CN100547010C - A kind of preparation method of non-ionic room temperature-cured aqueous epoxy curing agent - Google Patents
A kind of preparation method of non-ionic room temperature-cured aqueous epoxy curing agent Download PDFInfo
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- CN100547010C CN100547010C CNB2007100262841A CN200710026284A CN100547010C CN 100547010 C CN100547010 C CN 100547010C CN B2007100262841 A CNB2007100262841 A CN B2007100262841A CN 200710026284 A CN200710026284 A CN 200710026284A CN 100547010 C CN100547010 C CN 100547010C
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Abstract
The invention discloses a kind of preparation method of non-ionic room temperature-cured aqueous epoxy curing agent.This method is at first carried out chain extending reaction with polyether glycol diglycidylether or polyethers Resins, epoxy or the mixture of the two in the organic solvent of aromatic polyamine or aliphatic polyamine; Add epoxy resin solution then and carry out further chain extending reaction; Last under 20～90 ℃ temperature condition, it is 30～80% that dropping distilled water is diluted to solid content with product, promptly makes non-ionic room temperature-cured aqueous epoxy curing agent.The present invention has improved the consistency of solidifying agent and Resins, epoxy by introduce the Resins, epoxy molecule segment in the solidifying agent molecule, and aqueous epoxy curing agent also has the function of self-emulsifying liquid epoxies during with liquid epoxies curing use.It is simple that the present invention also has preparation technology, the advantage of reaction conditions gentleness.
Description
Technical field
The present invention relates to a kind of epoxy curing agent, be specifically related to the preparation method of non-ionic room temperature-cured aqueous epoxy curing agent.
Background technology
Advantages such as it is little that Resins, epoxy has shrinking percentage, and adhesiveproperties is good, and mechanical property, electric property and acid-proof alkaline are good are widely used in fields such as coating, tackiness agent.In Resins, epoxy was used, solidifying agent occupied crucial position.Though Resins, epoxy has good performance, but there is the more crisp defective of performance in its cured article.Though can improve its fragility by adding rubber elastomer or thermoplastic resin, this all can make troubles and inconvenience to forming process, uses the toughness solidifying agent that contains soft segment then to have corresponding superiority.At present, though the bibliographical information of a small amount of relevant tough epoxy solidifying agent is arranged, mostly be hot setting epoxy hardener in solvent-borne type or the anhydrides.
And solvent based coating brings harm because of containing a large amount of organic solvents to ecotope, and along with the raising day by day of environmental requirement, the Water-borne modification of epoxy coating becomes one of main development trend, one of main direction of the Water-borne modification development of epoxy hardener.
Patented technologies such as US 4246148 and US 460840 disclose the preparation method of room temperature-cured aqueous epoxy curing agent, but they mostly are the modified product of aliphatic polyamine greatly, because wetting ability descends after fatty amine and the Resins, epoxy addition, for guaranteeing solidifying agent good dispersity in water, use always in the organic acid (as acetate) and salify.And organic acid exists, and is used in easily to produce on the metal to dodge rust, causes film performance to descend; In addition, it is relatively more responsive to the pH value to add the salifiable cation-type water-thinned epoxy hardener of organic acid, when using with some alkaline color stuffings, is prone to unstable phenomenon.US 5567748, and US 6277928, and patented technologies such as US 6653369 relate to relevant non-ion aqueous epoxy hardener, but its preparation technology is very complicated, and the cost height is difficult to industrialization.
Summary of the invention
The objective of the invention is to provides a kind of non-ionic room temperature-cured aqueous epoxy curing agent and preparation method thereof at the deficiencies in the prior art.This method need not add in the organic acid and salify, and preparation technology is fairly simple, and reaction conditions is relatively gentleer.
Purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of non-ionic room temperature-cured aqueous epoxy curing agent comprises the steps and processing condition:
(1) chain extending reaction: under 50～80 ℃ of temperature condition, drip polyether glycol diglycidylether or polyethers Resins, epoxy or the mixture of the two in the organic solvent of aromatic polyamine or aliphatic polyamine, aromatic polyamine or aliphatic polyamine are carried out chain extending reaction; Used aromatic polyamine or aliphatic polyamine and the polyether glycol diglycidylether that is dripped or the molar ratio of material of polyethers Resins, epoxy are 2～8: 1; After reaction is finished, remove unreacted unnecessary aromatic polyamine or aliphatic polyamine;
(2) further chain extending reaction: in temperature is under 50～80 ℃ of conditions, drips epoxy resin solution in the organic solution of step (1) chain extension product, carries out further chain extending reaction; Remove organic solvent after the reaction, the mol ratio 1: 1.8～2.2 of described Resins, epoxy and step (1) chain extension product;
(3) under 20～90 ℃ temperature condition, drip distilled water in affixture, it is diluted to solid content is 30～80%, promptly makes non-ionic room temperature-cured aqueous epoxy curing agent.
The preferred polyethyleneglycol diglycidylether of described polyether glycol diglycidylether, polypropylene glycol diglycidyl ether or polytetramethylene glycol diglycidylether.
The preferred quadrol of described aliphatic polyamine, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine and polyethylene polyamine.Described aromatic polyamine is that mphenylenediamine or a benzene two methanediamines in order; Described aromatic polyamine or aliphatic polyamine and the polyether glycol diglycidylether that is dripped or the molar ratio of material preferred 2～4: 1 of polyethers Resins, epoxy.
Described Resins, epoxy is that epoxy equivalent (weight) is 150～1000 EPON828, EPON834, EPON1001, E-51, E-44 or E-20.
Described step (1) is removed unreacted unnecessary aromatic polyamine or the method for aliphatic polyamine is underpressure distillation.
The removal of described step (2) organic solvent is by the organic solvent in the underpressure distillation removal affixture.
With respect to prior art, the present invention has following advantage:
(1) the present invention introduces the flexible polyether segment of possess hydrophilic property simultaneously by adopting polyether glycol diglycidylether or the polyethers Resins, epoxy chain extending reaction to polyamines earlier in the solidifying agent molecule.With Resins, epoxy above-mentioned affixture is carried out chain extending reaction then, thereby in the solidifying agent molecule, introduce the Resins, epoxy molecule segment, to improve the consistency of solidifying agent and Resins, epoxy, and this aqueous epoxy curing agent and liquid epoxies are solidified when using, also have the function of self-emulsifying liquid epoxies.
(2) the present invention adopts a kind of non-ionic room temperature-cured toughness aqueous epoxy curing agent of two step chain extension method institute's synthetic, and it is simple to have preparation technology, the advantage of reaction conditions gentleness.
Description of drawings
Fig. 1 is the infrared spectrogram of the prepared aqueous epoxy curing agent of embodiment 1.
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
Under the drying nitrogen protection, 0.6 mole triethylene tetramine is put in the 1000mL four-hole reaction flask that 110mL propylene glycol monomethyl ether solution is housed.In the four-hole reaction flask reflux condensing tube is housed, temperature is taken into account agitator.The stirring rake pattern is an anchor formula impeller stirring arm, and about stirring velocity 500rm-1, the form of heating is a constant temperature water bath.When temperature rose to 65 ℃ in the question response bottle, the polyether glycol diglycidylether (NPER-032) that drips 0.2 mole with the speed of 60mL per hour reacted in reaction flask, insulation reaction about 2 hours again after dripping.
After unnecessary triethylene tetramine is removed in underpressure distillation, in the described in front reaction unit, when temperature in the reaction flask was 65 ℃, the liquid epoxies EPON828 that drips 0.1 mole with the speed of 60mL per hour reacted in the propylene glycol monomethyl ether solution of above-mentioned affixture.Insulation reaction 1 hour again after dripping after propylene glycol monomethyl ether is removed in underpressure distillation, under 50 ℃ to 60 ℃ condition, with the speed of 100mL per hour, drips 200 gram distilled water in the above-mentioned reaction flask that is in whipped state.Dripping the back restir disperseed 30 minutes.Last cooling discharge obtains the light aqueous epoxy curing agent of clear homogeneous.
Have the molecule segment similar to Resins, epoxy in the aqueous epoxy curing agent molecular structure of present embodiment preparation, the flexible poly ether alcohol segment of possess hydrophilic property also has the polyamines segment that solidifies function in addition simultaneously.Its infared spectrum is as shown in Figure 1: in the infrared spectrum at 1110cm
-1Strong and the roomy polyethers characteristic peak of DGEPG has appearred in the place, and the characteristic peak of the epoxy group(ing) of polyether glycol diglycidylether disappears, and shows and contains the Aethoxy Sklerol segment in the solidifying agent.At 1577cm
-1, 1509cm
-1, 1459cm
-1The skeletal vibration charateristic avsorption band of phenyl ring in the Resins, epoxy has appearred in the place, and at 829cm
-1Place and 770cm
-1Two peaks at place show that phenyl ring is a contraposition disubstituted benzenes ring, and the characteristic peak (915cm of the epoxy group(ing) of Resins, epoxy (EPON828)
-1) the basic disappearance.This shows and contains the Resins, epoxy molecule segment in the solidifying agent product.In addition among the figure at 3300-3500cm
-1The interval has also occurred being the charateristic avsorption band of polyamines, shows in this solidifying agent product and contains the polyamines segment.The product of following examples preparation has infared spectrum substantially the same manner as Example 1, no longer specifically describes.
Embodiment 2
Under the drying nitrogen protection, 0.6 mole quadrol is put in the 1000mL four-hole reaction flask that 120mL propylene glycol monomethyl ether solution is housed.In the 1000mL four-hole reaction flask reflux condensing tube is housed, temperature is taken into account agitator.The stirring rake pattern is an anchor formula impeller stirring arm, and about stirring velocity 500rm-1, the form of heating is a constant temperature water bath.When temperature rose to 70 ℃ in the question response bottle, the polyether glycol diglycidylether (NPER-032) that drips 0.3 mole with the speed of 60mL per hour reacted in reaction flask, insulation reaction about 2 hours again after dripping.
After unnecessary quadrol is removed in underpressure distillation, in the described in front reaction unit, when temperature in the reaction flask was 65 ℃, the liquid epoxies EPON828 that drips 0.15 mole with the speed of 60mL per hour reacted in the propylene glycol monomethyl ether solution of above-mentioned affixture.Insulation reaction 1 hour again after dripping after propylene glycol monomethyl ether is removed in underpressure distillation, under 50 ℃ to 60 ℃ condition, with the speed of 110mL per hour, drips 220 gram distilled water in the above-mentioned reaction flask that is in whipped state.Dripping the back restir disperseed 30 minutes.Last cooling discharge obtains the light aqueous epoxy curing agent of clear homogeneous.
Embodiment 3
Under the drying nitrogen protection, 0.6 mole diethylenetriamine is put in the 1000mL four-hole reaction flask that 100mL propylene glycol monomethyl ether solution is housed.In the four-hole reaction flask reflux condensing tube is housed, temperature is taken into account agitator.The stirring rake pattern is an anchor formula impeller stirring arm, and about stirring velocity 500rm-1, the form of heating is a constant temperature water bath.When temperature rose to 60 ℃ in the question response bottle, the polyether glycol diglycidylether (NPER-032) that drips 0.2 mole with the speed of 60mL per hour reacted in reaction flask, insulation reaction about 2 hours again after dripping.
After unnecessary diethylenetriamine is removed in underpressure distillation, in the described in front reaction unit, when temperature in the reaction flask was 65 ℃, the liquid epoxies E-51 that drips 0.1 mole with the speed of 60mL per hour reacted in the propylene glycol monomethyl ether solution of above-mentioned affixture.Insulation reaction 1 hour again after dripping after propylene glycol monomethyl ether is removed in underpressure distillation, under 50 ℃ to 60 ℃ condition, with the speed of 100mL per hour, drips 190 gram distilled water in the above-mentioned reaction flask that is in whipped state.Dripping the back restir disperseed 30 minutes.Last cooling discharge obtains the light yellow aqueous epoxy curing agent of clear homogeneous.
Embodiment 4
Under the drying nitrogen protection, 0.6 mole butanediamine is put in the 1000mL four-hole reaction flask that 120mL propylene glycol monomethyl ether solution is housed.In the 1000mL four-hole reaction flask reflux condensing tube is housed, temperature is taken into account agitator.The stirring rake pattern is an anchor formula impeller stirring arm, and about stirring velocity 500rm-1, the form of heating is a constant temperature water bath.When temperature rose to 70 ℃ in the question response bottle, the polyether glycol diglycidylether (NPER-032) that drips 0.1 mole with the speed of 60mL per hour reacted in reaction flask, insulation reaction about 2 hours again after dripping.
After unnecessary tetraethylene pentamine is removed in underpressure distillation, in the described in front reaction unit, when temperature in the reaction flask was 65 ℃, the liquid epoxies EPON828 that drips 0.056 mole with the speed of 60mL per hour reacted in the propylene glycol monomethyl ether solution of above-mentioned affixture.Insulation reaction 1 hour again after dripping after propylene glycol monomethyl ether is removed in underpressure distillation, under 50 ℃ to 60 ℃ condition, with the speed of 110mL per hour, drips 220 gram distilled water in the above-mentioned reaction flask that is in whipped state.Dripping the back restir disperseed 30 minutes.Last cooling discharge obtains the light aqueous epoxy curing agent of clear homogeneous.
Embodiment 5
Under the drying nitrogen protection, 0.8 mole mphenylenediamine is put in the 1000mL four-hole reaction flask that 120mL propylene glycol monomethyl ether solution is housed.In the 1000mL four-hole reaction flask reflux condensing tube is housed, temperature is taken into account agitator.The stirring rake pattern is an anchor formula impeller stirring arm, and about stirring velocity 500rm-1, the form of heating is a constant temperature water bath.When temperature rose to 70 ℃ in the question response bottle, the polyether glycol diglycidylether (NPER-032) that drips 0.1 mole with the speed of 60mL per hour reacted in reaction flask, insulation reaction about 2 hours again after dripping.
After unnecessary tetraethylene pentamine is removed in underpressure distillation, in the described in front reaction unit, when temperature in the reaction flask was 65 ℃, the liquid epoxies EPON828 that drips 0.045 mole with the speed of 60mL per hour reacted in the propylene glycol monomethyl ether solution of above-mentioned affixture.Insulation reaction 1 hour again after dripping after propylene glycol monomethyl ether is removed in underpressure distillation, under 50 ℃ to 60 ℃ condition, with the speed of 110mL per hour, drips 220 gram distilled water in the above-mentioned reaction flask that is in whipped state.Dripping the back restir disperseed 30 minutes.Last cooling discharge obtains the light aqueous epoxy curing agent of clear homogeneous.
Embodiment 6
Under drying nitrogen protection, benzene two methanediamines between 0.6 mole are put in the 1000mL four-hole reaction flask that 120mL propylene glycol monomethyl ether solution is housed.In the 1000mL four-hole reaction flask reflux condensing tube is housed, temperature is taken into account agitator.The stirring rake pattern is an anchor formula impeller stirring arm, and about stirring velocity 500rm-1, the form of heating is a constant temperature water bath.When temperature rose to 70 ℃ in the question response bottle, the polyether glycol diglycidylether (NPER-032) that drips 0.2 mole with the speed of 60mL per hour reacted in reaction flask, insulation reaction about 2 hours again after dripping.
After unnecessary tetraethylene pentamine is removed in underpressure distillation, in the described in front reaction unit, when temperature in the reaction flask was 65 ℃, the liquid epoxies EPON828 that drips 0.1 mole with the speed of 60mL per hour reacted in the propylene glycol monomethyl ether solution of above-mentioned affixture.Insulation reaction 1 hour again after dripping after propylene glycol monomethyl ether is removed in underpressure distillation, under 50 ℃ to 60 ℃ condition, with the speed of 110mL per hour, drips 220 gram distilled water in the above-mentioned reaction flask that is in whipped state.Dripping the back restir disperseed 30 minutes.Last cooling discharge obtains the light aqueous epoxy curing agent of clear homogeneous.
Claims (4)
1, a kind of preparation method of non-ionic room temperature-cured aqueous epoxy curing agent is characterized in that comprising the steps and processing condition:
(1) chain extending reaction: under 50～80 ℃ of temperature condition, drip polyether glycol diglycidylether or polyethers Resins, epoxy or the mixture of the two in the organic solvent of aromatic polyamine or aliphatic polyamine, aromatic polyamine or aliphatic polyamine are carried out chain extending reaction; Used aromatic polyamine or aliphatic polyamine and the polyether glycol diglycidylether that is dripped or the molar ratio of material of polyethers Resins, epoxy are 2～8: 1; After reaction is finished, remove unreacted unnecessary aromatic polyamine or aliphatic polyamine;
Described polyether glycol diglycidylether is polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether or polytetramethylene glycol diglycidylether;
Described aliphatic polyamine is quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine;
Described aromatic polyamine is mphenylenediamine or a benzene two methanediamines;
(2) further chain extending reaction: in temperature is under 50～80 ℃ of conditions, drips epoxy resin solution in the organic solution of step (1) chain extension product, carries out further chain extending reaction; Remove organic solvent after the reaction, the mol ratio 1: 1.8～2.2 of described Resins, epoxy and step (1) chain extension product; Described Resins, epoxy is that epoxy equivalent (weight) is 150～1000 EPON828, EPON834, EPON1001, E-51, E-44 or E-20;
(3) under 20～90 ℃ temperature condition, drip distilled water in affixture, it is diluted to solid content is 30～80%, promptly makes non-ionic room temperature-cured aqueous epoxy curing agent.
2, the preparation method of non-ionic room temperature-cured aqueous epoxy curing agent according to claim 1 is characterized in that described aromatic polyamine or aliphatic polyamine and the polyether glycol diglycidylether that is dripped or the molar ratio of material of polyethers Resins, epoxy are 2～4: 1.
3, the preparation method of non-ionic room temperature-cured aqueous epoxy curing agent according to claim 1 is characterized in that described step (1) is removed unreacted unnecessary aromatic polyamine or the method for aliphatic polyamine is underpressure distillation.
4, the preparation method of non-ionic room temperature-cured aqueous epoxy curing agent according to claim 1, the removal that it is characterized in that described step (2) organic solvent is by the organic solvent in the underpressure distillation removal affixture.
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