CN101418067B - Water dispersive polyisocyanate curing agent and preparation method thereof - Google Patents
Water dispersive polyisocyanate curing agent and preparation method thereof Download PDFInfo
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- CN101418067B CN101418067B CN 200810227818 CN200810227818A CN101418067B CN 101418067 B CN101418067 B CN 101418067B CN 200810227818 CN200810227818 CN 200810227818 CN 200810227818 A CN200810227818 A CN 200810227818A CN 101418067 B CN101418067 B CN 101418067B
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- curing agent
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Abstract
The invention relates to a water-dispersible polyisocyanate curing agent. The curing agent is the polyisocyanate which takes 2 to 30 weight portions of hydroxyl cyclic ether compound, 100 weight portions of polyisocyanate counted as solids and less than or equal to 30 weight portions of cosolvent as raw materials, is obtained through heating reaction and combined with the hydroxyl cyclic ether compound. The structural formula of the hydroxyl cyclic ether compound is as above, wherein R1, R2 and R3 are the alkyl of H, OH or C1 to C10 and one of the alkoxy of C1 to C10; the R1, the R2 and the R3 are the same or different; and at most two OH bases are provided. During preparation, the polyisocyanate is first added and subjected to vacuum-pumping at a temperature between 100 and 150 DEG C; after solvents in the polyisocyanate are removed, the cosolvent is added and the temperature is regulated to be between 60 and 90 DEG C; the hydroxyl cyclic ether compound is added between 1 and 3 hours; after heat is preserved for 3 to 6 hours, the materials are cooled and packaged so as to prepare the curing agent. When the curing agent is used for waterborne two-component anticorrosive coating, the anticorrosive property of a coating film is obviously improved.
Description
Technical field
The present invention relates to a kind of water dispersive polyisocyanate curing agent and preparation method thereof, be particularly suitable as the solidifying agent of aqueous dual-component anticorrosive coating.
Background technology
Two big classes of solvent-borne type anticorrosive coating and watery anti-corrosion paint are arranged in the anticorrosive coating field, wherein the development of solvent-borne type anticorrosive coating is very ripe, watery anti-corrosion paint then just became a research focus in recent years, and its over-all properties especially Corrosion Protection can't be mentioned in the same breath with the solvent-borne type anticorrosive coating.But increasingly serious along with increasing the weight of of polluting of world environments and petroleum resources situation, the environmental regulation of various countries is put into effect in succession, and the Water-borne modification of coating is extremely urgent.Aspect watery anti-corrosion paint, hydroxy acrylate emulsion and the water dispersible supporting system of isocyanic ester are one of research direction.Owing to contain hydrophilic small molecules such as emulsifying agent, pH regulator agent in the ordinary emulsion, and isocyanic ester also has hydrophilic radical, and therefore the non-corrosibility and the solvent reducible coatings of the same type of this watery anti-corrosion paint still have certain gap.Though grafting Resins, epoxy or bound phosphate groups improve to non-corrosibility on hydroxy acrylate, but because often there is extremely significantly influence in the grafting amount to stability of emulsion when big, so the grafting amount is often very little, raising degree to Corrosion Protection is limited like this, sometimes even not clear existing showing.And then influenced applying of watery anti-corrosion paint.
Summary of the invention
First purpose of the present invention is: a kind of water dispersive polyisocyanate curing agent is provided, and the non-corrosibility of filming with the aqueous dual-component anticorrosive coating of its preparation is improved.
The technical scheme that realizes first purpose of the present invention is: a kind of water dispersive polyisocyanate curing agent, its characteristics are, it is with 2～30 weight part hydroxyl cyclic ether compounds, in 100 weight part polyisocyanates of solid and≤30 weight part solubility promoters is raw material, obtain through reacting by heating with hydroxyl cyclic ether compounds bonded polyisocyanates;
The structural formula of described hydroxyl cyclic ether compounds is as follows:
Wherein: R1, R2, R3 are a kind of in the alkoxyl group of alkyl, C1～C10 of H, OH, C1～C10, and R1, R2, R3 are identical or different, and the OH base mostly is two most.
Above-mentioned water dispersive polyisocyanate curing agent, its described course that combines with hydroxyl cyclic ether compounds bonded polyisocyanates is: when hydroxyl cyclic ether compounds and polyisocyanates reacting by heating, first oxygen by its hydroxyl carries out nucleophilic reaction with the carbon atom of isocyanato and combines, the hydrogen of its hydroxyl is attracted by the oxygen of isocyanato simultaneously, hydrogen through the rearrangement reaction hydroxyl combines the formation ammonia ester bond with the nitrogen of isocyanato at last, thereby the hydroxyl cyclic ether compounds is combined with polyisocyanates.Be expressed as follows (wherein R ' OH representation hydroxy cyclic ether compounds) with chemical equation:
Above-mentioned water dispersive polyisocyanate curing agent, its described polyisocyanates are at least a in aliphatic polyisocyante, the aromatic polyisocyanate.
Above-mentioned water dispersive polyisocyanate curing agent, described aliphatic polyisocyante is 1, hexamethylene-diisocyanate dimer, 1, hexamethylene-diisocyanate tripolymer, isophorone diisocyanate dimer, isophorone diisocyanate trimer, at least a in hexamethylene diisocyanate/isophorone diisocyanate mixing dimer, the hexamethylene diisocyanate/isophorone diisocyanate mixed trimer; Described aromatic polyisocyanate is 4, at least a in 4-'-diphenylmethane diisocyanate, poly methylene poly phenyl poly isocyanate, the toluene diisocyanate trimer.
Above-mentioned water dispersive polyisocyanate curing agent, its described solubility promoter is acetone, butanone, N-BUTYL ACETATE, vinyl acetic monomer, N-Methyl pyrrolidone, N, at least a in dinethylformamide, N,N-dimethylacetamide, methyl ethyl diketone, 1-Methoxy-2-propyl acetate, the ethylene glycol ether acetate.
Second purpose of the present invention is: a kind of method for preparing above-mentioned water dispersive polyisocyanate curing agent is provided, and simple to operate, constant product quality.
The technical scheme that realizes second purpose of the present invention is: a kind of method for preparing above-mentioned water dispersive polyisocyanate curing agent, its characteristics are, in reaction vessel, add 100 weight part polyisocyanates in solid, be warmed up to 100～150 ℃, under the vacuum tightness of 0.05～0.1MPa, vacuumized 1～3 hour, after extracting the solvent that contains in the polyisocyanates, add≤30 weight part solubility promoters and attemperation to 60～90 ℃, add 2～30 weight part hydroxyl cyclic ether compounds then, added at 1～3 hour, be incubated after 3～6 hours, cooling, packing promptly makes the water dispersive polyisocyanate curing agent product.
Among the preparation method of above-mentioned water dispersive polyisocyanate curing agent, the structural formula of described hydroxyl cyclic ether compounds is as follows:
Wherein: R1, R2, R3 are a kind of in the alkoxyl group of alkyl, C1～C10 of H, OH, C1～C10, and R1, R2, R3 are identical or different, and the OH base mostly is two most.
Among the preparation method of above-mentioned water dispersive polyisocyanate curing agent, described polyisocyanates is at least a in aliphatic polyisocyante, the aromatic polyisocyanate.
Among the preparation method of above-mentioned water dispersive polyisocyanate curing agent, described solubility promoter is acetone, butanone, N-BUTYL ACETATE, vinyl acetic monomer, N-Methyl pyrrolidone, N, at least a in dinethylformamide, N,N-dimethylacetamide, methyl ethyl diketone, 1-Methoxy-2-propyl acetate, the ethylene glycol ether acetate.
Technique effect of the present invention is: because in the technical solution of the present invention, in polyisocyanates, combine an amount of hydroxyl cyclic ether compounds, like this, not only make the polyisocyanates possess hydrophilic property become the polyisocyanates that can be used for water-borne coatings, and its hydroxyl cyclic ether compounds can form inner complex with metal substrate, thereby make the substrate surface passivation, therefore, even use existing commercially available Hydroxylated acrylic resin emulsion preparation aqueous dual-component anticorrosive coating, its Corrosion Protection of filming also can be improved (seeing Table 2).
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
Embodiment 1～4 preparation water dispersive polyisocyanate curing agent
(1) prescription sees Table 1 (consumption is weight part)
Table 1
| Component | Material name | Consumption embodiment 1 | Consumption embodiment 2 | Consumption embodiment 3 | Consumption embodiment 4 |
| Polyisocyanates | N75, solid part 70 weight %N3390, solids constituent 90 weight % | 142.86/ | 142.86/ | /111.11 | /111，11 |
| The hydroxyl cyclic ether compounds | Alpha-hydroxy ring butyl ether Alpha-hydroxy, Beta-methyl ring butyl ether | 5.0/ | 15.0/ | /5.0 | /15.0 |
| Solubility promoter | N-Methyl pyrrolidone | 11.67 | 5.0 | 11.67 | 5.0 |
In the table 1:
N75 is the dimeric product grade of hexamethylene diisocyanate that Bayer company produces;
N3390 is the trimerical product grade of hexamethylene diisocyanate that Bayer company produces;
α-hydroxyl ring butyl ether and Alpha-hydroxy, Beta-methyl ring butyl ether is commercially available product;
N-Methyl pyrrolidone is the coating commercially available product;
(2) preparation method
Press table 1 prescription, in reaction vessel, add polyisocyanates and be warmed up to 140 ℃, under the vacuum tightness of 0.08Mpa, vacuumized 1 hour, after extracting the solvent that contains in the polyisocyanates, add solubility promoter and attemperation to 80 ℃, add the hydroxyl cyclic ether compounds then, added at 2 hours, be incubated after 4 hours cooling, packing promptly makes water dispersive polyisocyanate curing agent product A of the present invention (the isocyanate group mass contg is 17.8%) respectively, solidifying agent product B (the isocyanate group mass contg is 12.64%), solidifying agent products C (the isocyanate group mass contg is 16.25%) and solidifying agent product D (the isocyanate group mass contg is 11.88%).
Embodiment 5 preparation aqueous dual-component anticorrosive coating A
(1) preparation slurry
Get iron oxide red 24 weight parts; Zinc phosphate 15 weight parts; Mica powder 15 weight parts; Kaolin 16 weight parts; Deionized water 30 weight parts; Water soluble dispersing agent 270 0.7 weight parts.Said components is mixed the back evenly, be ground to fineness below 50 microns, preserve standby with sand mill;
(2) preparation coating
The solidifying agent product A that first component: embodiment 1 makes;
Second component: above-mentioned slurry is mixed than 100:82 by weight with hydroxy acrylate emulsion VPLS2227/1, add thickening material Tego3000 (its dosage be coating total weight parts 0.6%) and defoamer Tego902W (its dosage be coating total weight parts 0.2%) again, stirring is the second component;
Before the construction, component first component is mixed than 1:9.0 by weight with the second component, stirring obtains aqueous dual-component anticorrosive coating A.
Embodiment 6 preparation aqueous dual-component anticorrosive coating B
(1) the preparation slurry is identical with embodiment 5;
(2) preparation coating
The solidifying agent product B that first component: embodiment 2 makes;
Second component: above-mentioned slurry is mixed than 100:70 by weight with hydroxy acrylate emulsion VPLS2227/1, add thickening material Tego3000 (its dosage be coating total weight parts 0.6%) and defoamer Tego902W (its dosage be coating total weight parts 0.2%) again, stirring is the second component;
Before the construction, the first component is mixed than 1:6.9 by weight with the second component, stirring obtains aqueous dual-component anticorrosive coating B.
Embodiment 7 preparation aqueous dual-component anticorrosive coating C
(1) the preparation slurry is identical with embodiment 5;
(2) preparation coating
The solidifying agent products C that first component: embodiment 3 makes;
Second component: above-mentioned slurry is mixed than 100:79.5 by weight with hydroxy acrylate emulsion VPLS2227/1, add thickening material Tego3000 (its dosage be coating total weight parts 0.6%) and defoamer Tego902W (its dosage be coating total weight parts 0.2%) again, stirring is the second component;
Before the construction, the first component is mixed than 1:8.0 by weight with the second component, stirring obtains aqueous dual-component anticorrosive coating C.
Embodiment 8 preparation aqueous dual-component anticorrosive coating D
(1) the preparation slurry is identical with embodiment 5;
(2) preparation coating
The solidifying agent product D that first component: embodiment 4 makes;
Second component: above-mentioned slurry is mixed than 100:68.0 by weight with hydroxy acrylate emulsion VPLS2227/1, add thickening material Tego3000 (its dosage be coating total weight parts 0.6%) and defoamer Tego902W (its dosage be coating total weight parts 0.2%) again, stirring is the second component;
Before the construction, the first component is mixed than 1:6.2 by weight with the second component, stirring obtains aqueous dual-component anticorrosive coating D.
Comparative example: preparation comparative example aqueous dual-component anticorrosive coating
(1) the preparation slurry is identical with embodiment 5;
(2) preparation comparative example coating
The first component: water dispersive polyisocyanate curing agent is commercially available product Bayhydur3100 (the isocyanate group mass contg is 17.4% for German Bayer company product, solids content 100%);
Second component: above-mentioned slurry is mixed than 100:78.3 by weight with hydroxy acrylate emulsion VPLS2227/1, add again thickening material Tego3000 (for the coating total weight parts 0.6%) and defoamer Tego902W (be coating total weight parts 0.2%), stirring is the second component;
Before the construction, the first component is mixed than 1:9.0 by weight with the second component, stirring obtains comparative example aqueous dual-component anticorrosive coating.
In the foregoing description 5～8 and the comparative example, preparation used pigment of slurry and filler are the coating commercially available product; Used water soluble dispersing agent 270 is sky, a Changzhou justice chemical industry company limited product; Thickening material Tego3000 is a German degussa company product; Defoamer Tego902W is a German degussa company product; Hydroxy acrylate emulsion VPLS2227/1 is German Bayer company's product (solids content is 41%, and for solid, hydroxy radical content is 3.8%); Used water dispersive polyisocyanate curing agent Bayhydur 3100 is German Bayer company's product (solids content 100%, isocyanate group mass contg are 17.4%) in the Comparative Examples.
Adopt coatings industry concerned countries standard, the film performance of above-mentioned coating is detected, its result is as shown in table 2.
Table 2
| Test item | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example |
| Sticking power is drawn the circle method, level | 1 | 1 | 1 | 1 | 1 |
| Impact cm | 50 | 50 | 50 | 50 | 50 |
| Snappiness, mm | 1 | 1 | 1 | 1 | 1 |
| Water-fast, d | >60 | >60 | >60 | >60 | 40 |
| Salt water resistance, d | 31 | 35 | 35 | 34 | 20 |
| Salt spray resistance, d | 26 | 28 | 29 | 27 | 16 |
As seen from Table 2, with same hydroxy acrylate emulsion (for example, when hydroxy acrylate emulsion VPLS2227/1) preparing the aqueous dual-component anticorrosive coating, use the present invention and hydroxyl cyclic ether compounds bonded polyisocyanates (for example to make solidifying agent, the solidifying agent product A of embodiment 1～4～D), even if in hydroxy acrylate emulsion VPLS2227/1, do not contain epoxy group(ing) or phosphate-based, its Corrosion Protection of filming also obviously is better than with existing water dispersive polyisocyanate curing agent (for example, Bayhydur3100) filming of institute's coatings formulated (comparative example coating).
Claims (9)
1. water dispersive polyisocyanate curing agent, it is characterized in that, it is with 2～30 weight part hydroxyl cyclic ether compounds, is raw material in 100 weight part polyisocyanates of solid and≤30 weight part solubility promoters, obtain through reacting by heating with hydroxyl cyclic ether compounds bonded polyisocyanates;
The structural formula of described hydroxyl cyclic ether compounds is as follows:
Wherein: R1, R2, R3 are a kind of in the alkoxyl group of alkyl, C1～C10 of H, OH, C1～C10, and R1, R2, R3 are identical or different, and the OH base mostly is two most.
2. water dispersive polyisocyanate curing agent according to claim 1 is characterized in that, described polyisocyanates is at least a in aliphatic polyisocyante, the aromatic polyisocyanate.
3. water dispersive polyisocyanate curing agent according to claim 2, it is characterized in that, described aliphatic polyisocyante is 1, hexamethylene-diisocyanate dimer, 1, hexamethylene-diisocyanate tripolymer, isophorone diisocyanate dimer, isophorone diisocyanate trimer, 1, at least a in hexamethylene-diisocyanate/isophorone diisocyanate mixing dimer, the hexamethylene diisocyanate/isophorone diisocyanate mixed trimer.
4. water dispersive polyisocyanate curing agent according to claim 2, it is characterized in that, described aromatic polyisocyanate is 4, at least a in 4-'-diphenylmethane diisocyanate, poly methylene poly phenyl poly isocyanate, the toluene diisocyanate trimer.
5. water dispersive polyisocyanate curing agent according to claim 1, it is characterized in that, described solubility promoter is acetone, butanone, N-BUTYL ACETATE, vinyl acetic monomer, N-Methyl pyrrolidone, N, at least a in dinethylformamide, N,N-dimethylacetamide, methyl ethyl diketone, 1-Methoxy-2-propyl acetate, the ethylene glycol ether acetate.
6. method for preparing the described water dispersive polyisocyanate curing agent of claim 1, it is characterized in that, in reaction vessel, add 100 weight part polyisocyanates in solid, be warmed up to 100～150 ℃, under the vacuum tightness of 0.05～0.1MPa, vacuumized 1～3 hour, after extracting the solvent that contains in the polyisocyanates, add≤30 weight part solubility promoters and attemperation to 60～90 ℃, add 2～30 weight part hydroxyl cyclic ether compounds then, added at 1～3 hour, be incubated after 3～6 hours, cooling, packing promptly makes the water dispersive polyisocyanate curing agent product.
7. the preparation method of water dispersive polyisocyanate curing agent according to claim 6 is characterized in that, the structural formula of described hydroxyl cyclic ether compounds is as follows:
Wherein: R1, R2, R3 are a kind of in the alkoxyl group of alkyl, C1～C10 of H, OH, C1～C10, and R1, R2, R3 are identical or different, and the OH base mostly is two most.
8. the preparation method of water dispersive polyisocyanate curing agent according to claim 6 is characterized in that, described polyisocyanates is at least a in aliphatic polyisocyante, the aromatic polyisocyanate.
9. the preparation method of water dispersive polyisocyanate curing agent according to claim 6, it is characterized in that, described solubility promoter is acetone, butanone, N-BUTYL ACETATE, vinyl acetic monomer, N-Methyl pyrrolidone, N, at least a in dinethylformamide, N,N-dimethylacetamide, methyl ethyl diketone, 1-Methoxy-2-propyl acetate, the ethylene glycol ether acetate.
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| CN102936330A (en) * | 2012-11-19 | 2013-02-20 | 李莲 | Production process for water dispersible polyisocyanate cross-linking agents containing phosphate-radical functional groups |
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