CN101701059A - Preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid and application thereof - Google Patents
Preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid and an application thereof. In the method, terpenyl maleic anhydride epoxy resin of glycidyl ester or hydrogenated terpenyl maleic anhydride epoxy resin of glycidyl ester is utilized to react with diethanol amine and micromolecule hydroxy chain extender under the action of catalyst to obtain the polyalcohol product, the polyalcohol product is neutralized with acid and directly disperses in water to obtain self-emulsifying cationic terpenyl epoxy resin polyalcohol water dispersoid. The polyalcohol water dispersoid is a bicomponent aqueous polyurethane system which is combined by hydroxyl component and polyisocyanate and can be widely applied to water paint, binding agent and polymer materials. The preparation method is simple and convenient, the preparation process is clean, the reaction process has no solvent, and stable self-emulsifying water dispersoid can be obtained with no need of stirring at a high speed; the hydroxyl value and the glass transition temperature of the polyalcohol resin can be adjusted along with the type and use level of the micromolecule chain extender; and the prepared bicomponent aqueous polyurethane paint film has excellent ultraviolet resistance and anti-yellowing performances.
Description
Technical field
The present invention relates to a kind of preparation method of self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid and cooperate the purposes that obtains the dual-component aqueous polyurethane system with polymeric polyisocyanate as the water-based polyol component.
Background technology
Along with various countries' environmental regulation to the strictness of volatile organic compounds in the coating system (VOC) content restriction, the aqueous polyurethane coating that the low VOC content of the high-performance of solvent borne polyurethane coating and water-borne coatings is combined has become one of coating variety with fastest developing speed.The aqueous polyurethane coating kind is a lot, can be divided into onepot coating and two-component coating by packaged form.The easy construction of water-based mono-component polyurethane coating, but have the deficiency of many performances such as chemical-resistant, wear resistance, thermotolerance, hardness.And high-performance such as waterborne two-component polyurethane coating has that film-forming temperature is low, strong adhesion, wear resistance is good, hardness is big and chemicals-resistant, weather resisteant be good, the solvent-type double-component polyurethane coating be can replace, the surface decoration and the protection of numerous areas such as automobile, woodenware, plastics, industrial maintenance are widely used in.
Waterborne two-component polyurethane coating is made up of water-based polyol component that contains the OH base and the low viscosity polyisocyanate component that contains the NCO base, and its film performance is mainly determined by the The Nomenclature Composition and Structure of Complexes of hydroxy resin.Compare with two-pack solvent borne polyurethane coating, its polyvalent alcohol has good dispersiveness, can stably disperse in water with polyisocyanate curing agent.According to the difference of chemical structure, it can be divided into polyurethane polyol, polyacrylate(s) polyvalent alcohol and polyester polyol etc.More to this type of water-based polyvalent alcohol research both at home and abroad at present, U.S. Pat 5387642 has been reported in the synthesis technique of aqueous polyurethane dispersion, adopt excessive carboxylic monomer can obtain the hydroxyl polyurethane polyol dispersions, but adopt the functionality of this method hydroxyl lower.P.B.Jacobs etc. utilize part poly-hydroxy monomer such as TriMethylolPropane(TMP) to wait to improve hydroxy functionality, but this method causes the polyurethane polyol molecular weight to be difficult to control, and viscosity is very big.Zhou Xinhua etc. are initiator with the di-t-butyl peroxide, 1-Methoxy-2-propyl acetate is a solvent, carry out the acrylate solution copolymerization, dilute with water obtains acrylic dispersion, can be used as water-based polyol component polymeric polyisocyanate and forms aqueous two-component polyurethane; And think and replace hydroxyethyl methylacrylate to make carboxylic monomer with Hydroxyethyl acrylate, when the film coated surface of preparation has bubble, surface drying with short, snappiness is good.The polyester polyol facile hydrolysis utilizes the dibasic alcohol that contains side chain to prepare the big polyester polyol of probability factor usually and improves its anti-hydrolytic performance.World patent WO99/60046 has reported by 2-butyl-2-ethyl-1, ammediol, TriMethylolPropane(TMP), 1,4-cyclohexyl dioctyl phthalate, 1,4-cyclohexyl dimethanol, the trimellitic acid 1,2-anhydride condensation is again with in the dimethylethanolamine and prepared dual-component aqueous polyurethane hydrolysis-resistant polyester polyvalent alcohol.Acrylate copolymer is grafted on the molecular weight of petchem, prepares polyester-vinylformic acid Pluronic polyols dispersion, can improve the hydrolytic resistance of polyester chain equally.The US5336711 of Bayer house journal adopts phthalic acid (acid anhydride), TriMethylolPropane(TMP), maleic anhydride, hexylene glycol, the polyester polyol that condensation prepared such as new penta tetrol contain unsaturated group adds methacrylic acid, butyl acrylate again in polyester polyol, vinylbenzene, Hydroxyethyl acrylate, free radical causes synthesizing polyester-acrylate Pluronic polyols, the dimethylethanolamine neutralization, be scattered in the water that to obtain hydroxyl value be 130mg/g, acid number is the polymer polyatomic alcohol water dispersion of 26mg/g.It is less relatively to utilize Resins, epoxy to prepare the research of water-based polyvalent alcohol, Japanese Patent JP11228807 has reported and has utilized bisphenol A epoxide resin and para-amino benzoic acid reaction, with acquisition anionic Resins, epoxy polylol, obtain the dual-component aqueous polyurethane system in the triethylamine with the H12MDI reaction; U.S. Pat 6350796 has reported that the formic acid neutralization is dispersed in the water, obtains the epoxy resin-matrix polyalcohol water dispersoid, can be used for waterborne two-component polyurethane coating with bisphenol A epoxide resin and diethanolamine reaction.
Along with the worsening shortages of petroleum resources and becoming increasingly conspicuous of environmental problem, prepare environmentally friendly macromolecular material with the biomass renewable resources and more and more be subject to people's attention.Terpenes-maleic anhydride glycidyl ester type epoxy resin (TME) (CN1034211) and hydriding terpene-maleic anhydride glycidyl ester type epoxy resin (HTME) (CN101054437A) be to be raw material synthetic terpenyl epoxy resin with the by product kautschin of natural turps or artificial camphor and the affixture terpenes maleic anhydride (TMA) and the hydrogenated products hydrogenated terpinene maleic anhydride (HTMA) thereof of maleic anhydride respectively, it is the chemical deep processing product of natural reproducible resource, all comprise the bridged ring structure in its chemical structure, have excellent mechanical mechanics property and heat-resisting, chemical resistance.
Summary of the invention
The object of the present invention is to provide a kind of Preparation method and use of self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid.This method is utilized the self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid of natural reproducible resource preparation and the polyether polyols with reduced unsaturation excellent property of the poly-di-isocyanate reaction formation of hydrophilic modifying.
The present invention is by the following technical solutions: a kind of preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid, react under the lewis acid catalyst effect with terpenyl epoxy resin and diethanolamine (DEA), micromolecular hydroxyl chainextender, the product that makes in water, obtains stable transparent or semitransparent self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid with the direct dispersed with stirring in acid neutralization back.The hydroxyl value of self-emulsifying cation type terpenyl epoxy resin polyalcohol is 180-320mg/g, and the equal size of the Z of water dispersion is 10-100nm.
Described terpenyl epoxy resin is terpinene maleic anhydride glycidyl ester type epoxy resin or hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin, and oxirane value is 0.32-0.39mol/100g.Described terpenyl epoxy resin is that terpinene maleic anhydride glycidyl ester type epoxy resin or hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin are terpinene maleic anhydride glycidyl ester type epoxy resin (TME) or the hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resins (HTME) that utilizes terpenic derivative terpinene maleic anhydride of natural reproducible resource (TMA) or hydrogenated terpinene maleic anhydride (HTMA) and epichlorohydrin reaction to obtain.
Diethanolamine (DEA) provide cationic hydrophilic radical, and the consumption of diethanolamine is 10～12% of a terpenyl epoxy resin quality.
The micromolecular hydroxyl chainextender is 1, and 4-butyleneglycol, glycol ether, number-average molecular weight are any one in the polyoxyethylene glycol of 200-400, and consumption is 0.5 times-1 times of amount of substance of terpenyl epoxy resin, and optimum amount is 0.65 times-0.85 times.
Described lewis acid catalyst is any one in zinc chloride, boron trifluoride, the titanium tetrachloride, and optimum catalyst is a zinc chloride, and add-on is the 1%-4% of Resins, epoxy quality, and optimum amount is 2-3%.
Described temperature of reaction is 90-120 ℃, and the reaction times is 3-10h.
The used acid that neutralizes is any one in formic acid, acetate, the hydrochloric acid, and degree of neutralization is 60-100%.
The self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid of preparation method's preparation of described cationic terpenyl epoxy resin polyalcohol water dispersoid can cooperate the dual-component aqueous polyurethane system that obtains with the poly-vulcabond of hydrophilic modifying as hydroxy component, the polyether polyols with reduced unsaturation excellent property that reaction forms, detailed directions is:
The cationic terpenyl epoxy resin polyalcohol of aforesaid method acquisition is separated into the water dispersion of 30%wt solid content, the amount of pressing isocyanato and hydroxylated material with the poly-vulcabond of hydrophilic modifying is than 0.8-1.6: 1 mixed, add an amount of thinner regulation system viscosity, stir by hand, film, after room temperature condition maintains 7 days down, survey paint film property.Wherein said poly-vulcabond is the poly-vulcabond of hydrophilic modifying, thinks the fertile chemical EC385 of company limited etc. as Bayhydur series, the Shanghai of Bayer Material Science; Described thinner is 1-Methoxy-2-propyl acetate (PMA), N-Methyl pyrrolidone environmentally friendly inert solvents such as (NMP).
Beneficial effect:
1. the present invention utilizes terpenic derivative terpinene maleic anhydride of natural reproducible resource (TMA) or hydrogenated terpinene maleic anhydride (HTMA) to react synthetic polyvalent alcohol product with terpinene maleic anhydride glycidyl ester type epoxy resin (TME) or the hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin (HTME) that epichlorohydrin reaction obtains with diethanolamine (DEA), micromolecular hydroxyl chainextender under catalyst action, obtain self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid in the water with directly being dispersed in after the acid neutralization, the equal size of Z is at 10-100nm.This manufacture method is easy, the manufacturing processed cleaning.Reaction process is solvent-free, and need not high-speed stirring and just can obtain stable self-emulsifying water dispersion.The hydroxyl value of polyol resin, second-order transition temperature is adjustable with kind, the consumption of small molecule chain extender.
2. the dual-component aqueous polyurethane polymer performance of the present invention's preparation is good, terpenyl epoxy resin is introduced the dual-component aqueous polyurethane system with water-based polyvalent alcohol form, low contaminative, the security of elasticity, snappiness and the water-based system of excellent properties such as its rigidity, thermotolerance, chemical resistant properties and urethane are organically combined, realize composite modified in water-based system of Resins, epoxy and urethane.
3. the used hydriding terpene-maleic anhydride glycidyl ester type epoxy resin (HTME) of the present invention contains unique saturated bridged ring structure, when giving paint film superior mechanical mechanical property, make paint film have excellent anti-ultraviolet, anti-yellowing property again, this is that common bisphenol A epoxide resin is not available.
4. the present invention provides new approach for utilizing the biomass renewable resources to prepare environment-friendly aqueous polymkeric substance.
Description of drawings
Fig. 1 is the infrared spectrogram of embodiment 1 gained polyvalent alcohol.
Fig. 2 is the size distribution figure of embodiment 5 gained polyalcohol water dispersoids.
Embodiment
In the three-necked bottle that thermometer, agitator, prolong are housed, add 48.8gTME respectively, 5.9g DEA, 14.3g Macrogol 200 and 0.976g zinc chloride, heated and stirred is reacted 7h down in 100 ℃; Reaction finishes postcooling to 70 ℃, with 3.2g acetate (being diluted in the 5.0g water) neutralized reaction product, uses the deionized water dispersed with stirring then, obtains yellow transparent shape polyalcohol water dispersoid, hydroxyl value 248mgg
-1(solid resin), viscosity 2.047Pas (25 ℃, 30% solid content), the equal particle diameter 35.4nm of Z, the infrared spectra of gained polyvalent alcohol is as shown in Figure 1.
Get the above-mentioned polyalcohol water dispersoid of 20.0g (30% solid content), add the poly-vulcabond EC385 and the 2.0gPMA of 9.6g hydrophilic modifying, mix the back and stir by hand, film, survey paint film property such as table 1 after 7 days in maintenance under the room temperature condition.
Embodiment 2
In the three-necked bottle that thermometer, agitator, prolong are housed, add 36.5gTME respectively, 4.4g DEA, 4.8g1, the 4-butyleneglycol, heated and stirred is even, adds the 0.3ml titanium tetrachloride in the time of 70 ℃, is warming up to continue reaction 3h about 105 ℃; Reaction finishes postcooling to 65 ℃, with 2.4g acetate (being diluted in the 5.0g water) neutralized reaction product, uses the deionized water dispersed with stirring then, obtains yellow transparent shape polyalcohol water dispersoid, hydroxyl value 288mgg
-1(solid resin), viscosity 2.451Pas (25 ℃, 30% solid content), the equal particle diameter 40.2nm of Z.
Get the above-mentioned polyalcohol water dispersoid of 20.0g (30% solid content), add the poly-vulcabond EC385 and the 2.0gPMA of 10.9g hydrophilic modifying, mix the back and stir by hand, film, survey paint film property such as table 1 after 7 days in maintenance under the room temperature condition.
Embodiment 3
In the three-necked bottle that thermometer, agitator, prolong are housed, add 35.1gTME respectively, 4.2g DEA, 5.5g glycol ether and 0.702g zinc chloride, heated and stirred is in 100 ℃ of reaction 7h reactions down; Finish postcooling to 70 ℃,, use the deionized water dispersed with stirring then, obtain yellow transparent shape polyalcohol water dispersoid, hydroxyl value 277mgg with 2.3g acetate (being diluted in the 5.0g water) neutralized reaction product
-1(solid resin), viscosity 2.221Pas (25 ℃, 30% solid content), the equal particle diameter 36.9nm of Z, the TME oxirane value is between the 0.32-0.39mol/100g.
Get the above-mentioned polyalcohol water dispersoid of 20.0g (30% solid content), add the poly-vulcabond EC385 and the 2.0gPMA of 10.6g hydrophilic modifying, mix the back and stir by hand, film, survey paint film property such as table 1 after 7 days in maintenance under the room temperature condition.
Embodiment 4
In the three-necked bottle that thermometer, agitator, prolong are housed, add 36.9gHTME respectively, 4.4g DEA, 4.9g1,4-butyleneglycol and 0.73g zinc chloride, heated and stirred is in 100 ℃ of reaction 6h reactions down; Finish postcooling to 80 ℃,, use the deionized water dispersed with stirring then, obtain yellow translucent polyalcohol water dispersoid, hydroxyl value 283mgg with 2.5g acetate (being diluted in the 5.0g water) neutralized reaction product
-1(solid resin), viscosity 2.530Pas (25 ℃, 30% solid content), the equal particle diameter 43.5nm of Z.
Get the above-mentioned polyalcohol water dispersoid of 20.0g (30% solid content), add the poly-vulcabond EC385 and the 2.0gPMA of 10.8g hydrophilic modifying, mix the back and stir by hand, film, survey paint film property such as table 1 after 7 days in maintenance under the room temperature condition.
In the three-necked bottle that thermometer, agitator, prolong are housed, add 34.0gHTME respectively, 4.1g DEA, 10g Macrogol 200 and 0.680g zinc chloride, heated and stirred is in 100 ℃ of reaction 7h reactions down; Finish postcooling to 70 ℃,, use the deionized water dispersed with stirring then, obtain yellow transparent shape polyalcohol water dispersoid, hydroxyl value 244mgg with 2.3g acetate (being diluted in the 5.0g water) neutralized reaction product
-1(solid resin), viscosity 2.108Pas (25 ℃, 30% solid content), the equal particle diameter 32.3nm of Z, Fig. 2 is the size distribution figure of gained polyalcohol water dispersoid.
Get the above-mentioned polyalcohol water dispersoid of 20.0g (30% solid content), add the poly-vulcabond EC385 and the 2.0gPMA of 9.5g hydrophilic modifying, mix the back and stir by hand, film, survey paint film property such as table 1 after 7 days in maintenance under the room temperature condition.
Embodiment 6
In the three-necked bottle that thermometer, agitator, prolong are housed, add 45.9gHTME respectively, 5.5g DEA, 7.2g glycol ether and 0.918g zinc chloride, heated and stirred is in 100 ℃ of reaction 7h reactions down; Finish postcooling to 75 ℃,, use the deionized water dispersed with stirring then, obtain yellow transparent shape polyalcohol water dispersoid, hydroxyl value 269mgg with 3.1g acetate (being diluted in the 5.0g water) neutralized reaction product
-1(solid resin), viscosity 2.334Pas (25 ℃, 30% solid content), the equal particle diameter 38.7nm of Z.
Get the above-mentioned polyalcohol water dispersoid of 20.0g (30% solid content), add the poly-vulcabond EC385 and the 2.0gPMA of 10.3g hydrophilic modifying, mix the back and stir by hand, film, survey paint film property such as table 1 after 7 days in maintenance under the room temperature condition.
Annotate: EC385 is the aliphatic polymeric isocyanate of hydrophilic modifying, solid content 85%wt, NCO content 14%wt, viscosity 300-800mPas.
The performance of paint film among each embodiment of table 1
Annotate: measure the drying varniss time by standard GB 1728-89; Measure the paint film impact resistance by standard GB 1732-93; Measure paint film adhesion by standard GB 1720-93; Measure paint film flexibility by standard GB1731-93; Measure the paint film pencil hardness by standard GB 6739-96; Measure the gloss of film degree by standard GB 9754-88; Press HG/T 3828-2006 and survey paint film water tolerance, stain resistance, resistance to blocking, alkali resistance, alcohol resistance.
Claims (8)
1. the preparation method of a cationic terpenyl epoxy resin polyalcohol water dispersoid, it is characterized in that, react under the lewis acid catalyst effect with terpenyl epoxy resin and diethanolamine, micromolecular hydroxyl chainextender, the product that makes directly is dispersed in the water after neutralizing with acid, obtain stable transparent or semitransparent self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid, the hydroxyl value of self-emulsifying cation type terpenyl epoxy resin polyalcohol is 180-320mg/g, and the equal size of the Z of water dispersion is 10-100nm.
2. the preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid as claimed in claim 1, it is characterized in that, described terpenyl epoxy resin is terpinene maleic anhydride glycidyl ester type epoxy resin or hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin, and oxirane value is 0.32-0.39mol/100g.
3. the preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid as claimed in claim 1 is characterized in that, the consumption of diethanolamine is 10～12% of a terpenyl epoxy resin quality.
4. the preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid as claimed in claim 1, it is characterized in that, the micromolecular hydroxyl chainextender is 1,4-butyleneglycol, glycol ether, number-average molecular weight are any one in the polyoxyethylene glycol of 200-400, and consumption is 0.5 times-1 times of amount of substance of terpenyl epoxy resin.
5. the preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid as claimed in claim 1, it is characterized in that, described lewis acid catalyst is any one in zinc chloride, boron trifluoride, the titanium tetrachloride, and add-on is the 1%-4% of Resins, epoxy quality.
6. the preparation method of self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid as claimed in claim 1 is characterized in that, described temperature of reaction is 90-120 ℃, and the reaction times is 3-10h.
7. the preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid as claimed in claim 1 is characterized in that, the used acid that neutralizes is any one in formic acid, acetate, the hydrochloric acid, and degree of neutralization is 60-100%.
8. the application of the self-emulsifying cation type terpenyl epoxy resin polyalcohol water dispersoid of the preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid as claimed in claim 1 preparation in preparation waterborne two-component polyurethane coating, tackiness agent and polymer materials.
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