CN108047653A - A kind of Toughening Modification of Epoxy micro-sphere material - Google Patents
A kind of Toughening Modification of Epoxy micro-sphere material Download PDFInfo
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- CN108047653A CN108047653A CN201711392274.XA CN201711392274A CN108047653A CN 108047653 A CN108047653 A CN 108047653A CN 201711392274 A CN201711392274 A CN 201711392274A CN 108047653 A CN108047653 A CN 108047653A
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- epoxy resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of Toughening Modification of Epoxy micro-sphere materials, belong to Epoxy Resin Technology field.The material uses phase reversal emulsion polymerization, add in the toughening monomer that flexibility is good, high and low temperature resistance is good in situ in epoxy resin solidifying system, micron order modified epoxy micro-sphere material is prepared in one-step method, the microballoon flexibility is good, anti-aging property and excellent in mechanical performance, have a extensive future.
Description
Technical field
The present invention relates to Epoxy Resin Technology fields, are more particularly to a kind of modified epoxy micro-sphere material.
Background technology
Polymer microballoon is a kind of new function material of function admirable, has skin effect, bulk effect, functional group
Etc. characteristics, be widely used in fields such as analytical chemistry, colloid chemistry and chromatographic isolations, become research in recent years
Hot spot.
The epoxide resin microballoon of existing literature document announcement is mainly hollow microsphere or porous microsphere, Wu Yang etc.（Reaction lures
Lead the research [J] that phase separation method prepares epoxide resin microballoon, Guilin Electronic Science and Technology Univ.'s journal, 2008,28（1）：27-30）It adopts
Although the micron order epoxide resin microballoon surface successfully prepared with Polymerization induced phase separation method is smooth, no damaged and defect,
There is no further correlative study is carried out to the toughening modifying of epoxide resin microballoon, the microballoon internal stress is big, flexibility is insufficient, should
With being extremely restricted, its preparation method is too excessively cumbersome.Therefore, modified epoxy micro-sphere material is prepared, improves asphalt mixtures modified by epoxy resin
The mechanical property of lipid microspheres material so as to meet the high performance demand of epoxide resin microballoon material there is important research to anticipate
Justice.Toughening Modification of Epoxy micro-sphere material has not yet to see relevant report.
The content of the invention
In view of the problems of the existing technology, present invention aims at providing, a kind of mechanical property is good, flexibility is good and hot
The epoxide resin microballoon material of excellent in stability.
Purpose to realize the present invention, the present invention are added in soft in situ using emulsion template method in epoxy resin solidifying system
Epoxide resin microballoon material is prepared in the good toughening monomer of good toughness, resistant of high or low temperature, one-step method, and toughening effect is notable.
The preparation method of the epoxide resin microballoon material is specific as follows：
1st, obtained after epoxy resin, curing agent, solvent, emulsifier, toughening phase, azodiisobutyronitrile stirring are weighed in flask
It is for use to be subsequently placed in precuring in 50 ~ 60 DEG C of water-baths for even mixture.
The toughening is mutually acrylate, the mixture of the organosiloxane containing double bond.
Wherein：Epoxy resin is bisphenol A polyethenoxy ether epoxy resin, para aminophenol three glycidyl epoxy resin
Etc. common low viscosity epoxy resin, preferably bisphenol A polyethenoxy ether epoxy resin；Curing agent is room temperature low viscosity curing agent, excellent
Select oligomer polyamide 6 50；Solvent is organic solvent of the boiling point between 100 ~ 200 DEG C, preferably methyl iso-butyl ketone (MIBK)；Acrylic acid
Ester is at least one of butyl acrylate, ethyl acrylate, methyl methacrylate；Organosiloxane containing double bond is vinyl
Trimethoxy silane, vinyltriethoxysilane, acrylic trimethoxy silane, γ-methacryloxypropyl front three
One kind in oxysilane.
Emulsifier is cetyl trimethylammonium bromide and the compound system of sorbester p17.
2nd, step 1 gained mixture is placed in mechanical agitation, deionized water is slowly added to while stirring, after being added dropwise
Milky stable emulsion is obtained, the quality of 1 mixture of rate-determining steps is 1 ~ 1.5 times of deionized water quality, then puts system
The reaction was continued in 50 ~ 60 DEG C of water-baths terminates to reaction, with constant weight is dried under vacuum at room temperature after acetone wash products, is increased
Tough modified epoxy micro-sphere material.
1 epoxy resin of above-mentioned steps, curing agent, solvent, emulsifier, toughening phase, azodiisobutyronitrile 1： 0.7~0.9：
0.8~1.0：0.2~0.4：0.1~0.3：0.0005~0.01.
Acrylate, the mass ratio of organosiloxane are 1 in toughening phase： 0.2~0.3.
Cetyl trimethylammonium bromide, the mass ratio of sorbester p17 are 2 in the compound system of emulsifier in above-mentioned steps 1：
1。
The present invention has the beneficial effect that：（1）The organosiloxane containing double bond is carried out free radical with acrylate monomer to be total to
It is poly-, siloxanes is introduced on C-C main chains, makes it have good thermal oxidation resistance, anti-aging, high and low temperature resistance and flexibility,
The toughening phase can form semi-interpenetrating polymer cross-linked network structure, the copolymerization point of acrylate and siloxanes with epoxy-resin systems
Subchain is dispersed in epoxy-resin systems, is declined the whole crosslink density of epoxy resin, but not is destroyed it and integrally handed over
It is coupled structure, maintains the flexibility that the preferable heat resistance of epoxy resin substantially increases system simultaneously；（2）The present invention using sun from
Sub- emulsifier and the mode of nonionic emulsifier compounding obtain stable epoxy resin W/O emulsion systems, and quality of the emulsion fraction reaches
To more than 50%, system solid content is high；（3）The present invention reacts simple and easy to control, room temperature curing, is suitble to production amplification.
Description of the drawings
Illustrate the embodiment of the present invention or technical solution of the prior art in order to clearer, we will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it is clear that, the accompanying drawings in the following description is only this hair
Some bright embodiments, for those of ordinary skill in the art, without creative efforts, can be with root
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the scanning electron microscope diagram of the Toughening Modification of Epoxy micro-sphere material prepared by the embodiment of the present invention 1
Piece.As can be seen from the figure the self toughening epoxide resin microballoon surface of gained is smooth, is solid microsphere.
Specific implementation method
It is as follows for embodiment to be better illustrated to the present invention：Following embodiment cannot be used for for illustrating the present invention
It limits the scope of the invention.
Embodiment 1：
（1）5.0g E44 type bisphenol A polyethenoxy ethers epoxy resin, 2.5g methyl-isobutyls are weighed in round-bottomed flask at room temperature
Ketone, heating stirring is to being completely dissolved.4g oligomer polyamide 6 50,2.5g methyl iso-butyl ketone (MIBK)s are weighed in beaker again, heating is stirred
It mixes to after being completely dissolved to pour into round-bottomed flask and is mixed and stirred for the two uniformly, to add 0.5g butyl acrylates, 0.5g third
Olefin(e) acid ethyl ester, 0.3g vinyltrimethoxysilanes, 0.04g azodiisobutyronitriles, 1g sorbester p17s, 0.5g cetyl trimethyls
Ammonium bromide is stirred to uniform state, is placed in 50 DEG C of water-baths after precuring 30min for use.
（2）Under mechanical stirring, 10g deionized waters are added dropwise to step（1）In, control time for adding is about 8 ~
10min obtains milky stable emulsion, and system is placed in 50 ~ 60 DEG C of water-baths the reaction was continued, and the reaction of 8h solidify afterwards terminates, with third
After ketone cleans 2 ~ 3 times, constant weight is dried under vacuum at room temperature and can obtain Toughening Modification of Epoxy micro-sphere material.
Embodiment 2：
（1）5.0g E44 type bisphenol A polyethenoxy ethers epoxy resin, 2.5g methyl-isobutyls are weighed in round-bottomed flask at room temperature
Ketone, heating stirring is to being completely dissolved.4g oligomer polyamide 6 50,2.5g methyl iso-butyl ketone (MIBK)s are weighed in beaker again, heating is stirred
It mixes to after being completely dissolved to pour into round-bottomed flask and is mixed and stirred for the two uniformly, to add 0.8g butyl acrylates, 0.2g first
Base methyl acrylate, 0.2 g acrylic trimethoxy silanes, 0.003g azodiisobutyronitriles, 1g sorbester p17s, 0.5g cetyls
Trimethylammonium bromide is stirred to uniform state, is placed in 50 DEG C of water-baths after precuring 30min for use.
（2）Under mechanical stirring, 9.83g deionized waters are added dropwise to step（1）In, control time for adding is about 8 ~
10min obtains milky stable emulsion, and system is placed in 50 ~ 60 DEG C of water-baths the reaction was continued, and the reaction of 8h solidify afterwards terminates, with third
After ketone cleans 2 ~ 3 times, constant weight is dried under vacuum at room temperature and can obtain self toughening epoxide resin microballoon material.
Embodiment 3：Contrast test
（1）5.0g E44 type bisphenol A polyethenoxy ethers epoxy resin, 2.5g methyl-isobutyls are weighed in round-bottomed flask at room temperature
Ketone, heating stirring is to being completely dissolved.Weighed again in beaker 4g oligomer polyamide 6 50,2.5g methyl iso-butyl ketone (MIBK)s, heating
Stirring, which is poured into after being completely dissolved in round-bottomed flask, to be mixed and stirred for the two uniformly, to add 1g sorbester p17s, 0.5g hexadecanes
Base trimethylammonium bromide is stirred to uniform state, is placed in 50 DEG C of water-baths after precuring 30min for use.
（2）Under mechanical stirring, 10g deionized waters are added gradually to step（1）In, control time for adding for 8 ~
10min obtains milky stable emulsion, and system is placed in 50 ~ 60 DEG C of water-baths the reaction was continued, and 8h curing reactions terminate, and use acetone
After cleaning 2 ~ 3 times, constant weight is dried under vacuum at room temperature and can obtain ordinary epoxy resin micro-sphere material.
Above-described embodiment glass transition temperature test result is shown in Table 1（Using German NETZSCH synchronous solvings STA449C
It measures, 10 DEG C/min of heating rate, High Purity Nitrogen atmosphere）.
1. glass transition temperature test result of table compares
| Sequence number | Glass transition temperature（℃） |
| Embodiment 1 | 62.3 |
| Embodiment 2 | 62.5 |
| Embodiment 3：Contrast experiment | 67.8 |
As can be seen from Table 1, using epoxide resin microballoon material glass temperature made from the method for the present invention compared with comparative example 3
It is substantially reduced, toughening effect is apparent.
The micro-sphere material of embodiment 2 is clayed into power shape, uniform powder is obtained after sieving repeatedly, is added it at 70 DEG C
In the homogeneous mixture system of E44 type bisphenol A polyethenoxy ether epoxy resin and oligomer polyamide 6 50（Epoxy resin：Curing agent
Mass ratio=1：0.8）, addition is respectively 0,5%, the 10% of epoxy resin mixed system mass fraction, according to GB/T1843-
2008 tests, test result are shown in Table 2.
2. impact strength test result of table
| 2 addition of embodiment, % | Impact strength, kJ/m2 |
| 0 | 20.84 |
| 5 | 25.28 |
| 10 | 27.92 |
As can be seen from Table 2, addition of the invention can significantly improve the impact strength of epoxy resin-base.
Claims (3)
1. a kind of Toughening Modification of Epoxy micro-sphere material, which is characterized in that be made by following steps：
（1）It is obtained after epoxy resin, curing agent, solvent, emulsifier, toughening phase, azodiisobutyronitrile stirring are weighed in flask
It is for use to be subsequently placed in precuring in 50 ~ 60 DEG C of water-baths for uniform mixture；
The toughening is mutually acrylate, the mixture of the organosiloxane containing double bond；
（2）By step（1）Gained mixture is placed in mechanical agitation, is slowly added to deionized water while stirring, after being added dropwise
Obtain lotion, rate-determining steps（1）The quality of mixture is 1 ~ 1.5 times of deionized water quality, and system then is placed in 50 ~ 60 DEG C
The reaction was continued in water-bath terminates to reaction, with constant weight is dried under vacuum at room temperature after acetone wash products, obtains toughening modifying ring
Oxygen resin microsphere material；
The epoxy resin is bisphenol A polyethenoxy ether epoxy resin or para aminophenol three glycidyl epoxy resin；Institute
It states curing agent and selects oligomer polyamide 6 50；Organic solvent of the solvent between 100 ~ 200 DEG C of boiling point；Emulsifier is cetyl
The compound system of trimethylammonium bromide and sorbester p17；
Wherein：Epoxy resin, curing agent, solvent, emulsifier, toughening phase, the mass ratio of azodiisobutyronitrile are 1： 0.7~0.9：
0.8~1.0：0.2~0.4：0.1~0.3：0.0005~0.01；The mass ratio of acrylate, the organosiloxane containing double bond in toughening phase
For 1： 0.2~0.3.
2. as described in claim 1 increase modified tough epoxide resin microballoon material, which is characterized in that step（1）Middle emulsifier
Cetyl trimethylammonium bromide, the mass ratio of sorbester p17 are 2 in compound system：1.
3. self toughening epoxide resin microballoon material as claimed in claim 1 or 2, which is characterized in that epoxy resin selects polymer with bis phenol A
Ethylene oxide ether epoxy resin；Solvent is methyl iso-butyl ketone (MIBK)；Organosiloxane containing double bond is vinyltrimethoxysilane, ethylene
One kind in ethyl triethoxy silicane alkane, acrylic trimethoxy silane, γ-methacryloxypropyl trimethoxy silane；
Acrylate is butyl acrylate, the one or more in ethyl acrylate, methyl methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711392274.XA CN108047653A (en) | 2017-12-21 | 2017-12-21 | A kind of Toughening Modification of Epoxy micro-sphere material |
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| CN201711392274.XA CN108047653A (en) | 2017-12-21 | 2017-12-21 | A kind of Toughening Modification of Epoxy micro-sphere material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727781A (en) * | 2018-05-21 | 2018-11-02 | 江苏傲达康复合材料股份有限公司 | A kind of high-strength high-toughness epoxy resin combination and preparation method thereof being used to prepare carbon fibre reinforced composite prepreg |
| CN113480747A (en) * | 2021-07-02 | 2021-10-08 | 江南大学 | Preparation and application of epoxy acrylate microsphere emulsion |
| CN116478536A (en) * | 2023-04-25 | 2023-07-25 | 吉林大学 | Core-shell particle for toughening thermosetting resin, composite material and preparation method |
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|---|---|---|---|---|
| CN101074311A (en) * | 2007-03-29 | 2007-11-21 | 苏州大学 | Production of micron-solid epoxy-resin microsphere containing surface active group |
| CN105199322A (en) * | 2015-10-10 | 2015-12-30 | 苏州大学 | Epoxy resin microsphere and preparation method thereof |
| CN105586018A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Drilling fluid containing epoxy resin microspheres |
| CN106519567A (en) * | 2016-10-17 | 2017-03-22 | 长安大学 | Method for preparing shape-memory epoxy resin particles |
-
2017
- 2017-12-21 CN CN201711392274.XA patent/CN108047653A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074311A (en) * | 2007-03-29 | 2007-11-21 | 苏州大学 | Production of micron-solid epoxy-resin microsphere containing surface active group |
| CN105586018A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Drilling fluid containing epoxy resin microspheres |
| CN105199322A (en) * | 2015-10-10 | 2015-12-30 | 苏州大学 | Epoxy resin microsphere and preparation method thereof |
| CN106519567A (en) * | 2016-10-17 | 2017-03-22 | 长安大学 | Method for preparing shape-memory epoxy resin particles |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727781A (en) * | 2018-05-21 | 2018-11-02 | 江苏傲达康复合材料股份有限公司 | A kind of high-strength high-toughness epoxy resin combination and preparation method thereof being used to prepare carbon fibre reinforced composite prepreg |
| CN113480747A (en) * | 2021-07-02 | 2021-10-08 | 江南大学 | Preparation and application of epoxy acrylate microsphere emulsion |
| CN113480747B (en) * | 2021-07-02 | 2022-07-15 | 江南大学 | Preparation and application of epoxy acrylate microsphere emulsion |
| CN116478536A (en) * | 2023-04-25 | 2023-07-25 | 吉林大学 | Core-shell particle for toughening thermosetting resin, composite material and preparation method |
| CN116478536B (en) * | 2023-04-25 | 2024-04-12 | 吉林大学 | Core-shell particle for toughening thermosetting resin, composite material and preparation method |
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Application publication date: 20180518 |