CN102153724A - Aromatic polyether glycidyl ether epoxide resin and preparation method of aromatic polyether glycidyl ether epoxide resin - Google Patents
Aromatic polyether glycidyl ether epoxide resin and preparation method of aromatic polyether glycidyl ether epoxide resin Download PDFInfo
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- CN102153724A CN102153724A CN 201010111978 CN201010111978A CN102153724A CN 102153724 A CN102153724 A CN 102153724A CN 201010111978 CN201010111978 CN 201010111978 CN 201010111978 A CN201010111978 A CN 201010111978A CN 102153724 A CN102153724 A CN 102153724A
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Abstract
The invention relates to an epoxide resin and a preparation method of the epoxide resin, in particular to an aromatic polyether glycidyl ether epoxide resin which has high toughness after being cured and a preparation method of the aromatic polyether glycidyl ether epoxide resin. The aromatic polyether glycidyl ether epoxide resin with the following structure is prepared by performing a reaction of aromatic polyether and epoxy chloropropane. The aromatic polyether glycidyl ether epoxide resin has the advantages of low viscosity and good processing technological property, can be independently used as the epoxide resin and can also be used as a toughening modifier of other epoxide resins. When the aromatic polyether glycidyl ether epoxide resin is independently used as the epoxide resin, a cured product of the aromatic polyether glycidyl ether epoxide resin has greatly excellent toughness; and when the aromatic polyether glycidyl ether epoxide resin is used as the toughening modifier of other epoxide resins, the toughness of other epoxide resins can be greatly improved and meanwhile the tensile strength, bending strength and heat resistance of other epoxide resins are not reduced.
Description
Technical field
The present invention relates to Resins, epoxy and preparation method thereof, particularly have aromatic polyether tetraglycidel ether epoxy resin of high tenacity and preparation method thereof after the curing.
Background technology
Resins, epoxy has a very wide range of applications in fields such as sizing agent, coating, microelectronics Packaging and matrices of composite materials owing to have advantages such as good cementability, mechanical strength, chemical resistance and processing performance.But Resins, epoxy commonly used such as bisphenol A epoxide resin all exist shock strength low after solidifying, and the shortcoming that fragility is big often need be carried out toughness reinforcing to Resins, epoxy in actual applications.Common method for toughening is that the matrix that adds second component such as rubber elastomer, inorganic rigid particle or thermoplastics and Resins, epoxy in the matrix of Resins, epoxy forms phase separation structure, absorb energy or be separated by elastomer particles and induce epoxy viscous deformation at the interface to improve the toughness of Resins, epoxy (as document European PolymerJournal.V38,2002,251-264; Polymer.V41,2000,4451-4459; Polymer.V48,2007, reports such as 530-541), perhaps adopt have with Resins, epoxy toughness such as the hyper-branched polyester of certain consistency or segmented copolymer preferably superpolymer add form half in the Resins, epoxy/that full inierpeneirating network structure strengthens Resins, epoxy is toughness reinforcing (as Polym.Adv.Technol.V19,2008,1597-1607; Macromol.Symp.2007,256,55-64).But the toughening effect to Resins, epoxy that above method has is limited; the stretching that usually can cause Resins, epoxy that has, flexural strength descend, resistance toheat reduces or poor processability; and have if reach toughening effect; to bigger dependency be arranged to fabrication process condition, thereby limit its range of application.
Summary of the invention
The objective of the invention is to overcome the fragility of existing Resins, epoxy, and the deficiency of existing epoxy resin roughening method, the aromatic polyether tetraglycidel ether epoxy resin that has high tenacity behind a kind of the curing is provided.
Another object of the present invention is to provide the preparation method of above-mentioned aromatic polyether tetraglycidel ether epoxy resin.
The preparation method of aromatic polyether tetraglycidel ether epoxy resin of the present invention is simple, and the viscosity of resin is low, and complete processing is good, can use as Resins, epoxy separately, also can be used as other TOUGHENING MODIFICATION OF EPOXY RESINS agent.When using as Resins, epoxy separately, the cured article of this aromatic polyether tetraglycidel ether epoxy resin has extremely good toughness; When using, can increase substantially the toughness of other Resins, epoxy as other TOUGHENING MODIFICATION OF EPOXY RESINS agent.Because when this aromatic polyether tetraglycidel ether epoxy resin uses as Resins, epoxy or as other TOUGHENING MODIFICATION OF EPOXY RESINS agent separately, cured article after the curing has the characteristics of high-strength and high ductility, therefore, aromatic polyether tetraglycidel ether epoxy resin of the present invention can be used as the component that constitutes coating, tackiness agent, electron device package material, carbon fiber or glass fiber compound material matrix resin and is used widely.
Aromatic polyether tetraglycidel ether epoxy resin of the present invention has following structure:
Wherein: R is
Preferred described aromatic polyether tetraglycidel ether epoxy resin has following structure:
Wherein: n=1.
The synthetic route of aromatic polyether tetraglycidel ether epoxy resin of the present invention is as follows:
Wherein: R is
Described aromatic polyether is
Wherein: R is,,
Preparation aromatic polyether tetraglycidel ether epoxy resin used raw material aromatic polyether can adopt above-mentioned commercially available prod among the present invention, or adopts the ordinary method of this area, and aromatic series phenolic monomers and oxyethane addition by one of following structure make.
The method for preparing bisphenol A epoxide resin commonly used is not suitable for preparation aromatic polyether tetraglycidel ether epoxy resin of the present invention; In addition because aromatic polyether mostly is solid-state or high viscosity liquid, and solvability is bad in organic solvent commonly used, also be not suitable for adopting Lewis acid that traditional preparation Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether uses catalyzer, so use solid alkali among the present invention as catalyzer as ring-opening reaction.The present invention's used solid base catalyst in preparation process is the oxyhydroxide of I family metallic element, and as lithium hydroxide, sodium hydroxide or potassium hydroxide etc., wherein preferred solid catalyst is a sodium hydroxide.
The preparation method of aromatic polyether tetraglycidel ether epoxy resin of the present invention is:
Mole number by the reactant aromatic polyether, in rare gas element (as nitrogen) atmosphere, the epoxy chloropropane (preferably use 5～20 mole epoxy chloropropane) of 1 mole aromatic polyether with 2～30 moles mixed, the solid base catalyst (solid base catalyst that preferably adds 2～4 moles) that adds 2～6 moles, in temperature of reaction is to react under 50～90 ℃ (preferable reaction temperature is 60～80 ℃), reaction times is 5～20 hours (the preferred reaction time is 8～16 hours, and more preferably the reaction times is 10～12 hours); Reaction finishes the back and adds the organic solvent diluting product, and the product after diluting with deionized water wash is to neutral; Isolating organic phase then, is that 90～120 ℃ and pressure are that underpressure distillation is removed the liquid that obtains behind the fugitive constituent in the organic phase and is aromatic polyether glycidyl ether epoxy of the present invention under 1～10mmHg in temperature.
Mole number by the reactant aromatic polyether, 1 mole aromatic polyether mixes with 2～30 moles epoxy chloropropane, the amount of epoxy chloropropane is less than 2 moles of meetings and causes the hydroxyl residual volume at aromatic polyether two ends to increase, reaction not exclusively, if the amount of epoxy chloropropane more than 30 moles, causes a large amount of wastes of epoxy chloropropane or cost recovery to increase.The consumption of preferred epoxy chloropropane is 5～20 moles.The add-on of solid base catalyst is 2～6 moles, and it is incomplete to be less than 2 molar reactives, causes side reaction to increase greater than 6 moles of meetings, and therefore, the consumption of preferred solid base catalyst is 2～4 moles.Above-mentioned temperature of reaction is 50～90 ℃, and is low if reaction temperature is spent, and the required reaction times is oversize, if temperature of reaction is higher than 90 ℃, the side reaction aggravation can cause product viscosity to increase, and oxirane value reduces, and preferred temperature of reaction is 60～80 ℃.Reaction times is 5～20 hours, if the reaction times is less than 5 hours, reaction yield is low, improve reaction yield if the reaction times, not only can not advance one more than 20 hours, also can cause by product to increase on the contrary, viscosity raises, oxirane value reduces, and the preferred reaction times is 8～16 hours, and the preferred reaction times is 10～12 hours.Above-mentioned building-up reactions is preferably in rare gas element (as the nitrogen) atmosphere carries out, if carry out in air atmosphere, will cause the product color burn.
Described organic solvent is at least a in the group formed of toluene, dimethylbenzene, trichloromethane, methylene dichloride.
Described solid base catalyst is the oxyhydroxide of I family metallic element, and as lithium hydroxide, sodium hydroxide or potassium hydroxide etc., wherein preferred solid catalyst is a sodium hydroxide.
The preparation method of aromatic polyether tetraglycidel ether epoxy resin of the present invention is simple, and resin viscosity is low, and complete processing is good.Aromatic polyether tetraglycidel ether epoxy resin of the present invention can use as Resins, epoxy separately, can be used as the component that constitutes coating, tackiness agent, electron device package material, carbon fiber or glass fiber compound material matrix resin; Or as other TOUGHENING MODIFICATION OF EPOXY RESINS agent, other Resins, epoxy after the modification can be used as the component that constitutes coating, tackiness agent, electron device package material, carbon fiber or glass fiber compound material matrix resin.
When the aromatic polyether tetraglycidel ether epoxy resin used as Resins, epoxy separately, the solidifying agent of use did not have particular restriction.Epoxy curing agent commonly used all is effective solidifying agent of above-mentioned aromatic polyether tetraglycidel ether epoxy resin, as is selected from least a in the group that amine curing agent, acid anhydride type curing agent, imidazole curing agent, dicy-curing agent etc. are formed.The consumption of solidifying agent can be different and different according to the kind of solidifying agent.
Described amine curing agent is selected from least a in the group that aliphatics amine, aromatic amine, alicyclic amine form.
Described aliphatics amine is diethylenetriamine, tetraethylene pentamine or their mixture etc.
Described aromatic amine is selected from 4,4`-diaminodiphenyl oxide, 4,4`-diaminodiphenylmethane, 4, at least a in the group that 4`-diaminodiphenylsulfone(DDS), mphenylenediamine etc. are formed.
Described alicyclic amine is isophorone diamine, N-aminoethyl piperazine or their mixture etc.
Described acid anhydride type curing agent is selected from least a in the group that Tetra hydro Phthalic anhydride, methyl carbic anhydride, methyl hexahydrophthalic anhydride etc. are formed.
In addition, also can optionally add this area additives such as filler, curing catalyst and/or other plasticized modifier commonly used in the above-mentioned aromatic polyether tetraglycidel ether epoxy resin according to actual needs.
Whether the condition of cure of above-mentioned aromatic polyether tetraglycidel ether epoxy resin can be according to the kind of solidifying agent, use the type of promotor and promotor different and different.
When the aromatic polyether tetraglycidel ether epoxy resin uses as other TOUGHENING MODIFICATION OF EPOXY RESINS agent, there is not particular restriction for described other Resins, epoxy.Described other Resins, epoxy is selected from tetraglycidel ether epoxy resin or glycidyl amine Resins, epoxy etc.Aromatic polyether tetraglycidel ether epoxy resin among the present invention and above-mentioned other Resins, epoxy have good consistency, can dissolve each other in any proportional range.
When above-mentioned aromatic polyether tetraglycidel ether epoxy resin during as plasticized modifier, the usage quantity of aromatic polyether tetraglycidel ether epoxy resin is not particularly limited.If but wish to reach modified effect preferably, in the Resins, epoxy that is modified is 100 weight parts, the minimum usage quantity of aromatic polyether tetraglycidel ether epoxy resin is 5 weight parts, and preferred minimum usage quantity is 10 weight parts, and preferred minimum usage quantity is 15 weight parts.The highest usage quantity without limits, usually, along with the increase of above-mentioned aromatic polyether tetraglycidel ether epoxy resin consumption, the toughness of modified epoxy resin condensate increases.
When above-mentioned aromatic polyether tetraglycidel ether epoxy resin used as plasticized modifier, the solidifying agent of use did not have particular restriction.Epoxy curing agent commonly used all is effective solidifying agent of above-mentioned aromatic polyether tetraglycidel ether epoxy resin.As be selected from least a in the group that amine curing agent, acid anhydride type curing agent, imidazole curing agent, dicy-curing agent etc. are formed.The consumption of solidifying agent can be different and different according to the kind of solidifying agent.
Described amine curing agent is selected from least a in the group that aliphatics amine, aromatic amine, alicyclic amine form.
Described aliphatics amine is diethylenetriamine, tetraethylene pentamine or their mixture etc.
Described aromatic amine is selected from 4,4`-diaminodiphenyl oxide, 4,4`-diaminodiphenylmethane, 4, at least a in the group that 4`-diaminodiphenylsulfone(DDS), mphenylenediamine etc. are formed.
Described alicyclic amine is isophorone diamine, N-aminoethyl piperazine or their mixture etc.
Described acid anhydride type curing agent is selected from least a in the group that Tetra hydro Phthalic anhydride, methyl carbic anhydride, methyl hexahydrophthalic anhydride etc. are formed.
In addition, also can optionally add this area additives such as filler, curing catalyst and/or other plasticized modifier commonly used in the above-mentioned modified epoxy resin system according to actual needs.
Whether the condition of cure of above-mentioned modified epoxy resin system can be according to the kind of solidifying agent, use the type of promotor and promotor different and different.
The present invention has synthesized the aromatic polyether tetraglycidel ether epoxy resin by aromatic polyether and epichlorohydrin reaction.It is low that this aromatic polyether tetraglycidel ether epoxy resin has viscosity, the advantage that process industrial art performance is good.It can use as Resins, epoxy separately, also can be used as other TOUGHENING MODIFICATION OF EPOXY RESINS agent.When using as Resins, epoxy separately, the cured article of this aromatic polyether tetraglycidel ether epoxy resin has extremely good toughness; When using as other TOUGHENING MODIFICATION OF EPOXY RESINS agent, can increase substantially the toughness of other Resins, epoxy, do not reduce stretching, flexural strength and the resistance toheat of other Resins, epoxy simultaneously.
Embodiment
Further specify the present invention below by specific embodiment, but the present invention is not limited to following embodiment.
Following embodiment 1～3 is the preparation of aromatic polyether tetraglycidel ether epoxy resin.Embodiment 4～9 is the preparation of the cured article and the aromatic polyether glycidyl ether modified bisphenol A epoxy resin cured matter of aromatic polyether tetraglycidel ether epoxy resin.
Embodiment 1
Mechanical stirring is being housed, reflux condensing tube, temperature is taken into account and is added 64g structural formula aromatic polyether as follows in the 500ml there-necked flask of nitrogen airway, and 148g epoxy chloropropane and 16g solid sodium hydroxide were heated to 60 ℃ of afterreactions 8 hours.After reaction finishes, in reaction system, add 250ml dilution with toluene product, and extremely neutral with the product after the deionized water wash dilution; Isolate organic phase then and under 100 ℃/3mmHg underpressure distillation remove fugitive constituent in the organic phase, obtain the aromatic polyether tetraglycidel ether epoxy resin 59g of following structure, productive rate 70%.The product oxirane value is that 0.41,25 ℃ of following viscosity is 2800cp.
Aromatic polyether
The aromatic polyether tetraglycidel ether epoxy resin
Embodiment 2
Mechanical stirring is being housed, reflux condensing tube, temperature is taken into account and is added 81g structural formula aromatic polyether as follows in the 500ml there-necked flask of nitrogen airway, and 111g epoxy chloropropane and 16g solid sodium hydroxide were heated to 70 ℃ of afterreactions 10 hours.After reaction finishes, in reaction system, add 320ml trichloromethane cut back, and extremely neutral with the product after the deionized water wash dilution; Isolate organic phase then and under 90 ℃/10mmHg underpressure distillation remove fugitive constituent in the organic phase, obtain the aromatic polyether tetraglycidel ether epoxy resin 79.3g of following structure, productive rate 80%.The product oxirane value is that 0.37,25 ℃ of following viscosity is 1600cp.
Aromatic polyether
The aromatic polyether tetraglycidel ether epoxy resin
Embodiment 3
Mechanical stirring is being housed, reflux condensing tube, temperature is taken into account and is added 99g structural formula aromatic polyether as follows in the 500ml there-necked flask of nitrogen airway, and 111g epoxy chloropropane and 16g solid sodium hydroxide were heated to 80 ℃ of afterreactions 12 hours.After reaction finishes, in reaction system, add 360ml dimethylbenzene cut back, and extremely neutral with the product after the deionized water wash dilution; Isolate organic phase then and under 120 ℃/5mmHg underpressure distillation remove fugitive constituent in the organic phase, obtain the aromatic polyether tetraglycidel ether epoxy resin 106g of following structure, productive rate 88%.The product oxirane value is that 0.33,25 ℃ of following viscosity is 900cp.
Aromatic polyether
The aromatic polyether tetraglycidel ether epoxy resin
Embodiment 4
In the weight part of aromatic polyether tetraglycidel ether epoxy resin, get aromatic polyether tetraglycidel ether epoxy resin 100 weight parts that obtain among the embodiment 1,4,4 '-diaminodiphenylmethane solidifying agent, 25 weight parts, mix after the heating for dissolving, vacuum defoamation is cast in the tetrafluoro mould.Place baking oven to solidify 3 hours down on mould, solidified 3 hours down at 180 ℃ then at 100 ℃.Slowly cool to room temperature after solidifying end, obtain yellow transparent, the flawless cured article of smooth surface behind the disengaging mould.The stretching of cured article, bending and impact property see Table 1, and thermal characteristics sees Table 2.
The performance test methods of cured article:
With the batten that cured article makes, employing INSTRON 3365 universal testing machines (American I nstron company) stretch, crooked test.The stretching clamp spacing is 40mm, and trial speed is 2mm/min, and crooked span is 48mm, and trial speed is 1mm/min.The JC-25 charpy impact test machine that shock strength adopts Chengde microtest machine company limited to produce carries out the non-notch shock test, and batten is of a size of 60mm * 10mm * 4mm.Thermostability adopts the comprehensive thermal analyzer TG/DTA 6300 of NSK thermogravimetric differential thermal to test under nitrogen atmosphere, and heat-up rate is 10 ℃/min.
Embodiment 5
In the weight part of aromatic polyether tetraglycidel ether epoxy resin, get aromatic polyether tetraglycidel ether epoxy resin 100 weight parts that obtain among the embodiment 2,4,4 '-diaminodiphenylmethane solidifying agent, 20 weight parts, mix after the heating for dissolving, vacuum defoamation is cast in the tetrafluoro mould.Place baking oven to solidify 3 hours down on mould, solidified 3 hours down at 180 ℃ then at 100 ℃.Slowly cool to room temperature after solidifying end, obtain yellow transparent, the flawless cured article of smooth surface behind the disengaging mould.The stretching of cured article, bending and impact property see Table 1, and thermal characteristics sees Table 2.
The performance test methods of cured article is with embodiment 1.
Embodiment 6
Weight part in E-51 Resins, epoxy, get aromatic polyether tetraglycidel ether epoxy resin 7.5 weight parts that obtain among the embodiment 3, E-51 Resins, epoxy 92.5 weight parts, 4,4 '-diaminodiphenylmethane solidifying agent, 25 weight parts, mix after the heating for dissolving, vacuum defoamation is cast in the tetrafluoro mould.Place baking oven to solidify 3 hours down on mould, solidified 3 hours down at 180 ℃ then at 100 ℃.Slowly cool to room temperature after solidifying end, obtain yellow transparent, the flawless cured article of smooth surface behind the disengaging mould.The stretching of cured article, bending and impact property see Table 1, and thermal characteristics sees Table 2.
The performance test methods of cured article is with embodiment 1.
Embodiment 7
Weight part in E-51 Resins, epoxy, get aromatic polyether tetraglycidel ether epoxy resin 15 weight parts that obtain among the embodiment 3, E-51 Resins, epoxy 85 weight parts, 4,4 '-diaminodiphenylmethane solidifying agent, 25 weight parts, mix after the heating for dissolving, vacuum defoamation is cast in the tetrafluoro mould.Place baking oven to solidify 3 hours down on mould, solidified 3 hours down at 180 ℃ then at 100 ℃.Slowly cool to room temperature after solidifying end, obtain yellow transparent, the flawless cured article of smooth surface behind the disengaging mould.The stretching of cured article, bending and impact property see Table 1, and thermal characteristics sees Table 2.
The performance test methods of cured article is with embodiment 1.
Embodiment 8
Weight part in E-51 Resins, epoxy, get aromatic polyether tetraglycidel ether epoxy resin 30 weight parts that obtain among the embodiment 3, E-51 Resins, epoxy 70 weight parts, 4,4 '-diaminodiphenylmethane solidifying agent, 25 weight parts, mix after the heating for dissolving, vacuum defoamation is cast in the tetrafluoro mould.Place baking oven to solidify 3 hours down on mould, solidified 3 hours down at 180 ℃ then at 100 ℃.Slowly cool to room temperature after solidifying end, obtain yellow transparent, the flawless cured article of smooth surface behind the disengaging mould.The stretching of cured article, bending and impact property see Table 1, and thermal characteristics sees Table 2.
The performance test methods of cured article is with embodiment 1.
Embodiment 9
Weight part in E-51 Resins, epoxy, get aromatic polyether tetraglycidel ether epoxy resin 50 weight parts that obtain among the embodiment 3, E-51 Resins, epoxy 50 weight parts, 4,4 '-diaminodiphenylmethane solidifying agent, 25 weight parts, mix after the heating for dissolving, vacuum defoamation is cast in the tetrafluoro mould.Place baking oven to solidify 3 hours down on mould, solidified 3 hours down at 180 ℃ then at 100 ℃.Slowly cool to room temperature after solidifying end, obtain yellow transparent, the flawless cured article of smooth surface behind the disengaging mould.The stretching of cured article, bending and impact property see Table 1, and thermal characteristics sees Table 2.
The performance test methods of cured article is with embodiment 1.
Comparative example 1
In the weight part of E-51 Resins, epoxy, get E-51 Resins, epoxy 100 weight parts, 4,4 '-diaminodiphenylmethane solidifying agent, 25 weight parts mix after the heating for dissolving, and vacuum defoamation is cast in the tetrafluoro mould.Place baking oven to solidify 3 hours down on mould, solidified 3 hours down at 180 ℃ then at 100 ℃.Fixed line slowly cools to room temperature after finishing, and obtains yellow transparent, the flawless cured article of smooth surface behind the disengaging mould.The stretching of cured article, bending and impact property see Table 1, and thermal characteristics sees Table 2.
The performance test methods of cured article is with embodiment 1.
Table 1
| Tensile strength (MPa) | Flexural strength (MPa) | Shock strength (KJ/m 2) | |
| Embodiment 4 | 1847 | 2862 | 60.1 |
| Embodiment 5 | 1908 | 2750 | 64.5 |
| Embodiment 6 | 1920 | 2801 | 14.6 |
| Embodiment 7 | 1985 | 3016 | 20.8 |
| Embodiment 8 | 2064 | 3128 | 27.4 |
| Embodiment 9 | 1986 | 2715 | 61.9 |
| Comparative example 1 | 1773 | 2766 | 10.8 |
Table 2
| The 5wt% weightless temperature (℃) | Temperature of initial decomposition (℃) | 600 ℃ residual heavy | |
| Embodiment 4 | 374.8 | 377.9 | 13.7％ |
| Embodiment 5 | 376.3 | 381.2 | 10.5％ |
| Embodiment 6 | 372.4 | 376.1 | 16.3％ |
| Embodiment 7 | 373.8 | 379.2 | 14.8％ |
| Embodiment 8 | 374.2 | 382.1 | 13.0％ |
| Embodiment 9 | 375.8 | 384.5 | 12.6％ |
| Comparative example 1 | 371.9 | 375.8 | 17.7％ |
Claims (10)
1. an aromatic polyether tetraglycidel ether epoxy resin is characterized in that, described resin has following structure:
Wherein: R is
2. aromatic polyether tetraglycidel ether epoxy resin according to claim 1 is characterized in that, described resin has following structure:
Wherein: n=1.
3. the preparation method of an aromatic polyether tetraglycidel ether epoxy resin according to claim 1 and 2 is characterized in that:
Mole number by the reactant aromatic polyether, in inert gas atmosphere, the epoxy chloropropane of 1 mole aromatic polyether with 2～30 moles mixed, add 2～6 moles solid base catalyst, in temperature of reaction is to react under 50～90 ℃, and the reaction times is 5～20 hours; Reaction finishes the back and adds the organic solvent diluting product, and the product after diluting with deionized water wash is to neutral; Isolating organic phase then, is the aromatic polyether glycidyl ether epoxy that obtains following structure after 90～120 ℃ and pressure are that fugitive constituent in the organic phase is removed in underpressure distillation under 1～10mmHg in temperature;
Wherein: R is
Described solid base catalyst is the oxyhydroxide of I family metallic element.
4. preparation method according to claim 3 is characterized in that: described aromatic polyether is
Wherein: R is
5. preparation method according to claim 3 is characterized in that: the usage quantity of described epoxy chloropropane is 5～20 moles.
6. preparation method according to claim 3 is characterized in that: described temperature of reaction is 60～80 ℃.
7. preparation method according to claim 3 is characterized in that: the described reaction times is 8～16 hours.
8. preparation method according to claim 7 is characterized in that: the described reaction times is 10～12 hours.
9. preparation method according to claim 3 is characterized in that: described organic solvent is at least a in the group formed of toluene, dimethylbenzene, trichloromethane, methylene dichloride.
10. preparation method according to claim 3 is characterized in that: the oxyhydroxide of described I family metallic element is lithium hydroxide, sodium hydroxide or potassium hydroxide.
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Cited By (5)
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| CN103289057A (en) * | 2013-05-25 | 2013-09-11 | 北京化工大学 | Method of preparing glycidyl ether epoxy resin through monomer containing alcoholic hydroxyl group and/or phenolic hydroxyl group |
| WO2017038603A1 (en) * | 2015-09-04 | 2017-03-09 | 株式会社Adeka | Resin composition for fiber-reinforced plastic, cured product thereof, fiber-reinforced plastic containing said cured product, and method for producing said fiber-reinforced plastic |
| CN108290354A (en) * | 2015-11-25 | 2018-07-17 | 株式会社Adeka | Molding machine, manufacturing method and fibre reinforced resin material |
| CN109897528A (en) * | 2019-02-14 | 2019-06-18 | 安庆北化大科技园有限公司 | A kind of modified coating and the preparation method and application thereof |
| CN112778948A (en) * | 2020-12-23 | 2021-05-11 | 北京康美特科技股份有限公司 | Conductive silver adhesive and preparation method and application thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103289057A (en) * | 2013-05-25 | 2013-09-11 | 北京化工大学 | Method of preparing glycidyl ether epoxy resin through monomer containing alcoholic hydroxyl group and/or phenolic hydroxyl group |
| CN103289057B (en) * | 2013-05-25 | 2016-08-17 | 北京化工大学 | A kind of method that monomer by alcoholic hydroxy and/or phenolic hydroxyl group prepares tetraglycidel ether epoxy resin |
| JPWO2017038603A1 (en) * | 2015-09-04 | 2018-07-26 | 株式会社Adeka | Resin composition for fiber reinforced plastic, cured product thereof, fiber reinforced plastic containing the cured product, and method for producing the fiber reinforced plastic |
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