CN105622984A - Core-shell rubber particle and epoxy resin complex thereof and preparation method - Google Patents
Core-shell rubber particle and epoxy resin complex thereof and preparation method Download PDFInfo
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- CN105622984A CN105622984A CN201610115221.2A CN201610115221A CN105622984A CN 105622984 A CN105622984 A CN 105622984A CN 201610115221 A CN201610115221 A CN 201610115221A CN 105622984 A CN105622984 A CN 105622984A
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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
- C08K9/10—Encapsulated ingredients
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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
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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Abstract
The invention discloses a submicron core-shell rubber particle which comprises a silicon dioxide spherical particle inner core and an outer shell covering the surface of the inner core. The submicron core-shell rubber particle has the advantages of being high in degree of sphericity, uniform in size and small in particle size distribution. The submicron core-shell rubber particle is applied to strengthening and toughening of epoxy resin, and toughness and impact-resistance strength of the epoxy resin can be greatly improved.
Description
Technical field
The invention belongs to aqueous epoxy resins toughner field, particularly relate to epoxy resin composite and the preparation method of the two of a kind of submicron Core-shell rubber particles and activeness and quietness thereof.
Background technology
Epoxy resin is a kind of three-dimensional netted thermosetting polymer, is the material that a kind of fragility is very strong, and its toughening modifying is the important research content of polymer science and the fundamental research of material field and application and development, is all subject to extensive concern all the time. but adopt merely rubber or elastomerics or rigid particles that epoxy resin roughening is all also existed some shortcomings. for example, simple employing rubber or elastic body toughening epoxy resin, the addition content of rubber or elastomerics requires very high, usually the volume needing to reach more than 20wt% just can play toughening effect, like this, although impelling strength is improved, but this often causes the strength and modulus loss of material too many, and it is tough to adopt inorganic rigid particle that it carries out increasing, although the strength and modulus of material can not lose, but the toughness of material can not get improving substantially, and due to the poor compatibility of inorganic particulate and organic resin epoxy, usually can there is the problem that inorganic particulate cannot be dispersed in epoxy resin-base, particularly micro-or nano size Inorganic Fillers Filled epoxy-resin systems, owing to size of particles is little, there is very high surface energy, occurrence of large-area agglomeration very easily in the base, thus make epoxy resin produces bigger defect, like this, instead the toughness of epoxy resin is reduced, the enhancing of epoxy resin is tough with increasing becomes a kind of contradiction, restrict this product further to the development of more dominance energy.
Summary of the invention
In view of this, the submicron Core-shell rubber particles that object one side is to provide a kind of clad ratio height, size is even, shell thickness is consistent of the present invention and its preparation method, be to provide epoxy resin composite and its preparation method of the submicron Core-shell rubber particles activeness and quietness of a kind of high strength and high tenacity on the other hand.
In order to achieve the above object, on the one hand, the present invention provides a kind of submicron Core-shell rubber particles, it comprises spherical kernel, and it being coated on the outer shell of core surface, in spherical, nuclear diameter is 0.2��0.5 ��m, and outer shell is the multipolymer of butyl acrylate and glycidyl methacrylate, the monomer mass ratio of glycidyl methacrylate and butyl acrylate is 1:20��1:5, and shell mean thickness is 0.01��0.2 ��m.
Second aspect, the present invention provides the preparation method of the submicron Core-shell rubber particles described in first aspect, comprises the following steps:
Steps A, under 10��90 DEG C of conditions, the submicron silicon dioxide that application sol-gel method preparation evenly disperses, adopts silane coupling agent that it is carried out surface hydrophobicity modification, obtains hydrophobic nature submicron silicon dioxide;
Step B, under 40��98 DEG C of conditions, adopting pre-emulsification seed emulsion polymerization, the hydrophobic nature submicron silicon dioxide obtained taking steps A is as kernel, carry out with butyl acrylate and glycidyl methacrylate monomer being polymerized coated, obtain Core-shell rubber particles emulsion;
Step C, utilizes liquid nitrogen to carry out quick cooling curing step B gained core-shell particles emulsion and becomes ice, removes moisture and obtains submicron Core-shell rubber particles powder.
The third aspect, the present invention provides the epoxy resin composite adopting the submicron Core-shell rubber particles activeness and quietness described in first aspect present invention, described epoxy resin composite feed composition comprises epoxy resin, solidifying agent, submicron Core-shell rubber particles, wherein, described content of epoxy resin accounts for the 80��97% of feed composition gross weight, described hardener dose is the 3��8% of weight epoxy, and the consumption of submicron Core-shell rubber particles is the 3��25% of weight epoxy.
Fourth aspect, the present invention provides the preparation method of the epoxy resin composite of the submicron Core-shell rubber particles activeness and quietness of the third aspect, comprises the steps:
Step 1, preparation submicron Core-shell rubber particles, is dispersed in thinner, then is mixed with epoxy resin, obtains the epoxy resin compound prepolymer containing submicron Core-shell rubber particles of evenly dispersion;
Step 2, adds solidifying agent, is vented after being uniformly dispersed, and solidification, obtains final product.
The useful effect of the present invention is as follows: (1) this patent preparation-obtained submicron Core-shell rubber particles sphericity height, the feature that size is even, size distribution is little; (2) in the epoxy resin composite of the submicron Core-shell rubber particles activeness and quietness of the present invention, the soft interface that shell rubber molecular chain is substantially all in epoxy resin molecule segment contacts, toughening efficiency height, therefore, the same rubber content required for toughness increase rate is very high, more having both kernel is hard inorganic rigid particle, so, such mixture microtexture can maintain the modulus and intensity that even strengthen matrix; (3) the rubber shell of Core-shell rubber particles is designed to butyl acrylate and glycidyl methacrylate monomer carries out copolymerization, the epoxide group of this rubber molecule chain end can form covalent linkage with the hydroxyl of epoxy resin, epoxy group(ing) isoreactivity radical reaction, it is to increase the interface interaction between product and matrix; And owing to the kernel of Core-shell rubber particles is hard inorganic rigid particle, focal point of stress is formed when being subject to shock action, stress is carried out disperseing and conducting to matrix by the function served as bridge of the rubber molecular chain then closed by surface chemistry bond, impel matrix yielding deformation thus absorb a large amount of impact energys, increase substantially epoxy resin toughness; (4) in the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness of the present invention and preparation method, by adopting that liquid nitrogen quick freezing is shaping and lyophilize mode achieves the granulating of core-shell particles, avoid in emulsion breaking process adhesion between this type latex particle agglomerating, for the soft shell water based emulsion particle of stone evenly disperse to enter oiliness epoxy resin provides may; (5) in this mixture, toughner Core-shell rubber particles is in submicron-scale, evenly can be disperseed in epoxy resin-base by the dispersing technology step of the present invention, after product content reaches threshold value, coordination plasticizing between each increasing tough particle, increases substantially the resistance to impact shock of whole toughened system.
Accompanying drawing explanation
Fig. 1 is the impact fracture surface scanning electron microscope (SEM) photograph of the epoxy resin composite of the submicron Core-shell rubber particles activeness and quietness that the embodiment of the present invention 2 prepares.
Fig. 2 is the impact fracture surface scanning electron microscope (SEM) photograph of the epoxy resin composite that the embodiment of the present invention 4 prepares.
Embodiment
On the one hand, the present invention provides a kind of submicron Core-shell rubber particles, it comprises spherical kernel, and it is coated on the outer shell of core surface, in spherical, nuclear diameter is 0.2��0.5 ��m, outer shell is the monomer mass ratio of the multipolymer of butyl acrylate and glycidyl methacrylate, glycidyl methacrylate and butyl acrylate is 1:20��1:5, and shell mean thickness is 0.01��0.2 ��m.
Second aspect, the present invention provides the preparation method of the submicron Core-shell rubber particles described in first aspect, comprises the following steps:
Steps A, under 10��90 DEG C of conditions, the submicron silicon dioxide that application sol-gel method preparation evenly disperses, adopts silane coupling agent that it is carried out surface hydrophobicity modification, obtains hydrophobic nature submicron silicon dioxide;
Step B, under 40��98 DEG C of conditions, adopting pre-emulsification seed emulsion polymerization, the hydrophobic nature submicron silicon dioxide obtained taking steps A is as kernel, carry out with butyl acrylate and glycidyl methacrylate monomer being polymerized coated, obtain Core-shell rubber particles emulsion;
Step C, utilizes liquid nitrogen to carry out quick cooling curing step B gained core-shell particles emulsion and becomes ice, removes moisture and obtains submicron Core-shell rubber particles powder.
Preferably, in described steps A, the add-on of each component is by the metering of following volume parts:
Its preparation process comprises,
A1, getting segment polarity organic solvent, deionized water and promotor adds in reactor, 6��12min is stirred with 100��400 revs/min of rotating speeds, subsequently rotating speed is increased to 800��1500 revs/min, simultaneously measure residue polar organic solvent and tetraethoxy mix, then its mixed solution is dropped in reactor, in question response device mixed solution color by transparent become oyster white after rotating speed is reduced to 100��380 revs/min, keep this rotating speed reaction 2��8h;
A2, continuation is stirred and is adjusted the temperature to 40��50 DEG C, then adds silane coupling agent in reactor, keeps whipping temp reaction 12��30h, and oven dry, washing, again oven dry obtain hydrophobic nature submicron silicon dioxide.
Preferred further, described silane coupling agent is KH570.
Preferably, in described step B, the add-on of each component is by the metering of following mass fraction:
Its preparation process comprises,
B1, adds water, emulsifying agent and assistant for emulsifying agent at reactor, stirs 15��50min, obtains the aqueous solution of emulsifying agent;
B2, hydrophobic nature submicron silicon dioxide steps A obtained is added in the aqueous solution of the emulsifying agent that step B1 obtains, and adds butyl acrylate after being uniformly dispersed, and stirs evenly, lead to into nitrogen 15��35min, then being heated to 40��90 DEG C, the reaction times is 3��10h, drips and adds glycidyl methacrylate, temperature is brought up to 70��96 DEG C, continue reaction 0.5��2h again, regulate PH value to 7��8, obtain Core-shell rubber particles emulsion.
Preferred further, described emulsifying agent is sodium lauryl sulphate, Sodium palmityl sulfate, alkylpolyoxyethylene sodium sulfate, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.
Preferred further, described assistant for emulsifying agent is hexadecanol, n-Hexadecane, palmitic acid, cetylamine, stearyl alcohol or octadecane.
Preferred further, described initiator is hydrogen peroxide, benzoyl peroxide, benzoyl peroxide acetyl or dicumyl peroxide.
The third aspect, the present invention provides the epoxy resin composite adopting the submicron Core-shell rubber particles activeness and quietness described in first aspect present invention, described epoxy resin composite feed composition comprises epoxy resin, solidifying agent, submicron Core-shell rubber particles, wherein, described content of epoxy resin accounts for the 80��97% of feed composition gross weight, described hardener dose is the 3��8% of weight epoxy, and the consumption of submicron Core-shell rubber particles is the 3��25% of weight epoxy.
Preferably, described epoxy resin is bisphenol A type epoxy resin, and its molecular-weight average is 320��650, and epoxy equivalent (weight) is 184��198g/eq.
Preferably, described solidifying agent is one or several the mixture in m-xylene diamine, diamino diphenyl sulfone, diethylaminopropylamine, diethylenetriamine, isophorone diamine, 2-ethyl-4-methylimidazole.
Fourth aspect, the present invention provides the preparation method of the epoxy resin composite of the submicron Core-shell rubber particles activeness and quietness of the third aspect, comprises the steps:
Step 1, preparation submicron Core-shell rubber particles, is dispersed in thinner, then is mixed with epoxy resin, obtains the epoxy resin compound prepolymer containing submicron Core-shell rubber particles of evenly dispersion;
Step 2, adds solidifying agent, is vented after being uniformly dispersed, and solidification, obtains final product.
Preferably, described thinner is one or several the mixture in ethanol, butanone, butyl methacrylate, butyl acrylate, methyl methacrylate, glycidyl methacrylate, acetone.
Preferably, in described step 1, submicron Core-shell rubber particles is added in thinner, submicron Core-shell rubber particles and thinner weight ratio are 1:5��1:40, at 10��70 DEG C, ultrasonic disperse becomes molecule suspension, then this hanging drop is added in 10��45 DEG C of epoxy resin, drip while stirring and add, stir evenly, then keep reducing mixture temperature to room temperature under whipped state, vacuum suction device extracting thinner is adopted to emerge to solution surface bubble-free, obtain the epoxy resin compound prepolymer containing submicron Core-shell rubber particles of evenly dispersion.
Preferably, adopt mechanical stirrer that with the speed of 400��500 turns/min, the mixed solution obtained is stirred 5��10min after step 2 adds solidifying agent, then exhaust-gas disposal is placed in vacuum drying oven to fluid surface bubble-free, then build in mould, put into air dry oven, after being warming up to 60 DEG C, constant temperature 1.5��3h carries out Procuring, it is warming up to 150 DEG C of constant temperature 6��10h again and carries out deeply-curing, close baking oven switch naturally cooling after solidification, form the epoxy resin composite of activeness and quietness.
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Step 1, the preparation of submicron Core-shell rubber particles
A. measure 45 parts of ethanol, 25 parts of deionized waters and 10 parts of ammoniacal liquor to add in the reactor with magnetic stirring apparatus and stir 10 minutes with 300 revs/min of rotating speeds, subsequently rotating speed is increased to 1000 revs/min, measure 15 parts of ethanol and 4.5 parts of tetraethoxys mix simultaneously, then its mixed solution is dropped in reactor fast, in question response device mixed solution color by transparent become oyster white after rotating speed is reduced to 300 revs/min, keep this rotating speed reaction 4h; Continue to stir and adjust the temperature to 40��50 DEG C, then in system, add 2 parts of silane coupling agent KH570, keep whipping temp reaction 24h, after dispersion liquid be placed in 50 DEG C of air dry ovens dry to pulverulence, then the vacuum drying oven being placed in 80 DEG C dries 24h, again with ethanol centrifuge washing 3��4 times, finally dry and obtain modification hydrophobic nature submicron silicon dioxide particle;
B. the water of 400 parts is added at reactor, 1 part of sodium lauryl sulphate and 0.08 part of n-Hexadecane, stir 30min, the modification hydrophobic nature submicron silicon dioxide simultaneously prepared by 3 parts of above-mentioned steps A is added in the aqueous solution of aforementioned emulsifying agent ultrasonic 1 hour, transfer them to subsequently in reactor and stir 1h with 300 revs/min, then 2 parts of butyl acrylates and 0.04 portion of benzoyl peroxide mixed solution it is added dropwise to, lead to into nitrogen 30min after continuing to stir 1h, then 80 DEG C are started to be heated to, reaction times is 5h, drip and add function monomer 0.5 part of glycidyl methacrylate, temperature is brought up to 90 DEG C, continue reaction 1h again, PH value is regulated namely to obtain Core-shell rubber particles emulsion to 7-8,
C. the core-shell particles emulsion rapid condensation utilizing liquid nitrogen above-mentioned step B to be prepared becomes ice cake mass, then adopt freeze drier to take off except forming cotton-shaped powder by the water sublimed in above-mentioned ice cake mass to be namely exactly submicron Core-shell rubber particles, be positioned in refrigerator stand-by.
Utilizing the submicron Core-shell rubber particles prepared by above-mentioned steps, silicon-dioxide kernel mean sizes is 0.3 ��m, and shell mean thickness is 0.05 ��m.
Get submicron Core-shell rubber particles 2.5g prepared by above step, add in 15g acetone, then adopt 500W ultrasonic wave separating apparatus ultrasonic disperse to molecule suspension at 60 DEG C, this hanging drop is added the mixing of 50g bisphenol A type epoxy resin again, drip while stirring at 40 DEG C and add, stir evenly, then keep reducing mixture temperature to room temperature under whipped state, adopt vacuum suction device extracting thinner to emerge to solution surface bubble-free, obtain the epoxy resin compound prepolymer containing submicron Core-shell rubber particles of evenly dispersion. Wherein, described bisphenol A type epoxy resin adopts the CYD-128 of Yueyang petrochemical industry.
Step 2, contain to above-mentioned steps 1 gained the epoxy resin compound prepolymer of submicron Core-shell rubber particles is mixed and add 3g solidifying agent, adopt mechanical stirrer that with the speed of 400��500 turns/min, the mixed solution obtained is stirred 8min, then room temperature exhaust-gas disposal is placed in vacuum drying oven to solution surface bubble-free, then build to mould and put into air dry oven, after being warming up to 60 DEG C, constant temperature 2h carries out Procuring, then after being warming up to 150 DEG C, constant temperature 8h carries out deeply-curing, close baking oven switch after solidification and naturally cool to the epoxy resin cured product that room temperature forms activeness and quietness. wherein, described solidifying agent is 2-ethyl-4-methylimidazole.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, and difference is: in the preparation process of the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness, and submicron Core-shell rubber particles consumption is 4g, and acetone consumption is 24g.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, and difference is: in the preparation process of the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness, and submicron Core-shell rubber particles consumption is 5g, and acetone consumption is 30g.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, and difference is: in the preparation process of the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness, and submicron Core-shell rubber particles consumption is 0g, and acetone consumption is 0g.
Product test:
The notched Izod impact strength of the sample that testing example 1��4 prepares, modulus in flexure, result is as shown in table 1 below.
The Mechanics Performance Testing result of table 1 embodiment 1��4 sample
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Notched Izod impact strength (kJ/m2) | 1.84 | 2.28 | 2.15 | 0.97 |
| Modulus in flexure (GPa) | 2.80 | 2.85 | 2.87 | 2.62 |
By above result it will be seen that embodiment 4 pure epoxy resin cured article of comparing, the modulus that other embodiment submicron Core-shell rubber particles increase tough epoxy resin composite has a small amount of raising, and notched Izod impact strength increase rate is very big, most high growth 1.35 times.
The sample impact fracture surface scanning electron microscope (SEM) photograph of testing example 2 and embodiment 4, obtains photo described in Fig. 1 and Fig. 2 respectively. By above-mentioned 2 rupture cross section microcosmic pictures, we can find Fig. 2 pure epoxy resin rupture cross section flat smooth, presents typical case's brittle rupture phenomenon, and therefore shock strength is low; And the existence of Fig. 1 sub-micron Core-shell rubber particles becomes the concentrated point of shock stress, by rubber shell, shock stress is carried out dispersion to conduct, causing two-phase interface place matrix big area to there occurs bigger shear yielding, dissipated a large amount of impact energy, so that resistance to impact shock increases substantially.
Claims (10)
1. a submicron Core-shell rubber particles, it comprises spherical kernel, and it is coated on the outer shell of core surface, in spherical, nuclear diameter is 0.2��0.5 ��m, outer shell is the multipolymer of butyl acrylate and glycidyl methacrylate, the monomer mass ratio of glycidyl methacrylate and butyl acrylate is 1:20��1:5, and shell mean thickness is 0.01��0.2 ��m.
2. the preparation method of submicron Core-shell rubber particles as claimed in claim 1, it is characterised in that, comprise the following steps:
Steps A, under 10��90 DEG C of conditions, the submicron silicon dioxide that application sol-gel method preparation evenly disperses, adopts silane coupling agent that it is carried out surface hydrophobicity modification, obtains hydrophobic nature submicron silicon dioxide;
Step B, under 40��98 DEG C of conditions, adopting pre-emulsification seed emulsion polymerization, the hydrophobic nature submicron silicon dioxide obtained taking steps A is as kernel, carry out with butyl acrylate and glycidyl methacrylate monomer being polymerized coated, obtain Core-shell rubber particles emulsion;
Step C, utilizes liquid nitrogen to carry out quick cooling curing step B gained core-shell particles emulsion and becomes ice, removes moisture and obtains submicron Core-shell rubber particles powder.
3. the preparation method of submicron Core-shell rubber particles as claimed in claim 2, it is characterised in that, in described steps A, the add-on of each component is by the metering of following volume parts:
Its preparation process comprises,
A1, getting segment polarity organic solvent, deionized water and promotor adds in reactor, 6��12min is stirred with 100��400 revs/min of rotating speeds, subsequently rotating speed is increased to 800��1500 revs/min, simultaneously measure residue polar organic solvent and tetraethoxy mix, then its mixed solution is dropped in reactor, in question response device mixed solution color by transparent become oyster white after rotating speed is reduced to 100��380 revs/min, keep this rotating speed reaction 2��8h;
A2, continuation is stirred and is adjusted the temperature to 40��50 DEG C, then adds silane coupling agent in reactor, keeps whipping temp reaction 12��30h, and oven dry, washing, again oven dry obtain hydrophobic nature submicron silicon dioxide.
4. the preparation method of submicron Core-shell rubber particles as claimed in claim 2, it is characterised in that, in described step B, the add-on of each component is by the metering of following mass fraction:
Its preparation process comprises,
B1, adds water, emulsifying agent and assistant for emulsifying agent at reactor, stirs 15��50min, obtains the aqueous solution of emulsifying agent;
B2, hydrophobic nature submicron silicon dioxide steps A obtained is added in the aqueous solution of the emulsifying agent that step B1 obtains, and adds butyl acrylate after being uniformly dispersed, and stirs evenly, lead to into nitrogen 15��35min, then being heated to 40��90 DEG C, the reaction times is 3��10h, drips and adds glycidyl methacrylate, temperature is brought up to 70��96 DEG C, continue reaction 0.5��2h again, regulate PH value to 7��8, obtain Core-shell rubber particles emulsion.
5. the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness as claimed in claim 1, it is characterized in that: described epoxy resin composite feed composition comprises epoxy resin, solidifying agent, submicron Core-shell rubber particles, wherein, described content of epoxy resin accounts for the 80��97% of feed composition gross weight, described hardener dose is the 3��8% of weight epoxy, and the consumption of submicron Core-shell rubber particles is the 3��25% of weight epoxy.
6. the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness as claimed in claim 5, it is characterised in that: described epoxy resin is bisphenol A type epoxy resin, and its molecular-weight average is 320��650, and epoxy equivalent (weight) is 184��198g/eq.
7. the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness as claimed in claim 5, it is characterised in that: described solidifying agent is one or several the mixture in m-xylene diamine, diamino diphenyl sulfone, diethylaminopropylamine, diethylenetriamine, isophorone diamine, 2-ethyl-4-methylimidazole.
8. the preparation method of the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness as claimed in claim 5, comprises the steps:
Step 1, preparation submicron Core-shell rubber particles, is dispersed in thinner, then is mixed with epoxy resin, obtains the epoxy resin compound prepolymer containing submicron Core-shell rubber particles of evenly dispersion;
Step 2, adds solidifying agent, is vented after being uniformly dispersed, and solidification, obtains final product.
9. the preparation method of the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness as claimed in claim 8, it is characterised in that: described thinner is one or several the mixture in ethanol, butanone, butyl methacrylate, butyl acrylate, methyl methacrylate, glycidyl methacrylate, acetone.
10. the preparation method of the epoxy resin composite of submicron Core-shell rubber particles activeness and quietness as claimed in claim 8, it is characterized in that: in described step 1, submicron Core-shell rubber particles is added in thinner, submicron Core-shell rubber particles and thinner weight ratio are 1:5��1:40, at 10��70 DEG C, ultrasonic disperse becomes molecule suspension, then this hanging drop is added in 10��45 DEG C of epoxy resin, drip while stirring and add, stir evenly, then keep reducing mixture temperature to room temperature under whipped state, vacuum suction device extracting thinner is adopted to emerge to solution surface bubble-free, obtain the epoxy resin compound prepolymer containing submicron Core-shell rubber particles of evenly dispersion, adopt mechanical stirrer that with the speed of 400��500 turns/min, the mixed solution obtained is stirred 5��10min after step 2 adds solidifying agent, then exhaust-gas disposal is placed in vacuum drying oven to solution surface bubble-free, then build in mould, put into air dry oven, after being warming up to 60 DEG C, constant temperature 1.5��3h carries out Procuring, it is warming up to 150 DEG C of constant temperature 6��10h again and carries out deeply-curing, after solidification, close baking oven switch naturally cooling, form the epoxy resin composite of activeness and quietness.
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