CN102190800A - Preparation method of nonionic waterborne epoxy curing agent - Google Patents
Preparation method of nonionic waterborne epoxy curing agent Download PDFInfo
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Abstract
The invention provides a preparation method of a nonionic waterborne epoxy curing agent, which comprises the following steps: (1) heating and dissolving epoxy resin and polyether polyol, evenly mixing, dropwisely adding catalyst at 50-130 DEG C to carry out polymerization reaction, and after the reaction finishes, dissolving the product in the epoxy resin and solvent to prepare a mixed solution; (2) while stirring, dropwisely adding a monoepoxy compound into basic amine, and reacting at 10-100 DEG C; (3) dropwisely adding the mixed solution in the step (1) into the reaction product in the step (2) at 30-120 DEG C, and enabling the reaction at 10-90 DEG C; and after the reaction finishes, diluting by adding water until the solid content reaches 30-80%, thereby obtaining the nonionic waterborne epoxy curing agent. The method has the advantages of simple technique and mild reaction conditions; the adopted cosolvent has the advantages of low toxicity or no toxicity, and low VOC (volatile organic compound) content; and the substance cured by the product has the advantages of favorable compatibility with epoxy resin and high toughness of the paint film.
Description
Technical field
The present invention relates to a kind of preparation method of non-ion aqueous epoxy hardener.
Background technology
Aqueous epoxy coating development in recent years is very fast, and it is the eco-friendly macromolecular material of a class, has plurality of advantages such as organic solvent content is low, smell is little, chemical-resistant, insulativity, has been widely used and application prospect.Solidifying agent is one of key factor that influences the bi-component epoxy coating property, is the key component of decision product Technology and characteristic.Common aliphatics amine self-vulcanizing agent stimulates bigger to human body, easy again and carbon dioxide in air reaction generates salt or absorbs the moisture whiting.The aqueous epoxy curing agent of the self-vulcanizing that use on the historical facts or anecdotes border adopts their modified product mostly, comprise amidated polyamines, polymeric amide and epoxy-polyamines affixture, because water tolerance of filming and chemical-resistant after the amides solidifying agent solidifies are relatively poor, using more at present is epoxy-polyamines affixture.
Along with the development of aqueous epoxy coating, the research of waterborne curing agent also begins development, but its correlative study is also fewer.Common in the market aqueous epoxy curing agent has ionic waterborne curing agent and non-ion aqueous solidifying agent etc., the ionic solidifying agent is because adopt in the organic acid and salify, its organic acid exists, be used in easily to produce on the metal and dodge rust, because of organic acid exists, when using, be prone to unstable phenomenon simultaneously with some alkaline color stuffings.
The waterborne curing agent that the US6277928 patented technology relates to is in preparation process, and amine is excessive, needs to deviate from unnecessary amine, the energy consumption height after reaction is finished; And add noxious solvents such as toluene in the reaction process, need to remove this part solvent after reaction is finished on the one hand, require the expenditure of energy not environmental protection of production process on the other hand.
CN 101007863 discloses a kind of preparation method of non-ion aqueous epoxy hardener, but its preparation technology is in chain extending reaction, amine is a large amount of excessive, and add a large amount of solvents in the reaction process, after finishing, reaction need remove unnecessary amine and solvent, on the one hand the boiling point height of amine, remove unnecessary amine and need very high temperature, the energy consumption height, in subtractive process, amine and solvent can not be separated fully on the other hand; Further add a large amount of solvents in the chain extending reaction, need carry out the underpressure distillation desolventizing after reaction is finished.Whole technology more complicated, the energy consumption height.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of non-ion aqueous epoxy hardener is provided, this method technology is fairly simple, reaction conditions is relatively gentleer, raw materials used amine is inexcessive, the solubility promoter low toxicity of employing or nontoxic, and VOC (volatile organic compounds) content is low, the cured article and the epoxy resin compatibility of products therefrom are good, the paint film good toughness.
The preparation method of a kind of non-ion aqueous epoxy hardener provided by the invention comprises the steps:
(1) Resins, epoxy and polyethers alcohols material heating fusion are mixed, under 50 ℃～130 ℃ temperature, drip catalyzer, carry out polyreaction, wherein: the mol ratio of Resins, epoxy and polyethers alcohols material is 0.5: 1～5: 1; Catalyst consumption is 0.1%～1% of Resins, epoxy and a polyethers alcohols material gross weight sum.After reaction is finished, resultant and Resins, epoxy, dissolution with solvents are made into mixing solutions, solvent load is 1～80% of a mixing solutions gross weight.
(2) under agitation condition, drip mono-epoxy compounds in basic amine, under 10 ℃～100 ℃ temperature, react, wherein: the mol ratio of basic amine and mono-epoxy compounds is 1: 0.05～1: 3.
(3) under the temperature of 30～120 ℃ of temperature, the mixing solutions of step (1) is added drop-wise in the reaction product of step (2), under 10 ℃～90 ℃ temperature, it is reacted; The mol ratio of epoxy group(ing) and basic amine is 0.1: 1～4: 1 in the hierarchy of control, and the polyether segment that the polyethers alcohols material provides accounts for 10～50% of total solids part, and total solids part is basic amine, mono-epoxy compounds, Resins, epoxy and polyethers alcohols material sum; Add entry after reaction is finished, it is diluted to solid content is 30～80%, promptly obtains non-ion aqueous epoxy hardener.
Described Resins, epoxy is that epoxy equivalent (weight) is 150～1000 bisphenol A type epoxy resin, bisphenol f type epoxy resin.
Described polyethers alcohols material is one or more the composition in polyethylene glycol type, polypropylene glycol type, the polyether-type.
Described catalyzer is lewis acid catalyst or Louis's bases catalyzer, and lewis acid catalyst is Potassium Persulfate, boron trifluoride diethyl etherate, tin tetrachloride, Zinc Chloride Anhydrous etc.; Lewis-base catalyst is ammonia, amine, water, carbon monoxide, CH3OH, CH3COCH3 etc.
Described solvent is gylcol ether and propylene glycol kind solvent.
Described mono-epoxy compounds comprises: methyl glycidyl ether, propyl glycidyl ether, butylglycidyl ether, ethylene glycol diglycidylether, hexanediol diglycidyl ether, phenyl glycidyl ether etc.
Described basic amine is one or more the mixture in aromatic amine, aliphatic amide, the aliphatic cyclic amine; Described aromatic amine has mphenylenediamine, a benzene two methanediamines, diaminodiphenyl-methane etc.; Described aliphatic cyclic amine has alkane diamines in the Meng, isophorone diamine, N-aminoethyl piperazine etc.; Described aliphatic amide has quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diethylaminopropylamine etc.
With respect to prior art, the present invention has following advantage:
(1) the present invention carries out the end capping of part or all of primary amine hydrogen by adopting earlier mono-epoxy compounds to basic amine, can prevent that too much primary amine hydrogen from absorbing airborne moisture and paint film is turned white, and improved water resistance; Also can improve the consistency of solidifying agent and Resins, epoxy; And the working life of prolongation Resins, epoxy.
(2) the present invention carries out further addition reaction with Resins, epoxy to the end-blocking product, thereby introduces the Resins, epoxy molecule segment in the solidifying agent molecular structure, further improves the consistency of solidifying agent and Resins, epoxy.
(3) the present invention carries out further addition reaction with the intermediate materials with hydrophilicity to the end-blocking product, introduces the flexible polyether segment of possess hydrophilic property in the solidifying agent molecular structure, increases the wetting ability of solidifying agent and the snappiness of paint film.
(4) the prepared aqueous epoxy curing agent of the present invention has the function of self-emulsifying epoxy resin.
(5) the prepared aqueous epoxy curing agent VOC of the present invention content is low, and product does not fire.
(6) preparation method's technology of the present invention is fairly simple, the solubility promoter add-on seldom, reaction removes or does not remove after finishing, because add-on is few, removes also and is easy to, energy consumption is low, synthesis condition is relatively gentleer.
Embodiment
In order to understand the present invention better, 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 represented scope of embodiment.
Embodiment 1
200g Macrogol 2000 and 69gCYD-128 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, the heating fusion, 100 ℃ of temperature, under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature, the mixing solutions of the 0.65g boron trifluoride diethyl etherate of under normal pressure, progressively increasing and 7g ethylene glycol ethyl ether, dropwised in 70 minutes, and kept reaction 3 hours, obtain light solid matter.Get this material of 19g and 35g CYD-128 and under 70 ℃ temperature, be dissolved in the 2g ethylene glycol ethyl ether and make mixing solutions, keep temperature stand-by.
The 31g triethylene tetramine is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, and normal temperature drips the 13g butylglycidyl ether down in reaction flask, dropwises in 20 minutes, and insulation reaction is 3 hours under the condition of 50 ℃ of temperature.Be cooled to 40 ℃, drip above-mentioned mixing solutions so far in the material of four-hole reaction flask, added in 60 minutes, temperature maintenance after reaction is finished, removes solubility promoter 65～75 ℃ of insulation reaction, drip the 98g pure water, added in 30 minutes, obtain the aqueous epoxy curing agent of solid content 50%, VOC＜1g/L.
It is composite that this waterborne curing agent and aqueous epoxy resins are pressed epoxy equivalent (weight) and amine hydrogen equivalent 1: 1, and its pencil hardness is 3H, and sticking power is 1 grade, and shock resistance is 60cmKg, and in 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have and bubble.
Embodiment 2
200g Macrogol 2000 and 69gCYD-128 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, the heating fusion, 100 ℃ of temperature, under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature, the mixing solutions of the 0.65g boron trifluoride diethyl etherate of under normal pressure, progressively increasing and 7g ethylene glycol ethyl ether, dropwised in 70 minutes, and kept reaction 3 hours, obtain light solid matter.Get this material of 35g and 40g E-44 and under 60 ℃ temperature, be dissolved in the 3g propylene glycol monomethyl ether and make mixing solutions, keep temperature stand-by.
The 22g mphenylenediamine is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, and normal temperature drips the 16g phenyl glycidyl ether down in reaction flask, dropwises in 30 minutes, and insulation reaction is 2 hours under the condition of 60 ℃ of temperature.Drip above-mentioned mixing solutions in the material of this four-hole reaction flask, added in 75 minutes, temperature maintenance is 50～70 ℃ of insulation reaction, after reaction is finished, improve stirring velocity, drip the 110g pure water, added in 30 minutes, and obtained the aqueous epoxy curing agent of solid content 50%, VOC13g/L.
It is composite that this waterborne curing agent and aqueous epoxy resins are pressed epoxy equivalent (weight) and amine hydrogen equivalent 1: 1, and its pencil hardness is 2H, and sticking power is 1 grade, and shock resistance is 70cmKg, and in 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have and bubble.
Embodiment 3
200g Macrogol 4000 and 26gE-44 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, the heating fusion, 100 ℃ of temperature, under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature, the mixing solutions of the 0.45g boron trifluoride diethyl etherate of under normal pressure, progressively increasing and 8.5g butyl glycol ether, dropwised in 50 minutes, and kept reaction 3 hours, obtain light solid intermediate material.This material of 40g and 32g CYD-1283g are dissolved in the mixing solutions of butyl glycol ether under 65 ℃ temperature, keep temperature stand-by.
With 15g1, the 3-propylene diamine is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, and normal temperature drips 20g CYDPG660 down in reaction flask, dropwises in 30 minutes, and insulation reaction is 3 hours under the condition of 65 ℃ of temperature.Be cooled to 50 ℃, drip above-mentioned mixing solutions in the material of this four-hole reaction flask, added in 100 minutes, temperature maintenance after reaction is finished, improves stirring velocity 70～80 ℃ of insulation reaction, drip the 104g pure water, added in 30 minutes, obtain the aqueous epoxy curing agent of solid content 50%, VOC14g/L.
It is composite that this waterborne curing agent and standardized liquid bisphenol A epoxide resin are pressed epoxy equivalent (weight) and amine hydrogen equivalent 1: 1, and its pencil hardness is 3H, and sticking power is 1 grade, shock resistance is 70cmKg, in 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have foaming.
Embodiment 4
200g Macrogol 2000 and 69gCYD-128 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, the heating fusion, 100 ℃ of temperature, under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature, the mixing solutions of the 0.65g boron trifluoride diethyl etherate of under normal pressure, progressively increasing and 7g ethylene glycol ethyl ether, dropwised in 70 minutes, and kept reaction 3 hours, obtain light solid matter.Get this material of 41.8g and 31.2g CYD-128 and under 55 ℃ temperature, be dissolved in the 4g propylene glycol monomethyl ether and make mixing solutions, keep temperature stand-by.
The 33g isophorone diamine is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, thermometer, agitator, normal temperature drips the 12g phenyl glycidyl ether down in reaction flask, dropwised in 30 minutes, insulation reaction is 2 hours under the condition of 55～65 ℃ of temperature.Drip above-mentioned mixing solutions in the material of this four-hole reaction flask, added in 90 minutes, temperature maintenance after reaction is finished, adds the 114g pure water 50～90 ℃ of insulation reaction, obtains the aqueous epoxy curing agent of solid content 50%, VOC17g/L.
It is composite that this waterborne curing agent and standardized liquid bisphenol A epoxide resin are pressed epoxy equivalent (weight) and amine oxygen equivalent 1: 1, and its pencil hardness is 3H, and sticking power is 1 grade, shock resistance is 70cmKg, in 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have foaming.
Claims (7)
1. the preparation method of a non-ion aqueous epoxy hardener is characterized in that: comprise the steps:
(1) Resins, epoxy and polyethers alcohols material heating fusion are mixed, under 50 ℃～130 ℃ temperature, drip catalyzer, carry out polyreaction, wherein: the mol ratio of Resins, epoxy and polyethers alcohols material is 0.5: 1～5: 1; Catalyst consumption is 0.1%～1% of Resins, epoxy and a polyethers alcohols material gross weight sum; After reaction is finished, resultant and Resins, epoxy, dissolution with solvents are made into mixing solutions, solvent load is 1～80% of a mixing solutions gross weight;
(2) under agitation condition, drip mono-epoxy compounds in basic amine, under 10 ℃～100 ℃ temperature, react, wherein: the mol ratio of basic amine and mono-epoxy compounds is 1: 0.05～1: 3;
(3) under the temperature of 30～120 ℃ of temperature, the mixing solutions of step (1) is added drop-wise in the reaction product of step (2), under 10 ℃～90 ℃ temperature, it is reacted; The mol ratio of epoxy group(ing) and basic amine is 0.1: 1～4: 1 in the hierarchy of control, and the polyether segment that the polyethers alcohols material provides accounts for 10～50% of total solids part, and total solids part is basic amine, mono-epoxy compounds, Resins, epoxy and polyethers alcohols material sum; Add entry after reaction is finished, it is diluted to solid content is 30～80%, promptly obtains non-ion aqueous epoxy hardener.
2. method according to claim 1 is characterized in that: described Resins, epoxy is that epoxy equivalent (weight) is 150～1000 bisphenol A type epoxy resin, bisphenol f type epoxy resin.
3. method according to claim 1 is characterized in that: described polyethers alcohols material is one or more the composition in polyethylene glycol type, polypropylene glycol type, the polyether-type.
4. method according to claim 1 is characterized in that: described solvent is gylcol ether and propylene glycol kind solvent.
5. method according to claim 1 is characterized in that: described catalyzer is lewis acid catalyst or Louis's bases catalyzer, and lewis acid catalyst is Potassium Persulfate, boron trifluoride diethyl etherate, tin tetrachloride, Zinc Chloride Anhydrous etc.; Lewis-base catalyst is ammonia, amine, water, carbon monoxide, CH3OH, CH3COCH3.
6. method according to claim 1 is characterized in that: described mono-epoxy compounds comprises: methyl glycidyl ether, propyl glycidyl ether, butylglycidyl ether, ethylene glycol diglycidylether, hexanediol diglycidyl ether, phenyl glycidyl ether etc..
7. method according to claim 1 is characterized in that: described basic amine is one or more the mixture in aromatic amine, aliphatic amide, the aliphatic cyclic amine; Described aromatic amine has mphenylenediamine, a benzene two methanediamines, diaminodiphenyl-methane; Described aliphatic cyclic amine has alkane diamines in the Meng, isophorone diamine, N-aminoethyl piperazine etc.; Described aliphatic amide has quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diethylaminopropylamine.
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| CN103145955A (en) * | 2013-02-04 | 2013-06-12 | 广东工业大学 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
| CN103450448A (en) * | 2012-05-31 | 2013-12-18 | 中国石油化工股份有限公司 | Preparation method of compound aqueous curing agent |
| CN103910856A (en) * | 2013-01-08 | 2014-07-09 | 深圳市景江化工有限公司 | Nonionic aqueous epoxy hardener and its preparation method |
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