CN104479296A - Method for improving impact strength of epoxy resin/carbon fiber composite material - Google Patents
Method for improving impact strength of epoxy resin/carbon fiber composite material Download PDFInfo
- Publication number
- CN104479296A CN104479296A CN201410809836.6A CN201410809836A CN104479296A CN 104479296 A CN104479296 A CN 104479296A CN 201410809836 A CN201410809836 A CN 201410809836A CN 104479296 A CN104479296 A CN 104479296A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- carbon
- carbon fiber
- bisphenol
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a method for improving impact strength of an epoxy resin/carbon fiber composite material. An epoxy resin matrix is modified with four-functionality organosilicon epoxy resin N,N,N',N'-tetraglycidyl-1,3-diaminopropyl-1,1,3,3-tetramethyldisiloxane, the impact resistance of the epoxy resin/carbon fiber composite material is effectively improved, both the compatibility and the impact strength of the material are considered, the preparation method is simple, and the cost is low.
Description
Technical field
The invention belongs to carbon-fibre composite field, relate to the improvement opportunity of resin base/carbon-fibre composite, particularly a kind of by heavily introducing polyfunctionality organosilicon epoxy resin to improve the method for matrix material shock strength at epoxy resin.
Background technology
Epoxy resin/carbon-fibre composite with its high specific strength, high ratio modulus, high temperature resistant, numerous excellent properties such as corrosion-resistant and being widely used on space flight, automobile, electronics, sports goods and medicine equipment.The performance of epoxy resin/carbon-fibre composite is by fiber bodies, and resin matrix and bonding strength therebetween determine.As everyone knows, obtain after epoxy resin cure a kind of three-dimensional insolublely not melting reticulated structure, the feature that this structural expression matter is crisp, easily spread rapidly when the tiny crack produced due to load or defect and make material failure, thus affecting its use range.Therefore need to carry out toughness reinforcing process to improve its shock strength to epoxy resin/carbon-fibre composite.
At present Toughened With High Performance Thermoplastics is mainly contained to such composite material toughening method, rubber toughened, the methods such as electrodeless particle and fiber hybrid.These methods can improve the shock strength of matrix material undoubtedly to a certain extent, but have the material modified defect poor with epoxy resin compatibility.
Summary of the invention
In order to solve problems of the prior art, the present invention adopts a kind of four functionality organosilicon epoxy resins to carry out modification to epoxy resin-base, this properties-correcting agent and epoxy resin have good consistency, effectively can improve the erosion-resisting characteristics of epoxy resin/carbon-fibre composite.
The present invention adopts following technical scheme: a kind of method improving epoxy resin/carbon-fibre composite shock strength, comprises the following steps:
(1) pre-treatment of carbon fiber: carbon cloth is placed in organic solvent and soaks to remove small molecule organic compound, then takes out to be positioned in vacuum drying oven and dries, at the temperature of 50 ~ 80 DEG C, preserve 30 ~ 60min;
(2) epoxy resin and four functionality organosilicon epoxy resins are compared mixing and stirring according to the quality of 100:5 ~ 35, the solidifying agent adding 20 ~ 30mt% again stirs, the last thinner adding 15 ~ 30mt% again, reduces mixed system viscosity to 500 ~ 800mPa.S;
(3) the above-mentioned resin compound of vacuum bag pressure method is adopted to infiltrate carbon fiber, then according to constant temperature 1h under 80 DEG C of environment, then constant temperature 2h under 120 DEG C of environment, finally under 150 DEG C of environment, the curing process (i.e. the curing process of 80/1h+120/2h+150/2h) of constant temperature 2h is cured, and obtains epoxy resin/carbon-fibre composite that fibre content is 54 ~ 62%;
Four described functionality organosilicon epoxy resins are N, N, N ', N '-four glycidyl group-1,3-bis-aminopropyl-1,1,3,3-tetramethyl disiloxane.
Wherein, N, N, N ', N '-four glycidyl group-1,3-bis-aminopropyl-1,1,3,3-tetramethyl disiloxane, its chemical structure is as follows:
It is brown color thick liquid, viscosity is 3500 ~ 4000mPa.S, can prepare according to the preparation method of the epoxy resin organosilicon modifier of Chinese patent CN102532482A, such as by the following method: by 124 g(0.5mol) 1,3-bis-aminopropyl-1,1,3,3-tetramethyl disiloxane is dissolved in 124g toluene, under stirring at room temperature, at the uniform velocity drip 231g(2.5mol in 2h) epoxy chloropropane, after dropwising, be warming up to 60 DEG C reaction 4h; Afterwards under 90 DEG C × 700mmHg condition, excess epoxy chloropropane is reclaimed in underpressure distillation; Until steam without overhead product.Be cooled to 70 DEG C, heating up and maintaining temperature of charge is 75 DEG C, adds 0.12g phase-transfer catalyst benzyltriethylammoinium chloride, adds NaOH chip solid 40g, adds NaOH chip solid 40g again after reaction 2h; Continue reaction 2h.Stopped reaction, adds ionized water/toluene mixture liquid 100g that mass ratio is 1:1, washs 20min under violent stirring; And be neutral by saturated biphosphate sodium water solution regulation system, filter and remove water layer; Above reactant is placed in Rotary Evaporators underpressure distillation, obtains viscous brown shape four glycidyl amine epoxy resin organosilicon modifier, its oxirane value is the viscosity that at 0.5 mol/100g 5,25 DEG C, rotational viscosimeter measures is 5470mPas.
In a preferred embodiment in accordance with this invention, the organic solvent in step (1) is acetone, tetrahydrofuran (THF), one or more in ethanol.
In a preferred embodiment in accordance with this invention, the epoxy resin in step (2) is bisphenol A epoxide resin, bisphenol F epoxy resin, one or more in bisphenol-s epoxy resin, viscosity 2200 ~ 4000mPa.S.
In a preferred embodiment in accordance with this invention, the solidifying agent in step (2) is diethylenetriamine, triethylene tetramine, one or more in m-xylene diamine.
In a preferred embodiment in accordance with this invention, in step (2), thinner is acetone.
Compared to prior art, the present invention adopts four functionality organosilicon epoxy resin N of certain proportioning, N, N ', N '-four glycidyl group-1,3-bis-aminopropyl-1,1,3,3-tetramethyl disiloxane carries out modification to epoxy resin-base, viscosity is is effectively regulated and controled, and in conjunction with specific gradient curing process, the erosion-resisting characteristics of the epoxy resin/carbon-fibre composite prepared improves more than 20%, and has taken into account consistency and the resistance to impact shock of material, preparation method is easy, and cost is low.
Embodiment
Specifically the present invention is explained in detail below with reference to embodiment.But should be appreciated that embodiment is only used for explaining embodiment of the present invention, the present invention is not by the restriction of these embodiments.
Embodiment 1:(1) carbon cloth is placed in acetone soaks 2h to remove small molecule organic compound, then take out to be positioned in vacuum drying oven and dry, at the temperature of 50 DEG C, preserve 30min; (2) by viscosity be bisphenol F epoxy resin and the N of 2300mPa.S, N, N ', N '-four glycidyl group-1,3-bis-aminopropyl-1,1,3,3-tetramethyl disiloxane is according to the quality of 100:5 than mixing and stirring, then the m-xylene diamine adding 30mt% stirs, finally add the acetone of 20mt% again as thinner, reduce mixed system viscosity to 750mPa.S; (3) adopt the above-mentioned resin compound of vacuum bag pressure method to infiltrate carbon fiber, be then cured according to the curing process of 80/1h+120/2h+150/2h, obtain epoxy resin/carbon-fibre composite that fibre content is 55%.Prepare blank's sample, result shows that modified matrix material shock strength improves 18% simultaneously.
Embodiment 2:(1) carbon cloth is placed in organic solvent-acetone soaks 2h to remove small molecule organic compound, then take out to be positioned in vacuum drying oven and dry, at the temperature of 75 DEG C, preserve 60min; (2) by viscosity be bisphenol A epoxide resin and the N of 3500mPa.S, N, N ', N '-four glycidyl group-1,3-bis-aminopropyl-1,1,3,3-tetramethyl disiloxane is according to the quality of 100:15 than mixing and stirring, then the diethylenetriamine adding 25mt% stirs, finally add the acetone of 15mt% again as thinner, reduce mixed system viscosity to 500mPa.S; (3) adopt the above-mentioned resin compound of vacuum bag pressure method to infiltrate carbon fiber, be then cured according to the curing process of 80/1h+120/2h+150/2h, obtain epoxy resin/carbon-fibre composite that fibre content is 61%.Prepare blank's sample, result shows that modified matrix material shock strength improves 25% simultaneously.
Above embodiment display and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; instead of limit the scope of the invention by any way; without departing from the scope of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in claimed scope.
Claims (5)
1. improve a method for epoxy resin/carbon-fibre composite shock strength, it is characterized in that, comprise the following steps:
(1) pre-treatment of carbon fiber: carbon cloth is placed in organic solvent and soaks to remove small molecule organic compound, then takes out to be positioned in vacuum drying oven and dries, at the temperature of 50 ~ 80 DEG C, preserve 30 ~ 60min;
(2) epoxy resin and four functionality organosilicon epoxy resins are compared mixing and stirring according to the quality of 100:5 ~ 35, the solidifying agent adding 20 ~ 30mt% again stirs, the last thinner adding 15 ~ 30mt% again, reduces mixed system viscosity to 500 ~ 800mPa.S;
(3) the above-mentioned resin compound of vacuum bag pressure method is adopted to infiltrate carbon fiber, then according to constant temperature 1h under 80 DEG C of environment, then constant temperature 2h under 120 DEG C of environment, finally under 150 DEG C of environment, the curing process of constant temperature 2h is cured, and obtains epoxy resin/carbon-fibre composite that fibre content is 54 ~ 62%;
Four described functionality organosilicon epoxy resins are N, N, N ', N '-four glycidyl group-1,3-bis-aminopropyl-1,1,3,3-tetramethyl disiloxane.
2. method according to claim 1, is characterized in that, the organic solvent in step (1) is acetone, tetrahydrofuran (THF), one or more in ethanol.
3. method according to claim 1, is characterized in that, the epoxy resin in step (2) is bisphenol A epoxide resin, bisphenol F epoxy resin, one or more in bisphenol-s epoxy resin, viscosity 2200 ~ 4000mPa.S.
4. method according to claim 1, is characterized in that, the solidifying agent in step (2) is diethylenetriamine, triethylene tetramine, one or more in m-xylene diamine.
5. method according to claim 1, is characterized in that, in step (2), thinner is acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410809836.6A CN104479296B (en) | 2014-12-24 | 2014-12-24 | Method for improving impact strength of epoxy resin/carbon fiber composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410809836.6A CN104479296B (en) | 2014-12-24 | 2014-12-24 | Method for improving impact strength of epoxy resin/carbon fiber composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104479296A true CN104479296A (en) | 2015-04-01 |
| CN104479296B CN104479296B (en) | 2017-01-11 |
Family
ID=52753911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410809836.6A Active CN104479296B (en) | 2014-12-24 | 2014-12-24 | Method for improving impact strength of epoxy resin/carbon fiber composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104479296B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631080A (en) * | 2017-01-25 | 2017-05-10 | 厦门大学 | Manufacturing method of Si-O-C ceramic flexible substrate |
| CN107936273A (en) * | 2017-11-29 | 2018-04-20 | 西华大学 | A kind of high-performance light composite material of carbon fiber enhancement resin base and preparation method thereof |
| CN109180941A (en) * | 2018-08-23 | 2019-01-11 | 哈尔滨工业大学 | A kind of preparation method of eight functional epoxy's POSS resin of hybrid inorganic-organic and the preparation method of carbon fibre reinforced composite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532482A (en) * | 2011-12-15 | 2012-07-04 | 合肥工业大学 | Epoxy resin organosilicon modifier and preparation method thereof |
| CN103214792A (en) * | 2013-04-11 | 2013-07-24 | 奇瑞汽车股份有限公司 | Carbon fiber/epoxy resin composite material and preparation method thereof |
| CN103483552A (en) * | 2013-09-29 | 2014-01-01 | 东华大学 | Matrix resin for carbon fiber composite material and preparation method of matrix resin |
| CN103602042A (en) * | 2013-10-31 | 2014-02-26 | 中科院广州化学有限公司 | Liquid crystal epoxy resin - carbon fiber composite material and preparation method thereof |
-
2014
- 2014-12-24 CN CN201410809836.6A patent/CN104479296B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532482A (en) * | 2011-12-15 | 2012-07-04 | 合肥工业大学 | Epoxy resin organosilicon modifier and preparation method thereof |
| CN103214792A (en) * | 2013-04-11 | 2013-07-24 | 奇瑞汽车股份有限公司 | Carbon fiber/epoxy resin composite material and preparation method thereof |
| CN103483552A (en) * | 2013-09-29 | 2014-01-01 | 东华大学 | Matrix resin for carbon fiber composite material and preparation method of matrix resin |
| CN103602042A (en) * | 2013-10-31 | 2014-02-26 | 中科院广州化学有限公司 | Liquid crystal epoxy resin - carbon fiber composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄丽等: "《聚合物复合材料（第二版）》", 31 January 2012, article "纤维复合材料及其制造方法", pages: 152-159 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631080A (en) * | 2017-01-25 | 2017-05-10 | 厦门大学 | Manufacturing method of Si-O-C ceramic flexible substrate |
| CN106631080B (en) * | 2017-01-25 | 2019-04-16 | 厦门大学 | A kind of preparation method of Si-O-C ceramics flexible base board |
| CN107936273A (en) * | 2017-11-29 | 2018-04-20 | 西华大学 | A kind of high-performance light composite material of carbon fiber enhancement resin base and preparation method thereof |
| CN109180941A (en) * | 2018-08-23 | 2019-01-11 | 哈尔滨工业大学 | A kind of preparation method of eight functional epoxy's POSS resin of hybrid inorganic-organic and the preparation method of carbon fibre reinforced composite |
| CN109180941B (en) * | 2018-08-23 | 2021-04-23 | 哈尔滨工业大学 | Preparation method of organic-inorganic hybrid octafunctional epoxy POSS resin and preparation method of carbon fiber reinforced composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104479296B (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI557150B (en) | Curable resin composition and short-cure method | |
| CN102660874B (en) | Thermoplasticity sizing agent for carbon fiber and preparation and usage thereof | |
| CN104903332B (en) | The application of the preparation method of epoxide, the compound containing alkoxysilyl, the composition comprising the compound, the cured product prepared by said composition and said composition | |
| CN104497271A (en) | Modified epoxy resin and modified epoxy resin composition | |
| CN109852004B (en) | Epoxy resin matrix composition, epoxy resin matrix and preparation method thereof | |
| GB2460050A (en) | Epoxy composite | |
| CN102492116B (en) | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method | |
| CN104194273A (en) | Preparation method of environmentally-friendly flame-retardant epoxy resin composite material based modified epoxy-POSS (polysilsesquioxane) | |
| CN104479296A (en) | Method for improving impact strength of epoxy resin/carbon fiber composite material | |
| CN105237737A (en) | Dicyandiamide type epoxy resin curing agent and preparation method and application thereof | |
| CN106589837A (en) | Heat-resisting epoxy resin and carbon fiber composite cured at medium and low temperature and preparation method of composite | |
| CN106916413A (en) | A kind of composition epoxy resin and preparation method thereof, fiber resin composite material, aluminium/fiber/resin composite | |
| RU2705724C2 (en) | Resin composition | |
| CN105199317A (en) | Method for preparing high-tenacity high-strength epoxy-resin-based conductive composite | |
| CN105131531A (en) | Triblock copolymer modified epoxide resin and preparing method thereof | |
| CN104479297B (en) | Method for improving interface toughness of epoxy resin carbon fiber composite | |
| KR101884188B1 (en) | Manufacturing method of modified halloysite nanotube and polymer composite containing it | |
| CN107384281A (en) | A kind of antibiotic property epoxy resin adhesive | |
| CN111172762B (en) | Nano-reinforced environment-friendly impregnation system for fiber surface treatment and preparation method thereof | |
| CN105778429B (en) | A kind of agent of low hygroscopicity epoxy resin and preparation method thereof | |
| CN109880293A (en) | Toughened epoxy resin and preparation method thereof | |
| CN104403279A (en) | Preparation method of high-toughness epoxy resin/carbon fiber composite material | |
| CN109608889A (en) | A kind of high tenacity solid buoyancy material and preparation method thereof that POSS is modified | |
| WO2019011774A1 (en) | Improvements in resin curative systems | |
| CN107418151A (en) | A kind of composite of glass fibre modified epoxy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 241000 Anshan South Road, Wuhu economic and Technological Development Zone, Anhui Patentee after: Wuhu male lion Automobile Technology Co., Ltd. Address before: 241007 Hengshan Road 35, Wuhu economic and Technological Development Zone, Anhui Patentee before: WUHU RESEARCH INSTITUTE OF INSTITUTE TECHNOLOGY OF AUTOMOBILE CO., LTD. |