CN1958639A - Solidifying agent for aqueous epoxy resin, and preparation method - Google Patents
Solidifying agent for aqueous epoxy resin, and preparation method Download PDFInfo
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- CN1958639A CN1958639A CN 200610123761 CN200610123761A CN1958639A CN 1958639 A CN1958639 A CN 1958639A CN 200610123761 CN200610123761 CN 200610123761 CN 200610123761 A CN200610123761 A CN 200610123761A CN 1958639 A CN1958639 A CN 1958639A
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Abstract
This invention discloses a method for preparing waterborne epoxy resin curing agent. The method comprises: condensing epoxy resin and polyester diol, performing addition modification on polyethylene polyamine, mixing with acrylonitrile at nitril/amine H mol ratio of (1.1-1.2):1.0, reacting at 65-70 deg.C for 1.5-2.0 h for end-capping, and salifying. The obtained waterborne epoxy resin curing agent has a solid content of 45-50%, an amine value of 290-500, and a viscosity of 8.0-14 ps. The curing agent has a moderate amine equivalent, and can emulsify and cure low molecular weight epoxy resin at room temperature. Besides, the curing agent has no toxicity, no harm, no volatile organic solvent, and largely reduced stimulation of modified amine to skin.
Description
Technical field
The present invention relates to the solidifying agent technical field, be specifically related to a kind of aqueous epoxy resin curing agent and preparation method thereof.
Background technology
The polyamine based epoxy resin curing agent is divided into two kinds of single polyamine and modified amine, and wherein single polyamine is divided into four kinds of straight-chain fatty amine, polymeric amide, aliphatic cyclic amine and aromatic amines again.The straight chain fat polyamine has that curing speed is fast, form and aspect are excellent, viscosity is big, and it is big to solidify the back hardness of paint film, good luster, and adhesiveproperties is good, the excellent characteristics of acid-proof alkaline.But also there is its inherent shortcoming, big such as the volatilization pungency, toxicity is big, working life is short, ratio requirement strictness etc.; Easy and carbon dioxide in air reaction generates amine carbonate, makes the paint film whiting, solidifies incomplete.In order to overcome these shortcomings, must be to its further modification so as to obtain nontoxic or low toxicity, can solidify at ambient temperature, the amine curing agent at ratio requirement conscientious quarter.
Patent of invention (publication number is CN 1415680A) discloses a kind of polyamine-oxirane ring resin affixture, and discloses with butyl ester glycidyl ether sealing primary amine and make modified firming agent.The molecular weight of butyl ester glycidyl ether is 130, and the amine hydrogen equivalent of the modified firming agent that makes is bigger.The amine hydrogen equivalent of solidifying agent is big more, and when the Resins, epoxy proportioning was solidified, the amount of used solidifying agent will be bigger, thereby the hydrophilic radical polyethers section chain of introducing is just many, and the water tolerance of solidifying back coating is descended, and construction also can inconvenience.The human α-Jia Jibingxisuan is also arranged as end-capping reagent.And α-Jia Jibingxisuan is easy to take place auto-polymerization.
Summary of the invention
The object of the invention is to propose preparation method a kind of environment-friendly type, emulsification simultaneously and aqueous epoxy resin curing agent cured epoxy resin, excellent property.
Another object of the present invention is to provide the aqueous epoxy resin curing agent of method for preparing.
Purpose of the present invention by following technical solution.
A kind of preparation method of aqueous epoxy resin curing agent comprises the steps and processing condition:
(1) condensation reaction of Resins, epoxy and polyether Glycols: under zinc chloride catalysis, generate condensation product by Resins, epoxy and polyether Glycols, the mol ratio of Resins, epoxy and polyether Glycols is 2.2～2.0: 1.0, temperature of reaction is controlled at 90～100 ℃, and the reaction times is 6～8 hours.
Because the polarity of Resins, epoxy is relevant bigger with the polarity of water, its HLB (the hydrophilic water balance value of oleophylic) is 3, and therefore simple water is to be difficult to its emulsive.And add emulsifying agent, can to its performance bad influence be arranged in the filming after the residual curing of this emulsifying agent molecule.The present invention introduces nonionogenic tenside on the polyethylene polyamine chain, make it to Resins, epoxy the good emulsifying ability be arranged.This nonionogenic tenside is to be reacted under zinc chloride catalysis by Resins, epoxy and polyoxyethylene glycol to form.Resulting condenses is oyster white thick liquid or solid according to the molecular weight polyethylene glycol difference at normal temperatures.The type emulsifying agent is different with adding, and its two ends of nonionogenic tenside of Resins, epoxy and polyoxyethylene glycol reaction gained are epoxide groups, and can participate in the epoxy resin cure reaction becomes a part of filming now, less to the influence of filming.
(2) to the polyethylene polyamine addition modification: step (1) condensation product is mixed with low-molecular-weight epoxy resin, in the condensation product in epoxy group content and the low-molecular-weight epoxy resin molar equivalent ratio of epoxy group content be 1.0～1.2/2.0, and mix with polyethylene polyamine soluble in water, be 2～3 hours 65～70 ℃ of following reaction times of condition in temperature; Wherein in the mixture, amine hydrogen molar weight amount is 6.2～6.4: 1.0 with the ratio of total epoxy group(ing) molar weight, and water-content is 20%～30%.
Nonionogenic tenside that is prepared into and polyethylene polyamine reaction, polyether segment is added on the molecular chain of polyethylene polyamine, in order to obtain the solidifying agent of using value, carry out chain extension with Resins, epoxy, obtain the big solidifying agent of molecular weight.Because the epoxy segmental is introduced, also increased the consistency of solidifying agent and Resins, epoxy simultaneously.Because when addition reaction, can emit a large amount of reaction heat.For fear of gel takes place, need add entry as heat-eliminating medium.But because the polarity of the polarity of water and Resins, epoxy is relevant bigger, in order to prevent that when water-content is too high the Resins, epoxy of adding disperses irregular, separates out with the form of drop, is reflected at the drop surface and carries out, the Resins, epoxy excessive concentration causes curing cross-linked.Therefore the water yield that adds is advisable with 20～30%.
(3) end-blocking: by 1.1～1.2: 1.0 mixed in molar ratio, is 65～70 ℃ conditions under to react 1.5～2.0 hour in temperature with the polyethylene polyamine modifier of vinyl cyanide and step (2) gained.Because reaction is thermopositive reaction, therefore will slowly drip vinyl cyanide, performs cooling measure simultaneously.
(4) salify: to the product behind end-blocking, adopting has monobasic organic acid salify; Organic acid is 1.0: 4.5～5.0 with the equivalence ratio of residue amine hydrogen, 65～70 ℃ of temperature of reaction, and the reaction times has 1.0～1.5 hours, and reaction adds entry after finishing, and getting solid content is 45～50% aqueous epoxy resin curing agents.
By the aqueous epoxy resin curing agent of method for preparing, its solid content is 45～50%, and amine value scope is 290～500, and viscosity is 8.0ps～14ps.
The present invention has introduced the polyether segment in the polyoxyethylene glycol in solidifying agent, can play the effect as nonionogenic tenside, to the emulsification function of low-molecular-weight epoxy resin.Simultaneously, the nitrile ethylation reaction of vinyl cyanide and aliphatic polyamine, the consistency and having reduced that has improved solidifying agent and Resins, epoxy greatly resembles the bad pungency that has other modified aliphatic polyamine curing agent.
Compared with prior art, the present invention has following advantage:
1, the amine hydrogen equivalent of gained modified firming agent is few, when solidifying the Resins, epoxy of same weight, other modified firming agent consumption with the ether capped gained of ester class Racemic glycidol of the amount ratio of solidifying agent of the present invention will lack relatively, it is less to introduce hydrophilic polyether segment, water tolerance improves, and brings convenience to construction.
2, good with epoxy resin compatibility, mixing stirring after 5 minutes, on the liquid level of mixture, there is not or has only very micro-epoxy small droplets with low-molecular-weight epoxy resin, illustrate that the fine mixing of two energy is compatible.
3 compare with other most modified aliphatic polyamine, and solidifying agent of the present invention can reduce the pungency of modified multicomponent amine to skin greatly, and its volatile flavor of basically eliminate.
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is done detailed description further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
(1) condensation reaction of Resins, epoxy and polyether Glycols.
In the four-hole boiling flask that has water of condensation and nitrogen protection, drop into 43 gram Resins, epoxy E-51 and 100 gram Macrogol 2000s.The flask temperature is elevated to 70 ℃, makes the reaction mass thorough mixing even under stirring.Add zinc chloride 2.45 grams then as catalyzer.In the first section of reaction, have a large amount of reaction heat and emit, should note out water of condensation this moment, will strengthen the flow of shielding gas nitrogen simultaneously, it filled dissipate so that take away heat.Temperature is controlled at about 95 ℃ stirring reaction 8 hours.The sampling and measuring oxirane value.
(2) to the polyethylene polyamine addition modification
The triethylene tetramine of 48.5 grams is joined (this moment, flask should cool to earlier about 50 ℃) in the above four-hole boiling flask, stirred about 15 minutes, controlled temperature slowly is added dropwise to 39.2 gram Resins, epoxy E-51 about 65 ℃.The reaction heat of emitting when preventing addition causes gel, and therefore before adding Resins, epoxy E-51, the water that adds 60 milliliters is as heat-eliminating medium.After dripping E-51.Continued stirring reaction 3 hours.
(3) end-blocking
In the affixture of above gained, add an amount of distilled water, make solid content about 75%.After water injection, stirred 30 minutes, slowly drip 22 gram vinyl cyanide then and seal end-blocking.
Temperature of reaction is controlled at about 70 ℃.Reaction times is 2.0 hours.
(4) salify
To the material behind the end-blocking, adding has 16 gram acetate to be carried out to reactant salt, improves the water-soluble of solution.78 ℃ of temperature of reaction, 1.5 hours reaction times.After reaction finishes, add entry 160 grams, regulate solid content, be translucent light yellow thick liquid.
After testing, solid content is 45%, and amine hydrogen equivalent is 423; The about 13ps of viscosity (25 ± 1 ℃)
This solidifying agent does not have volatilizable organic compound (VOC), improves environmental-protecting performance; To low-molecular-weight epoxy resin, have emulsification and solidification simultaneously; Amine hydrogen equivalent is lower; During with low-molecular-weight epoxy resin mixed preparing aqueous epoxy resins; Hardener dose is less; It is less to introduce hydrophilic polyether segment, and water tolerance improves; Easy construction.
(5) preparation of aqueous epoxy resins
A component: E-51 10 grams
Butylglycidyl ether 1.2 grams
B component: modified firming agent 24.8 grams
Even two kinds of mixing of materials of A component, under high-speed stirring, slowly be added in the B component, dispersed with stirring 5min promptly makes aqueous epoxide resin paint.
The epoxypaint The performance test results is as follows:
Solidification value: (25 ± 1) ℃
Curing speed: surface drying 70min GB-1728-79 (88)
Hardness of paint film: 1H GB 6739-86
Paint film adhesion residue number of squares 95% GB 9286-88
Water tolerance 30 hours is non-foaming, does not peel off GB 1733-79 (88)
Embodiment 2
(1) condensation reaction of Resins, epoxy and polyether Glycols.
In the four-hole boiling flask that has water of condensation and nitrogen protection, the amount input that Resins, epoxy E-51 presses 250g by 216 grams and cetomacrogol 1000.The flask temperature is elevated to 70 ℃, makes the reaction mass thorough mixing even under stirring.Add 12.2 then and digest zinc as catalyzer.In the first section of reaction, have a large amount of reaction heat and emit, should note out water of condensation this moment, will strengthen the flow of shielding gas nitrogen simultaneously, it filled dissipate so that take away heat.Temperature is controlled at about 100 ℃ stirring reaction 6 hours.The sampling and measuring oxirane value.
In the condenses of above gained, the Resins, epoxy of 216 grams joins in the flask again, stirs.Cool to room temperature.
(2) end-blocking
In the another one four-hole boiling flask, add triethylene amine 242g.Add entry 200 grams then, stir heat radiation, temperature is controlled at 68 ℃, slowly drip vinyl cyanide 97g (1.83mol), reacted 1.5 hours with addition funnel.
(3) to the polyethylene polyamine addition modification
(1) gained and product are added drop-wise in (2), in 70 ℃ of 2 hours reaction times of temperature of reaction, note beginning to drip and to drip lentamente.
(4) salify
Add acetate 72 gram salifies, temperature of reaction is 75 ℃, 100 minutes reaction times, after the end, add water 530 grams, and stir 30min, get translucent light yellow thick liquid.
After testing, solid content is 45%, and viscosity is 8.4ps (25 ± 1 ℃), and amine hydrogen equivalent is 293.
This solidifying agent does not have volatilizable organic compound (VOC), improves environmental-protecting performance; To low-molecular-weight epoxy resin, have emulsification and solidification simultaneously; Amine hydrogen equivalent is low, and during with low-molecular-weight epoxy resin mixed preparing aqueous epoxy resins, hardener dose is less, and it is less to introduce hydrophilic polyether segment, and water tolerance improves, easy construction.
(5) preparation of aqueous epoxy resins
The first component:
E-51 Resins, epoxy 10 grams
Butyl ester glycidyl ether 1.0 grams
Second component: modified firming agent 17.5 grams
Even two kinds of mixing of materials of A component, under high-speed stirring, slowly be added in the B component, dispersed with stirring 5min promptly makes aqueous epoxy coating.
The epoxypaint The performance test results is as follows:
Solidification value: (25 ± 1) ℃
Curing speed: surface drying 85min GB-1728-79 (88)
Hardness of paint film 1H GB 6739-86
Paint film adhesion residue number of squares 90% GB 9286-88
Water tolerance 30 hours is non-foaming, does not peel off GB 1733-79 (88)
Embodiment 3
(1) condensation reaction of Resins, epoxy and polyether Glycols
In the four-hole boiling flask that has water of condensation and nitrogen protection, add 20 gram Resins, epoxy E-51 and 46.4 gram polyoxyethylene glycol PEG2000.The flask temperature is elevated to 70 ℃, makes the reaction mass thorough mixing even under stirring.Zinc chloride 1.3 grams that add then are as catalyzer.In the first section of reaction, have a large amount of reaction heat and emit, should note out water of condensation this moment, will strengthen the flow of shielding gas nitrogen simultaneously, it filled dissipate so that take away heat.Temperature is controlled at about 90 ℃, stirred anti-8 hours.The sampling and measuring oxirane value.
(2) to the aliphatic polyamine addition modification
24.0 gram triethylene tetramines are joined (this moment, flask should cool to earlier about 50 ℃) in the above four-hole boiling flask of dress, stirred about 15 minutes, controlled temperature slowly is added dropwise to 20.0 Resins, epoxy E-51 about 65 ℃.The reaction heat of emitting when preventing addition causes gel, therefore before adding Resins, epoxy E-51, adds 25 milliliters of entry.After dripping E-51.Continued stirring reaction 2.5 hours.
(3) end-blocking
In the affixture of above gained, add distilled water 15 grams, make solid content about 75%.After water injection, stirred 30 minutes, slowly drip 11 gram vinyl cyanide then and seal end-blocking.
Temperature of reaction is controlled at about 70 ℃.Reaction times is 2.0 hours.
(4) salify
In the product after end capped, add organic acid acetate 8.0 grams and be carried out to reactant salt, to improve the water-soluble of solution.Temperature of reaction is 80 ℃, 1.5 hours reaction times.After reaction finishes, add entry 75 grams, regulate solid content, be translucent light yellow thick liquid.
After testing, solid content is 45.2%, and amine hydrogen equivalent is 440, and viscosity is 11.95pas (25 ± 1 ℃).
This solidifying agent does not have volatilizable organic compound (VOC), improves environmental-protecting performance; To low-molecular-weight epoxy resin, have emulsification and solidification simultaneously; Amine hydrogen equivalent is lower, and during with low-molecular-weight epoxy resin mixed preparing aqueous epoxy resins, hardener dose is less, and water tolerance improves easy construction.
(5) preparation of aqueous epoxy resins
The A component
E-51 15 grams
Butylglycidyl ether 1.6 grams
The B component
Modified firming agent 25.8 grams
Even two kinds of mixing of materials of A component, under high-speed stirring, slowly be added in the B component, dispersed with stirring 5min promptly makes aqueous epoxy coating.
The epoxypaint The performance test results is as follows:
Solidification value: (25 ± 1) ℃
Curing speed: surface drying 70min GB-1728-79 (88)
Hardness of paint film: 1H GB 6739-86
Paint film adhesion residue number of squares 95% GB 9286-88
Water tolerance 30 hours is non-foaming, does not peel off GB 1733-79 (88)
This solidifying agent does not have volatilizable organic compound (VOC), improves environmental-protecting performance; To low-molecular-weight epoxy resin, have emulsification and solidification simultaneously; Amine hydrogen equivalent is lower, and during with low-molecular-weight epoxy resin mixed preparing aqueous epoxy resins, hardener dose is less, and it is less to introduce hydrophilic polyether segment, and water tolerance improves, easy construction.
Claims (6)
1, a kind of preparation method of aqueous epoxy resin curing agent is characterized in that comprising the steps and processing condition:
(1) condensation reaction of Resins, epoxy and polyether Glycols: under zinc chloride catalysis, generate condensation product by Resins, epoxy and polyether Glycols, the mol ratio of Resins, epoxy and polyether Glycols is 2.2～2.0: 1.0, temperature of reaction is controlled at 90～100 ℃, and the reaction times is 6～8 hours;
(2) to the polyethylene polyamine addition modification: by the epoxide group mol ratio is 1.0: 2.0～2.2, step (1) condensation product is mixed with low-molecular-weight epoxy resin, again be dissolved in distilled water in polyethylene polyamine mix, in temperature is 2～3 hours 65～70 ℃ of following reaction times of condition, in the mixture of integral body, amine hydrogen amount and epoxy group(ing) mol ratio are 6.2～6.4: 1.0, and water-content is 20%～30%;
(3) end-blocking: the polyethylene polyamine modifier of vinyl cyanide and step (2) gained is pressed itrile group and primary amine hydrogen with 1.1～1.2: 1.0 mixed in molar ratio is to react 1.5～2.0 hours under 65～70 ℃ of conditions in temperature;
(4) salify: to the product behind end-blocking, adopting has monobasic organic acid salify; The equivalence ratio of organic acid and residue amine hydrogen is 1.0: 4.5～5.0,65～70 ℃ of temperature of reaction, and the reaction times has 1.0～1.5 hours, after reaction finishes, adds distilled water, gets aqueous epoxy resin curing agent.
2, the preparation method of a kind of aqueous epoxy resin curing agent according to claim 1 is characterized in that described polyether Glycols is a polyoxyethylene glycol, and molecular-weight average is 1000～2000.
3, the preparation method of a kind of aqueous epoxy resin curing agent according to claim 1 is characterized in that described catalyzer is a zinc chloride, and its add-on is 1.0～3.0% of a system weight.
4, the preparation method of a kind of aqueous epoxy resin curing agent according to claim 1 is characterized in that described low-molecular-weight epoxy resin is the bisphenol-A liquid resin, comprises E-51 type or E-44 Resins, epoxy.
5, the preparation method of a kind of aqueous epoxy resin curing agent according to claim 1, the polyethylene polyamine that it is characterized in that described step 2 is diethylenetriamine, triethylene tetramine or tetraethylene pentamine.
6, by the aqueous epoxy resin curing agent of the described method preparation of claim 1, it is characterized in that: solid content is 45～50%, and amine value scope is 290～500, and viscosity is 8.0ps～14ps.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010121397A1 (en) * | 2009-04-23 | 2010-10-28 | 广州秀珀化工股份有限公司 | Water-soluble epoxy curing agent and method for preparing the same |
| CN101085898B (en) * | 2007-07-17 | 2010-12-08 | 马鞍山采石矶涂料有限公司 | Environment-friendly type normal temperature solidifying water epoxy resin coating and preparation method thereof |
| CN101643614B (en) * | 2009-08-14 | 2012-01-25 | 机械科学研究总院先进制造技术研究中心 | High temperature oxidation resistant environment-friendly coating with lubricating and heat conducting functions |
| CN104558529A (en) * | 2014-12-26 | 2015-04-29 | 江苏苏博特新材料股份有限公司 | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent |
| CN105713183A (en) * | 2016-02-02 | 2016-06-29 | 江苏丰彩新型建材有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN106495616A (en) * | 2016-11-10 | 2017-03-15 | 中国建材检验认证集团厦门宏业有限公司 | A kind of high-strength water-base epoxy colour self-leveling cement |
| CN112225879A (en) * | 2020-10-19 | 2021-01-15 | 南昌航空大学 | Modified amine curing agent and preparation method thereof |
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| US4197389A (en) * | 1977-07-18 | 1980-04-08 | Hoechst Aktiengesellschaft | Hardening agent for aqueous epoxy resin compositions |
| US4485229A (en) * | 1984-02-15 | 1984-11-27 | Texaco Inc. | Epoxy resin containing a combination of high and low molecular weight polyoxyalkylene polyamine curing agents |
| US6127459A (en) * | 1997-11-13 | 2000-10-03 | Shell Oil Company | Epoxy resin curing agent-reacting acid-terminated polyalkylene glycol with excess amine-terminated polyamine-epoxy resin adduct |
| CN100532480C (en) * | 2002-10-24 | 2009-08-26 | 同济大学 | Paint of aqueous epoxy resin and its preparation method |
| EP1647584A1 (en) * | 2004-10-13 | 2006-04-19 | Cytec Surface Specialties Austria GmbH | Aqueous epoxy resin systems |
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| CN101085898B (en) * | 2007-07-17 | 2010-12-08 | 马鞍山采石矶涂料有限公司 | Environment-friendly type normal temperature solidifying water epoxy resin coating and preparation method thereof |
| WO2010121397A1 (en) * | 2009-04-23 | 2010-10-28 | 广州秀珀化工股份有限公司 | Water-soluble epoxy curing agent and method for preparing the same |
| CN101643614B (en) * | 2009-08-14 | 2012-01-25 | 机械科学研究总院先进制造技术研究中心 | High temperature oxidation resistant environment-friendly coating with lubricating and heat conducting functions |
| CN104558529A (en) * | 2014-12-26 | 2015-04-29 | 江苏苏博特新材料股份有限公司 | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent |
| CN105713183A (en) * | 2016-02-02 | 2016-06-29 | 江苏丰彩新型建材有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN105713183B (en) * | 2016-02-02 | 2018-03-13 | 江苏丰彩新型建材有限公司 | Epoxy curing agent and preparation method thereof |
| CN106495616A (en) * | 2016-11-10 | 2017-03-15 | 中国建材检验认证集团厦门宏业有限公司 | A kind of high-strength water-base epoxy colour self-leveling cement |
| CN106495616B (en) * | 2016-11-10 | 2018-08-28 | 中国建材检验认证集团厦门宏业有限公司 | A kind of high-strength water-base epoxy colour self-leveling cement |
| CN112225879A (en) * | 2020-10-19 | 2021-01-15 | 南昌航空大学 | Modified amine curing agent and preparation method thereof |
| CN112225879B (en) * | 2020-10-19 | 2023-03-10 | 南昌航空大学 | Modified amine curing agent and preparation method thereof |
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Application publication date: 20070509 Assignee: Qingxin County Hanke Chemical Technology Co., Ltd. Assignor: South China University of Technology Contract record no.: 2010440000299 Denomination of invention: Solidifying agent for aqueous epoxy resin, and preparation method Granted publication date: 20090422 License type: Exclusive License Record date: 20100330 |
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