CN115746658B - Polyurethane and inorganic salt double modified epoxy emulsion and preparation method thereof - Google Patents
Polyurethane and inorganic salt double modified epoxy emulsion and preparation method thereof Download PDFInfo
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- CN115746658B CN115746658B CN202211363746.XA CN202211363746A CN115746658B CN 115746658 B CN115746658 B CN 115746658B CN 202211363746 A CN202211363746 A CN 202211363746A CN 115746658 B CN115746658 B CN 115746658B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 119
- 239000004593 Epoxy Substances 0.000 title claims abstract description 105
- 239000004814 polyurethane Substances 0.000 title claims abstract description 57
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 57
- 229910017053 inorganic salt Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000004945 emulsification Methods 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 9
- 239000006184 cosolvent Substances 0.000 claims abstract description 9
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 238000010008 shearing Methods 0.000 claims description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 238000009396 hybridization Methods 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- -1 TDI Chemical compound 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000003595 mist Substances 0.000 abstract 1
- 239000003995 emulsifying agent Substances 0.000 description 33
- 239000007787 solid Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000007385 chemical modification Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a polyurethane and inorganic salt double modified epoxy emulsion and a preparation method thereof. The polyurethane and inorganic salt double modified epoxy emulsion is prepared from the following raw materials in parts by weight: 50-70 parts of first epoxy resin; 0.01-0.04 part of catalyst, 80-100 parts of second epoxy resin, 5-9 parts of isocyanate, 12-17 parts of nonionic emulsifier, 3-7 parts of anionic emulsifier, 5-15 parts of cosolvent, 5-10 parts of silicate solution and 100-130 parts of water. The polyurethane and inorganic salt double modified epoxy emulsion has the advantages of good salt mist resistance, acid and alkali resistance, flexibility and the like, and the preparation process of the polyurethane and inorganic salt double modified epoxy emulsion is simple.
Description
Technical Field
The invention relates to an epoxy emulsion, in particular to a polyurethane and inorganic salt double modified epoxy emulsion and a preparation method thereof.
Background
With the development of paint science and technology and the new ideas and legal consciousness of people, the environmental protection is increasingly required. The organic solvent volatilized from the traditional solvent-based paint brings serious adverse effects to the atmosphere pollution and the human health, so the organic solvent-based paint develops to the low VOC, high efficiency, energy conservation and ecological direction, and research and development of the environment-friendly high-performance paint become the consensus of the paint industry and are the inevitable way of the development of the paint industry.
Epoxy resins have been widely used in military, civil, industrial maintenance, etc. due to their excellent properties such as good adhesion, good chemical resistance, excellent solvent resistance, high hardness, good abrasion resistance, etc. In particular, in coating applications, 40% of the epoxy resins currently used in coatings worldwide. The epoxy resin is insoluble in water and can not be emulsified by directly adding water, and the epoxy resin is prepared by introducing hydrophilic chain segments into molecular chains or adding hydrophilic components, and the preparation of the epoxy resin into emulsion is a technical path with the highest application value.
The epoxy resin is waterborne by the following three methods: mechanical, reverse and chemical modification. The mechanical method is also called as a direct emulsification method, which refers to a method that after the epoxy resin is ground in a ball mill, an aqueous solution of an emulsifier is added, and particles are uniformly dispersed in water through mechanical stirring, and the direct emulsification method has low cost and simple preparation process, but the prepared aqueous epoxy resin dispersion system has poor stability and larger size of dispersed phase particles. The reverse conversion method refers to the process of mutual conversion under certain conditions in continuous Fengshi in a multi-component system, almost all polymer resins can be used for preparing corresponding emulsion by means of the action of an external emulsifier and a physical emulsification method, but the disadvantage is that the stability of the emulsion is poor, the water-based epoxy curing agent, the filler and various auxiliary agents have great influence on the water-based epoxy curing agent, the filler and various auxiliary agents when being matched for use, and the existence of the external emulsifier has a certain influence on the coating performance. The self-emulsifying method is a chemical modification method, the size of disperse phase particles in the aqueous epoxy resin emulsion prepared by the chemical modification method is very small, about tens to hundreds of nanometers, and the chemical modification epoxy resin contains hydrophilic polar groups which can help the epoxy resin disperse in water, so that the modified resin has hydrophilic and hydrophilic amphiphilic properties, and thus has the function of a surfactant. When the modified polymer is emulsified with water, the hydrophobic polymer molecular chains are aggregated into particles, so that stable aqueous epoxy resin emulsion can be formed.
For example, patent CN101445583a discloses a preparation process of polyurethane modified epoxy resin suitable for use in composite wear-resistant coating materials, which adopts polyurethane modified solvent type epoxy resin, and the prepared paint film has excellent characteristics by introducing polyurethane prepolymer into the epoxy resin. However, the research is only improvement in the aspect of paint performance, and the product does not accord with the development trend of the paint industry at home and abroad, and cannot meet the requirements of low pollution or no pollution. In the field of water-based paint, epoxy resin modified water-based polyurethane is reported, and in order to make the water-based polyurethane system more suitable for the development requirement of paint industry, the branching points are introduced into the main chain of polyurethane to form a part of net structure by utilizing the advantages of high modulus, high strength, good chemical resistance and the like of epoxy resin. For example, articles ("development of waterborne epoxy modified polyurethane coatings" Xu Gewen et al, coatings industry 1998:3032) and articles ("Research of amine modification of expoxidizedpolybutadiene,Zhao Gongda,CHINA SYNTHETIC RUBBER INDUSTRY,2003：117118); reports of polyurethane modified waterborne epoxy resins, for example, articles ("waterborne polyurethane modified epoxy curing agent", liu Hanjie et al, coatings industry, volume 34, stage 2, 2003-11-09) improve the coating properties of epoxy resins by modifying the epoxy resin with polyurethane.
In summary, both the waterborne epoxy resin and the polyurethane modified epoxy resin are feasible, but no patent is known for preparing the polyurethane modified, emulsified and nano waterborne epoxy emulsion at present, and the inorganic salt modified epoxy emulsion is not mentioned. The invention organically combines the emulsification of epoxy resin, the modification of waterborne epoxy resin by polyurethane, the modification of epoxy emulsion by inorganic salt and the nanocrystallization of epoxy resin together, and provides a preparation method of the dual modification of waterborne epoxy emulsion by polyurethane and inorganic salt.
Disclosure of Invention
The invention aims to provide polyurethane and inorganic salt double-modified epoxy emulsion and a preparation method thereof. The polyurethane and inorganic salt double modified epoxy emulsion has the advantages of good salt fog resistance, acid and alkali resistance, flexibility and the like.
In order to solve the defects in the prior art, the technical scheme adopted by the invention is as follows:
the invention provides polyurethane and inorganic salt double modified epoxy emulsion which is prepared from the following raw materials in parts by weight:
50-70 parts of first epoxy resin; 0.01-0.04 part of catalyst, 80-100 parts of second epoxy resin, 5-9 parts of isocyanate, 12-17 parts of nonionic emulsifier, 3-7 parts of anionic emulsifier, 5-15 parts of cosolvent, 5-10 parts of silicate solution and 100-130 parts of water.
Preferably, the polyurethane and inorganic salt double modified epoxy emulsion is prepared from the following raw materials in parts by weight:
55-65 parts of first epoxy resin, 0.01-0.04 part of catalyst, 87-95 parts of second epoxy resin, 5-8 parts of isocyanate, 13-15 parts of nonionic emulsifier, 4-7 parts of anionic emulsifier, 8-15 parts of cosolvent, 6-8 parts of silicate solution and 110-120 parts of water
Further, the polyurethane and inorganic salt double modified epoxy emulsion is characterized in that the first epoxy resin consists of one or more of E51, E44 and E31.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is characterized in that the second epoxy resin consists of one or a mixture of more of E20, E12 and E06.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is prepared from one or more of IPDI, TDI, MDI.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is characterized in that the nonionic emulsifier is composed of one or a mixture of a plurality of polyether type, polyester type and polyurethane type.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is characterized in that the anionic emulsifier is composed of one or a mixture of more of sulfonate, hydroxy acid salt and sulfate.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is characterized in that the silicate solution consists of one or a mixture of more of potassium silicate, lithium silicate and calcium silicate.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is prepared by using dibutyltin dilaurate as a catalyst; the co-solvent consists of one or more mixtures of PM, DPNB, BCS, DBE.
The second aspect of the invention provides a preparation method of the polyurethane and inorganic salt double modified epoxy emulsion, which comprises the following steps:
s1, adding a first epoxy resin, a catalyst and isocyanate into a four-neck flask with a condenser pipe according to parts by weight, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h;
s2, adding a second epoxy resin and a cosolvent into the four-necked flask while stirring, keeping the temperature at 80 ℃, and mixing for 0.5h;
s3, adding a nonionic emulsifier and an anionic emulsifier into the four-necked flask while stirring, and keeping the temperature at 80 ℃ and stirring for 2 hours;
S4, removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. Obtaining epoxy emulsion;
s5, adding silicate into the epoxy emulsion under the stirring state, heating to 60 ℃, and carrying out hybridization reaction for 2 hours to prepare the double modified epoxy emulsion.
Compared with the prior art, the invention has the following advantages:
The beneficial effects of the invention are as follows: the polyurethane and inorganic salt double modified epoxy emulsion has the advantages of good salt spray resistance, acid and alkali resistance, flexibility and the like, and the salt spray resistance can reach more than 1500 hours and the flexibility can reach 1mm under the coating thickness of 60 mu m, so that the salt spray resistance is difficult to reach under the condition of single polyurethane modification. The polyurethane and inorganic salt double-modified epoxy emulsion has simple preparation process, relatively mild temperature in the preparation process and no need of excessive adjustment of the production equipment of the prior unmodified emulsion in the subsequent production process.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way.
Unless otherwise indicated, the reagents, methods and apparatus employed in the examples which follow are conventional in the art.
Reagents and materials used in the following examples were obtained from commercial sources unless otherwise specified.
Example 1
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
the E51-55g, the catalyst 0.01g and the IPDI-6g are added into a four-neck flask with a condensing tube, mixed for 15min at 60 ℃, slowly heated to 80 ℃ and reacted for 2h.
While stirring, E12-94g and PM-8g were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5h.
13G of polyether emulsifier and 4g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
While stirring, 6g of lithium silicate was added to the epoxy emulsion, the temperature was raised to 60℃and the hybridization was carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 2
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
Adding 51-60g of E, 0.02g of catalyst and 5g of IPDI into a four-neck flask with a condensing tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, 12-90g of E and 11g of PM were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5h.
14G of polyether emulsifier and 5g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
Under stirring, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 3
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
The E31-64g, the catalyst 0.04g and the IPDI-8g are added into a four-neck flask with a condensing tube, mixed for 15min at 60 ℃, slowly heated to 80 ℃ and reacted for 2h.
While stirring, 12-94g of E and 14g of PM were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
15G of polyether emulsifier and 7g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
Under stirring, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 4
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
31 g to 60g of E, 0.04g of catalyst and 7.9g of MDI are added into a four-neck flask with a condensing tube, mixed at 60 ℃ for 15 min, slowly heated to 80 ℃ and reacted for 2 hours.
While stirring, 20-87g of E and 5g of DPNB were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
14G of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
7G of potassium silicate is added into the epoxy emulsion under stirring, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 5
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
The E31-65g, the catalyst 0.04g and the IPDI-8g are added into a four-neck flask with a condensing tube, mixed for 15min at 60 ℃, slowly heated to 80 ℃ and reacted for 2h.
While stirring, 12-90g of E and 9g of DBE were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5h.
14G of polyether emulsifier and 4g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
While stirring, 6g of lithium silicate was added to the epoxy emulsion, the temperature was raised to 60℃and the hybridization was carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 6
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
adding 51-60g of E, 0.04g of catalyst and 8g of MDI into a four-neck flask with a condensing tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, 20-87g of E and 15g of PM were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
14G of polyether emulsifier and 5g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
Under stirring, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 7
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
31 g to 70g of E, 0.03g of catalyst and 9g of MDI are added into a four-neck flask with a condensing tube, mixed for 15min at 60 ℃, slowly heated to 80 ℃ and reacted for 2h.
While stirring, 12-80g of E and 9g of DPNB were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
12G of polyester emulsifier and 3g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
While stirring, 5g of lithium silicate was added to the epoxy emulsion, the temperature was raised to 60℃and the hybridization was carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 8
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
The E51-59g, the catalyst 0.04g and the IPDI-7g are added into a four-neck flask with a condensing tube, mixed for 15min at 60 ℃, slowly heated to 80 ℃ and reacted for 2h.
While stirring, 12-90g of E and 5g of DBE were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5h.
13G of polyether emulsifier and 7g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
10G of potassium silicate is added into the epoxy emulsion under stirring, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 9
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
31 g to 60g of E, 0.04g of catalyst and 7.5g of IPDI are added into a four-neck flask with a condenser, mixed at 60 ℃ for 15 min, slowly heated to 80 ℃ and reacted for 2 hours.
While stirring, 20-95g of E and 10g of PM were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
17G of polyether emulsifier and 3g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
While stirring, 9g of lithium silicate was added to the epoxy emulsion, the temperature was raised to 60℃and the hybridization was carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 10
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
The E51-62g, the catalyst 0.04g and the IPDI-7.4g are added into a four-neck flask with a condenser, mixed at 60 ℃ for 15 min, slowly heated to 80 ℃ and reacted for 2 hours.
While stirring, 12-91g of E and 10g of DPNB were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
14.8G of polyester emulsifier and 6.7g of sulfonate emulsifier were added to the four-necked flask while stirring, and the mixture was stirred at 80℃for 2 hours.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
8G of potassium silicate is added into the epoxy emulsion under stirring, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 11
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
adding 51-60g of E, 0.03g of catalyst and 9g of IPDI into a four-neck flask with a condensing tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, 12-95g of E and 9g of DBE were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
15G of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
While stirring, 10g of lithium silicate was added to the epoxy emulsion, the temperature was raised to 60℃and the hybridization was carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Example 12
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
E51-64.5g, catalyst 0.04g and IPDI-7.4g are added into a four-neck flask with a condenser, mixed for 15min at 60 ℃, slowly heated to 80 ℃ and reacted for 2h.
While stirring, 12-100g of E and 10g of PM were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5h.
17G of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
Under stirring, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2 hours.
The double modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Comparative example 1
Adding the 51-64.5g, the 12-95g and the PM-10g of E into a four-neck flask with a condenser, mixing for 15min at 60 ℃, adding 16g of polyether emulsifier and 6g of sulfonate emulsifier while stirring, slowly heating to 80 ℃, and stirring for 2h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
The emulsion had a solids content of 60%.
Comparative example 2
E51-64.5g, catalyst 0.04g and IPDI-7.4g are added into a four-neck flask with a condenser, mixed for 15min at 60 ℃, slowly heated to 80 ℃ and reacted for 2h.
While stirring, 12-95g of E and 10g of PM were added to the four-necked flask, and the mixture was stirred at 80℃for 0.5 hour.
16G of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-necked flask while stirring, and the temperature is kept at 80 ℃ and stirring is carried out for 2 h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
The modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
Comparative example 3
Adding the 51-64.5g, the 12-95g and the PM-10g of E into a four-neck flask with a condenser, mixing for 15min at 60 ℃, adding 16g of polyether emulsifier and 6g of sulfonate emulsifier while stirring, slowly heating to 80 ℃, and stirring for 2h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is completely dripped within 1.5 h. An epoxy emulsion is obtained.
Under stirring, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2 hours.
The modified epoxy emulsion is prepared.
The emulsion had a solids content of 60%.
After all the example emulsions were prepared, the same formulation was used to prepare a waterborne epoxy corrosion resistant primer, the formulation ratios are shown in Table 1:
table 1 formulation table of waterborne epoxy anticorrosive primer
| Composition of the composition | Proportioning of |
| Deionized water | 17 |
| Substrate wetting agent | 0.5 |
| Water-based anti-sedimentation wax | 3 |
| Dispersing agent | 1 |
| Defoaming agent | 0.2 |
| Leveling agent | 0.2 |
| Zinc phosphate | 5 |
| Aluminum tripolyphosphate | 9 |
| Titanium white powder | 14 |
| Barium sulfate | 9 |
| Epoxy emulsion | 60 |
| Water-based epoxy curing agent | 30 |
Test case
The performance of the corrosion resistant primer prepared from the epoxy emulsions of examples 1 to 12 and comparative examples 1 to 3 was tested according to established standards, the test results are shown in Table 3, and the standards are shown in Table 2:
TABLE 2 Performance test criteria
| Main technical parameters | Test standard |
| Flexibility of the product | GB/T1731-1993 |
| Acid-resistant | GB/T1763 |
| Alkali-proof | GB/T1763 |
| Salt spray resistance | GB/T1771-2007 |
TABLE 3 results of Performance test of epoxy anticorrosive primers prepared in examples 1-12 and comparative examples 1-3
As can be seen from table 3: the water-based anti-corrosion primer prepared from the polyurethane and inorganic salt double-modified epoxy emulsion has better salt fog resistance, acid-base resistance and flexibility than other modified products. Particularly, the salt spray resistance can reach more than 1500 hours under the condition of the coating thickness of 60 mu m, and the flexibility can reach 1mm.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A polyurethane and inorganic salt double modified epoxy emulsion is characterized in that: the material is prepared from the following raw materials in parts by weight:
50-70 parts of first epoxy resin; 0.01-0.04 part of catalyst, 80-100 parts of second epoxy resin, 5-9 parts of isocyanate, 12-17 parts of nonionic emulsifier, 3-7 parts of anionic emulsifier, 5-15 parts of cosolvent, 5-10 parts of silicate solution and 100-130 parts of water;
The first epoxy resin consists of one or more mixtures of E51, E44 and E31;
the second epoxy resin consists of one or more mixtures of E20, E12 and E06;
the preparation method of the polyurethane and inorganic salt double modified epoxy emulsion comprises the following steps:
S1, adding a first epoxy resin, a catalyst and isocyanate into a four-neck flask with a condenser pipe according to parts by weight, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h;
s2, adding a second epoxy resin and a cosolvent into the four-necked flask while stirring, keeping the temperature at 80 ℃, and mixing for 0.5h;
s3, adding a nonionic emulsifier and an anionic emulsifier into the four-necked flask while stirring, and keeping the temperature at 80 ℃ and stirring for 2 hours;
s4, removing the heating device, slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, and ensuring that all water is completely dripped within 1.5h to obtain epoxy emulsion;
S5, adding the silicate solution into the epoxy emulsion under the stirring state, heating to 60 ℃, and carrying out hybridization reaction for 2 hours to prepare the double modified epoxy emulsion.
2. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the material is prepared from the following raw materials in parts by weight:
55-65 parts of first epoxy resin, 0.01-0.04 part of catalyst, 87-95 parts of second epoxy resin, 5-8 parts of isocyanate, 13-15 parts of nonionic emulsifier, 4-7 parts of anionic emulsifier, 8-15 parts of cosolvent, 6-8 parts of silicate solution and 110-120 parts of water.
3. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the isocyanate is composed of one or more mixtures of IPDI, TDI, MDI.
4. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the nonionic emulsifier is composed of one or a mixture of more of polyether type, polyester type and polyurethane type.
5. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the anionic emulsifier is composed of one or a mixture of more of sulfonate, hydroxyl acid salt and sulfate.
6. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the silicate solution is composed of one or a mixture of more of potassium silicate, lithium silicate and calcium silicate.
7. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the catalyst is dibutyl tin dilaurate; the co-solvent consists of one or more mixtures of PM, DPNB, BCS, DBE.
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| CN113278346A (en) * | 2021-06-03 | 2021-08-20 | 武汉工程大学 | Water-based epoxy resin emulsion for heavy-duty anticorrosive paint and preparation method and application thereof |
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