CN102675826A - Temperature-resistant high-strength high-toughness composite epoxy resin and manufacturing method thereof - Google Patents
Temperature-resistant high-strength high-toughness composite epoxy resin and manufacturing method thereof Download PDFInfo
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- CN102675826A CN102675826A CN2012101257413A CN201210125741A CN102675826A CN 102675826 A CN102675826 A CN 102675826A CN 2012101257413 A CN2012101257413 A CN 2012101257413A CN 201210125741 A CN201210125741 A CN 201210125741A CN 102675826 A CN102675826 A CN 102675826A
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Abstract
The invention discloses a temperature-resistant high-strength high-toughness composite epoxy resin and a manufacturing method thereof. The temperature-resistant high-strength high-toughness composite epoxy resin is made by steps: subjecting 0-200 parts of solid epoxy resins and 100 parts of liquid epoxy resins to hot meting and well mixing, adding 0-80 parts of core-shell particle toughening agents, 0-100 parts of diluents, 5-80 parts of curing agents, 0-10 parts of catalysts and 0-15 parts of flame retardants, grinding and finally performing vacuum defoaming. The composite epoxy resin is excellent in shock resistance, shear resistance, bendability and temperature resistance.
Description
Technical field
The present invention relates to a kind of epoxy-resin systems of high-strength and high ductility, particularly relate to a kind of core-shell particles toughness reinforcing composite epoxy resin that contains bisphenol-s epoxy resin and method of manufacture thereof.
Background technology
Bisphenol-s epoxy resin has been introduced-SO
2-group, compound with other epoxy resin as resin matrix, thermotolerance and the adhesiveproperties of system are improved, the spy is suitable for fields such as military project and national defence, afterwards fragility is bigger but solidify, largely limit its in the high-end technology Application for Field.Therefore how to improve the toughness of epoxy resin, make the excellent more focus that becomes people's research of its over-all properties.At present relevant epoxy resin roughening research makes considerable progress, but still existing problems, though for example rubber-toughened epoxy resin improves its toughness, thermostability and mechanical property descend to some extent; The epoxy resin toughened thermotolerance that keeps original material of hot plastomer, but toughening effect is not obvious; The TLCP modified epoxy has also kept other mechanical property and the thermal property of material increasing flexible simultaneously, but the synthetic difficulty of TLCP, raw material is rare, heat-drawn wire is high, process relatively difficulty.For overcoming above-mentioned deficiency; People attempt a lot of methods; Wherein effective means is to adopt core-shell particles (soft nuclear/duricrust) epoxy resin toughened the most; This method for toughening can make the toughness of epoxy resin improve, and second-order transition temperature reduces hardly, like synthetic and 2009 the 18th volumes of modified epoxy " Chinese tackiness agent " the 9th phase P of the propenoate core-shell nano of researchs such as Zhang Xugang
14-18, when the core-shell particles add-on was 10 parts, shock strength reached 42kJ/m
2, and the pure relatively epoxy systems of second-order transition temperature slightly descends.PBA/PMMA type nucleocapsid elastic particle epoxy resin toughened " macromolecular material and engineering " calendar year 2001 the 17th volume the 1st phase P of the grand research of model and for example
121-124, when core-shell particles added 10 parts, toughness was greatly improved, and second-order transition temperature does not reduce simultaneously.More than these toughness reinforcing resins all be that a kind of epoxy resin is matrix, also do not appear in the newspapers about the toughness reinforcing composite epoxy resin of core-shell particles.
Summary of the invention
The objective of the invention is to propose a kind of heat-resistance type high-strength and high ductility composite epoxy resin forms and method of manufacture.Owing to contain bisphenol-s epoxy resin in the composite epoxy resin, can improve curing system mechanical property and thermal property, have good application prospects.
A kind of temperature tolerance high-strength and high ductility composite epoxy resin of the present invention is formed and is comprised following component: solid epoxy 0-200 part, 100 parts of liquid epoxiess, core-shell particles toughner 0-80 part; Thinner 0-100 part; Fire retardant 0-15 part, solidifying agent 5-80 part, catalyzer 0-10 part.
In this kind temperature tolerance high-strength and high ductility composite epoxy resin, the solid epoxy that is adopted is bisphenol-s epoxy resin and verivate thereof, and its structure is following:
R wherein
1And R
2Be in the alkyl that contains 1-6 C, vinyl, allyl group, Halogen group, epoxide group etc. one or more; R
1And R
2Can be identical can be different; M, n are the natural number of 1-4.The positive integer of K=0-100.
In this kind temperature tolerance high-strength and high ductility composite epoxy resin; The liquid epoxies that is adopted is bisphenol A epoxide resin, bisphenol F epoxy resin, AG-80 epoxy resin, glycolylurea epoxide resin, PARA AMINOPHENOL epoxy resin, m-xylene diamine epoxide resin, resorcinol type epoxy, dihydroxyphenyl propane D epoxy resin, hydrogenated bisphenol A epoxy resin, organic-silicon-modified bisphenol A epoxide resin, fluorinated epoxy resin, o-cresol formaldehyde epoxy resin, one or more in the allyl group bisphenol-type epoxy resin.
In this kind temperature tolerance high-strength and high ductility composite epoxy resin, as the core-shell particles of toughner, requirement is that nuclear is elastomerics, and shell is ability and epoxy resin compatibility.
In this kind temperature tolerance high-strength and high ductility composite epoxy resin, thinner adopts main chain to contain the epoxy resin diluent of representative examples of saturated aliphatic six-membered ring structure, and its structural formula is following three kinds;
In temperature tolerance high-strength and high ductility composite epoxy resin of the present invention,, one or more in nano level zinc borate, Marinco H, the trimeric cyanamide etc. are adopted in the fire retardant agent, and it is preferably the nano level zinc borate.
This kind temperature tolerance high-strength and high ductility hybrid epoxy resin system can be used arylamine class solidifying agent, diaminodiphenylsulfone(DDS) for example, MDA, mphenylenediamine, m-xylene diamine and 3,3 '-diethylammonium-4,4 '-diamino-benzhydrylamine.
This kind of temperature tolerance high-strength and high ductility hybrid epoxy resin system can be used the acid anhydride type curing agent Tetra hydro Phthalic anhydride, Pyromellitic Acid diamines, THPA, methyl four phthalic anhydrides, HHPA, methyl Di Nake acid anhydrides or succinyl oxide
This kind of temperature tolerance high-strength and high ductility hybrid epoxy resin system can also use catalytic curing agent such as Dyhard RU 100, catalyzer to adopt in imidazoles, ureas or the guanidine class one or more
The preparation method of the toughness reinforcing composite epoxy resin of the present invention is: composite epoxy resin (pressing certain mass than the mixing) heating and melting and even that contains bisphenol-s epoxy resin; Add toughner core-shell particles and solidifying agent, catalyzer, thinner and fire retardant by a certain percentage, grind several times.Then mixture is vacuumized except that bubble.Mixture is injected the mould of preheating, curing promptly obtains solidified epoxy resin under certain solidification value and set time again.
Toughness reinforcing composite epoxy resin of the present invention has excellent resistance to impact shock, shearing resistance, flexural strength, high glass transition and thermostability preferably, and preparation technology is simple, and Application Areas is wide.
Embodiment
Embodiment 1
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 20g puts into beaker, in 120 ℃ oil bath the heating and mechanical stirring until system be transparent till; Add 5g (PB/PMMA) core-shell particles, the 9.6g Dyhard RU 100, the 0.6g glyoxal ethyline grinds 6 times through three rollers; Under 60 ℃, vacuumize, pour in 60 ℃ the tetrafluoroethylene mould, solidified 1 hour, solidified 1 hour down at 120 ℃ again at 80 ℃; Sampling promptly gets goods, tests various performances, and test-results is seen table 1.
Embodiment 2
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 20g puts into beaker, in 120 ℃ oil bath the heating and mechanical stirring until system be transparent till; Naturally cool to room temperature, add 10g (PB/PMMA) core-shell particles, 9.6g Dyhard RU 100,0.6g glyoxal ethyline; Grind 6 times through three rollers, under 60 ℃, vacuumize, pour in 60 ℃ the tetrafluoroethylene mould, solidified 1 hour at 80 ℃; Solidified 1 hour down at 120 ℃, sampling promptly gets goods, tests various performances again, and test-results is seen table 1.
Embodiment 3
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 20g puts into beaker, in 120 ℃ oil bath the heating and mechanical stirring until system be transparent till; Naturally cool to room temperature, add 15g (PB/PMMA) core-shell particles, 9.6g Dyhard RU 100,0.6g glyoxal ethyline; Grind 6 times through three rollers, under 60 ℃, vacuumize, pour in 60 ℃ the tetrafluoroethylene mould, solidified 1 hour at 80 ℃; Solidified 1 hour down at 120 ℃, sampling promptly gets goods, tests various performances again, and test-results is seen table 1.
Embodiment 4
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 20g puts into beaker, in 120 ℃ oil bath the heating and mechanical stirring until system be transparent till; Naturally cool to room temperature, add 20g (PB/PMMA) core-shell particles, 9.6g Dyhard RU 100,0.6g glyoxal ethyline; Grind 6 times through three rollers, under 60 ℃, vacuumize, pour in 60 ℃ the tetrafluoroethylene mould, solidified 1 hour at 80 ℃; Solidified 1 hour down at 120 ℃, sampling promptly gets goods, tests various performances again, and test-results is seen table 1.
Embodiment 5
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 20g puts into beaker; In 120 ℃ oil bath heating and mechanical stirring until system be transparent till, naturally cool to room temperature, add 5g (PB/PMMA) core-shell particles; 38gDDS grinds 6 times through three rollers, vacuumizes; Pour in the tetrafluoroethylene mould of preheating, under the condition of 80 ℃/2h+120 ℃/2h+180 ℃/2h, solidify, promptly get sample.
Embodiment 6
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 40g puts into beaker, in 120 ℃ oil bath the heating and mechanical stirring until system be transparent till; Naturally cool to room temperature, add 20g (PB/PMMA) core-shell particles, 11.2g Dyhard RU 100,0.7g glyoxal ethyline; Grind 6 times through three rollers, under 60 ℃, vacuumize, pour in 60 ℃ the tetrafluoroethylene mould; Solidified 1 hour at 80 ℃, solidified 1 hour down at 120 ℃, sampling promptly gets goods
Embodiment 7
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 20g puts into beaker; In 120 ℃ oil bath heating and mechanical stirring until system be transparent till, naturally cool to room temperature, add the 20g thinner; 20g (PB/PMMA) core-shell particles, 10g nano level ZnBO
3, the 10.5g Dyhard RU 100, the 0.62g glyoxal ethyline grinds 6 times through three rollers, under 60 ℃, vacuumizes, and pours in 60 ℃ the tetrafluoroethylene mould, solidifies 1 hour at 80 ℃, solidifies 1 hour down at 120 ℃ again, and sampling promptly gets goods
Embodiment 8
Take by weighing 100g epoxy resin (E-51), bisphenol-s epoxy resin 20g puts into beaker; In 120 ℃ oil bath heating and mechanical stirring until system be transparent till, naturally cool to room temperature, add the 30g thinner; 10g (PB/PMMA) core-shell particles, 10g nano level ZnBO
3, methyl Na Dike acid anhydrides 100g, 2.4g 2-ethyl-4 methyl-imidazoles grinds 6 times through three rollers, vacuumizes, and pours in the tetrafluoroethylene mould of preheating, solidifies 2 hours at 90 ℃, solidifies 2 hours down at 140 ℃ again, and sampling promptly gets goods
Embodiment 9
Take by weighing 100g epoxy resin (AG-80), bisphenol-s epoxy resin 20g puts into beaker; In 120 ℃ oil bath heating and mechanical stirring until system be transparent till, naturally cool to room temperature, add the 40g thinner; 10g (PBA/PMMA) core-shell particles, 15g nano level ZnBO
3, the 18.0g Dyhard RU 100,3.6g dichlorophenyl dimethyl urea (DCMU) grinds 6 times through three rollers, vacuumizes, and pours in the tetrafluoroethylene mould of preheating, solidifies 4 hours at 80 ℃, solidifies 2 hours down at 130 ℃ again, and sampling promptly gets goods.
Comparative example 1
(PB/PMMA) changes 0g into core-shell particles, and all the other conditions are with embodiment 1, and test-results is seen table 1
Comparative example 2
Take by weighing 100g epoxy resin (E-51), AG-80 epoxy resin 20g, 5g (PB/PMMA) core-shell particles, 9.6g Dyhard RU 100; 0.6g glyoxal ethyline grinds 6 limits through three rollers, under 60 ℃, vacuumizes; Pour in 60 ℃ the tetrafluoroethylene mould, solidified 1 hour, solidified 1 hour down at 120 ℃ again at 80 ℃; Sampling promptly gets goods, tests various performances, and test-results is seen table 1.
Comparative example 3
Take by weighing 100g epoxy resin (E-51), 5g (PB/PMMA) core-shell particles, 8.0g Dyhard RU 100; 0.5g glyoxal ethyline grinds 6 limits through three rollers, under 60 ℃, vacuumizes; Pour in 60 ℃ the tetrafluoroethylene mould, solidified 1 hour, solidified 1 hour down at 120 ℃ again at 80 ℃; Sampling promptly gets goods, surveys its second-order transition temperature.
Table 1
| Project | Shock strength | Flexural strength | Shearing resistance | Second-order transition temperature |
| Unit | KJ/m 2 | MPa | MPa | ℃ |
| Embodiment 1 | 14.1 | 151.0 | 19.9 | 183.7 |
| Embodiment 2 | 15.5 | 131.2 | 24.3 | ?- |
| Embodiment 3 | 22.5 | 122.8 | 25.2 | 190.7 |
| Embodiment 4 | 22.8 | 154.6 | 25.7 | - |
| Comparative example 1 | 9.7 | 129.3 | 12.0 | 182.3 |
| Comparative example 2 | 12.2 | 107.2 | 16.7 | - |
| Testing standard | GB-T2571-95 | GB-T2571-95 | GB7124-86 | DMA |
Table 2
| Project | Second-order transition temperature | 2% heat decomposition temperature |
| Comparative example 3 | 139.7℃ | 286℃ |
| Embodiment 1 | 141.1℃ | 292℃ |
| Testing method | DSC | Thermal weight loss |
Claims (12)
1. a heat-resistance type high-strength and high ductility composite epoxy resin is formed and method of manufacture; It is characterized in that the toughness reinforcing composite epoxy system of this kind comprises following component: solid epoxy 0-200 part, 100 parts of liquid epoxiess, core-shell particles toughner 0-80 part; Thinner 0-100 part; Fire retardant 0-15 part, solidifying agent 5-80 part, catalyzer 0-10 part.
2. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture, it is characterized in that described solid epoxy is bisphenol-s epoxy resin and verivate thereof, and its structure is following:
R wherein
1And R
2Be in the alkyl that contains 1-6 C, vinyl, allyl group, Halogen group, epoxide group etc. one or more; R
1And R
2Can be identical can be different; M, n are the natural number of 1-4, and K=0-100 is a positive integer.
3. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture; It is characterized in that described liquid epoxies is bisphenol A epoxide resin, bisphenol F epoxy resin, AG-80 epoxy resin, glycolylurea epoxide resin, PARA AMINOPHENOL epoxy resin, m-xylene diamine epoxide resin, resorcinol type epoxy, dihydroxyphenyl propane D epoxy resin, hydrogenated bisphenol A epoxy resin, organic-silicon-modified bisphenol A epoxide resin, fluorinated epoxy resin, o-cresol formaldehyde epoxy resin, one or more in the allyl group bisphenol-type epoxy resin.
4. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture, it is characterized in that described toughner is core-shell particles (nuclear is elastomerics, shell ability and epoxy resin compatibility), its average particle size range 10-500nm.
5. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture, it is characterized in that described thinner is the epoxy resin diluent that main chain contains the representative examples of saturated aliphatic six-membered ring structure, has following three kinds of structural formulas:
6. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture, it is characterized in that described fire retardant is one or more in nano level zinc borate, Marinco H, the trimeric cyanamide etc.
7. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture, it is characterized in that described solidifying agent is arylamine class solidifying agent, acid anhydride type curing agent, one or more in the catalytic curing agent.
8. according to the solidifying agent described in the claim 7, it is characterized in that arylamine class solidifying agent is a diaminodiphenylsulfone(DDS), MDA, mphenylenediamine, m-xylene diamine and 3,3 '-diethylammonium-4, one or more in 4 '-diamino-benzhydrylamine.
9. solidifying agent according to claim 7 is characterized in that: acid anhydride type curing agent is a Tetra hydro Phthalic anhydride, one or more in Pyromellitic Acid diamines, THPA, methyl four phthalic anhydrides, HHPA, methyl Di Nake acid anhydrides or the succinyl oxide.
10. solidifying agent according to claim 7 is characterized in that: catalytic curing agent is Dyhard RU 100 or imidazoles.
11. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture, it is characterized in that described catalyzer is one or more in imidazoles, ureas or the guanidine class catalyzer.
12. a kind of heat-resistance type high-strength and high ductility composite epoxy resin according to claim 1 is formed and method of manufacture; It is characterized in that described method of manufacture for earlier with solid and liquid epoxies heating and melting even after; Add thinner, core-shell particles toughner, solidifying agent, catalyzer and fire retardant again and grind, last vacuum defoamation forms.
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| CN109679282A (en) * | 2018-11-27 | 2019-04-26 | 四川大学 | A kind of high-strength high-toughness epoxy composite material with particular nanostructure |
| CN109679282B (en) * | 2018-11-27 | 2024-05-17 | 四川大学 | High-strength high-toughness epoxy composite material with specific nano structure |
| CN110776719A (en) * | 2019-10-18 | 2020-02-11 | 合肥工业大学 | Method for dispersing nano inorganic particle filler in solid epoxy resin |
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Application publication date: 20120919 |