CN102731750A - Preparation method of latent epoxy resin curing system - Google Patents
Preparation method of latent epoxy resin curing system Download PDFInfo
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- CN102731750A CN102731750A CN2012102330948A CN201210233094A CN102731750A CN 102731750 A CN102731750 A CN 102731750A CN 2012102330948 A CN2012102330948 A CN 2012102330948A CN 201210233094 A CN201210233094 A CN 201210233094A CN 102731750 A CN102731750 A CN 102731750A
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Abstract
The invention belongs to the field of preparation of a latent epoxy resin curing system, in particular to a preparation method of the latent epoxy resin curing system. The preparation method comprises the following steps of: (1) putting dicyandiamide into a monohydric alcohol solvent, and completely dissolving the dicyandiamide at the temperature of 80-100 DEG C to form a dicyandiamide solution; (2) putting adipic acid dihydrazide which is a binary acid into the dicyandiamide solution, adding a monoether solvent which is a dihydric alcohol, heating and refluxing until the solution is completely transparent to obtain a mixed curing agent solvent; and (3) adding stoichiometric epoxy resin to the mixed curing agent solvent, decompressing and distilling to remove the solvent, and cooling to obtain the latent epoxy resin curing system. The latent epoxy resin curing system obtained by the invention has the advantages of good dispersity and storage performance, low curing temperature, and the like; and different from a method using polyols as a solvent to prepare the latent epoxy resin curing system, the preparation method has the characteristics of low decompressing and distilling temperature, easiness in removing the solvent and simplicity in operation.
Description
Technical field
The invention belongs to latent epoxy-resin systems preparation field, the concrete preparation method who relates to a kind of latent epoxy resin solidifying system.
Background technology
The technology of epoxy prepreg and curing performance depend on the latent curing agent of system to a great extent, and epoxy resin latent curing agent commonly used mainly contains Dyhard RU 100, two amido sulfobenzides (DDS) and organic hydrazide kind compound etc.The characteristics of Dyhard RU 100 are to have good storage period, and the quality guaranteed period is more than 2 years, and is cheap, and the prescription consumption is little, but solidification value is higher.The characteristics of DDS are to have good compatibility performance with epoxy resin, but the adhesivity of processing prepreg is not fine, and storage period is shorter simultaneously.Organic hydrazide kind compound; The characteristics that mainly are the binary acid dihydrazide are the latent curing agent whiles as epoxy resin, and system is had good toughening effect, and anti-chemical also obviously is superior to dicyandiamide system; But the price of binary acid dihydrazide solidifying agent is higher, large usage quantity.In fact, Dyhard RU 100 and modified system thereof are the latent curing agent of the general material prepreg of first-selection with epoxy resin.Toughness and chemical resistance in order to increase matrix material are used binary acid dihydrazide latent curing agent and Dyhard RU 100, can bring into play advantage separately.According to the pertinent data introduction, with Dyhard RU 100 and sebacic dihydrazide melting mixing, obtain composite curing agent after the cooling, its performance is superior to two kinds of independent solidifying agent.But there are some problems in this method, and most importantly melting mixing must be heated on the fusing point (207～209 ℃) of Dyhard RU 100, can cause Dyhard RU 100 to decompose like this, produces harmful and niff, reduces the productive rate of solidifying agent.Patent (CN1294142A) is introduced; Utilize hydroxyl-bearing solvent can be partly dissolved the characteristics of sebacic dihydrazide, with Dyhard RU 100 dissolving earlier, it is even to add the sebacic dihydrazide thorough mixing then; The solvent heating evaporation is obtained composite curing agent, be used for the powder coating of epoxy resin.But this method can not be used for preparing the latent curing agent of epoxy prepreg.Its reason is that sebacic dihydrazide solvability in containing the solvent of monohydroxy (like the aliphatic alcohols compound) is bad, can not be miscible with Dyhard RU 100, and the solidifying agent that obtains can not be dispersed in the epoxy resin.Contain polyhydric solvent (like divalent alcohol) if adopt, though under the high temperature sebacic dihydrazide is had good solubility property, the boiling point of solvent is higher; The vacuum distillation temperature of solvent is too high; Time is longer, also can cause the decomposition of Dyhard RU 100, reduces the service efficiency of solidifying agent.In addition, in order to solve the problem of solidifying agent difficulties in dispersion in epoxy resin, more satisfactory method is exactly, and, epoxy resin added in the solution all after the dissolving at composite curing agent, and underpressure distillation removes and desolvates then, obtains epoxy resin/solidifying agent glue.Because it is high to contain polyhydric solvent boiling point, the decompression temperature is high, and the time is long, is easy to cause epoxy-resin systems that gel just takes place when removing solvent.
Therefore, make binary acid dihydrazide (like sebacic dihydrazide) compound and the Dyhard RU 100 can be miscible, and evenly spread in the epoxy resin, must select a kind of low boiling point solvent that can all have fine solubility property two kinds of solidifying agent.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of binary acid dihydrazide and dicy-curing agent of can making miscible to above-mentioned prior art, and can be dispersed in the preparation method of the latent epoxy resin solidifying system in the epoxy resin.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of latent epoxy resin solidifying system includes following steps:
1) Dyhard RU 100 is thrown in the monoalcohol solvent, dissolving fully forms Dyhard RU 100 solution under 80～100 ℃;
2) the binary acid dihydrazide is put in the Dyhard RU 100 solution, and added the dialcohol monomethyl ether kind solvent, reflux until the complete bleach of solution, obtains mixing cured agent solution;
3) stoichiometric epoxy resin is joined in the mixing cured agent solution, solvent is removed in underpressure distillation, promptly gets the latent epoxy resin solidifying system after the cooling.
Press such scheme, the mass ratio of Dyhard RU 100 and binary acid dihydrazide is 1:1 ~ 1:2.
Press such scheme, the mass ratio of mixing cured agent solution and epoxy resin is 15:100 ~ 25:100.
Press such scheme, described dialcohol monomethyl ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1, any one in 2-Ucar 35-1-monomethyl ether or their mixing.
Press such scheme, described monohydroxy-alcohol is the mixing of any one or they in ethanol and the propyl alcohol.
Press such scheme, described binary acid dihydrazide is the mixing of any one or they in adipic dihydrazide, suberic acid two hydrazides and the sebacic dihydrazide.
Press such scheme, the temperature of Dyhard RU 100 and binary acid dihydrazide reflux is 90～120 ℃.
Press such scheme, the described vacuum distillation temperature of step 3) is 80～100 ℃, and the underpressure distillation time is within an hour.
The present invention utilizes different solvents with Dyhard RU 100 and the dissolving of binary acid dihydrazide, and the solvent of Dyhard RU 100 is a unary alcohol, and the solvent of binary acid dihydrazide is the dialcohol monomethyl ether compounds.
Primitive reaction principle of the present invention is: the binary acid dihydrazide is at ethylene glycol monomethyl ether (124.6 ℃ of boiling points), ethylene glycol monoethyl ether (135.0 ℃ of boiling points), 1; Solubleness in 2-Ucar 35-1-monomethyl ether dialcohol monomethyl ether compounds such as (121.0 ℃ of boiling points) and their mixture is apparently higher than ethanol (78.3 ℃ of boiling points) and propyl alcohol (97.2 ℃ of n-propyl alcohols; 82.5 ℃ of Virahols) monohydroxy-alcohol such as; And the boiling point of above-mentioned dialcohol monomethyl ether compounds is lower, removes through underpressure distillation easily.Comparatively speaking, the boiling point of divalent alcohol is much higher, and the boiling point of terepthaloyl moietie is 197.3 ℃, and 1, the boiling point of 2-Ucar 35 is 188.0 ℃.Though therefore under refluxad better to the solubility property of binary acid dihydrazide, the vacuum distillation process difficulty.Therefore, more help preparing the system of binary acid dihydrazide homodisperse and stable performance in epoxy resin with the dialcohol monomethyl ether compounds.
Under heating condition, ethanol and propyl alcohol etc. all can dissolve Dyhard RU 100 well.
After earlier Dyhard RU 100 being dissolved in ethanol, propyl alcohol or their mixture; Add the dialcohol monomethyl ether compounds; To the not influence of solvability of Dyhard RU 100, and the fine dissolving adipic dihydrazide of mixing solutions ability, suberic acid two hydrazides, sebacic dihydrazide or their mixture.The boiling point of above-mentioned monohydroxy-alcohol and dialcohol monomethyl ether compounds mixed solvent is lower, and after adding epoxy resin, underpressure distillation can not cause the resin system HTG except that desolvating under coldcondition easily.
Advantage of the present invention: the epoxy resin solidifying system of gained of the present invention has advantages such as disperse and storge quality is good, solidification value is low; The present invention is different from and uses polyvalent alcohol as the characteristics that solvent prepares the latent epoxy resin solidifying system to be: vacuum distillation temperature is low, remove easily and desolvate, and simple to operate.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed explanation, but this explanation can not be construed as limiting the invention.
Embodiment 1
(1) the 500ml four-hole boiling flask is installed in the oil bath constant temperature magnetic stirring apparatus, then 1g Dyhard RU 100 and 13ml absolute ethyl alcohol is added in the flask, start magnetic stirring apparatus, temperature is increased to 100 ℃, behind the 10min, Dyhard RU 100 all dissolves;
(2) the 1g sebacic dihydrazide is joined in the Dyhard RU 100 solution, after stirring, add the 10ml ethylene glycol monoethyl ether again, keep backflow 90min when temperature is risen to 110 ℃, sebacic dihydrazide dissolves fully, and solution is transparence, obtains mixing cured agent solution;
(3) bisphenol A epoxide resin E-51 10g is added in the mixing cured agent solution, mix the back and remove 80～100 ℃ of underpressure distillation in following 1 hour and desolvate, cooling obtains the latent epoxy resin solidifying system;
(4) pour mass that obtains at Procuring in 120 ℃/2 hours, 160 ℃/4 hours after fixing of gained system, its tensile strength, flexural strength and impelling strength are respectively 87.3MPa, 116.6MPa and 19.2KJ/m
2
Embodiment 2
Step (1) and (3) are with embodiment 1, step (2) as follows:
The 1g sebacic dihydrazide is joined in the Dyhard RU 100 solution, after stirring, add the 12ml ethylene glycol monomethyl ether again, keep backflow 90min when temperature is risen to 110 ℃, sebacic dihydrazide dissolves fully, and solution is transparence, obtains mixing cured agent solution;
The pour mass that the gained system obtains at Procuring in 120 ℃/2 hours, 160 ℃/4 hours after fixing, its tensile strength, flexural strength and impelling strength are respectively 88.5MPa, 114.6MPa and 19.1KJ/m
2
Embodiment 3
(1) the 500ml four-hole boiling flask is installed in the oil bath constant temperature magnetic stirring apparatus, then 1g Dyhard RU 100 and 10ml n-propyl alcohol is added in the flask, start magnetic stirring apparatus, temperature is increased to 100 ℃, behind the 10min, Dyhard RU 100 all dissolves;
(2) the 1g adipic dihydrazide is joined in the Dyhard RU 100 solution, after stirring, add 12ml 1 again; 2-Ucar 35-1-monomethyl ether keeps backflow 70min when temperature is risen to 120 ℃, adipic dihydrazide dissolves fully; Solution is transparence, obtains mixing cured agent solution;
(3) bisphenol A epoxide resin E-44 12g is added in the mixing cured agent solution, mix the back and remove 80～100 ℃ of underpressure distillation in following 1 hour and desolvate, cooling obtains the latent epoxy resin solidifying system;
(4) pour mass that obtains at Procuring in 120 ℃/2 hours, 160 ℃/4 hours after fixing of gained system, its tensile strength, flexural strength and impelling strength are respectively 83.9MPa, 119.2MPa and 17.4KJ/m
2
Embodiment 4
(1) the 500ml four-hole boiling flask is installed in the oil bath constant temperature magnetic stirring apparatus, with in 1g Dyhard RU 100 and 5ml absolute ethyl alcohol and the 5ml n-propyl alcohol adding flask, starts magnetic stirring apparatus then, temperature is increased to 100 ℃, behind the 10min, Dyhard RU 100 all dissolves;
(2) the 1g sebacic dihydrazide is joined in the Dyhard RU 100 solution, after stirring, add 12ml 1 again; 2-Ucar 35-1-monomethyl ether keeps backflow 70min when temperature is risen to 120 ℃, sebacic dihydrazide dissolves fully; Solution is transparence, obtains mixing cured agent solution;
(3) many epoxy resin of phenolic aldehyde F-51 10g is added in the mixing cured agent solution, mix the back and remove 80～100 ℃ of underpressure distillation in following 1 hour and desolvate, cooling obtains the latent epoxy resin solidifying system;
(4) pour mass that obtains at Procuring in 120 ℃/2 hours, 160 ℃/4 hours after fixing of gained system, its tensile strength, flexural strength and impelling strength are respectively 78.1MPa, 116.6MPa and 16.8KJ/m
2
Embodiment 5
(1) the 500ml four-hole boiling flask is installed in the oil bath constant temperature magnetic stirring apparatus, with in 1g Dyhard RU 100 and 5ml absolute ethyl alcohol and the 5ml n-propyl alcohol adding flask, starts magnetic stirring apparatus then, temperature is increased to 100 ℃, behind the 10min, Dyhard RU 100 all dissolves;
(2) the 1g sebacic dihydrazide is joined in the Dyhard RU 100 solution; After stirring, add ethylene glycol monomethyl ether and 1 again, 2-Ucar 35-each 6ml of 1-monomethyl ether; When being risen to 120 ℃, temperature keeps backflow 70min; Sebacic dihydrazide dissolves fully, and solution is transparence, obtains mixing cured agent solution;
(3) many epoxy resin of phenolic aldehyde E-53 10g is added in the mixing cured agent solution, mix the back and remove 80～100 ℃ of underpressure distillation in following 1 hour and desolvate, cooling obtains the latent epoxy resin solidifying system;
(4) pour mass that obtains at Procuring in 120 ℃/2 hours, 160 ℃/4 hours after fixing of gained system, its tensile strength, flexural strength and impelling strength are respectively 87.1MPa, 115.6MPa and 18.8KJ/m
2
Claims (9)
1. the preparation method of a latent epoxy resin solidifying system includes following steps:
1) Dyhard RU 100 is thrown in the monoalcohol solvent, dissolving fully forms Dyhard RU 100 solution under 80～100 ℃;
2) the binary acid dihydrazide is put in the Dyhard RU 100 solution, and added the dialcohol monomethyl ether kind solvent, reflux until the complete bleach of solution, obtains mixing cured agent solution;
3) stoichiometric epoxy resin is joined in the mixing cured agent solution, solvent is removed in underpressure distillation, promptly gets the latent epoxy resin solidifying system after the cooling.
2. according to the preparation method of the said latent epoxy resin solidifying system of claim 1, the mass ratio that it is characterized in that Dyhard RU 100 and binary acid dihydrazide is 1:1 ~ 1:2.
3. according to the preparation method of claim 1 or 2 said latent epoxy resin solidifying systems, the mass ratio that it is characterized in that mixing cured agent solution and epoxy resin is 15:100 ~ 25:100.
4. according to the preparation method of the said latent epoxy resin solidifying system of claim 3, it is characterized in that described dialcohol monomethyl ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1, any one in 2-Ucar 35-1-monomethyl ether or their mixing.
5. according to the preparation method of claim 3 or 4 said latent epoxy resin solidifying systems, it is characterized in that described monohydroxy-alcohol is the mixing of any one or they in ethanol and the propyl alcohol.
6. according to the preparation method of claim 3 or 4 said latent epoxy resin solidifying systems, it is characterized in that described binary acid dihydrazide is the mixing of any one or they in adipic dihydrazide, suberic acid two hydrazides and the sebacic dihydrazide.
7. according to the preparation method of claim 3 or 4 said latent epoxy resin solidifying systems, it is characterized in that the temperature of Dyhard RU 100 and binary acid dihydrazide reflux is 90～120 ℃.
8. according to the preparation method of claim 3 or 4 said latent epoxy resin solidifying systems, it is characterized in that the described vacuum distillation temperature of step 3) is 80～100 ℃, the underpressure distillation time is within an hour.
9. according to the preparation method of claim 3 or 4 said latent epoxy resin solidifying systems, it is characterized in that described epoxy resin is bisphenol A epoxide resin E-51, bisphenol A epoxide resin E-44, many epoxy resin of phenolic aldehyde F-51 or many epoxy resin of phenolic aldehyde E-53.
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| CN2012102330948A CN102731750A (en) | 2012-07-06 | 2012-07-06 | Preparation method of latent epoxy resin curing system |
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| CN2012102330948A CN102731750A (en) | 2012-07-06 | 2012-07-06 | Preparation method of latent epoxy resin curing system |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193959A (en) * | 2013-04-18 | 2013-07-10 | 艾达索高新材料无锡有限公司 | Degradable hydrazide latent epoxy resin curing agent and application thereof |
| CN106589319A (en) * | 2016-11-22 | 2017-04-26 | 天津翔盛新材料有限公司 | Four-functional-group super-flexible linear phenolic curing agent dedicated for heavy-duty anticorrosive powder coating, and synthetic method and application thereof |
| CN111116870A (en) * | 2019-12-31 | 2020-05-08 | 浙江华正新材料股份有限公司 | Latent resin composition, prepreg and epoxy composite material |
| CN113912850A (en) * | 2021-10-29 | 2022-01-11 | 珠海三臻新材料科技有限公司 | Dicyandiamide derivative, high-toughness epoxy resin and corresponding preparation method |
-
2012
- 2012-07-06 CN CN2012102330948A patent/CN102731750A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 丁洁: "DICY/SDH环氧树脂固化剂制备", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193959A (en) * | 2013-04-18 | 2013-07-10 | 艾达索高新材料无锡有限公司 | Degradable hydrazide latent epoxy resin curing agent and application thereof |
| CN106589319A (en) * | 2016-11-22 | 2017-04-26 | 天津翔盛新材料有限公司 | Four-functional-group super-flexible linear phenolic curing agent dedicated for heavy-duty anticorrosive powder coating, and synthetic method and application thereof |
| CN111116870A (en) * | 2019-12-31 | 2020-05-08 | 浙江华正新材料股份有限公司 | Latent resin composition, prepreg and epoxy composite material |
| CN111116870B (en) * | 2019-12-31 | 2023-12-26 | 浙江华正新材料股份有限公司 | Latent resin composition, prepreg and epoxy composite material |
| CN113912850A (en) * | 2021-10-29 | 2022-01-11 | 珠海三臻新材料科技有限公司 | Dicyandiamide derivative, high-toughness epoxy resin and corresponding preparation method |
| CN113912850B (en) * | 2021-10-29 | 2023-03-14 | 珠海三臻新材料科技有限公司 | Preparation method of dicyandiamide derivative and preparation method of high-toughness epoxy resin |
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Application publication date: 20121017 |