CN100371387C - Epoxidation silicon oil modified three kinds of composite material of epoxy resin - Google Patents
Epoxidation silicon oil modified three kinds of composite material of epoxy resin Download PDFInfo
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- CN100371387C CN100371387C CNB2004100774672A CN200410077467A CN100371387C CN 100371387 C CN100371387 C CN 100371387C CN B2004100774672 A CNB2004100774672 A CN B2004100774672A CN 200410077467 A CN200410077467 A CN 200410077467A CN 100371387 C CN100371387 C CN 100371387C
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Abstract
The present invention relates to three epoxy resin composite materials modified with epoxy silicone oil, which is characterized in that epoxy silicon oil and epoxy resin are combined, and a curing agent is used for curing and forming to obtain the epoxy resin composite materials modified with epoxy silicone oil, wherein three different preparation methods are used; in the first method, the epoxy silicon oil is directly combined with the epoxy resin; in the second method, the epoxy silicon oil is combined with the epoxy resin after epoxy silicon oil is modified by the curing agent; in the third method, the coupled epoxy silicon oil is combined with the epoxy resin. Thus, three new epoxy resin composite materials modified with epoxy silicone oil are obtained. Compared with unmodified epoxy resin, the epoxy resin three composite materials have the advantages of high impact strength, high tensile strength, high breaking elongation and high glass transition temperature; thus, the three epoxy resin composite materials can be used as high performance materials, such as paint, structural adhesives, electronic packaging materials, etc.
Description
Technical field
The present invention relates to three kinds of modified epoxy resin composites, especially relate to three kinds of epoxidation silicon oil modified epoxy resin composite materials.
Background technology
Resins, epoxy has advantages such as excellent mechanical property, mechanical property, electric property, chemical property, adhesiveproperties and easy-formation processing, and is widely used in the matrix of coating, tackiness agent, electric insulation and advanced composite material.Its application extension is to electric packaged materials such as sqtructural adhesive material, semiconductor sealing material, fiber-reinforced material, veneer sheet, Copper Foil, unicircuit in recent years, this just requires material to have higher performance, as high tenacity, inner low stressization, thermotolerance, water tolerance, chemical proofing etc.Yet because Resins, epoxy has the 3 D stereo reticulated structure, lack slip between molecular chain, C-C, less, the higher surface energy of carbon-oxygen bond bond energy have some hydroxyls etc., make that its existence is crisp, poor heat resistance, ductility is low and be subject to deficiency such as water influence.
In recent years, at the performance deficiency of epoxide resin material, done a large amount of modification work to improving epoxide resin material toughness, thermotolerance etc. both at home and abroad, wherein having relatively preferably with modifying epoxy resin by organosilicon, technology improves effect.The main chain of organo-siloxane is a stable skeleton of alternately being made up of Siliciumatom and Sauerstoffatom, and side chain links to each other by Siliciumatom and organic group such as methyl, phenyl, vinyl etc.Because this special construction and the composition of its molecule make it integrate the characteristic and the organic function of inorganics, have low temperature flexibility, low surface energy, heat-resisting, weather-proof, hydrophobic, dielectric strength advantages of higher.Therefore, be the internal stress that can reduce Resins, epoxy that development in recent years is got up with its modified epoxy, again can retaining ring epoxy resin system primary characteristic and improve the relative valid approach of thermostability.However, bibliographical information from present domestic and international modifying epoxy resin by organosilicon, or improve thermotolerance by introducing rigid chain segment, or play toughness reinforcing effect by introducing soft segment, but mechanical strength and thermotolerance have been reduced in the time of often toughness reinforcing, or improve the stable on heating toughness that reduces material simultaneously, and can not both take into account simultaneously.
Summary of the invention
The objective of the invention is to synthetic new modified epoxy resin composite, these epoxy resin composite materials will both have high mechanical strength, had performances such as high tenacity, high heat resistance and high impact-resistant again.
The present invention is by compound with epoxidation silicon oil and Resins, epoxy, use the solidifying agent curing molding again, obtain having high mechanical strength, the epoxidation silicon oil modified epoxy resin composite material of high tenacity, high heat resistance, high impact properties, owing to wherein adopted three kinds of preparation methods, thereby obtain three kinds of new epoxidation silicon oil modified epoxy resin composite materials, thereby realized purpose of the present invention.
A kind of epoxidation silicon oil modified epoxy resin composite material of the present invention, it is characterized in that the product that prepared by following method: epoxidation silicon oil and Resins, epoxy are solidified by aliphatic amide or aromatic amine after compound again, and described epoxidation silicon oil is represented by general formula (1):
Formula (1)
M=0～100 wherein, n=1～100.
Described preparation method reaction conditions routinely carries out; The ratio of components of raw material is 100 parts of Resins, epoxy according to the mass fraction, 0.1～80 part of epoxidation silicon oil, 5～60 parts in solidifying agent; Described epoxidation silicon oil is that oxirane value is the pendant epoxies base silicone oil of 0.01～0.5mol/100g; Described Resins, epoxy is the bisphenol A type epoxy resin of relative molecular mass 340～2500, and relative molecular mass is that 312～2500 bisphenol f type epoxy resins or relative molecular mass are 300～2500 phenol aldehyde type epoxy resin; Solidification value depends on used solidifying agent, and aliphatic amide is generally normal temperature, aromatic amine be generally 60～200 ℃.
Preferred 5～20 parts of the consumption of the epoxidation silicon oil described in the preparation method; Described bisphenol A type epoxy resin can be E-51, E-44, E-32 etc., and preferred relative molecular mass is 400～800; Described bisphenol f type epoxy resin can be BPF-45, BPF-55, BPF-68 etc., and preferred relative molecular mass is 372～772; Described phenol aldehyde type epoxy resin is novolac epoxy such as linear o-cresol formaldehyde epoxy resin, a linear phenolic epoxy resin etc. commonly used in the existing Electronic Packaging epoxide resin material technology, and preferred relative molecular mass is 450～900 novolac epoxy.
The epoxidation silicon oil modified epoxy resin composite material of another kind of the present invention, it is characterized in that the product for preparing by following method: curing agent modified epoxidation silicon oil and Resins, epoxy are solidified by fatty amine or aromatic amine curing agent after compound again, wherein curing agent modified epoxidation silicon oil is epoxidation silicon oil and solidifying agent are cured reaction in high boiling organic solvent a product, described epoxidation silicon oil is represented by above-mentioned general formula (1), m=0～100 wherein, n=1～100.
The ratio of components of described epoxidation silicon oil modified reaction is according to the mass fraction, 100 parts of epoxidation silicon oils, 0.1～100 part in solidifying agent; Described solidifying agent is aliphatic amide, arylamine class, cyanogen class, the phenolic solidifying agent of using always such as right, right '-diaminodiphenyl-methane, diamino diphenyl sulfone, dicyandiamide and resol etc.; Described epoxidation silicon oil is that oxirane value is the pendant epoxies base silicone oil of 0.01～0.5mol/100g; Described high boiling organic solvent such as toluene, dimethylbenzene, dimethyl formamide, dimethyl sulfoxide (DMSO) etc. are removed organic solvent after the reaction.
Preferred 20～50 parts of the hardener dose of described epoxidation silicon oil modified reaction.
Described complex reaction reaction conditions is routinely carried out, and the ratio of components of raw material is 100 parts of Resins, epoxy according to the mass fraction, and 0.1～100 part of the epoxidation silicon oil of modification is preferably 5～20 parts, 5～60 parts in solidifying agent; Described Resins, epoxy is the bisphenol A type epoxy resin of relative molecular mass 340～2500, and relative molecular mass is that 312～2500 bisphenol f type epoxy resin or relative molecular mass are 300～2500 phenol aldehyde type epoxy resin; Solidification value depends on used solidifying agent, and aliphatic amide is generally normal temperature, aromatic amine be generally 60～200 ℃.
Bisphenol A type epoxy resin described in the described complex reaction can be E-51, E-44, E-32 etc., and preferred relative molecular mass is 400～800; Described bisphenol f type epoxy resin can be BPF-45, BPF-55, BPF-68 etc., and preferred relative molecular mass is 372～772; Described phenol aldehyde type epoxy resin is novolac epoxy such as linear o-cresol formaldehyde epoxy resin, a linear phenolic epoxy resin etc. commonly used in the existing Electronic Packaging epoxide resin material technology, and preferred relative molecular mass is 450～900 novolac epoxy.
Another epoxidation silicon oil modified epoxy resin composite material of the present invention, it is characterized in that the product for preparing by following method: the epoxidation silicon oil of coupling modification and Resins, epoxy are solidified by fatty amine or aromatic amine curing agent after compound again, wherein the epoxidation silicon oil of coupling modification is the product that epoxidation silicon oil and end amino containing silane coupling agent carry out linked reaction, described epoxidation silicon oil is represented by above-mentioned general formula (1), m=0～100 wherein, n=1～100.
Described epoxidation silicon oil linked reaction reaction conditions is routinely carried out, and ratio of components is according to the mass fraction, 100 parts of epoxidation silicon oils, 0.1～100 part of coupling agent; Described coupling agent such as γ-An Jibingjisanyiyangjiguiwan (KH-550), N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan (A-1120) etc.; Described epoxidation silicon oil is that oxirane value is the pendant epoxies base silicone oil of 0.01～0.5mol/100g.
Preferred 5～15 parts of the coupling agent consumption of described linked reaction.
Described complex reaction reaction conditions is routinely carried out, and the ratio of components of raw material is 100 parts of Resins, epoxy according to the mass fraction, and 0.1～100 part of the epoxidation silicon oil of modification is preferably 5～20 parts, 5～60 parts in solidifying agent; Described Resins, epoxy is the bisphenol A type epoxy resin of relative molecular mass 340～2500, and relative molecular mass is that 312～2500 bisphenol f type epoxy resin and relative molecular mass are 300～2500 phenol aldehyde type epoxy resin; Solidification value depends on used solidifying agent, and aliphatic amide is generally normal temperature, aromatic amine be generally 60～200 ℃.
Bisphenol A type epoxy resin described in the described complex reaction can be E-51, E-44, E-32 etc., and preferred relative molecular mass is 400～800; Described bisphenol f type epoxy resin can be BPF-45, BPF-55, BPF-68 etc., and preferred relative molecular mass is 312～772; Described phenol aldehyde type epoxy resin is novolac epoxy such as linear o-cresol formaldehyde epoxy resin, a linear phenolic epoxy resin etc. commonly used in the existing Electronic Packaging epoxide resin material technology, and preferred relative molecular mass is 450～900 novolac epoxy.
Three kinds of epoxidation silicon oil modified epoxy resin composite materials of the present invention, with there not being the Resins, epoxy of modification to compare, all have higher shock strength, tensile strength, elongation at break and second-order transition temperature, therefore can be used as coating, the contour performance materials of sqtructural adhesive and electronic package material.
Embodiment
Following embodiment further specifies of the present invention, is not limitation of the present invention.
Embodiment 1
Get oxirane value and be the E-51 Resins, epoxy 100g of 0.51mol/100g and epoxidation silicon oil 0.1g that oxirane value is 0.16mol/100g and place beaker, stir, it is right to add again, right '-diaminodiphenyl-methane 25.26g, then the heating make right, right '-the diaminodiphenyl-methane dissolving, stir, deaeration, reverse mould, solidify by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtain epoxidation silicon oil modified epoxy resin composite material, record tensile strength and be 41.31MPa, elongation at break and be 5.42%, shock strength is 10.24KJm
-2, second-order transition temperature is 158 ℃.
Embodiment 2
Get oxirane value and be the F-51 Resins, epoxy 100g of 0.51mol/100g and epoxidation silicon oil 80g that oxirane value is 0.01mol/100g and place beaker, heating is also stirred, add diamino diphenyl sulfone 29.78g again, heating makes the diamino diphenyl sulfone dissolving then, restir, deaeration, reverse mould, solidify by 80 ℃/1h+160 ℃/2h+180 ℃/2h curing process, obtain epoxidation silicon oil modified epoxy resin composite material.Record tensile strength and be 43.47MPa, elongation at break and be 6.71%, shock strength is 11.62KJm
-2, second-order transition temperature is 163 ℃.
Embodiment 3
The epoxidation silicon oil 100g that gets oxirane value and be 0.16mol/100g with the dimethyl formamide dissolving after, with right, right '-diaminodiphenyl-methane 32g places reactor together, the heating of oil bath is simultaneously also stirred, then 140 ℃ of following back flow reaction 3 hours, after reaction finishes, with the reaction mixture underpressure distillation, boil off dimethyl formamide, obtain modified epoxy silicone oil, the E-44 Resins, epoxy 100g that gets 100g and oxirane value and be 0.44mol/100g stirs in beaker, adds dicyandiamide 5g again, solidify by 80 ℃/1h+160 ℃/1h+180 ℃/0.5h curing process, obtain epoxidation silicon oil modified epoxy resin composite material.Record tensile strength and be 47.54MPa, elongation at break and be 11.38%, shock strength is 14.45KJm
-2, second-order transition temperature is 171 ℃.
Embodiment 4
Getting oxirane value is the epoxidation silicon oil 100g of 0.16mol/100g, after xylene soluble, place reactor together with the 30g diamino diphenyl sulfone, the heating of oil bath is simultaneously also stirred, 130 ℃ of following back flow reaction 2 hours, after reaction finishes, with the reaction mixture underpressure distillation, boil off dimethylbenzene, obtain modified epoxy silicone oil, the E-32 Resins, epoxy 100g that gets 0.1g and oxirane value and be 0.32mol/100g stirs in beaker, adds diamino diphenyl sulfone 6.72g again, solidify by 80 ℃/1h+160 ℃/2h+180 ℃/2h curing process, obtain epoxidation silicon oil modified epoxy resin composite material.Recording it, to stretch intensity be that 42.74MPa, elongation at break are 7.38%, shock strength is 13.16KJm
-2, second-order transition temperature is 168 ℃.
Embodiment 5
Epoxidation silicon oil 100g and the 8g γ-An Jibingjisanyiyangjiguiwan (KH-550) of getting oxirane value and be 0.16mol/100g place reactor, stirring reaction.The reaction back obtains modified epoxy silicone oil, the o-cresol formaldehyde epoxy resin 100g that gets 0.1g and oxirane value and be 0.51mol/100g stirs in beaker, add diethylenetriamine 10.50g again, normal temperature is placed to solidify in one month and is obtained epoxidation silicon oil modified epoxy resin composite material mould.Record tensile strength and be 45.23MPa, elongation at break and be 10.73%, shock strength is 15.12KJm
-2, second-order transition temperature is 130 ℃.
Embodiment 6
The epoxidation silicon oil 100g that gets oxirane value and be 0.16mol/100g with xylene soluble after, right with 32g, right '-diaminodiphenyl-methane places reactor together, the heating of oil bath is simultaneously also stirred, 140 ℃ of following back flow reaction 5 hours, after reaction finishes, with the reaction mixture underpressure distillation, boil off dimethylbenzene, obtain modified epoxy silicone oil, the BPF-55 Resins, epoxy 100g that gets 10g and oxirane value and be 0.55mol/100g stirs in beaker, adds dicyandiamide 12.12g again, solidifies by 80 ℃/1h+160 ℃/1h+180 ℃/0.5h curing process to obtain epoxidation silicon oil modified epoxy resin composite material mould.Record tensile strength and be 59.04MPa, elongation at break and be 15.176, shock strength is 20.26KJm
-2, second-order transition temperature is 183 ℃.
Embodiment 7
Get oxirane value and be the E-51 Resins, epoxy 100g of 0.51mol/100g and epoxidation silicon oil 5g that oxirane value is 0.01mol/100g and place beaker, stir, add diethylenetriamine 10.6g again, normal temperature is placed to solidify in one month and is obtained product 1.Get oxirane value and be the E-51 Resins, epoxy 100g of 0.51mol/100g and epoxidation silicon oil 20g that oxirane value is 0.16mol/100g and place beaker, stir, add diethylenetriamine 10.9g again, normal temperature is placed to solidify in one month and is obtained product 2.Be oxirane value E-51 Resins, epoxy 100g and the diethylenetriamine 10.5g mixing of 0.51mol/100g in addition, normal temperature is placed to solidify in one month and is obtained product 0.The performance comparison data of these three products see Table 1.
The bisphenol A type epoxy resin that table 1 is epoxidation silicon oil modified and the performance comparison of unmodified epoxy resin
| The product numbering | Physicals | |||
| Tensile strength (MPa) | Elongation at break (%) | Shock strength (KJm -2) | Glass transition temperature (℃) | |
| 0 | 41.48 | 3.89 | 10.31 | 123.35 |
| 1 | 45.40 | 11.10 | 15.25 | 133.70 |
| 2 | 45.44 | 10.87 | 11.68 | 127.46 |
Embodiment 8
Get oxirane value and be the F-51 novolac epoxy 100g of 0.51mol/100g and epoxidation silicon oil 5g that oxirane value is 0.16mol/100g and place beaker, stir, it is right to add again, right '-diaminodiphenyl-methane 25.64g, then heating make right, right '-the diaminodiphenyl-methane dissolving, stir deaeration, reverse mould, solidify by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtain product 1.Get oxirane value and be the F-51 novolac epoxy 100g of 0.51mol/100g and epoxidation silicon oil 20g that oxirane value is 0.16mol/100g and place beaker, stir, it is right to add again, right '-diamino-diphenyl first 26.45g, then heating make right, right '-the diaminodiphenyl-methane dissolving, stir deaeration, reverse mould, solidify by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtain product 2.In addition oxirane value be 0.51mol/100g F-51 Resins, epoxy 100g and right, right '-diaminodiphenyl-methane 25.25g mixes, and solidifies by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtains product 0.The performance comparison data of these three products see Table 2.
The novolac epoxy that table 2 is epoxidation silicon oil modified and the performance comparison of unmodified novolac epoxy
| The product numbering | Physicals | |||
| Tensile strength (MPa) | Elongation at break (%) | Shock strength (KJm -2) | Glass transition temperature (℃) | |
| 0 | 53.89 | 5.89 | 6.76 | 164.38 |
| 1 | 58.54 | 15.11 | 14.25 | 168.55 |
| 2 | 57.67 | 16.24 | 12.84 | 175.56 |
Embodiment 9
The epoxidation silicon oil 100g that gets oxirane value and be 0.01mol/100g with the dimethyl formamide dissolving after, with right, right '-diaminodiphenyl-methane 2g places reactor together, the heating of oil bath is simultaneously also stirred, then 140 ℃ of following back flow reaction 4 hours, after reaction finishes, with the reaction mixture underpressure distillation, boil off dimethyl formamide, obtain modified epoxy silicone oil, getting 5g and oxirane value is that 0.51mol/100g E-51 Resins, epoxy 100g stirs in beaker, adds diethylenetriamine 10.6g again, and normal temperature is placed to solidify in one month and obtained product 1.The epoxidation silicon oil 100g that gets oxirane value and be 0.01mol/100g with the dimethyl formamide dissolving after, with right, right '-diaminodiphenyl-methane 2g places reactor together, the heating of oil bath is simultaneously also stirred, then 140 ℃ of following back flow reaction 4 hours, after reaction finishes, with the reaction mixture underpressure distillation, boil off dimethyl formamide, obtain modified epoxy silicone oil, getting 20g and oxirane value is that 0.51mol/100g E-51 Resins, epoxy 100g stirs in beaker, adds diethylenetriamine 10.9g again, and normal temperature is placed to solidify in one month and obtained product 2.Be oxirane value E-51 Resins, epoxy 100g and the diethylenetriamine 10.5g mixing of 0.51mol/100g in addition, place a curing in month by normal temperature and obtain product 0.The performance comparison data of these three products see Table 3.
Table 3 is with the modified bisphenol A type Resins, epoxy of curing agent modified epoxidation silicon oil and the performance comparison of unmodified epoxy resin
| The product numbering | Physicals | |||
| Tensile strength (MPa) | Elongation at break (%) | Shock strength (KJm -2) | Glass transition temperature (℃) | |
| 0 | 41.48 | 3.89 | 10.31 | 123.35 |
| 1 | 49.67 | 13.43 | 17.33 | 135.70 |
| 2 | 46.74 | 14.79 | 14.23 | 141.05 |
Embodiment 10
The epoxidation silicon oil 100g that gets oxirane value and be 0.16mol/100g with the dimethyl formamide dissolving after, with right, right '-diaminodiphenyl-methane 32g places reactor together, the heating of oil bath is simultaneously also stirred, reaction, refluxed 5 hours down at 140 ℃, after reaction finishes, with the reaction mixture underpressure distillation, boil off dimethyl formamide, modified epoxy silicone oil 5g that obtains and oxirane value are that 0.51mol/100g F-51 Resins, epoxy 100g stirs in beaker, it is right to add again, right '-diaminodiphenyl-methane 25.61g, solidify by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtain product 1.The epoxidation silicon oil 100g that gets oxirane value and be 0.16mol/100g with the dimethyl formamide dissolving after, with right, right '-diaminodiphenyl-methane 32g places reactor together, the heating of oil bath is simultaneously also stirred, reaction, refluxed 5 hours down at 140 ℃, after reaction finishes, with the reaction mixture underpressure distillation, boil off dimethyl formamide, modified epoxy silicone oil 20g that obtains and oxirane value are that 0.51mol/100g F-51 Resins, epoxy 100g stirs in beaker, it is right to add again, right '-diaminodiphenyl-methane 26.36g, solidify by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtain product 2.Be oxirane value the F-51 Resins, epoxy 100g of 0.51mol/100g and right in addition, to '-diaminodiphenyl-methane 25.25g mixes, and solidifies by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtains product 0.The performance comparison data of these three products see Table 4.
Table 4 is with the modified phenolic Resins, epoxy of curing agent modified epoxidation silicon oil and the performance comparison of unmodified epoxy resin
| The product numbering | Physicals | |||
| Tensile strength (MPa) | Elongation at break (%) | Shock strength (KJm -2) | Glass transition temperature (℃) | |
| 0 | 53.89 | 5.89 | 6.76 | 164.38 |
| 1 | 63.36 | 17.84 | 18.12 | 171.40 |
| 2 | 60.24 | 16.53 | 13.68 | 183.46 |
Embodiment 11
Get epoxidation silicon oil and the 0.5g γ-An Jibingjisanyiyangjiguiwan (KH-550) that oxirane value is 0.01mol/100g and place reactor, stirring reaction.It is that the E-51 Resins, epoxy 100g of 0.51mol/100g stirs in beaker that the modified epoxy silicone oil that reaction back obtains is got 5g and oxirane value, adds diethylenetriamine 10.52g again, and normal temperature is placed a curing in month and obtained product 1.Get epoxidation silicon oil and the 0.5g γ-An Jibingjisanyiyangjiguiwan (KH-550) that oxirane value is 0.01mol/100g and place reactor, stirring reaction.The E-51 Resins, epoxy 100g that modified epoxy silicone oil 20g that the reaction back obtains and oxirane value are 0.51mol/100g stirs in beaker, adds diethylenetriamine 10.61g again, and normal temperature is placed to solidify in one month and obtained product 2.Be oxirane value E-51 Resins, epoxy 100g and the diethylenetriamine 10.50g mixing of 0.51mol/100g in addition, normal temperature is placed to solidify in one month and is obtained product 0.The performance comparison data of these three products see Table 5.
The modified bisphenol A type Resins, epoxy of the epoxidation silicon oil of table 5 coupling modification and the performance comparison of unmodified epoxy resin
| The product numbering | Physicals | |||
| Tensile strength (MPa) | Elongation at break (%) | Shock strength (KJm -2) | Glass transition temperature (℃) | |
| 0 | 41.48 | 3.89 | 10.31 | 123.35 |
| 1 | 48.56 | 15.49 | 16.23 | 140.34 |
| 2 | 46.84 | 12.39 | 13.81 | 135.64 |
Embodiment 12
Get epoxidation silicon oil and the 8g γ-An Jibingjisanyiyangjiguiwan (KH-550) that oxirane value is 0.16mol/100g and place reactor, stirring reaction.It is that the F-51 Resins, epoxy 100g of 0.51mol/100g stirs in beaker that the modified epoxy silicone oil that reaction back obtains is got 5g and oxirane value, it is right to add again, right '-diaminodiphenyl-methane 24.86g, then heating make right, right '-diaminodiphenyl-methane dissolving, stir, deaeration, reverse mould solidifies by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtains product 1.Get epoxidation silicon oil and the 8g γ-An Jibingjisanyiyangjiguiwan (KH-550) that oxirane value is 0.16mol/100g and place reactor, stirring reaction.The F-51 Resins, epoxy 100g that modified epoxy silicone oil 20g that the reaction back obtains and oxirane value are 0.51mol/100g stirs in beaker, it is right to add again, right '-diaminodiphenyl-methane 24.98g, then heating make right, right '-diaminodiphenyl-methane dissolving, stir, deaeration, reverse mould solidifies by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtains product 2.In addition oxirane value be 0.51mol/100g F-51 Resins, epoxy 100g and right, right '-diaminodiphenyl-methane 25.25g mixes, and solidifies by 80 ℃/3h+150 ℃/2h+175 ℃/1h curing process, obtains product 0.The performance comparison data of these three products see Table 6.
The modified phenolic Resins, epoxy of the epoxidation silicon oil of table 6 coupling modification and the performance comparison of unmodified epoxy resin
| The product numbering | Physicals | |||
| Tensile strength (MPa) | Elongation at break (%) | Shock strength (KJm -2) | Glass transition temperature (℃) | |
| 0 | 53.89 | 5.89 | 6.76 | 164.38 |
| 1 | 63.37 | 18.34 | 20.22 | 179.44 |
| 2 | 67.49 | 19.60 | 14.98 | 177.61 |
Claims (6)
1. epoxidation silicon oil modified epoxy resin composite material, it is characterized in that the product for preparing by following method: curing agent modified epoxidation silicon oil and Resins, epoxy are solidified by fatty amine or aromatic amine curing agent after compound again, wherein curing agent modified epoxidation silicon oil is epoxidation silicon oil and solidifying agent are cured reaction in high boiling organic solvent a product, solidifying agent in the described curing agent modified epoxidation silicon oil is right, right '-diaminodiphenyl-methane, diamino diphenyl sulfone, dicyandiamide or resol, described epoxidation silicon oil is represented by following general formula (1):
M=0～100 wherein, n=1～100, oxirane value is 0.01～0.5mol/100g.
2. according to a kind of epoxidation silicon oil modified epoxy resin composite material of claim 1, the ratio of components that it is characterized in that described epoxidation silicon oil modified reaction is according to the mass fraction, 100 parts of epoxidation silicon oils, 0.1～100 part in solidifying agent; Described high boiling organic solvent is toluene, dimethylbenzene, dimethyl formamide or dimethyl sulfoxide (DMSO); The ratio of components of described complex reaction is 100 parts of Resins, epoxy according to the mass fraction, 0.1～100 part of the epoxidation silicon oil of modification, 5～60 parts in solidifying agent; Described Resins, epoxy is the bisphenol A type epoxy resin of relative molecular mass 340～2500, and relative molecular mass is that 312～2500 bisphenol f type epoxy resin or relative molecular mass are 300～2500 phenol aldehyde type epoxy resin; The solidification value of aliphatic amide is a normal temperature, and the solidification value of aromatic amine is 60～200 ℃.
3. according to a kind of epoxidation silicon oil modified epoxy resin composite material of claim 2, the hardener dose that it is characterized in that the epoxidation silicon oil modified reaction described in the epoxidation silicon oil modified reaction is 20～50 parts; The consumption of the epoxidation silicon oil of the modification described in the described complex reaction is 5～20 parts, and described bisphenol A type epoxy resin is the bisphenol A type epoxy resin of relative molecular mass 400～800; Described bisphenol f type epoxy resin is the bisphenol f type epoxy resin of relative molecular mass 372～772; Described phenol aldehyde type epoxy resin is the novolac epoxy of relative molecular mass 450～900.
4. epoxidation silicon oil modified epoxy resin composite material, it is characterized in that the product for preparing by following method: the epoxidation silicon oil of coupling modification and Resins, epoxy are solidified by fatty amine or aromatic amine curing agent after compound again, wherein the epoxidation silicon oil of coupling modification is the product that epoxidation silicon oil and end amino containing silane coupling agent carry out linked reaction, described epoxidation silicon oil requires 1 general formula (1) expression by aforesaid right, m=0～100 wherein, n=1～100, oxirane value are 0.01～0.5mol/100g.
5. according to a kind of epoxidation silicon oil modified epoxy resin composite material of claim 4, the ratio of components that it is characterized in that described epoxidation silicon oil linked reaction is according to the mass fraction, 100 parts of epoxidation silicon oils, 0.1～100 part of coupling agent, described coupling agent are γ-An Jibingjisanyiyangjiguiwan or N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan; The ratio of components of described complex reaction raw material according to the mass fraction, be 100 parts of Resins, epoxy, 0.1～100 part of the epoxidation silicon oil of modification, 5～60 parts in solidifying agent, described Resins, epoxy is the bisphenol A type epoxy resin of relative molecular mass 340～2500, and relative molecular mass is that 312～2500 bisphenol f type epoxy resin or relative molecular mass are 300～2500 phenol aldehyde type epoxy resin; The solidification value of aliphatic amide is a normal temperature, and the solidification value of aromatic amine is 60～200 ℃.
6. according to a kind of epoxidation silicon oil modified epoxy resin composite material of claim 5, the coupling agent consumption that it is characterized in that described linked reaction is 5～15 parts; The consumption of the epoxidation silicon oil of the modification described in the described complex reaction is 5～20 parts, described bisphenol A type epoxy resin is the bisphenol A type epoxy resin of relative molecular mass 400～800, described bisphenol f type epoxy resin is the bisphenol f type epoxy resin of relative molecular mass 372～772, and described phenol aldehyde type epoxy resin is the novolac epoxy of relative molecular mass 450～900.
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| CN100590168C (en) * | 2007-04-24 | 2010-02-17 | 中国科学院广州化学研究所 | Composite epoxy type electron packaging material and preparation method thereof |
| CN100560632C (en) * | 2007-06-11 | 2009-11-18 | 中国科学院广州化学研究所 | A kind of silicon-phosphor-containing heat-stable hybridized epoxide resin and its production and application |
| CN101475731B (en) * | 2009-01-06 | 2011-06-08 | 中国科学院广州化学研究所 | Epoxy resin composite material added with modified polysiloxane and preparation thereof |
| CN101792574B (en) * | 2010-03-30 | 2012-02-08 | 中科院广州化学有限公司 | Modified epoxy resin composite material of prereacted material of epoxy-terminated silicone oil and preparation method and application thereof |
| CN109021898A (en) * | 2018-06-27 | 2018-12-18 | 湖北三江航天江北机械工程有限公司 | It is used to prepare the two-component toughening winding gas cylinder glue and preparation method thereof of compressed natural gas steel inner container hoop winding gas cylinder |
| CN110229464A (en) * | 2019-05-11 | 2019-09-13 | 常州宝利美石墨烯有限公司 | A kind of epoxy silicon oil modified graphene oxide and epoxy resin composite material preparation method |
| CN113929874B (en) * | 2021-11-16 | 2024-02-06 | 华东理工大学华昌聚合物有限公司 | Epoxy resin composition and preparation method thereof |
| CN114835901B (en) * | 2022-06-17 | 2023-06-20 | 四川大学 | Epoxy modified vinyl silicone rubber and preparation method and application thereof |
| CN115651402B (en) * | 2022-10-17 | 2023-10-13 | 天津凯华绝缘材料股份有限公司 | Epoxy resin toughening modified cyanate resin powder encapsulating material, preparation method and application |
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