano composites.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
A kind of preparation method of epoxy resin nano composites, it comprises following steps:
1) pre-treatment of raw material: liquid epoxy resin E51 (oxirane value is between 0.48～0.52mol/100g) vacuum-drying under 50 ℃ condition dewater (vacuum tightness for-0.1MPa); The vacuum-drying time of dewatering is 120min, up to liquid-state epoxy resin become clarification and do not have bubble and emerge till;
Before using, diethylenetriamine (solidifying agent), makes the purity >=95wt% of solidifying agent through underpressure distillation purification process (collecting the cut about 85～90 ℃ under the vacuum tightness of 0.098MPa);
2) through the extraction of the nanometer starch crystal of sulphuric acid soln effect: press H
2SO
4The proportioning of solution, pea starch, deionized water is 250mL: 36.00g: 100mL, chooses 3.16mol/L H
2SO
4Solution, pea starch and deionized water, subsequent use;
Under stirring condition, pea starch joined 3.16mol/L H is housed
2SO
4In the container of solution; Container is placed 40 ℃ oil bath pan, and mechanical stirring 5d under the speed of 100rpm obtains white suspension liquid A;
Suspension liquid A is centrifuge washing extremely approaching neutral (pH is 6～8) again, and goes upper strata suspension-s and sedimentary upper part (half deposition), obtains the more closely knit white solid B of bottom settlings;
White solid B is mixed with deionized water, the back dialysis 1d that stirs (my god), rapid freezing and vacuum lyophilization after packing obtains the flower-shaped nanometer starch crystal of white cotton again;
3) the melt blending process of pretreated liquid-state epoxy resin and nanometer starch crystal: by pretreated liquid-state epoxy resin quality: the quality of nanometer starch crystal is that 100: 0.5 proportioning joins raw material in the container (like round-bottomed flask); And container placed 75 ℃ oil bath pan; 350rpm stirs 15min down; Ultrasonic again 15min, ultrasonic postcooling get epoxy resin/nanometer starch crystal mixture to room temperature;
4) the solidifying agent adition process of epoxy resin/nanometer starch crystal mixture: epoxy resin/nanometer starch crystal mixture is inserted in the mixing vessel; At room temperature add with step 3) in the solidifying agent of the corresponding stoichiometric ratio of pretreated liquid-state epoxy resin quality (quality according to liquid-state epoxy resin in the step 3) is confirmed); Stir 5～30min and make it thorough mixing, obtain prepolymer; Prepolymer at room temperature vacuumize degassing 5min (vacuum tightness is-0.1MPa),, obtain epoxy resin/nanometer starch crystal prepolymer to remove air and a small amount of steam in the prepolymer;
5) the curing molding process of epoxy resin/nanometer starch crystal prepolymer: with mould and die preheating to 30 ℃; Subsequently epoxy resin/nanometer starch crystal prepolymer is poured in the mould; With mould together with epoxy resin/nanometer starch crystal prepolymer together vacuumize the 5min that outgases again (vacuum tightness for-0.1MPa); Solidify 2d under the prepolymer room temperature after the degassing, 100 ℃ of after fixing 3h obtain epoxy resin nano composites (product) again.
Epoxy resin nano composites (product) is carried out the test of flexural strength, and the result sees table 1.The testing standard of flexural strength is GB/T 2567-2008.
Embodiment 2:
A kind of preparation method of epoxy resin nano composites, it comprises following steps:
1) pre-treatment of raw material: bisphenol A type epoxy resin E51 vacuum-drying under 100 ℃ condition dewater (vacuum tightness for-0.1MPa), the vacuum-drying time of dewatering is 180min, up to liquid-state epoxy resin become clarification and do not have bubble and emerge till;
Before using, diethylenetriamine (solidifying agent), makes the purity >=95wt% of solidifying agent through underpressure distillation purification process (collecting the cut about 85～90 ℃ under the vacuum tightness of 0.098MPa); Solidifying agent can be diethylenetriamine, triethylene tetramine, TEPA or diethylin in the aliphatic polyamines such as propylamine any.
2) at first prepare 250mL 3.16mol/L H
2SO
4Solution when treating that the sulphuric acid soln temperature drops to room temperature, is transferred to it in round-bottomed flask of 500mL.Take by weighing 36.00g exsiccant pea starch raw material, under stirring condition, it is joined the above-mentioned 3.16mol/L of being equipped with H
2SO
4In the 500mL round-bottomed flask of solution.Round-bottomed flask is placed 40 ℃ oil bath pan, and mechanical stirring 5d under the speed of 100rpm obtains white suspension liquid A.Suspension liquid A is centrifuge washing extremely approaching neutral (pH is 6～8) again, and goes upper strata suspension-s and sedimentary upper part (half deposition), obtains the more closely knit white solid B of bottom settlings.With white solid B mixing 100mL deionized water, the back dialysis 1d that stirs, rapid freezing and vacuum lyophilization after packing obtains the flower-shaped nanometer starch crystal of white cotton again.
3) the melt blending process of pretreated liquid-state epoxy resin and nanometer starch crystal: by pretreated liquid-state epoxy resin quality: the quality of nanometer starch crystal is that 100: 1.0 proportioning joins raw material in the container (like round-bottomed flask); And container placed 60 ℃ oil bath pan; 1000rpm stirs 30min down; Ultrasonic again 15min, ultrasonic postcooling get epoxy resin/nanometer starch crystal mixture to room temperature;
4) the solidifying agent adition process of epoxy resin/nanometer starch crystal mixture: epoxy resin/nanometer starch crystal mixture is inserted in the mixing vessel; At room temperature the solidifying agent of the corresponding stoichiometric ratio of pretreated liquid-state epoxy resin quality (quality according to liquid-state epoxy resin in the step 3) is confirmed) stirs 5min and makes it thorough mixing in adding and the step 3), obtains prepolymer; Prepolymer at room temperature vacuumize degassing 5min (vacuum tightness is-0.1MPa),, obtain epoxy resin/nanometer starch crystal prepolymer to remove air and a small amount of steam in the prepolymer;
5) the curing molding process of epoxy resin/nanometer starch crystal prepolymer: with mould and die preheating to 30 ℃; Subsequently epoxy resin/nanometer starch crystal prepolymer is poured in the mould; With mould together with epoxy resin/nanometer starch crystal prepolymer together vacuumize the 5min that outgases again (vacuum tightness for-0.1MPa); Solidify 2d under the prepolymer room temperature after the degassing, 100 ℃ of after fixing 2h obtain epoxy resin nano composites (product) again.
Embodiment 3:
With embodiment 1, with the epoxy resin E51 in the 3rd step { being step 3) }: the mass ratio of nanometer starch crystal changes 100: 1.5 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 60 ℃, 800rpm, 50min and 30min respectively into; The churning time and the vacuum outgas time in the 4th step become 10min and 10min respectively; The degassing time in the 5th step changes 10min into, solidifies 3d under the room temperature, 90 ℃ of after fixing 8h.
Embodiment 4:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 2.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 70 ℃, 700rpm, 60min and 40min respectively into; The churning time and the vacuum outgas time in the 4th step become 15min and 15min respectively; The degassing time in the 5th step changes 15min into, solidifies 3d under the room temperature, 110 ℃ of after fixing 6h.
Embodiment 5:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 3.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 80 ℃, 400rpm, 50min and 60min respectively into; The churning time and the vacuum outgas time in the 4th step become 20min and 15min respectively; The degassing time in the 5th step changes 15min into, solidifies 4d under the room temperature, 110 ℃ of after fixing 7h.
Embodiment 6:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 5.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 90 ℃, 300rpm, 50min and 60min respectively into; The churning time and the vacuum outgas time in the 4th step become 20min and 20min respectively; The degassing time in the 5th step changes 20min into, solidifies 5d under the room temperature, 90 ℃ of after fixing 4h.
Embodiment 7:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 0.01 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 80 ℃, 100rpm, 60min and 60min respectively into; The churning time and the vacuum outgas time in the 4th step become 20min and 30min respectively; The degassing time in the 5th step changes 25min into, solidifies 5d under the room temperature, 120 ℃ of after fixing 2h.
Embodiment 8:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 10.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 90 ℃, 200rpm, 50min and 40min respectively into; The churning time and the vacuum outgas time in the 4th step become 20min and 20min respectively; The degassing time in the 5th step changes 25min into, solidifies 5d under the room temperature, 90 ℃ of after fixing 8h.
Embodiment 9:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 30.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 80 ℃, 200rpm, 50min and 40min respectively into; The churning time and the vacuum outgas time in the 4th step become 25min and 30min respectively; The degassing time in the 5th step changes 30min into, solidifies 5d under the room temperature, 90 ℃ of after fixing 8h.
Embodiment 10:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 50.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 80 ℃, 200rpm, 50min and 40min respectively into; The churning time and the vacuum outgas time in the 4th step become 25min and 30min respectively; The degassing time in the 5th step changes 30min into, solidifies 5d under the room temperature, 90 ℃ of after fixing 8h.
Embodiment 11:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 70.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 80 ℃, 200rpm, 50min and 50min respectively into; The churning time and the vacuum outgas time in the 4th step become 30min and 25min respectively; The degassing time in the 5th step changes 30min into, solidifies 4d under the room temperature, 120 ℃ of after fixing 3h.
Embodiment 12:
With embodiment 1, with the epoxy resin E51 in the 3rd step: the mass ratio of nanometer starch crystal changes 100: 95.0 into, and oil bath temperature, stir speed (S.S.), churning time and ultrasonic time change 90 ℃, 100rpm, 50min and 60min respectively into; The churning time and the vacuum outgas time in the 4th step become 30min and 30min respectively; The degassing time in the 5th step changes 30min into, solidifies 4d under the room temperature, 90 ℃ of after fixing 8h.
The mechanical property of the nanocrystalline modified epoxy resin of table 1 pea starch nano composite material
| Embodiment | Content/the wt% of nanometer starch crystal | б f/MPa | ε/％ | E f/MPa |
| With reference to embodiment 1 | 0.0 | 85.68 | 3.62 | 2717.31 |
| Embodiment 1 | 0.5 | 88.90 | 4.25 | 2513.03 |
| Embodiment 2 | 1.0 | 91.27 | 4.83 | 2496.33 |
| Embodiment 3 | 1.5 | 94.18 | 4.26 | 2691.14 |
| Embodiment 4 | 2.0 | 90.55 | 4.01 | 2740.78 |
| Embodiment 5 | 3.0 | 87.93 | 3.90 | 2756.68 |
| Embodiment 6 | 5.0 | 78.39 | 3.23 | 2768.68 |
| Embodiment 7 | 10.0 | 65.17 | 2.39 | 2951.25 |
Table 1 explanation flexural strength (б of the present invention
f/ MPa) reaching requirement, the effect of illustrative embodiment 2～4 is best.
Each cited raw material of the present invention can both be realized the present invention; The bound value and the interval value thereof of each raw material can both be realized the present invention; The bound value of processing parameter of the present invention (like temperature, time and rotating speed etc.) with and interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (4)
1. the preparation method of an epoxy resin nano composites is characterized in that it comprises following steps:
1) pre-treatment of raw material: liquid-state epoxy resin vacuum-drying under 50～100 ℃ condition dewaters, up to liquid-state epoxy resin become clarification and do not have bubble and emerge till, obtain pretreated liquid-state epoxy resin;
Before using, solidifying agent, makes the purity >=95wt% of solidifying agent through the underpressure distillation purification process;
2) through the extraction of the nanometer starch crystal of sulphuric acid soln effect: press H
2SO
4The proportioning of solution, starch, deionized water is 250mL: 36.00g: 100mL, chooses 3.16mol/L H
2SO
4Solution, starch and deionized water, subsequent use;
Under stirring condition, starch joined 3.16mol/L H is housed
2SO
4In the container of solution; Container is placed 40 ℃ oil bath pan, and mechanical stirring 5d under the speed of 100rpm obtains white suspension liquid A;
Suspension liquid A centrifuge washing again is extremely approaching neutral, and goes upper strata suspension-s and sedimentary upper part, obtains the more closely knit white solid B of bottom settlings;
White solid B is mixed with deionized water, the back dialysis 1d that stirs, rapid freezing and vacuum lyophilization after packing obtains the flower-shaped nanometer starch crystal of white cotton again;
3) the melt blending process of pretreated liquid-state epoxy resin and nanometer starch crystal: by pretreated liquid-state epoxy resin quality: the quality of nanometer starch crystal is that 100: 0.01～95 proportioning joins raw material in the container; And container placed 60～90 ℃ oil bath pan; 100～1000rpm stirs 15～60min down; Ultrasonic again 15～60min, ultrasonic postcooling get epoxy resin/nanometer starch crystal mixture to room temperature;
4) the solidifying agent adition process of epoxy resin/nanometer starch crystal mixture: epoxy resin/nanometer starch crystal mixture is inserted in the mixing vessel; At room temperature add with step 3) in the solidifying agent of the corresponding stoichiometric ratio of pretreated liquid-state epoxy resin quality; Stir 5～30min and make it thorough mixing, obtain prepolymer; Prepolymer at room temperature vacuumize degassing 5～30min obtains epoxy resin/nanometer starch crystal prepolymer to remove air and a small amount of steam in the prepolymer;
5) the curing molding process of epoxy resin/nanometer starch crystal prepolymer: with mould and die preheating to 20～40 ℃; Subsequently epoxy resin/nanometer starch crystal prepolymer is poured in the mould; Mould is together vacuumized the 5～30min that outgases again together with epoxy resin/nanometer starch crystal prepolymer; Solidify 2～5d under the prepolymer room temperature after the degassing, 90～120 ℃ of after fixing 2～8h obtain epoxy resin nano composites again.
2. the preparation method of a kind of epoxy resin nano composites according to claim 1 is characterized in that: described liquid-state epoxy resin is that any one or they in the epoxy resin that under heating condition, is in a liquid state of E54, E51, E44, E42, E35, E31, E20 are by the mixture of any proportioning.
3. the preparation method of a kind of epoxy resin nano composites according to claim 1, it is characterized in that: solidifying agent can be that diethylenetriamine, triethylene tetramine, TEPA or diethylin are for propylamine.
4. the preparation method of a kind of epoxy resin nano composites according to claim 1, it is characterized in that: described starch is any one in pea starch, yam starch, green starch, tapioca(flour), sweet potato starch, sweet potato starch, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch, the W-Gum.
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| CN103435705A (en) * | 2013-08-14 | 2013-12-11 | 江南大学 | Method for preparing starch nanocrystal |
| CN110283426A (en) * | 2019-07-11 | 2019-09-27 | 江南大学 | A kind of bio-based source degradable starch filling epoxy resin composite material and preparation method thereof |
| CN110790519A (en) * | 2019-12-20 | 2020-02-14 | 内江华原电子材料有限公司 | Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof |
| CN113214605A (en) * | 2021-06-28 | 2021-08-06 | 安徽绿洲危险废物综合利用有限公司 | Method for preparing epoxy resin composite material from circuit board reclaimed materials |
| CN114316550A (en) * | 2022-01-29 | 2022-04-12 | 清华大学 | Resin and preparation method thereof |
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| CN103435705A (en) * | 2013-08-14 | 2013-12-11 | 江南大学 | Method for preparing starch nanocrystal |
| CN103435705B (en) * | 2013-08-14 | 2015-07-08 | 江南大学 | Method for preparing starch nanocrystal |
| CN110283426A (en) * | 2019-07-11 | 2019-09-27 | 江南大学 | A kind of bio-based source degradable starch filling epoxy resin composite material and preparation method thereof |
| CN110283426B (en) * | 2019-07-11 | 2021-12-03 | 江南大学 | Bio-based degradable starch filled epoxy resin composite material and preparation method thereof |
| CN110790519A (en) * | 2019-12-20 | 2020-02-14 | 内江华原电子材料有限公司 | Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof |
| CN110790519B (en) * | 2019-12-20 | 2022-01-11 | 内江华原电子材料有限公司 | Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof |
| CN113214605A (en) * | 2021-06-28 | 2021-08-06 | 安徽绿洲危险废物综合利用有限公司 | Method for preparing epoxy resin composite material from circuit board reclaimed materials |
| CN113214605B (en) * | 2021-06-28 | 2022-05-31 | 安徽绿洲危险废物综合利用有限公司 | Method for preparing epoxy resin composite material from circuit board reclaimed materials |
| CN114316550A (en) * | 2022-01-29 | 2022-04-12 | 清华大学 | Resin and preparation method thereof |
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