CN102924690A - Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof - Google Patents
Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof Download PDFInfo
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- CN102924690A CN102924690A CN2012104423006A CN201210442300A CN102924690A CN 102924690 A CN102924690 A CN 102924690A CN 2012104423006 A CN2012104423006 A CN 2012104423006A CN 201210442300 A CN201210442300 A CN 201210442300A CN 102924690 A CN102924690 A CN 102924690A
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Abstract
The invention relates to an epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and a preparation method thereof. An epoxy resin/ hyperbranched polyether type epoxy hybrid material is formed by utilizing bisphenol A linear epoxy resin as a base material, utilizing the hyperbranched polyether type epoxy resin as a superstrong toughening agent and adding a curing agent and an accelerant. The weight of the hyperbranched polyether type epoxy polymer occupies 3-50% of that of epoxy resin. The hyperbranched polyether type epoxy polymer is obtained by utilizing triphenol methane as a first monomer and E51 as a second monomer and conducting one-step combination through a proton transfer polymerization method. Impact strength of the epoxy resin material reaches 35.2kJ/<2>, elongation at break reaches 11%, tensile strength reaches 89.2MPa, bending strength reaches 145.6MPa, and glass-transition temperature reaches 142 DEG C. The performance indexes are greatly improved compared with that of bisphenol A epoxy resin.
Description
Technical field
The present invention relates to a kind of Resins, epoxy hybrid material by the toughness reinforcing enhancing of hyperbranched polyether type epoxy polymer, and preparation method thereof, the organic polymer field belonged to.
Background technology
Resins, epoxy is owing to having the advantages such as the curing molding shrinking percentage is low, processibility good, formulating of recipe is versatile and flexible, and its cured article has good physical and mechanical properties, electrical insulation capability, chemical resistance and adhesive property, and is widely used in electronic apparatus industry, coating glue paste and field of compound material.But Resins, epoxy resistance to fatigue, thermotolerance and impelling strength are relatively poor, and elongation is low, make its application be subject to certain restriction (LEE, H.; Neville, K., Handbook of Epoxy Resins. Mcgraw-Hill:New York, 1967).
The method of existing Toughening Modification of Epoxy has: sneak into the disperse phase such as rigid inorganic filler, rubber particles, thermoplastic resin or liquid crystalline polymers in Resins, epoxy.In epoxy-resin systems, form IPN, semi-intercrossing network or island structure and reach toughness reinforcing purpose.Perhaps in the body of epoxy resin structure, introduce " soft segment " and play toughness reinforcing purpose.Although above method is significantly improved shock strength, sacrificed the tensile strength of Resins, epoxy.In recent years, the epoxy resin toughened research method of hyperbranched epoxy polymer attracts wide attention (Zhang, X., Polymer International, 2011. 60 (2): p. 153-166).Owing to containing in the super branched molecule a large amount of epoxy terminated, make it have good consistency to Resins, epoxy, the curing molding thing is by the cavitation effect of hyperbranched polymer, namely utilize the interior large free volume (hole) of super branched molecule to absorb energy, thereby play toughness reinforcing purpose (Mezzenga, R.; Boogh, L.; M nson, J. E., Composites Science and Technology 2001,61 (5), 787-795).
J. Russell(Varley, Russell J.; Wendy Tian, 2004. 53 (1): p. 69-77) etc. with molecular weight approximately 10 500 Hyperbranched Epoxy Compounds DGEBA type EP/phenolic aldehyde EP mixture system is carried out modification.When the content of Hyperbranched Epoxy Compounds was 0～20%, the fracture toughness property of system can improve nearly 2 times, and bending elastic modulus and flexural strength all reduce approximately 30%, and second-order transition temperature reduces approximately 10%.
The synthetic report of relevant hyperbranched polymer is a lot, in the patent (CN 101475685A) take polyamine or polyvalent alcohol or their mixture as the first monomer, take polyprotonic acid or acid anhydrides or their mixture as the second monomer, reaction obtains the hyperbranched polymer of function end group, generates afterwards the hyperbranched polymer of end ring oxygen with epichlorohydrin reaction again.Take dihydroxyl amido ester as the chain extension monomer, adding the multifunctional molecule polyvalent alcohol is " nuclear " in the patent (CN101665568A), and reaction obtains the amino hyperbranched poly (amine-ester) of terminal hydroxy group; Again its terminal hydroxy group and epichlorohydrin reaction are generated epoxy-terminated hyperbranched poly (amine-ester).Although the preparation method of hyperbranched fluidized polymer is a lot of in the document, step is often comparatively loaded down with trivial details, needs two-step approach to synthesize.Therefore seek the method for simple and effective to preparation and the large-scale production of hyperbranched polymer, enhancing productivity has a very big significance.
Summary of the invention
Key of the present invention provides a kind of preparation method by the hyperbranched polyether type epoxy polymer, and by the preparation method of the Resins, epoxy hybrid material of the toughness reinforcing enhancing of this hyperbranched polyether type epoxy polymer, hyperbranched epoxy polymer synthetic method is simple in the method, toughness, tensile strength and flexural strength that can the Effective Raise bisphenol A type epoxy resin.
The technical scheme that the present invention takes is: 1. take the triphenol methylmethane as the first monomer, E51 is the second monomer, obtains hyperbranched polyether type Resins, epoxy by proton transfer polymerization method one-step synthesis.2. carry out blend by the ratio that changes hyperbranched polyether type epoxy polymer and Resins, epoxy, improve the performance of product.Owing to containing a large amount of rigidity phenyl ring in the hyperbranched polymer skeleton structure, the polyfunctionality of hyperbranched polymer can improve the cross-linking density of resin simultaneously, and the intensity of Resins, epoxy is improved; The existence in the hole in the super branched molecule (free volume) is again so that the toughness raising.
A kind of hyperbranched polyether type epoxy polymer, its structural formula is as follows:
The preparation method of described hyperbranched polyether type epoxy polymer is characterized in that adopting one of following two kinds of methods:
Method I, substance law: with the bisphenol A diglycidyl ether of 100 mass parts, the triphenol methylmethane of 20 ~ 45 mass parts, the catalyzer of 2 ~ 7 mass parts adds reactor together, under the nitrogen protection, in 80 ~ 160 ℃ of reactions 6 ~ 20 hours; Reaction is used the dissolution with solvents reactant after finishing, and with the mixed solution precipitation of alcohol or alcohol and water, drying obtains white or light yellow solid;
Method II, solution method: with the bisphenol A diglycidyl ether of 100 mass parts, the triphenol methylmethane of 20 ~ 45 mass parts, the catalyzer of 2 ~ 7 mass parts, add together reactor, under the nitrogen protection, 70 ~ 180 ℃ were reacted 24 ~ 96 hours in 40 ~ 220 mass parts organic solvents; Reaction is used the dissolution with solvents reactant after finishing, and with the mixed solution precipitation of alcohol or alcohol and water, drying obtains white or light yellow solid.
Catalyzer is potassium tert.-butoxide, tetrabutylammonium, Tetrabutyl amonium bromide, tetrabutylammonium chloride, KOH a kind of in the hexaoxacyclooctadecane-6-6.
Organic solvent is tetrahydrofuran (THF), dioxane, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), glycol dimethyl ether, a kind of in the ethylene glycol dibutyl ether.
Alcohol in the mixed solution of alcohol or alcohol and water is from ethanol or methyl alcohol.
Described hyperbranched polyether type epoxy polymer is used for the preparation method of the Resins, epoxy of toughness reinforcing enhancing, it is characterized in that, may further comprise the steps:
Resins, epoxy and described hyperbranched polyether type epoxy polymer be in 50-100 ° of C stir rear adding solidifying agent and promotor, restir evenly after in 50-100 ° of C vacuum defoamation, inject mould, put into baking oven Program intensification curing molding; Wherein the quality of hyperbranched polyether type Resins, epoxy is to be the 3-50% of Resins, epoxy quality, and the quality of solidifying agent is the 90-120% of Resins, epoxy quality, and the quality of promotor is the 0.5-2% of Resins, epoxy quality.
Described hyperbranched polyether type epoxy polymer is used for the preparation method of the Resins, epoxy of toughness reinforcing enhancing, it is characterized in that, may further comprise the steps:
Resins, epoxy and described hyperbranched polyether type epoxy polymer be in 50-100 ° of C stir rear adding solidifying agent and promotor, restir evenly after in 50-100 ° of C vacuum defoamation, inject mould, put into baking oven Program intensification curing molding; Wherein the quality of hyperbranched polyether type Resins, epoxy is to be the 3-50% of Resins, epoxy quality, and the quality of solidifying agent is the 90-120% of Resins, epoxy quality, and the quality of promotor is the 0.5-2% of Resins, epoxy quality.
Hyperbranched polyether type epoxy polymer of the present invention, so that the preparation of 1 method to be described, its main chain contains rigidity phenyl ring and ehter bond, end group is epoxy group(ing) and hydroxyl, can with the good consistency of Resins, epoxy, when improving Resins, epoxy toughness, do not reduce again tensile strength and the flexural strength of Resins, epoxy, can be used as the purpose that a kind of additive plays toughness reinforcing enhancing.
Resins, epoxy of the present invention is bisphenol A type epoxy resin.
Solidifying agent of the present invention is the organic acid anhydride class.
Promotor of the present invention is a kind of in carbamide compounds, imidazolium compounds and the compound with similar structures.
4. the shock strength of pure epoxy resin cured article is 19.1kJ/m
2, tensile strength is 69.1MPa, and elongation at break is 4.4%, and flexural strength is 112.8MPa,
The shock strength of the Resins, epoxy that the present invention makes/hyperbranched polyether type epoxy hybrid material can reach 33.7kJ/m
2, elongation at break reaches 11.1%, and tensile strength reaches 89.2MPa, and flexural strength reaches 145.6MPa.
Beneficial effect:
1. the present invention adopts the synthetic hyperbranched epoxy polymer of single stage method, the synthon wide material sources, and cheap, synthetic method is simple, is easy to suitability for industrialized production.
2. the present invention carries out blend by the ratio that changes hyperbranched polyether type epoxy and Resins, epoxy, can improve the multiple performance of product, such as shock strength, tensile strength, elongation at break and flexural strength etc.The hybrid resin material of the present invention's preparation has overcome the crisp characteristics of pure epoxy resin matter, does not reduce again its stretching and bending property when improving the impact property of Resins, epoxy, has improved well toughness and the intensity of Resins, epoxy.Particularly the present invention just can reach optimum over-all properties when a small amount of interpolation hyperbranched polyether type epoxy polymer (5%), and this hyperbranched polyether type epoxy polymer has played good toughness reinforcing reinforced effects to Resins, epoxy.
Description of drawings:
Fig. 1 is the schematic arrangement of hyperbranched polyether type epoxy polymer.
Fig. 2 is the infrared spectrogram of gained hyperbranched polyether type epoxy polymer in the case study on implementation 1.
Fig. 3 is gained hyperbranched polyether type epoxy polymer in the case study on implementation 1
1HNMR spectrogram (CDCl
3).
Fig. 4 be case study on implementation 14,15,16,17,18,19 and the contrast case 20 the tensile strength histogram.
Fig. 5 be case study on implementation 14,15,16,17,18,19 and the contrast case 20 the elongation at break histogram.
Fig. 6 be case study on implementation 14,15,16,17,18,19 and the contrast case 20 the shock strength histogram.
Fig. 7 be case study on implementation 14,15,16,17,18,19 and the contrast case 20 the flexural strength histogram.
Fig. 8 is case study on implementation 14,15,16,17,18,19 and the DMA tangent damage curve of contrast case 20, and its peak temperature represent case study on implementation 14,15,16,17,18,19 and contrast the second-order transition temperature of case 20.
Table 1 is case study on implementation 1,2,3,4,5,6,7,8,9,10,11,12,13 implementation condition and products thereof data.
Table 1 be case study on implementation 14,15,16,17,18,19 and the contrast case 20 mechanical performance data.
Table 2 be case study on implementation 14,15,16,17,18,19 and the contrast case 20 the thermal characteristics data.
Embodiment:
The invention will be further elaborated below in conjunction with the implementation case.Should be understood that to the invention is not restricted to following case study on implementation, described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.Among the present invention, the structure of hyperbranched epoxy polymer as shown in Figure 1.
Case 1-13 is the preparation case of hyperbranched polyether type epoxy polymer (HBPEE).
Case study on implementation 1
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,80g triphenol methylmethane is dissolved in the 150ml dioxane, adds the 10g Tetrabutyl amonium bromide, reacts 72h under reflux temperature.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methyl alcohol, gets white precipitate, and supernatant liquid is poured out, and with 100ml tetrahydrofuran (THF) dissolve polymer, pours ethanol/water (8:1) into again, so repeatedly washes 3 times.With the white precipitate oven dry, getting weight average is 7696, and molecular weight distribution is 2.5 hyperbranched polyether type epoxy polymer 215g.The infrared spectrogram of this polymkeric substance is seen Fig. 2,
1The HNMR spectrogram is seen Fig. 3.
Case study on implementation 2
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,80g triphenol methylmethane is dissolved in the 150ml dioxane, adds the 15g Tetrabutyl amonium bromide, reacts 72h under reflux temperature.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methyl alcohol, gets white precipitate, and supernatant liquid is poured out, and with 100ml tetrahydrofuran (THF) dissolve polymer, pours methanol/ethanol mixed solution (3:7) into again, so repeatedly washes 3 times.With the white precipitate oven dry, getting weight average is 14618, and molecular weight distribution is 3.1 hyperbranched polyether type epoxy polymer 220g.
Case study on implementation 3
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,80g triphenol methylmethane is dissolved in the 150ml glycol dimethyl ether, adds 5g tetrabutylphosphoniuhydroxide hydroxide amine, reacts 96h under reflux temperature.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methyl alcohol, gets white precipitate, and supernatant liquid is poured out, and with 100ml tetrahydrofuran (THF) dissolve polymer, pours methanol/ethanol mixed solution (2:8) into again, so repeatedly washes 3 times.With the white precipitate oven dry, getting weight average is 20913, and molecular weight distribution is 2.8 hyperbranched polyether type epoxy polymer 225g.
Case study on implementation 4
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,50g triphenol methylmethane is dissolved in the 100ml N,N-dimethylacetamide, adds the 10g Tetrabutyl amonium bromide, at 100 ℃ of lower reaction 72h.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methyl alcohol, gets white precipitate, and supernatant liquid is poured out, and with 100ml tetrahydrofuran (THF) dissolve polymer, pours ethanol into again, so repeatedly washes 3 times.With the white precipitate oven dry, getting weight average is 32394, and molecular weight distribution is 3.3 hyperbranched polyether type epoxy polymer 200g.
Case study on implementation 5
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,80g triphenol methylmethane is dissolved in the 100ml ethylene glycol dibutyl ether, add 10gKOH hexaoxacyclooctadecane-6-6, at 180 ℃ of lower reaction 24h.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methyl alcohol, gets white precipitate, and supernatant liquid is poured out, and with 100ml tetrahydrofuran (THF) dissolve polymer, pours methanol/ethanol mixed solution (2:1) into again, so repeatedly washes 3 times.With the white precipitate oven dry, getting weight average is 24568, and molecular weight distribution is 2.7 hyperbranched polyether type epoxy polymer 210g.
Case study on implementation 6
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,100g triphenol methylmethane is dissolved in the 100ml tetrahydrofuran (THF), adds the 10g Tetrabutyl amonium bromide, reacts 96h under reflux temperature.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methyl alcohol, gets white precipitate, and supernatant liquid is poured out, and with 100ml tetrahydrofuran (THF) dissolve polymer, pours methyl alcohol into again, so repeatedly washes 3 times.With the white precipitate oven dry, getting weight average is 23561, and molecular weight distribution is 3.0 hyperbranched polyether type epoxy polymer 235g.
Case study on implementation 7
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,100g triphenol methylmethane is dissolved in 150ml N, in the N-dimethylformamide, adds the 10g Tetrabutyl amonium bromide, at 80 ℃ of lower reaction 72h.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methanol/ethanol mixed solution (2:3), get white precipitate, supernatant liquid is poured out, with 100ml tetrahydrofuran (THF) dissolve polymer, pour again methanol/water mixed solution (7:1) into, so repeatedly wash 3 times.With the white precipitate oven dry, getting weight average is 10069, and molecular weight distribution is 2.1 hyperbranched polyether type epoxy polymer 194g.
Case study on implementation 8
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,100g triphenol methylmethane is dissolved in the 500ml dimethyl sulfoxide (DMSO), adds the 10g Tetrabutyl amonium bromide, reacts 24h under reflux temperature.Reaction is poured reactant in the 2000ml beaker into after finishing, and slowly adds methyl alcohol, gets white precipitate, and supernatant liquid is poured out, and with 100ml tetrahydrofuran (THF) dissolve polymer, pours methyl alcohol into again, so repeatedly washes 3 times.With the white precipitate oven dry, getting weight average is 6736, and molecular weight distribution is 1.7 hyperbranched polyether type epoxy polymer 190g.
Case study on implementation 9
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,50g triphenol methylmethane stirs rear adding 10g Tetrabutyl amonium bromide, and 120 ℃ were reacted 6 hours.After reaction finishes, pour reactant into the 2000ml beaker with the dissolving of 200ml tetrahydrofuran (THF), slowly add methanol/water mixed solution (3:1), get white precipitate, supernatant liquid is poured out, with 100ml tetrahydrofuran (THF) dissolve polymer, pour again methyl alcohol into, so repeatedly wash 3 times.With the white precipitate oven dry, getting weight average is 6455, and molecular weight distribution is 2.1 hyperbranched polyether type epoxy polymer 192g.
Case study on implementation 10
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,80g triphenol methylmethane stirs rear adding 5g Tetrabutyl amonium bromide, and 100 ℃ were reacted 8 hours.After reaction finishes, pour reactant into the 2000ml beaker with the dissolving of 200ml tetrahydrofuran (THF), slowly add methyl alcohol, get white precipitate, supernatant liquid is poured out, with 100ml tetrahydrofuran (THF) dissolve polymer, pour again ethanol into, so repeatedly wash 3 times.With the white precipitate oven dry, getting weight average is 2502, and molecular weight distribution is 1.5 hyperbranched polyether type epoxy polymer 180g.
Case study on implementation 11
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,100g triphenol methylmethane stirs rear adding 15g Tetrabutyl amonium bromide, and 160 ℃ were reacted 6 hours.After reaction finishes, pour reactant into the 2000ml beaker with the dissolving of 200ml tetrahydrofuran (THF), slowly add methanol/water mixed solution (9:1), get white precipitate, supernatant liquid is poured out, with 100ml tetrahydrofuran (THF) dissolve polymer, pour again methyl alcohol into, so repeatedly wash 3 times.With the white precipitate oven dry, getting weight average is 24849, and molecular weight distribution is 3.2 hyperbranched polyether type epoxy polymer 227g.
Case study on implementation 12
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,80g triphenol methylmethane stirs rear adding 10g tetrabutylammonium chloride, and 100 ℃ were reacted 8 hours.After reaction finishes, pour reactant into the 2000ml beaker with the dissolving of 200ml tetrahydrofuran (THF), slowly add methyl alcohol, get white precipitate, supernatant liquid is poured out, with 100ml tetrahydrofuran (THF) dissolve polymer, pour again methyl alcohol into, so repeatedly wash 3 times.With the white precipitate oven dry, getting weight average is 7123, and molecular weight distribution is 2.2 hyperbranched polyether type epoxy polymer 190g.
Case study on implementation 13
At 1000ml mechanical stirring is housed, in the four-hole boiling flask of prolong, under the nitrogen protection, adds 230g E51,80g triphenol methylmethane stirs rear adding 10g potassium tert.-butoxide, and 80 ℃ were reacted 20 hours.After reaction finishes, pour reactant into the 2000ml beaker with the dissolving of 200ml tetrahydrofuran (THF), slowly add methanol/ethanol mixed solution (4:5), get white precipitate, supernatant liquid is poured out, with 100ml tetrahydrofuran (THF) dissolve polymer, pour again methyl alcohol into, so repeatedly wash 3 times.With the white precipitate oven dry, getting weight average is 27893, and molecular weight distribution is 3.5 hyperbranched polyether type epoxy polymer 227g.
Case study on implementation 14-20 is the Resins, epoxy hybrid material of preparation by the toughness reinforcing enhancing of hyperbranched polyether type epoxy polymer (HBPEE).
Case study on implementation 14
With 100gCYD-128(E51) with 3g case 1 in gained hyperbranched polyether type epoxy polymer at 50 ℃ of lower mixings, add again 91.8g methyl hexahydrophthalic anhydride and 1.016g 2-ethyl-4-methylimidazole, abundant stirring and evenly mixing, pour into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 15
With 100gCYD-128(E51) with 5g case 1 in gained hyperbranched polyether type epoxy polymer at 60 ℃ of lower mixings, add again 92.7g methyl hexahydrophthalic anhydride and 1.027g 2-ethyl-4-methylimidazole, abundant stirring and evenly mixing, pour into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, behind 200 ℃ of 2 hours completion of cures, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 16
With 100gCYD-128(E51) with 10g case 1 in gained hyperbranched polyether type epoxy polymer at 70 ℃ of lower mixings, add again 95.2g methyl hexahydrophthalic anhydride and 1.053g 2-ethyl-4-methylimidazole, abundant stirring and evenly mixing, pour into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 17
With 100gCYD-128(E51) with 15g case 1 in gained hyperbranched polyether type epoxy polymer at 80 ℃ of lower mixings, add again 97.6g methyl hexahydrophthalic anhydride and 1.080g 2-ethyl-4-methylimidazole, abundant stirring and evenly mixing, pour into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 18
With 100gCYD-128(E51) with 20g case 1 in gained hyperbranched polyether type epoxy polymer at 90 ℃ of lower mixings, add again 100g methyl hexahydrophthalic anhydride and 1.107g 2-ethyl-4-methylimidazole, abundant stirring and evenly mixing, pour into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 19
With 100gCYD-128(E51) with 50g case 1 in gained hyperbranched polyether type epoxy polymer at 100 ℃ of lower mixings, add again 114g methyl hexahydrophthalic anhydride and 1.267g 2-ethyl-4-methylimidazole, abundant stirring and evenly mixing, pour into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Contrast case 20
With 100gCYD-128(E51), 90.3g methyl hexahydrophthalic anhydride and 1g 2-ethyl-4-methylimidazole, abundant stirring and evenly mixing, pour into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 21
With 100gCYD-128(E44) with 20g case 1 in gained hyperbranched polyether type epoxy polymer, 83.7g methyl hexahydrophthalic anhydride is in 80 ℃ of lower mixings, add the 0.927g benzyldimethylamine, fully stirring and evenly mixing pours into after the vacuum defoamation in the homemade mould, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 22
With 100gCYD-128(E20) with 20g case 1 in gained hyperbranched polyether type epoxy polymer, 43.3g the methyl carbic anhydride is at 80 ℃ of lower mixings, add the 0.479g triethylamine, fully stirring and evenly mixing pours into after the vacuum defoamation in the homemade mould again, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
Case study on implementation 23
With 100gCYD-128(E12) with 20g case 1 in gained hyperbranched polyether type epoxy polymer, 29.8g methyl tetrahydro phthalic anhydride is at 80 ℃ of lower mixings, add and the 0.330g methyl piperidine, fully stirring and evenly mixing pours into after the vacuum defoamation in the homemade mould again, 100 ℃ 2 hours, 150 ℃ 6 hours, 200 ℃ 2 hours, behind the completion of cure, the demoulding behind the naturally cooling makes hyperbranched polyether type epoxy polymer/Resins, epoxy hybrid material.
The epoxide resin material tensile strength of case 14-20 and elongation at break are measured according to GB/T 2568-1995 method, shock strength is impacted spline method mensuration according to non-notch described in the GB/T 2571-1995, and flexural strength is measured according to GB/T 2570-1995 method.The result is as shown in table 1:
Table 1
Table 2
Table 3
Claims (9)
1. hyperbranched polyether type epoxy polymer, its structural formula is as follows:
2. the preparation method of hyperbranched polyether type epoxy polymer according to claim 1 is characterized in that adopting one of following two kinds of methods:
Method I, substance law: with the bisphenol A diglycidyl ether of 100 mass parts, the triphenol methylmethane of 20 ~ 45 mass parts, the catalyzer of 2 ~ 7 mass parts adds reactor together, under the nitrogen protection, in 80 ~ 160 ℃ of reactions 6 ~ 20 hours; Reaction is used the dissolution with solvents reactant after finishing, and with the mixed solution precipitation of alcohol or alcohol and water, drying obtains white or light yellow solid;
Method II, solution method: with the bisphenol A diglycidyl ether of 100 mass parts, the triphenol methylmethane of 20 ~ 45 mass parts, the catalyzer of 2 ~ 7 mass parts, add together reactor, under the nitrogen protection, 70 ~ 180 ℃ were reacted 24 ~ 96 hours in 40 ~ 220 mass parts organic solvents; Reaction is used the dissolution with solvents reactant after finishing, and with the mixed solution precipitation of alcohol or alcohol and water, drying obtains white or light yellow solid.
3. according to claim 2 preparation method, it is characterized in that: catalyzer is potassium tert.-butoxide, tetrabutylammonium, Tetrabutyl amonium bromide, tetrabutylammonium chloride, KOH a kind of in the hexaoxacyclooctadecane-6-6.
4. according to claim 2 preparation method, it is characterized in that: organic solvent is tetrahydrofuran (THF), dioxane, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), glycol dimethyl ether, a kind of in the ethylene glycol dibutyl ether.
5. according to claim 2 preparation method is characterized in that: the alcohol in the mixed solution of alcohol or alcohol and water is from ethanol or methyl alcohol.
According to claim 1 described in the hyperbranched polyether type epoxy polymer be used for the preparation method of the Resins, epoxy of toughness reinforcing enhancing, it is characterized in that, may further comprise the steps:
Resins, epoxy and described hyperbranched polyether type epoxy polymer be in 50-100 ° of C stir rear adding solidifying agent and promotor, restir evenly after in 50-100 ° of C vacuum defoamation, inject mould, put into baking oven Program intensification curing molding; Wherein the quality of hyperbranched polyether type Resins, epoxy is to be the 3-50% of Resins, epoxy quality, and the quality of solidifying agent is the 90-120% of Resins, epoxy quality, and the quality of promotor is the 0.5-2% of Resins, epoxy quality.
According to claim 6 described in method, it is characterized in that: Resins, epoxy is bisphenol A type epoxy resin.
According to claim 6 described in method, it is characterized in that: solidifying agent is the organic acid anhydride class.
According to claim 6 described in method, it is characterized in that: promotor is a kind of in carbamide compounds, the imidazolium compounds.
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| CN103772155A (en) * | 2013-09-30 | 2014-05-07 | 北京化工大学 | AB2 monomer and series of fluoro end group hyperbranched polyphenyl ether prepared from AB2 monomer, as well as preparation method of AB2 monomer and fluoro end group hyperbranched polyphenyl ether |
| CN104448245A (en) * | 2014-12-16 | 2015-03-25 | 北京光华纺织集团有限公司 | Preparation method of hyper-branched epoxy emulsion |
| CN105925130A (en) * | 2016-05-23 | 2016-09-07 | 北京化工大学 | Hyper-branched polyether epoxy resin/epoxy resin composite anti-corrosion coating and preparation method thereof |
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| CN115651165A (en) * | 2022-11-29 | 2023-01-31 | 新创碳谷集团有限公司 | Recyclable epoxy resin and preparation method and recycling method thereof |
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| CN116113179A (en) * | 2023-02-01 | 2023-05-12 | 江苏贺鸿电子有限公司 | Multilayer printed circuit board and preparation method thereof |
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