CN104987668A - Preparation method of flexible and transparent epoxy resin - Google Patents
Preparation method of flexible and transparent epoxy resin Download PDFInfo
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- CN104987668A CN104987668A CN201510393514.2A CN201510393514A CN104987668A CN 104987668 A CN104987668 A CN 104987668A CN 201510393514 A CN201510393514 A CN 201510393514A CN 104987668 A CN104987668 A CN 104987668A
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Abstract
Provided is a preparation method of flexible and transparent epoxy resin. The method comprises the steps that oxidation and reduction reactions for removing epoxy functional groups are conducted through epoxy resin and reducing agents to prepare modified resin; then the modified resin is mixed with the epoxy resin, and a curing reaction is conducted on the mixture to prepare a flexible and transparent epoxy resin cured product. The preparation method of the flexible and transparent epoxy resin has the advantages of being novel in design, simple in preparation technology, mild in involved reaction conditions, easy to operate and the like; the prepared epoxy resin is good in flexibility, high in transparency and low in production cost.
Description
Technical field
The present invention relates to pliable and tough epoxy resin field, be specifically related to a kind of preparation method of pliable and tough transparent epoxy resin.
Background technology
Epoxy resin is widely used in the national economy various fields such as space flight and aviation, wind-powered electricity generation generating, tackiness agent, machinery, coating because of advantages such as its good cementability with excellence, wear resistance, mechanical property, chemical stability and shrinking percentage are low and with low cost.But the textural defect such as asphalt mixtures modified by epoxy resin lipid is crisp, and shock strength is low, make it apply and are subject to certain restrictions, be difficult to the requirement meeting many engineering increasingly stringents.Therefore, the snappiness how improving epoxy resin becomes the study hotspot widening epoxy resin range of application.
Usually, improving the flexible method of epoxy resin is waited until in epoxy resin-base to reach improved the flexible effect of epoxy resin by interpolation rubber elastomer, thermoplastic resin, rigid inorganic filler, TLCP.But, because the two-phase consistency of additive and epoxy resin is poor, be separated so the epoxy resin prepared by the method can produce, cause the transparency of epoxy resin significantly to reduce, limit the application of modified epoxy resin in the field that transparency requirement is higher.
Summary of the invention
The technical problem solved: the object of the invention is the preparation method providing a kind of pliable and tough transparent epoxy resin, the method has the advantages such as modern design, simple, the involved reaction conditions gentleness of preparation technology, easy handling, and prepared epoxy resin snappiness is high, the transparency is high, production cost is low.
Technical scheme: a kind of preparation method of pliable and tough transparent epoxy resin, is first carried out the redox reaction of epoxy-functional, prepares modified resin by epoxy resin and reductive agent; Then modified resin is mixed with epoxy resin, then through curing reaction, prepare pliable and tough transparent epoxy resin solidifying product, concrete preparation process is as follows:
The first step: epoxy resin is joined in organic solvent, the mass ratio of its epoxy resin and organic solvent is 1:4 ~ 1:10, and stirred at ambient temperature 0.3 ~ 0.5h makes epoxy resin be dissolved in solvent, obtains colourless transparent solution; Subsequently, epoxy resin solution is heated to 60 ~ 100 DEG C, adds reductive agent and react, reaction 4 ~ 6h, solvent is removed in underpressure distillation, obtains the modified resin of yellow transparent thick liquid nano;
Second step: by modified resin with epoxy resin by mixing, add D230 type polyetheramine solidifying agent again, the mixing quality ratio of modified resin and epoxy resin is 1:9 ~ 1:3, the mass ratio of solidifying agent and hybrid resin is 1:3 ~ 1:5, Procuring 6 ~ 12h at 20 ~ 30 DEG C, and then 3 ~ 5h is solidified at 80 DEG C, prepare pliable and tough transparent epoxy resin cured product.
The epoxy resin of the above-mentioned the first step and the mass ratio of solvent are 1:10, and this produces gelation effect in the system that to be reduced in process in order to avoid epoxide group.
The organic solvent used of the above-mentioned the first step is selected from the one in acetone, toluene, dimethylbenzene, pimelinketone.
Above-mentioned the first step reductive agent used is selected from the one in hydration hydrazine and its derivative, vitamins C, sodium borohydride, hydroiodic acid HI, Resorcinol.
The mass ratio of the reductive agent that the above-mentioned the first step is used and epoxy resin is 2:1.
The temperature of above-mentioned the first step reaction is 60 DEG C, and the reaction times is 4h.
The modified resin of above-mentioned second step and the mixing quality ratio of epoxy resin are 1:3.
The solidifying agent of above-mentioned second step and the mass ratio of hybrid resin are 1:4.
The solidification value of above-mentioned second step and set time be: at room temperature Procuring 6h, and then solidify 3h at 80 DEG C.
Above-mentioned epoxy resin used is selected from least one in bisphenol A type epoxy resin, bis-phenol H type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin.
Beneficial effect:
1. with generally improve compared with the flexible method of epoxy resin, the raw material of decyclization oxidation modification resin prepared by the present invention is from epoxy resin, therefore modified resin and epoxy resin have excellent consistency, ensure that the epoxy resin prepared has the excellent transparency, when the mass ratio of modified resin and epoxy resin is 1:3, the transmittance of the epoxy resin-cured product prepared can reach 85%, be greater than 82% of unmodified epoxy resin, much larger than 62.07% (mass ratio of paracril and epoxy resin is 1:3) with acrylonitrile butadiene rubber modified epoxy resin.
2. the decyclization oxidation modification resin that prepared by the present invention does not participate in crosslinking reaction in the curing process, play self-plasticizing action, therefore the epoxy resin prepared has excellent snappiness, when the mass ratio of modified resin and epoxy resin is 1:3, the elongation at break of the epoxy resin-cured product prepared can reach 110%, much larger than 14.07% (mass ratio of paracril and epoxy resin is 1:3) with acrylonitrile butadiene rubber modified epoxy resin.
3. the present invention take epoxy resin as raw material, cheap, and wide material sources, can reduce the production cost of product greatly.
4. preparation process technique is simple, reaction conditions is gentle, constant product quality, energy consumption are low, the three wastes are few, is a kind of preparation method of environmental protection and economy.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of epoxy resin, 913cm in figure
-1it is the characteristic peak of epoxide group.
Fig. 2 is the infrared spectrogram of modified resin, does not occur 913cm in figure
-1epoxide group characteristic peak, illustrates through reduction reaction, and the epoxide group in epoxy resin is successfully got rid of.
Embodiment
Be specifically described the present invention below by example, embodiment provides detailed embodiment and concrete operation steps, only for further illustrating of the present invention, can not be interpreted as limiting the scope of the invention.
Embodiment 1
The bisphenol A epoxide resin (its infrared spectrum as shown in Figure 1) taking 20g is dissolved in 200g acetone, be heated to 60 DEG C subsequently, add 40g hydrazine hydrate to react, reaction 4h, underpressure distillation removing acetone, obtain the modified resin of yellow transparent thick liquid nano, its infrared spectrum as shown in Figure 2.Comparison diagram 1 and Fig. 2, we can find that modified resin does not occur 913cm
-1epoxide group characteristic peak, this illustrates that the epoxide group of epoxy resin is successfully removed.
Take 10g modified resin and be placed in single port flask, add 90g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 2
The bisphenol A epoxide resin taking 30g is dissolved in 300g acetone, is heated to 60 DEG C subsequently, adds 60g hydrazine hydrate and reacts, reaction 4h, and underpressure distillation removing acetone, obtains the modified resin of yellow transparent thick liquid nano.
Take 20g modified resin and be placed in single port flask, add 80g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 3
The bisphenol A epoxide resin taking 30g is dissolved in 300g acetone, is heated to 60 DEG C subsequently, adds 60g hydrazine hydrate and reacts, reaction 4h, and underpressure distillation removing acetone, obtains the modified resin of yellow transparent thick liquid nano.
Take 25g modified resin and be placed in single port flask, add 75g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 4
The bisphenol A epoxide resin taking 30g is dissolved in 120g dimethylbenzene, is heated to 100 DEG C subsequently, adds 150g hydrazine hydrate and reacts, and reaction 6h, underpressure distillation, except removal xylene, obtains the modified resin of yellow transparent thick liquid nano.
Take 25g modified resin and be placed in single port flask, add 75g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 10h, at 80 DEG C, solidify 4h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 5
The bisphenol A epoxide resin taking 30g is dissolved in 180g acetone, is heated to 60 DEG C subsequently, adds 60g Resorcinol and reacts, reaction 6h, and underpressure distillation removing acetone, obtains the modified resin of yellow transparent thick liquid nano.
Take 25g modified resin and be placed in single port flask, add 75g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 12h, at 80 DEG C, solidify 5h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 6
The bisphenol A epoxide resin taking 30g is dissolved in 300g dimethylbenzene, is heated to 80 DEG C subsequently, adds 60g Resorcinol and reacts, and reaction 6h, underpressure distillation, except removal xylene, obtains the modified resin of yellow transparent thick liquid nano.
Take 25g modified resin and be placed in single port flask, add 75g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 20g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 7
The bisphenol A epoxide resin taking 30g is dissolved in 300g dimethylbenzene, is heated to 85 DEG C subsequently, adds 150g hydroiodic acid HI and reacts, and reaction 6h, underpressure distillation, except removal xylene, obtains the modified resin of yellow transparent thick liquid nano.
Take 15g modified resin and be placed in single port flask, add 45g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 20g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 8
The bisphenol A epoxide resin taking 30g is dissolved in 300g acetone, is heated to 90 DEG C subsequently, adds 60g hydroiodic acid HI and reacts, reaction 6h, and underpressure distillation removing acetone, obtains the modified resin of yellow transparent thick liquid nano.
Take 25g modified resin and be placed in single port flask, add 75g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 9
The bis-phenol H epoxy resin taking 30g is dissolved in 300g acetone, is heated to 60 DEG C subsequently, adds 90g hydrazine hydrate and reacts, reaction 4h, and underpressure distillation removing acetone, obtains the modified resin of yellow transparent thick liquid nano.
Take 25g modified resin and be placed in single port flask, add 75g bis-phenol H epoxy resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Embodiment 10
The bisphenol F epoxy resin taking 30g is dissolved in 300g acetone, is heated to 60 DEG C subsequently, adds 60g hydrazine hydrate and reacts, reaction 4h, and underpressure distillation removing acetone, obtains the modified resin of yellow transparent thick liquid nano.
Take 25g modified resin and be placed in single port flask, add 75g bisphenol F epoxy resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 1.
Comparative example 1
Take 80g bisphenol A epoxide resin and be placed in single port flask, then add D230 type polyetheramine 20g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 2.
Comparative example 2
Take 10g paracril and be placed in single port flask, add 90g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 2.
Comparative example 3
Take 25g paracril and be placed in single port flask, add 75g bisphenol A epoxide resin subsequently, under the rotating speed of 400rpm, carry out stirring make two kinds of mixed with resin even.Then in hybrid resin, add D230 type polyetheramine 25g, stir 30min.Then system is poured in dumbbell shape mould, after room temperature Procuring 6h, at 80 DEG C, solidify 3h again.The curing system prepared carries out tensile property and transmittance test is as shown in table 2.
The mechanical property of table 1 modified epoxy curing system and transmittance
The mechanical property of table 2 pure epoxy resin and acrylonitrile butadiene rubber modified epoxy resin curing system and transmittance
Shown by the data of table 1, along with the increase of modified resin consumption, the continuous reduction of the tensile strength of epoxy resin, elongation at break constantly raises, and transmittance loses hardly, and some sample transmittance even improve.Shown by the data of table 2, very little by its elongation at break of acrylonitrile butadiene rubber modified epoxy resin i.e. its flexible amplification, the epoxy resin that the modified resin prepared well below the present invention is toughness reinforcing.And the transmittance of acrylonitrile butadiene rubber modified epoxy resin significantly reduces along with the increase of paracril content.Therefore can be prepared by method of the present invention and have the pliable and tough epoxy resin of higher transparency, its snappiness and transparency are better than the toughness reinforcing epoxy resin of conventional rubber, can be used for the embedding and the sealing that have flexibility, transparency requirement product surface.
Claims (10)
1. a preparation method for pliable and tough transparent epoxy resin, is characterized in that, is first carried out the redox reaction of epoxy-functional by epoxy resin and reductive agent, prepares modified resin; Then modified resin is mixed with epoxy resin, then through curing reaction, prepare pliable and tough transparent epoxy resin solidifying product, concrete preparation process is as follows:
The first step: epoxy resin is joined in organic solvent, the mass ratio of its epoxy resin and organic solvent is 1:4 ~ 1:10, and stirred at ambient temperature 0.3 ~ 0.5 h makes epoxy resin be dissolved in solvent, obtains colourless transparent solution; Subsequently, epoxy resin solution is heated to 60 ~ 100 DEG C, adds reductive agent and react, reaction 4 ~ 6 h, wherein the mass ratio of reductive agent and epoxy resin is 2:1 ~ 5:1; After reaction terminates, solvent is removed in underpressure distillation, obtains the modified resin of yellow transparent thick liquid nano;
Second step: by modified resin with epoxy resin by mixing, add D230 type polyetheramine solidifying agent again, the mixing quality ratio of modified resin and epoxy resin is 1:9 ~ 1:3, the mass ratio of solidifying agent and hybrid resin is 1:3 ~ 1:5, Procuring 6 ~ 12 h at 20 ~ 30 DEG C, and then 3 ~ 5 h are solidified at 80 DEG C, prepare pliable and tough transparent epoxy resin cured product.
2. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that the epoxy resin of the first step and the mass ratio of organic solvent are 1:10.
3. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that the first step organic solvent used is selected from the one in acetone, toluene, dimethylbenzene, pimelinketone.
4. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that the first step reductive agent used is selected from the one in hydration hydrazine and its derivative, vitamins C, sodium borohydride, hydroiodic acid HI, Resorcinol.
5. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that the mass ratio of the reductive agent that the first step is used and epoxy resin is 2:1.
6. the preparation method of pliable and tough transparent epoxy resin according to claim 1, it is characterized in that the temperature that the first step is reacted is 60 DEG C, the reaction times is 4 h.
7. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that the modified resin of second step and the mixing quality ratio of epoxy resin are 1:3.
8. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that the solidifying agent of second step and the mass ratio of hybrid resin are 1:4.
9. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that the solidification value of second step and set time be: at room temperature Procuring 6 h, and then solidify 3 h at 80 DEG C.
10. the preparation method of pliable and tough transparent epoxy resin according to claim 1, is characterized in that epoxy resin used is selected from least one in bisphenol A type epoxy resin, bis-phenol H type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112046031A (en) * | 2020-08-05 | 2020-12-08 | 赵军 | Luminous technology for glass fiber reinforced plastic sculpture |
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| US20090099312A1 (en) * | 2007-10-15 | 2009-04-16 | Carl Duane Weber | Amine terminated tougheners for epoxy resin based adhesives and materials |
| CN103011150A (en) * | 2012-12-27 | 2013-04-03 | 上海交通大学 | Flexible graphene composite film and preparation method thereof |
| CN104136479A (en) * | 2011-12-20 | 2014-11-05 | 陶氏环球技术有限责任公司 | Toughening agent for epoxy thermoset |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090099312A1 (en) * | 2007-10-15 | 2009-04-16 | Carl Duane Weber | Amine terminated tougheners for epoxy resin based adhesives and materials |
| CN104136479A (en) * | 2011-12-20 | 2014-11-05 | 陶氏环球技术有限责任公司 | Toughening agent for epoxy thermoset |
| CN103011150A (en) * | 2012-12-27 | 2013-04-03 | 上海交通大学 | Flexible graphene composite film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112046031A (en) * | 2020-08-05 | 2020-12-08 | 赵军 | Luminous technology for glass fiber reinforced plastic sculpture |
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