CN104448238A - Low-viscosity, low-exothermicity, high-strength, high-toughness epoxy resin/curing agent system for liquid infusion molding of composite material - Google Patents
Low-viscosity, low-exothermicity, high-strength, high-toughness epoxy resin/curing agent system for liquid infusion molding of composite material Download PDFInfo
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- CN104448238A CN104448238A CN201410646155.2A CN201410646155A CN104448238A CN 104448238 A CN104448238 A CN 104448238A CN 201410646155 A CN201410646155 A CN 201410646155A CN 104448238 A CN104448238 A CN 104448238A
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Abstract
The invention discloses a low-viscosity, low-exothermicity, high-strength, high-toughness epoxy resin/curing agent system for liquid infusion molding of a composite material and relates to the technical field of epoxy resin. The epoxy resin/curing agent system comprises the following components in percentages by mass: 39%-65% of an epoxy resin component, 34%-60% of a curing agent component and 0.1%-1.5% of a curing accelerator component, wherein the epoxy resin component is prepared by uniformly mixing amine-modified epoxy resin and an epoxy resin active diluents; the curing agent component is acid anhydride, the curing accelerator component is a curing accelerator and the total mass of the components is 100%. The low-viscosity, low-exothermicity, high-strength, high-toughness epoxy resin/curing agent system for liquid infusion molding of a composite material has low viscosity of 100-500mPa.s at 25 DEG C, low curing exothermic peak temperature of 90-120 DEG C, tensile strength of 80-90MPa, tensile modulus of 3.2-3.4GPa and elongation at break of 4%-5% and can be used in liquid infusion molding of large-size composite material parts.
Description
Technical field
The present invention relates to a kind of composite liquid form low viscosity, low heat release, high-performance epoxy resin/curative systems, belong to Epoxy Resin Technology field.
Background technology
Fibre reinforced epoxy resin composite has that specific tenacity is high, specific modulus is high, the advantage such as density is little, scantlings of the structure is stable, corrosion-resistant, antifatigue and material property can design, has been widely used in the fields such as aerospace, communications and transportation, wind electricity blade manufacture, chemical anticorrosion, construction work and sports equipment.
Pouring liquid forming technique is the novel process of matrix material rapid shaping, that liquid resin injects and lays in the mould of fiber reinforced material in advance under vacuum pressure field action, application fluids resin by negative pressure evenly fully floods, permeates whole layer of fibers, and completes self-crosslinking curing reaction formation goods simultaneously.Pouring liquid moulding process has the advantage that efficiency is high, with short production cycle, process is simple, cost is low.
Epoxy resin/curative systems has low viscosity, low curing reaction heat release, excellent comprehensive mechanical property ensure that pouring liquid moulding process is implemented and the prerequisite of the large-scale product stability of fibre composite.
Reducing epoxy-resin systems viscosity effective means is adopt to add Mars thinner, and the reactive thinner usually adopted has: butyleneglycol glycidyl ether, Polyethylene Glycol Bisglycidyl Ether, hexalin glycidyl ether etc.But, add the mechanical properties decrease that thinner can bring material usually, meanwhile, also can cause the rising of curing reaction heat release when the oxirane value of thinner is larger.
Chinese invention patent application CN101880443A discloses and adopts polyethyleneglycol diglycidylether to be reactive thinner, when addition is 10 parts, system viscosity significantly reduces, but tensile strength <70MPa, modulus <2.8GPa, comprehensive mechanical property is poor.In addition, this patent also adopts the hexalin diglycidylether thinner adding 25 parts to reduce viscosity, mechanical property is at about 75MPa, but because the oxirane value of thinner hexalin diglycidylether is high, cause whole system oxirane value high, curing exotherm amount and curing exotherm peak temperature can be caused to raise.
Chinese invention patent application CN200610116710.6 discloses a kind of synthesis technique of resin of epoxy vinyl ester with low exothermal peak, adopt bisphenol A epoxide resin and monocarboxylic acid Reactive Synthesis epoxy vinyl ester resin, curing exothermic peak is at about 120 DEG C, but, epoxy vinyl ester resin erosion resistance especially alkali resistance is poor, can not show a candle to epoxy resin.
Chinese invention patent application CN201010597675.0 discloses a kind of low heat release room-temperature curing epoxy sizing agent, adopts and adds 1 ~ 10 part low heat release altax P-30, but mechanical strength can be caused to reduce.
Chinese invention patent application CN200980113220.2, disclose experience heat absorption phase transformation to reduce the application based on the filler of the exothermic heat of reaction amount of the composition of epoxy resin, adopt and add endothermic transition additive, such as polyethylene powders, but system viscosity can be caused acutely to increase, and system viscosity is large.
Curing exotherm is the important factor affecting large-scale composite material production of articles and quality, if curing exotherm is concentrated, can local superheating be caused on the one hand, cause products solidifying uneven, produce internal stress, poor product quality, whole curing system is overheated on the other hand, and speed of response is too fast, wayward, product may be made to produce incipient scorch, even initiation potential.Therefore, need to develop low heat release, solidification rate epoxy resin faster.
Summary of the invention
The object of the invention is to propose a kind of composite liquid form low viscosity, low heat release, high strength epoxy resin/curative systems, the method of adding a small amount of thinner and pre-polymerization is adopted to carry out modification, keeping low viscous while, there is epoxy group content low, fundamentally reduce the feature of curing exotherm, simultaneously, because it is few to add dilution dosage, and can add more promotor, improve speed of reaction, the present invention is suitable for various epoxy resin, and method is simple.
The low viscosity that the present invention proposes, low heat release, high strength, high-toughness epoxy resin/curative systems comprise three parts, comprise matrix resin, solidifying agent, promotor; Wherein, matrix resin is amine modified epoxy and reactive epoxies diluent mixture, and solidifying agent is acid anhydrides.By material choice, prepolymerization reaction, solidification and obtain cured article, it is low that system of the present invention has viscosity, is applicable to composite liquid form; The curing reaction of system of the present invention has that reacting balance, curing reaction heat release are low, the fireballing feature of curing molding; Cured article has that tensile strength is high, tensile modulus is high, the feature of good toughness.
To achieve these goals, the technical solution adopted in the present invention is: by aminated compounds modified epoxy, reduce epoxy group content, add a small amount of epoxide resin reactive diluent, reduce viscosity, employing acid anhydrides is solidifying agent, while the viscosity of further reduction system, ensure complete cross-linked network, improve intensity and toughness.Adopt curing catalyst regulation system curing speed and curing exotherm.The epoxy resin of amine modification mixes with epoxide resin reactive diluent and becomes epoxy resin ingredient, and acid anhydrides is curing agent component, and curing catalyst is curing catalyst component.
In the present invention, composite liquid form low viscosity, low heat release, high strength, high-toughness epoxy resin/curative systems, it is characterized in that, comprise matrix resin, solidifying agent, promotor, described each constituent mass percentage composition: matrix resin is 39% ~ 65%, solidifying agent acid anhydrides is 34% ~ 60%, and promotor is 0.1% ~ 1.5%, and its total mass is by 100%.
In the present invention, matrix resin is amine modified epoxy and reactive epoxies diluent mixture.
Described amine modified epoxy is amine modifiers and epoxy resin is that 1:5 ~ 1:25 carries out mixed and modified forming according to the mol ratio of amine modifiers and epoxide group, preferred 1:10 ~ 1:20.Preferred modification temperature 80 ~ 100 DEG C.
In the present invention, described epoxy resin is bisphenol A epoxide resin, bisphenol F epoxy resin, aliphatic category epoxy resin, in cycloaliphatic epoxy resin one or more.
In the present invention, described amine modifiers is one or more in aliphatic amide, ether amine, aromatic amine etc., and the reactive hydrogen number in its molecule is more than or equal to 2.
In the present invention, described reactive thinner is BDO glycidyl ether, Polyethylene Glycol Bisglycidyl Ether, polypropylene glycol glycidyl ether, carbon 12-14 alkyl glycidyl ether, the one such as 1,6-hexylene glycol glycidyl ether, or several mixtures.The consumption of described reactive thinner is 2% ~ 20% of amine modified epoxy quality, preferably 5% ~ 15%.
In the present invention, described solidifying agent acid anhydrides is one or more mixtures in HHPA, methyl hexahydrophthalic anhydride, carbic anhydride, methyl Na Dike acid anhydrides, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, methyl tetrahydro phthalic anhydride etc.
In the present invention, described promotor is the mixture of one or more in trolamine, DMP-30, dimethyl benzylamine, N-2-glycidyl aniline, quaternary ammonium salt etc.
In the present invention, system is used for the curing process of composite liquid form is that, at 70 ~ 160 DEG C of temperature, preferred consolidation temperature is 80 ~ 140 DEG C, and solidify 3 ~ 8 hours, the preferred consolidation time is 4 ~ 6 hours.Preferably point temperature section solidification.
A kind of composite liquid form low viscosity of the present invention, low heat release, high strength epoxy resin/curative systems, system viscosity is low, be 100 ~ 500mPas at 25 DEG C, curing exotherm peak value temperature is 90 ~ 120 DEG C, tensile strength is 80 ~ 90MPa, tensile modulus is 3.2 ~ 3.4GPa, and elongation at break is 4% ~ 5%, can be applied to large-scale composite material product pouring liquid shaping.
Embodiment
Further illustrate the present invention below by embodiment, but the present invention is not limited to these embodiments.
Embodiment 1
Benzylamine and bisphenol F epoxy resin epoxide group are mixed in flask in molar ratio=1:20, are placed in thermostatical oil bath moderate-speed mixer, react 4 hours at 80 ~ 100 DEG C of temperature, the amine modified epoxy prepared is collected for subsequent use.
Amine modified epoxy 100g and 1,4-butyleneglycol glycidyl ether 5g and HHPA 91g, with DMP-30 promotor 0.27g, stir, vacuumize the bubble that degass, by 90 DEG C/2h+130 DEG C/2h cast cured explosive, can obtain epoxy resin cured product, curing exotherm peak value temperature and performance list in table 1.
Embodiment 2
Benzylamine and bisphenol F epoxy resin epoxide group are mixed in flask in molar ratio=1:15, are placed in thermostatical oil bath moderate-speed mixer, react 4 hours at 80 ~ 100 DEG C of temperature, the amine modified epoxy prepared is collected for subsequent use.
Amine modified epoxy 100g, 1,4-butyleneglycol glycidyl ether 5g, HHPA and methyl hexahydrophthalic anhydride are according to mass ratio 1:1 mixed acid anhydride 88g, with DMP-30 promotor 0.24g, stir, vacuumize the bubble that degass, by 90 DEG C/2h+130 DEG C/2h cast cured explosive, can obtain epoxy resin cured product, curing exotherm peak value temperature and performance list in table 1.
Embodiment 3
Benzylamine and bisphenol F epoxy resin epoxide group are mixed in flask in molar ratio=1:15, are placed in thermostatical oil bath moderate-speed mixer, react 4 hours at 80 ~ 100 DEG C of temperature, the amine modified epoxy prepared is collected for subsequent use.
Amine modified epoxy 100g, Polyethylene Glycol Bisglycidyl Ether 10g, HHPA and methyl hexahydrophthalic anhydride are by quality 1:1 mixed acid anhydride 87g, with DMP-30 promotor 0.26g, stir, vacuumize the bubble that degass, namely by 90 DEG C/2h+130 DEG C/2h cast cured explosive, can obtain epoxy resin cured product, curing exotherm peak value temperature and performance list in table 1.
Comparative example 4
Bisphenol F epoxy resin 100g, 1,4-butyleneglycol glycidyl ether 5g, HHPA and methyl hexahydrophthalic anhydride are according to mass ratio 1:1 mixed acid anhydride 100g, with DMP-30 promotor 0.5g, stir, vacuumize the bubble that degass, namely by 90 DEG C/2h+130 DEG C/2h cast cured explosive, can obtain epoxy resin cured product, curing exotherm peak value temperature and performance list in table 1.
Table 1 embodiment 1-3 and comparative example 4 curing exotherm temperature and performance acquired results table look-up
Note: promotor tertiary amine mole component is mole component of all tertiary amines in system (comprising the amount of tertiary amine in promotor and amine modified epoxy)
The above, be only the specific embodiment of the present invention, the present invention can not be defined as content described by specification sheets.Anyly be familiar with those skilled in the art in the timely scope of conclusion of the present invention, the various change expected easily or change carried out to the present invention, all should be encompassed in protection scope of the present invention.
Claims (10)
1. a composite liquid form low viscosity, low heat release, high strength, high-toughness epoxy resin/curative systems, it is characterized in that, comprise matrix resin, solidifying agent, promotor, described each constituent mass percentage composition: matrix resin is 39% ~ 65%, solidifying agent acid anhydrides is 34% ~ 60%, and promotor is 0.1% ~ 1.5%; Matrix resin is amine modified epoxy and reactive epoxies diluent mixture.
2. according to the epoxy resin/curative systems of claim 1, it is characterized in that, amine modified epoxy is amine modifiers and epoxy resin is that 1:5 ~ 1:25 carries out mixed and modified forming according to the mol ratio of amine modifiers and epoxide group.
3. according to the epoxy resin/curative systems of claim 2, it is characterized in that, epoxy resin is bisphenol A epoxide resin, bisphenol F epoxy resin, aliphatic category epoxy resin, in cycloaliphatic epoxy resin one or more.
4. according to the epoxy resin/curative systems of claim 2, it is characterized in that, amine modifiers is one or more in aliphatic amide, ether amine, aromatic amine, and the reactive hydrogen number in its molecule is more than or equal to 2.
5. according to the epoxy resin/curative systems of claim 1, it is characterized in that, reactive thinner is 1,4-butyleneglycol glycidyl ether, Polyethylene Glycol Bisglycidyl Ether, polypropylene glycol glycidyl ether, carbon 12-14 alkyl glycidyl ether, the one such as 1,6-hexylene glycol glycidyl ether, or several mixtures; The consumption of described reactive thinner is 2% ~ 20% of amine modified epoxy quality.
6. according to the epoxy resin/curative systems of claim 1, it is characterized in that, the consumption of reactive thinner is 5% ~ 15% of amine modified epoxy quality.
7. according to the epoxy resin/curative systems of claim 1, it is characterized in that, described solidifying agent acid anhydrides is one or more mixtures in HHPA, methyl hexahydrophthalic anhydride, carbic anhydride, methyl Na Dike acid anhydrides, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, methyl tetrahydro phthalic anhydride.
8. according to the epoxy resin/curative systems of claim 1, it is characterized in that, described promotor is the mixture of one or more in trolamine, DMP-30, dimethyl benzylamine, N-2-glycidyl aniline, quaternary ammonium salt.
9. arbitrary epoxy resin/curative systems of claim 1-8 is used for composite liquid form.
10. arbitrary epoxy resin/curative systems of claim 1-8 is used for composite liquid form, and it is characterized in that, curing process is, at 70 ~ 160 DEG C of temperature, solidifies 3 ~ 8 hours.
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| CN201410646155.2A CN104448238A (en) | 2014-11-14 | 2014-11-14 | Low-viscosity, low-exothermicity, high-strength, high-toughness epoxy resin/curing agent system for liquid infusion molding of composite material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107629412A (en) * | 2017-09-29 | 2018-01-26 | 安徽众博新材料有限公司 | A kind of high-strength epoxy isolator material and preparation method thereof |
| CN107641192A (en) * | 2016-07-22 | 2018-01-30 | 北京化工大学 | A kind of high-strength high-toughness epoxy resin |
| CN107641193A (en) * | 2016-07-22 | 2018-01-30 | 北京化工大学 | One-step method prepares low viscosity high-strength and high-ductility epoxy resin |
| CN107686632A (en) * | 2017-09-27 | 2018-02-13 | 卡本复合材料（天津）有限公司 | A kind of epoxy-resin systems of pultrusion carbon fiber sheet |
| CN109074902A (en) * | 2016-03-15 | 2018-12-21 | 亨斯迈先进化工材料许可(瑞士)有限公司 | Preparation is used for the method for the insulation system of electrical engineering, thus obtained product and application thereof |
| CN109422867A (en) * | 2017-09-05 | 2019-03-05 | 北京化工大学 | A kind of high-modulus low viscosity epoxy resin and preparation method |
| CN112646521A (en) * | 2020-12-18 | 2021-04-13 | 深圳市彩田化工有限公司 | Preparation process of low-heat-release epoxy resin adhesive |
| CN112694372A (en) * | 2020-12-25 | 2021-04-23 | 石仲仑 | Epoxy composite propellant, preparation method and application thereof |
| CN113789034A (en) * | 2021-10-13 | 2021-12-14 | 航天特种材料及工艺技术研究所 | Low-heat-release epoxy resin composition and preparation method thereof |
| CN113817291A (en) * | 2021-09-30 | 2021-12-21 | 广东博汇新材料科技股份有限公司 | Carbon fiber vacuum infusion epoxy resin |
| CN115340746A (en) * | 2021-12-22 | 2022-11-15 | 道生天合材料科技(上海)股份有限公司 | Epoxy anhydride system material for perfusion process, use method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109074902A (en) * | 2016-03-15 | 2018-12-21 | 亨斯迈先进化工材料许可(瑞士)有限公司 | Preparation is used for the method for the insulation system of electrical engineering, thus obtained product and application thereof |
| CN107641192A (en) * | 2016-07-22 | 2018-01-30 | 北京化工大学 | A kind of high-strength high-toughness epoxy resin |
| CN107641193A (en) * | 2016-07-22 | 2018-01-30 | 北京化工大学 | One-step method prepares low viscosity high-strength and high-ductility epoxy resin |
| CN109422867A (en) * | 2017-09-05 | 2019-03-05 | 北京化工大学 | A kind of high-modulus low viscosity epoxy resin and preparation method |
| CN109422867B (en) * | 2017-09-05 | 2020-06-16 | 北京化工大学 | High-modulus low-viscosity epoxy resin and preparation method thereof |
| CN107686632A (en) * | 2017-09-27 | 2018-02-13 | 卡本复合材料（天津）有限公司 | A kind of epoxy-resin systems of pultrusion carbon fiber sheet |
| CN107629412A (en) * | 2017-09-29 | 2018-01-26 | 安徽众博新材料有限公司 | A kind of high-strength epoxy isolator material and preparation method thereof |
| CN112646521A (en) * | 2020-12-18 | 2021-04-13 | 深圳市彩田化工有限公司 | Preparation process of low-heat-release epoxy resin adhesive |
| CN112646521B (en) * | 2020-12-18 | 2022-02-11 | 深圳市彩田化工有限公司 | Preparation process of low-heat-release epoxy resin adhesive |
| CN112694372A (en) * | 2020-12-25 | 2021-04-23 | 石仲仑 | Epoxy composite propellant, preparation method and application thereof |
| CN113817291A (en) * | 2021-09-30 | 2021-12-21 | 广东博汇新材料科技股份有限公司 | Carbon fiber vacuum infusion epoxy resin |
| CN113789034A (en) * | 2021-10-13 | 2021-12-14 | 航天特种材料及工艺技术研究所 | Low-heat-release epoxy resin composition and preparation method thereof |
| CN115340746A (en) * | 2021-12-22 | 2022-11-15 | 道生天合材料科技(上海)股份有限公司 | Epoxy anhydride system material for perfusion process, use method and application thereof |
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