CN103642021B - Nitrogen-containing epoxy thermoset toughner and preparation method thereof - Google Patents
Nitrogen-containing epoxy thermoset toughner and preparation method thereof Download PDFInfo
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- CN103642021B CN103642021B CN201310669595.5A CN201310669595A CN103642021B CN 103642021 B CN103642021 B CN 103642021B CN 201310669595 A CN201310669595 A CN 201310669595A CN 103642021 B CN103642021 B CN 103642021B
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Abstract
<b> the invention provides a kind of nitrogenous </b><bGreatT.Gre aT.GT epoxy resin toughener and preparation method thereof </b><bGreatT.Gre aT.GT.Pure epoxy resin has high crosslinking structure, so there is the shortcomings such as matter is crisp, resistance to fatigue, toughness difference, makes it apply and is subject to a definite limitation.The inventive method </b><bGreatT.Gre aT.GT step comprises: (</b><bGreatT.Gre aT.GT1</b><bGrea tT.GreaT.GT) is by hexanodioic acid, dibasic alcohol, urea, acid anhydrides and catalyst mix heating for dissolving are warming up to temperature </b><bGreatT.Gre aT.GTT again
1</b><bGreatT.Gre aT.GT, </b><bGreatT.Gre aT.GT is held for some time </b><bGreatT.Gre aT.GTt under condensation recovering condition
1</b><bGreatT.Gre aT.GT0.1MPa</b>< b> certain hour </b><bGreatT.Gre aT.GTt is evacuated to again after </b><bGreatT.Gre aT.GT
2</b><bGreatT.Gre aT.GT, temperature is risen to </b><bGreatT.Gre aT.GTT by (</b><bGreatT.Gre aT.GT2</b><bGrea tT.GreaT.GT) subsequently
2</b><bGreatT.Gre aT.GT, </b><bGreatT.Gre aT.GT held for some time </b><bGreatT.Gre aT.GTt
3certain hour </b><bGreatT.Gre aT.GTt is vacuumized again after </b><bGreatT.Gre aT.GT
4</b><bGreatT.Gre aT.GT, (</b><bGreatT.Gre aT.GT3</b><bGrea tT.GreaT.GT) is warming up to </b><bGreatT.Gre aT.GTT subsequently again
3</b><bGreatT.Gre aT.GT held for some time </b><bGreatT.Gre aT.GTt
5</b><bGreatT.Gre aT.GT, then be warming up to </b><bGreatT.Gre aT.GTT
4</b><bGreatT.Gre aT.GT held for some time </b><bGreatT.Gre aT.GTt
6</b><bGreatT.Gre aT.GT, then be warming up to </b><bGreatT.Gre aT.GTT
5</b><bGreatT.Gre aT.GT held for some time </b><bGreatT.Gre aT.GTt
7</b><bGreatT.Gre aT.GT, </b><bGreatT.Gre aT.GT(</b><bGrea tT.GreaT.GT4</b>LEssT.LTssT.L Tb>) be cooled to </b><bGreatT.Gre aT.GT70</b><bGre atT.GreaT.GT DEG C of below </b><bGreatT.Gre aT.GT, discharging.</b><bGreatT.Gre aT.GT the present invention is applied to all kinds of epoxy resin solidifying system.</b>
Description
technical field:
the present invention relates to a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof.
background technology:
epoxy resin is a kind of thermosetting resin, because it has the excellent characteristic such as cohesiveness, physical strength, electrical insulating property, and is widely used in the aspects such as the cast of electronic material, encapsulation and coating, tackiness agent, matrices of composite material.But pure epoxy resin has high crosslinking structure, so there is the shortcomings such as matter is crisp, resistance to fatigue, toughness difference, make it apply and be subject to a definite limitation.Thus epoxy resin toughened is the study hotspot in epoxy resin field.Its main method for toughening has: (1) adds Rigid Particles Toughened; (2) rubber particles formation island structure is added toughness reinforcing; (3) thermoplastics is added toughness reinforcing; (4) toughness reinforcing by forming interpenetrating(polymer)networks; (5) core-shell particles is formed toughness reinforcing; (6) special epoxy toughner is added.And epoxy resin is combustible material, along with widely using of epoxy resin, the hidden danger of fire, also in increase, therefore improves the task of top priority that its flame retardant resistance has been epoxy resin research.
high polymer long chain containing soft segment is introduced in epoxy resin and is improved its shearing resistance, shock strength, elongation at break by epoxy resin toughner of the present invention, a large amount of ester group amido linkage isopolarity group is introduced in epoxy resin and improves its cohesive strength, obvious to the toughening effect of resin, and toughness reinforcing technique is simple.And nitrogen element can be introduced in epoxy resin by this toughner, the ability that nitrogen element has the free radical that capture reaction process produces can be released under resin high temperature, make free radical lose reactive behavior, combustion processes can not occur and continue, thus has flame retardant resistance.And utilize this method raising resins fire retardant not pollute the environment, be a kind of environmental friendliness shaped material.The present invention is raw materials used is poisonous material and with low cost, does not have toxic gas or liquid to release in process of production, belongs to green chemical products.To the multinomial performance Be very effective improving epoxy resin, be conducive to epoxy resin and apply widely in the industrial production, have broad application prospects and good economic benefit.
summary of the invention:
the object of this invention is to provide a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof.This preparation method's technique is simple, with low cost, easy and simple to handle; The epoxy resin toughener using present method to prepare, can effectively improve epoxy resin shearing resistance, shock strength, elongation at break and cohesive strength, and make it have obvious flame retardant effect, and this toughner storage time is long.
above-mentioned purpose is achieved through the following technical solutions:
a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof, the method comprising the steps of:
a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof, its step comprises:
(1) hexanodioic acid, dibasic alcohol, urea, acid anhydrides and catalyst mix heating for dissolving are warming up to temperature T again
1
, held for some time t under condensation recovering condition
1
after be evacuated to 0.1MPa certain hour t again
2
;
(2) subsequently temperature is risen to T
2
, held for some time t
3
after vacuumize certain hour t again
4
;
(3) T is warming up to again subsequently
3
held for some time t
5
, then be warming up to T
4
held for some time t
6
, then be warming up to T
5
held for some time t
7
;
(4) less than 70 DEG C are cooled to, discharging.
described a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof, the described dibasic alcohol described in step (1) is 1, one or both mixtures in 3-methyl propanediol, diethylene glycol, Triethylene glycol, described acid anhydrides is the one in phthalic anhydride, cis-butenedioic anhydride, and described catalyzer is the one in dibutyl tin laurate, antimonous oxide, tosic acid.
described a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof, the ratio of the amount of substance of the described hexanodioic acid described in step (1), described dibasic alcohol, described urea, described acid anhydrides is 10:9:1:1 or 10:8:2:2 or 10:7:3:3 or 10:6:4:4, and described catalyst levels is 0.5 ~ 0.8wt% of system total mass.
described a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof, the described temperature of reaction T described in step (1)
1
be 130 DEG C ~ 150 DEG C, the described temperature of reaction T described in step (2)
2
be 150 DEG C ~ 170 DEG C, the described temperature of reaction T described in step (3)
3
be 170 DEG C ~ 190 DEG C, described temperature of reaction T
4
be 190 DEG C ~ 210 DEG C, described temperature of reaction T
5
be 210 DEG C ~ 240 DEG C,
described a kind of nitrogen-containing epoxy thermoset toughner and preparation method thereof, the described soaking time t described in step (1)
1
be 0.8 ~ 1 hour, described pumpdown time t
2
it is 0.5 ~ 1 hour; The described soaking time t described in step (2)
3
be 0.25 ~ 0.45 hour, described pumpdown time t
4
it is 0.25 ~ 0.45 hour; The described soaking time t described in step (3)
5
be 0.5 ~ 1 hour, described soaking time t
6
be 0.5 ~ 1 hour, described soaking time t
7
it is 1 ~ 2 hour.
beneficial effect:
1. the epoxy resin toughener using present method to prepare, effectively can improve epoxy resin shock strength and not reduce flexural strength and modulus in flexure, and make it have obvious flame retardant effect, and this toughner storage time is long.Product is coffee-like evenly thick liquid, and standing storage is without precipitation.
2. this preparation method cost is low, and advantages of nontoxic raw materials evil, technique is simple, and technological process is released without toxic substance, easy to operate, is easy to industrialization.Be widely used in all kinds of epoxy resin solidifying system, and have potential using value in the toughness reinforcing field of other material.
embodiment:
embodiment 1:
24.5g cis-butenedioic anhydride, 15g urea, 202.5g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=1:1:9:10) and 3.64g antimonous oxide are mixed and heated to and melt completely, be warming up to 140 DEG C of insulation 30min under condensation recovering condition after, be evacuated to 0.1MPa50min again.At the uniform velocity be warming up to 160 DEG C with 1 DEG C/min subsequently, after insulation 15min, vacuumize 15min again.180 DEG C of held for some time 30min are at the uniform velocity warming up to again subsequently with 1 DEG C/min, 200 DEG C of insulation 30min are at the uniform velocity warming up to again with 1 DEG C/min, stop heating after being at the uniform velocity warming up to 220 DEG C of insulation 90min with 1 DEG C/min again, be cooled to less than 70 DEG C, discharging obtains toughner.
get 100gE44 epoxy resin, 10g toughner Hybrid Heating be warming up to 110 DEG C and under condensation recovering condition insulation reaction 180min, obtain toughening-modifiedepoxy resin 110g.35g methyl hexahydrophthalic anhydride, 35g methylnadic anhydride and 4.7g pyridine to be added in the toughness reinforcing epoxy resin of 110g and to mix, test gel time, then 80 DEG C 0.5 hour, 110 DEG C 2 hours, under 160 DEG C of curing process of 6 hours, curing molding obtains epoxy resin cured product, and is numbered 1.
embodiment 2:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 2.
embodiment 3:
73.5g cis-butenedioic anhydride, 45g urea, 157.5g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=3:3:7:10) and 3.64g antimonous oxide are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 3.
embodiment 4:
98g cis-butenedioic anhydride, 60g urea, 135g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=4:4:6:10) and 3.64g antimonous oxide are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 4.
the mechanical property of different toughening agent modified epoxy resin E44 cured article and thermogravimetric analysis test result are as following table, wherein numbering 5 be after 100g epoxy resin E44 mixes with 35g methyl hexahydrophthalic anhydride, 35g methylnadic anhydride and 4.7g pyridine 80 DEG C 0.5 hour, 110 DEG C 2 hours, under 160 DEG C of curing process of 6 hours, curing molding obtains epoxy resin cured product:
embodiment 5:
49g cis-butenedioic anhydride, 30g urea, 212g glycol ether, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: glycol ether: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 6.
embodiment 6:
49g cis-butenedioic anhydride, 30g urea, 300g Triethylene glycol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: Triethylene glycol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 7.
embodiment 7:
49g cis-butenedioic anhydride, 30g urea, 90g methyl propanediol, 106g glycol ether, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: glycol ether: hexanodioic acid=2:2:4:4:10) and 3.64g antimonous oxide are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 8.
the mechanical property of different toughening agent modified epoxy resin E44 cured article and thermogravimetric analysis test result are as following table (note: numbering 5 is do not add the epoxy resin cured product that toughner obtains):
embodiment 8:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g tosic acid are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 9.
embodiment 9:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g dibutyl tin laurate are prepared toughner according to embodiment 1 technique, and prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 10.
the mechanical property of different toughening agent modified epoxy resin E44 cured article and thermogravimetric analysis test result are as following table (note: numbering 5 is do not add the epoxy resin cured product that toughner obtains):
embodiment 10:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are prepared toughner, then get 100gE44 epoxy resin, 15g toughner Hybrid Heating be warming up to 110 DEG C and under condensation recovering condition insulation reaction 180min, obtain toughness reinforcing epoxy resin 115g.35g methyl hexahydrophthalic anhydride, 35g methylnadic anhydride and 4.7g pyridine to be added in the toughness reinforcing epoxy resin of 115g and to mix, test gel time, then obtain epoxy resin cured product according to embodiment 1 curing process curing molding, and be numbered 11.
embodiment 11:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are mixed and obtains toughner by embodiment 1 technique, then get 100gE44 epoxy resin, 5g toughner Hybrid Heating be warming up to 110 DEG C and under condensation recovering condition insulation reaction 180min, obtain toughness reinforcing epoxy resin 105g.35g methyl hexahydrophthalic anhydride, 35g methylnadic anhydride and 4.7g pyridine to be added in the toughness reinforcing epoxy resin of 105g and to mix, test gel time, then obtain epoxy resin cured product according to embodiment 1 curing process curing molding, and be numbered 12.
the mechanical property of different toughening agent modified epoxy resin E44 cured article and thermogravimetric analysis test result are as following table (note: numbering 5 is do not add the epoxy resin cured product that toughner obtains):
embodiment 12:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are mixed and heated to and melt completely, be warming up to 140 DEG C of insulation 50min under condensation recovering condition after, be evacuated to 0.1MPa30min again.At the uniform velocity be warming up to 160 DEG C with 1 DEG C/min subsequently, after insulation 15min, vacuumize 15min again.180 DEG C of held for some time 50min are at the uniform velocity warming up to again subsequently with 1 DEG C/min, 200 DEG C of insulation 50min are at the uniform velocity warming up to again with 1 DEG C/min, stop heating after being at the uniform velocity warming up to 220 DEG C of insulation 90min with 1 DEG C/min again, be cooled to less than 70 DEG C, discharging obtains toughner.And prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 13.
embodiment 13:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are mixed and heated to and melt completely, be warming up to 140 DEG C of insulation 30min under condensation recovering condition after, be evacuated to 0.1Mpa50min again.At the uniform velocity be warming up to 160 DEG C with 1 DEG C/min subsequently, after insulation 15min, vacuumize 30min again.180 DEG C of held for some time 30min are at the uniform velocity warming up to again subsequently with 1 DEG C/min, 200 DEG C of insulation 30min are at the uniform velocity warming up to again with 1 DEG C/min, stop heating after being at the uniform velocity warming up to 220 DEG C of insulation 120min with 1 DEG C/min again, be cooled to less than 70 DEG C, discharging obtains toughner.And prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 14.
embodiment 14:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are mixed and heated to and melt completely, be warming up to 150 DEG C of insulation 30min under condensation recovering condition after, be evacuated to 0.1Mpa30min again.At the uniform velocity be warming up to 170 DEG C with 1 DEG C/min subsequently, after insulation 15min, vacuumize 15min again.190 DEG C of held for some time 25min are at the uniform velocity warming up to again subsequently with 1 DEG C/min, 210 DEG C of insulation 25min are at the uniform velocity warming up to again with 1 DEG C/min, stop heating after being at the uniform velocity warming up to 230 DEG C of insulation 120min with 1 DEG C/min again, be cooled to less than 70 DEG C, discharging obtains toughner.And prepare modified epoxy by embodiment 1 technique and obtain epoxy resin cured product, and be numbered 15.
the mechanical property of different toughening agent modified epoxy resin E44 cured article and thermogravimetric analysis test result are as following table (note: numbering 5 is do not add the epoxy resin cured product that toughner obtains):
embodiment 15:
49g cis-butenedioic anhydride, 30g urea, 180g methyl propanediol, 365g hexanodioic acid (ratio of each amount of substance is cis-butenedioic anhydride: urea: methyl propanediol: hexanodioic acid=2:2:8:10) and 3.64g antimonous oxide are prepared toughner according to embodiment 1 technique, then get 100gE44 epoxy resin, 10g toughner to be directly uniformly mixed under not heating condition, obtain toughness reinforcing epoxy resin 110g.35g methyl hexahydrophthalic anhydride, 35g methylnadic anhydride and 4.7g pyridine to be added in the toughness reinforcing epoxy resin of 110g and to mix, test gel time, then obtain epoxy resin cured product according to embodiment 1 curing process curing molding, and be numbered 16
the mechanical property of different toughening agent modified epoxy resin E44 cured article and thermogravimetric analysis test result are as following table (note: numbering 5 is do not add the epoxy resin cured product that toughner obtains):
Claims (1)
1.
a preparation method for nitrogen-containing epoxy thermoset toughner, is characterized in that: its step comprises:
(1) hexanodioic acid, dibasic alcohol, urea, acid anhydrides and catalyst mix heating for dissolving are warming up to temperature T1 again, are incubated under condensation recovering condition, after be evacuated to 0.1MPa again;
(2) subsequently temperature is risen to T2, vacuumize again after insulation;
(3) be warming up to T3 insulation subsequently again, then be warming up to T4 insulation, then be warming up to T5 insulation;
(4) less than 70 DEG C are cooled to, discharging;
the described dibasic alcohol described in step (1) is 1, one or both mixtures in 3-methyl propanediol, diethylene glycol, Triethylene glycol, described acid anhydrides is the one in phthalic anhydride, cis-butenedioic anhydride, and described catalyzer is the one in dibutyl tin laurate, antimonous oxide, tosic acid;
the ratio of the amount of substance of the described hexanodioic acid described in step (1), described dibasic alcohol, described urea, described acid anhydrides is 10:9:1:1 or 10:8:2:2 or 10:7:3:3 or 10:6:4:4, and described catalyst levels is 0.5 ~ 0.8wt% of system total mass;
the described temperature of reaction T1 described in step (1) is 130 DEG C ~ 150 DEG C, the described temperature of reaction T2 described in step (2) is 150 DEG C ~ 170 DEG C, the described temperature of reaction T3 described in step (3) is 170 DEG C ~ 190 DEG C, described temperature of reaction T4 is 190 DEG C ~ 210 DEG C, and described temperature of reaction T5 is 210 DEG C ~ 240 DEG C;
the described soaking time described in step (1) is 0.8 ~ 1 hour, and the described pumpdown time is 0.5 ~ 1 hour; The described soaking time described in step (2) is 0.25 ~ 0.45 hour, and the described pumpdown time is 0.25 ~ 0.45 hour;
in described step (3), T3 soaking time is 0.5 ~ 1 hour, and T4 soaking time is 0.5 ~ 1 hour, and T5 soaking time is 1 ~ 2 hour.
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|---|---|---|---|
| CN201310669595.5A CN103642021B (en) | 2013-12-07 | 2013-12-07 | Nitrogen-containing epoxy thermoset toughner and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059733A (en) * | 1990-05-28 | 1992-03-25 | 中国科学院化学研究所 | Epoxy resin toughened preparation method |
| CN103304962A (en) * | 2013-06-20 | 2013-09-18 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with excellent flexibility and flame retardance, and preparation method thereof |
-
2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059733A (en) * | 1990-05-28 | 1992-03-25 | 中国科学院化学研究所 | Epoxy resin toughened preparation method |
| CN103304962A (en) * | 2013-06-20 | 2013-09-18 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with excellent flexibility and flame retardance, and preparation method thereof |
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