CN110511432A - A kind of epoxy resin toughener and preparation method thereof - Google Patents
A kind of epoxy resin toughener and preparation method thereof Download PDFInfo
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- CN110511432A CN110511432A CN201910777115.4A CN201910777115A CN110511432A CN 110511432 A CN110511432 A CN 110511432A CN 201910777115 A CN201910777115 A CN 201910777115A CN 110511432 A CN110511432 A CN 110511432A
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- toughener
- epoxy resin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
- C07F7/0879—Hydrosilylation reactions
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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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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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
Abstract
The invention proposes a kind of toughener, just like structure shown in following formula I:In formula, R=H, CH3, C2H5, Ph, OCH3, OH, F, Cl, Br, I, COOCH3.A kind of epoxy resin toughener, the raw material including following parts by weight: such as above-mentioned toughener 70-100 parts, 10-20 parts of polyethylene glycol, 5-10 parts of m-phenylene diamine (MPD), 12-17 parts of polysulfide rubber.Epoxy resin toughener prepared by the present invention makes epoxy resin have preferable impact strength, tensile strength and bending strength, has broad application prospects.
Description
Technical field
The present invention relates to Epoxy Resin Technology fields, and in particular to a kind of epoxy resin toughener and preparation method thereof and answers
With.
Background technique
Epoxy resin is widely used in vapour as adhesive, coating and insulating materials etc. because having a variety of excellent performances
The fields such as vehicle, shipbuilding, aviation, machinery, chemical industry, electronics.But matter is crisp after epoxy resin cure, and heat resistance, humidity resistance etc. are poor,
It is greatly limited in the application in certain fields.In recent years, structural bond material, encapsulating material, fiber reinforcement material
The high performance of the materials such as material, laminate, integrated circuit requires epoxide resin material to have better performance, and such as good toughness is interior
Stress is low, and heat resistance, water resistance, chemical resistance are excellent etc..Lot of domestic and foreign researcher has been carried out many Zhuos and has thus
The study on the modification of effect works.
Organosilicon has thermal stability good, and low-surface-energy, low temperature flexibility, weather-proof, hydrophobic, resistance to oxidation, dielectric strength are high
The advantages that.The functional groups such as epoxy group, hydroxyl that epoxy resin contains, can in organosilicon amido, hydroxyl, alkoxy and draw
Other function base entered etc. is reacted, and modified epoxy copolymer or crosslinking curing material are generated, introduce in the structure stablize and
Silicon oxygen chain flexible with flexibility, thermal stability and the light passband etc. for improving epoxy resin, while can also enhance and epoxy
The compatibility etc. of resin.
Summary of the invention
The present invention provides a kind of epoxy resin toughener and its preparation method and application, it is intended that providing a kind of ring
The impact strength of epoxy resin can be improved 3KJ/ ㎡ -6KJ/ ㎡ by oxygen resin flexibilizer, tensile strength improves 6MPa-
10MPa, bending strength improve 15MPa-20MPa.
The present invention provides a kind of toughener, just like structure shown in following formula I:
In formula, R=H, CH3, C2H5, Ph, OCH3, OH, F, Cl, Br, I, COOCH3。
As further improvement of the invention, include the following steps: for substituted phenylethylene and Karstedt catalyst to be added
It filling in the reactor of organic solvent, heats, dissolution is sufficiently stirred, continues to heat up, temperature is no more than 120 DEG C, it is added dropwise 1,1,3,
Bis- -2- phenylethyl disiloxane of 3- tetramethyl -1,3-, control temperature is no more than 130 DEG C when dropwise addition, after dripping off, in 110-
2-5h is kept the temperature at 130 DEG C, is cooled to room temperature, is filtered, washing obtains toughener.
Reaction equation is as follows:
As further improvement of the invention, the substituted phenylethylene and 1,1,3,3- tetramethyl -1,3-, bis- -2- phenyl second
The ratio between amount of substance of base disiloxane is (2.2-2.4): 1.
The present invention further protects a kind of above-mentioned toughener to be used for the purposes of toughening in epoxy resin product.
The present invention further protects a kind of epoxy resin toughener, including following raw material: toughening as described in claim 1
Agent, polyethylene glycol, m-phenylene diamine (MPD) and polysulfide rubber.
As further improvement of the invention, the raw material including following parts by weight: toughener 70- as described in claim 1
100 parts, 10-20 parts of polyethylene glycol, 5-10 parts of m-phenylene diamine (MPD), 12-17 parts of polysulfide rubber.
As further improvement of the invention, the average molecular weight of the polyethylene glycol is 200-400.
The present invention further protects a kind of method for preparing above-mentioned epoxy resin toughener, comprising the following steps: will be such as power
Benefit requires 1 toughener to be dissolved in polyethylene glycol, and heating stirring dissolution sequentially adds m-phenylene diamine (MPD) and polysulfide rubber, mixes
After uniformly, it is cooled to room temperature, obtains the epoxy resin toughener.
As further improvement of the invention, the heating temperature is 50-70 DEG C.
The present invention further protects a kind of above-mentioned epoxy resin toughener to be used for the use of toughening in epoxy resin product
On the way.
The invention has the following beneficial effects: in the present invention, the toughener can significantly improve the tough of epoxy resin
Property, it is improved into 3KJ/ ㎡-by the impact strength of the epoxy resin obtained after being modified in normal rates addition epoxy resin
6KJ/ ㎡, tensile strength improve 6MPa-10MPa, bending strength improves 15MPa-20MPa；
Epoxy resin toughener prepared by the present invention makes epoxy resin have preferable impact strength, tensile strength and bending
Intensity.The experimental results showed that the impact strength for the epoxy resin that epoxy resin toughener provided by the invention is modified improves 5KJ/
㎡ -10KJ/ ㎡, tensile strength improve 12MPa-20MPa, bending strength improves 22MPa-40MPa.
Detailed description of the invention
Fig. 1 is a kind of liquid chromatogram of toughener prepared by the embodiment of the present invention 1；
Fig. 2 is various performance comparison figures in test case 1 of the present invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, this field are general
Other all embodiments obtained belong to protection of the invention to logical technical staff without making creative work
Range.
Embodiment 1
A kind of preparation method of toughener:
2.2mol styrene and 0.01mol Karstedt catalyst are added in the reactor for filling organic solvent, added
Dissolution is sufficiently stirred in heat, continues to heat up, and temperature is no more than 120 DEG C, and 1,1,3,3- tetramethyl -1,3- of 1mol, bis- -2- benzene is added dropwise
Base ethylization disiloxane, control temperature is no more than 130 DEG C when dropwise addition, after dripping off, keeps the temperature 2h at 110 DEG C, is cooled to room temperature,
Filtering, washing, obtains toughener, yield 85%.
It is the liquid chromatogram (acetonitrile: water=4:1) of new type of toughening agent prepared by the present invention referring to attached drawing 1, from map
It is found that the compound is sterling, in 45min or so appearance.
Embodiment 2
A kind of preparation method of toughener:
2.4mol 1- chlorostyrene and 0.01mol Karstedt catalyst are added to the reactor for filling organic solvent
In, heating is sufficiently stirred dissolution, continues to heat up, and temperature is no more than 120 DEG C, 1,1,3,3- tetramethyl -1,3- bis- of dropwise addition 1mol -
2- phenylethyl disiloxane, control temperature is no more than 130 DEG C when dropwise addition, after dripping off, keeps the temperature 5h at 130 DEG C, is cooled to
Room temperature filters, and washing obtains toughener, yield 92%.
Embodiment 3
A kind of preparation method of toughener:
2.3mol 1- methoxy styrene and 0.01mol Karstedt catalyst are added to the reaction for filling organic solvent
In device, heating is sufficiently stirred dissolution, continues to heat up, and temperature is no more than 120 DEG C, and 1,1,3,3- tetramethyl -1,3- of 1mol is added dropwise
Two -2- phenylethyl disiloxane, control temperature is no more than 130 DEG C when dropwise addition, and after dripping off, 4h is kept the temperature at 120 DEG C, cools down
It to room temperature, filters, washing obtains toughener, yield 97%.
Embodiment 4
Raw material forms (parts by weight): 70 parts of toughener, 10 parts of the polyethylene glycol 200, m-phenylene diamine (MPD) 5 of the preparation of embodiment 1
Part, 12 parts of polysulfide rubber.
Preparation method, comprising the following steps: toughener as described in claim 1 is dissolved in polyethylene glycol, is heated to 50
DEG C stirring and dissolving, sequentially adds m-phenylene diamine (MPD) and polysulfide rubber, after mixing, is cooled to room temperature, obtain the epoxy resin
Toughener.
Embodiment 5
Raw material forms (parts by weight): 100 parts of the toughener of the preparation of embodiment 1,20 parts of polyethylene glycol 400, m-phenylene diamine (MPD) 10
Part, 17 parts of polysulfide rubber.
Preparation method, comprising the following steps: toughener as described in claim 1 is dissolved in polyethylene glycol, is heated to 70
DEG C stirring and dissolving, sequentially adds m-phenylene diamine (MPD) and polysulfide rubber, after mixing, is cooled to room temperature, obtain the epoxy resin
Toughener.
Test case 1
The toughener of this law embodiment 1-5 preparation and common commercially available toughener are changed with epoxy resin 1:100 in mass ratio
Property, modified epoxy is obtained, is tested for the property, as a result sees Fig. 2.Annotation: a be compared with unmodified epoxy resin group, p <
0.05；B is p < 0.05 compared with unmodified epoxy resin group；C is p < 0.05 compared with unmodified epoxy resin group.
As shown in Figure 2, the toughener of 1-3 of embodiment of the present invention preparation can significantly improve the toughness of epoxy resin, by it
Be added in epoxy resin by normal rates the impact strength of epoxy resin obtained after being modified improve 3KJ/ ㎡ -6KJ/ ㎡,
Tensile strength improves 6MPa-10MPa, bending strength improves 15MPa-20MPa；It is substantially better than commercially available toughening agent modified asphalt mixtures modified by epoxy resin
Rouge.4-5 of the embodiment of the present invention preparation epoxy resin toughener make epoxy resin have preferable impact strength, tensile strength and
Bending strength.The experimental results showed that the impact strength for the epoxy resin that epoxy resin toughener provided by the invention is modified improves
5KJ/ ㎡ -10KJ/ ㎡, tensile strength improve 12MPa-20MPa, bending strength improves 22MPa-40MPa.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also
Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by
The range of claims determines.
Claims (10)
1. a kind of toughener, which is characterized in that just like structure shown in following formula I:
In formula, R=H, CH3, C2H5, Ph, OCH3, OH, F, Cl, Br, I, COOCH3。
2. a kind of preparation method of toughener as described in claim 1, which comprises the steps of: by substituted benzene second
Alkene and Karstedt catalyst are added in the reactor for filling organic solvent, and heating is sufficiently stirred dissolution, continues to heat up, temperature
No more than 120 DEG C, 1,1,3,3- tetramethyl -1,3-, bis- -2- phenylethyl disiloxane is added dropwise, control temperature does not surpass when dropwise addition
130 DEG C, after dripping off are crossed, keeps the temperature 2-5h at 110-130 DEG C, is cooled to room temperature, is filtered, washing obtains toughener.
3. the preparation method of toughener according to claim 2, which is characterized in that the substituted phenylethylene and 1,1,3,3- tetra-
Methyl-1, the ratio between amount of substance of bis- -2- phenylethyl disiloxane of 3- are (2.2-2.4): 1.
4. the purposes that a kind of toughener as described in claim 1 is used for toughening in epoxy resin product.
5. a kind of epoxy resin toughener, which is characterized in that including following raw material: toughener, poly- second two as described in claim 1
Alcohol, m-phenylene diamine (MPD) and polysulfide rubber.
6. a kind of epoxy resin toughener according to claim 5, which is characterized in that the raw material including following parts by weight: such as
Toughener 70-100 parts described in claim 1,10-20 parts of polyethylene glycol, 5-10 parts of m-phenylene diamine (MPD), 12-17 parts of polysulfide rubber.
7. according to the epoxy resin toughener of claim 5 or 6, which is characterized in that the average molecular weight of the polyethylene glycol
For 200-400.
8. a kind of method for preparing the epoxy resin toughener as described in claim 5 or 6, which comprises the following steps:
Toughener as described in claim 1 is dissolved in polyethylene glycol, heating stirring dissolution sequentially adds m-phenylene diamine (MPD) and polysulfide rubber
Glue is cooled to room temperature after mixing, obtains the epoxy resin toughener.
9. the method for epoxy resin toughener according to claim 8, which is characterized in that the heating temperature is 50-70 DEG C.
10. a kind of epoxy resin toughener as described in any one of claim 4-7 claim is used in epoxy resin product
In the purposes of toughening.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910777115.4A CN110511432A (en) | 2019-08-22 | 2019-08-22 | A kind of epoxy resin toughener and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910777115.4A CN110511432A (en) | 2019-08-22 | 2019-08-22 | A kind of epoxy resin toughener and preparation method thereof |
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| CN110511432A true CN110511432A (en) | 2019-11-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651843A (en) * | 2021-08-20 | 2021-11-16 | 福建师范大学 | Bio-based toughening agent containing rigid-flexible structure and preparation method thereof |
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| US6297340B1 (en) * | 1999-06-21 | 2001-10-02 | Dow Corning Asia, Ltd. | Method for manufacturing silicon compound having substituents bonded to silicon atoms via Si-C bonds |
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2019
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|---|---|---|---|---|
| JP2000256374A (en) * | 1999-03-10 | 2000-09-19 | Dow Corning Asia Ltd | Production of silicon compounds having substituent bonded to silicon atom through sic bond |
| US6297340B1 (en) * | 1999-06-21 | 2001-10-02 | Dow Corning Asia, Ltd. | Method for manufacturing silicon compound having substituents bonded to silicon atoms via Si-C bonds |
| US6175031B1 (en) * | 2000-03-07 | 2001-01-16 | Dow Corning Asia, Ltd. | Method for synthesizing silicon compounds that contain a substituent bonded to silicon through a silicon-carbon linkage |
| CN103694644A (en) * | 2013-12-30 | 2014-04-02 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition, metal-based copper-clad plate and manufacturing method thereof |
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| DAOHONG ZHANG: "Environment-friendly synthesis and performance of a novel hyperbranched epoxy resin with a silicone skeleton", 《RSC ADVANCES》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651843A (en) * | 2021-08-20 | 2021-11-16 | 福建师范大学 | Bio-based toughening agent containing rigid-flexible structure and preparation method thereof |
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