CN1752163A - A kind of aqueous epoxide resin paint and preparation method thereof - Google Patents
A kind of aqueous epoxide resin paint and preparation method thereof Download PDFInfo
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- CN1752163A CN1752163A CN 200510030679 CN200510030679A CN1752163A CN 1752163 A CN1752163 A CN 1752163A CN 200510030679 CN200510030679 CN 200510030679 CN 200510030679 A CN200510030679 A CN 200510030679A CN 1752163 A CN1752163 A CN 1752163A
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 97
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003973 paint Substances 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002966 varnish Substances 0.000 claims abstract description 10
- 238000004945 emulsification Methods 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 120
- 229920005989 resin Polymers 0.000 claims description 70
- 239000011347 resin Substances 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 33
- -1 polyoxyethylene Polymers 0.000 claims description 28
- 229920000768 polyamine Polymers 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000004816 latex Substances 0.000 claims description 24
- 229920000126 latex Polymers 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000006184 cosolvent Substances 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 150000002334 glycols Chemical class 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229960001124 trientine Drugs 0.000 claims description 7
- 238000007259 addition reaction Methods 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 238000001723 curing Methods 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000005187 foaming Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000002791 soaking Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000005028 tinplate Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 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 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
本发明属化工技术领域，具体涉及一种水性环氧树脂涂料及其制备方法。涂料由低分子量液体环氧树脂、环氧树脂醚溶液或环氧树脂乳液中一种与水性环氧树脂固化剂两个组分组成，其中固化剂由多乙烯多胺经封端、加成、成盐工艺改性制得。乳液和固化剂按一定的比例配制得水性环氧树脂涂料清漆。本发明所制得的固化剂分子链段中既有亲水基团，又有亲油基团，所以具有乳化作用，能够直接乳化环氧树脂而不用再外加乳化剂。此种固化剂乳化的环氧树脂涂料硬度高，附着力强，具有较好的耐水性和耐腐蚀性。本发明制得的涂料，其乳化效果更好，其硬度较高，附着力强，同时具有较好的耐水性和耐腐蚀性。The invention belongs to the technical field of chemical industry, and in particular relates to a water-based epoxy resin coating and a preparation method thereof. The coating consists of two components of low molecular weight liquid epoxy resin, epoxy resin ether solution or epoxy resin emulsion and water-based epoxy resin curing agent. It is prepared by modifying the salt-forming process. The emulsion and the curing agent are prepared in a certain ratio to obtain a water-based epoxy resin paint varnish. There are both hydrophilic groups and lipophilic groups in the molecular chain segment of the curing agent prepared by the present invention, so it has emulsifying effect and can directly emulsify epoxy resin without adding emulsifier. The epoxy resin coating emulsified by this curing agent has high hardness, strong adhesion, and good water resistance and corrosion resistance. The coating prepared by the invention has better emulsification effect, higher hardness, strong adhesion, and better water resistance and corrosion resistance.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of aqueous epoxide resin paint and preparation method thereof.
Technical background
Epoxypaint is a kind of high-performance coating, uses very extensive.It has multiple advantage, and comprising with various basic units all has very strong sticking power, and the hardness height of coating has well water-fast and chemical resistant properties, and good wear resistance etc. can be used as floor coating, metal rust preventing priming paint, marine finish etc.But present most epoxypaint is a solvent based coating, contains a large amount of volatilizable organic compound (VOC), and is poisonous, inflammable, thereby environment and human body are worked the mischief.Along with the requirement to the epoxy protection improves day by day, the cry that attenuating VOC is not even contained the coating of VOC grows to even greater heights.
Quite popular to the research of water borne epoxy resin anticorrosive paint in recent years both at home and abroad.Abroad from last century the nineties develop some water-base epoxy products successively, as the epoxy emulsion EPI-REZ 3520-WY-55 and the aqueous epoxy curing agent EPI-CURE 8290-Y-60 of U.S. Shell company, the epoxy emulsion PZ 3961 of the Waterpoxy140 of Henkel companies such as the epoxy emulsion PZ 3961 of Air Products company and aqueous epoxy curing agent HZ 340, Air Products company and aqueous epoxy curing agent HZ 340 etc.SHELL company has just begun research to the aqueous epoxide resin paint system sixties as far back as eighties of last century, till now, has developed serial aqueous epoxide resin paint.Its research situation in recent years mainly concentrate on following some:
At first be research to the aqueous epoxy resin emulsion preparation.1999, SHELL company successfully developed a kind of epoxy resin latex.This epoxy resin latex is the dispersion system of many ammonia of polyamine and Resins, epoxy.Its solidifying agent is a kind of polyamine curing agent, and it is mainly synthetic by the polycondensation of aminoalkyl piperazine and long alkyl chain dicarboxylic acid, and uses the liquid amine end-blocking.This kind epoxy resin latex is as the solidifying agent of aqueous epoxy resin systems.2000, SHELL developed a kind of water-dispersed epoxy resin emulsion.This epoxy resin latex is the liquid epoxies acetone soln and the phase reversion preparation in the presence of deionized water of Resins, epoxy-surface active agent emulsions of hydrophobic nature.Resins, epoxy-surface active agent emulsions is that low-molecular-weight Resins, epoxy and polyoxyethylene surfactant prepare under non-acetone solvent and get.Domestic research also concentrates on above the preparation of aqueous epoxy emulsion.Usefulness phase reversion methods such as Wu Liming have prepared epoxy resin and acrylic ester complexes emulsion.Chen Zhimings etc. have also prepared water-base epoxy-acrylic ester emulsion, and film performance is studied.Inst. of Marine Chemical Engineering adopts nucleocapsid structure, self-emulsifying letex polymerization manufacturing technology, the water-based anticorrosive paint of having developed the amino fine latex of water-based epoxy acrylic and having been prepared by latex.Gu Guofang etc. have carried out more deep research to I type and II type aqueous epoxy resins.
Secondly be exactly research to the aqueous epoxy resin curing agent preparation.1998, SHELL company just successfully developed the aqueous epoxide resin paint of a kind of room temperature or low-temperature curing.The solidifying agent of this coating is to be external phase with water, and disperse phase is that the inside has comprised a kind of solidifying agent with surfactant component of reactive behavior.Surfactant component is phenolic composite or the end carboxyl polyoxyethylene that contains carboxyl and hydroxyl.The composition of solidifying agent mainly is to contain polyamines amino more than two and monoglycidyl ether prepared in reaction.2000, SHELL developed a kind of aqueous epoxy resin systems.The solidifying agent of this epoxy-resin systems is a kind of bad epoxy resins-amine affixture.Mainly by low-molecular-weight Resins, epoxy with have a plurality of active ammonia atomic reaction of hydrogen and prepare amine end-blocking intermediate product, this then amine end-blocking intermediate product with the reaction of carboxyl polyvinyl alcohol after the mono-epoxy compounds end-blocking obtains amine end-blocking solidifying agent.More research has also been done in the aqueous epoxy resin curing agent field by CIBA company: 1999, it developed a kind of curable epoxy mixture of moisture workability polyamine solidifying agent.It comprises a kind of water-soluble, emulsifying water, water-dispersible epoxy resins and a kind of special synthetic polyamine mixture and at least a fat, alicyclic ring, fragrance/aliphatic monoamine or polyamines.The same year, developed a kind of solidifying agent again, it is the mixture of Racemic glycidol and amine such as polyamine polyamines, and is promotor with the linear phenolic resin.Epoxy curing agent also contains other compositions, as softening agent, UV light stabilizing agent, pigment, filler etc.AIR PRODUCT ﹠amp; CHEM prepared Two-Component Waterborne Epoxy Resin Coating in 1996.Its solidifying agent is also to be a kind of polycaprolactam polyamine-epoxy resin composite.Generate intermediate by the reaction of polycaprolactam polyamine and polyepoxy compound, intermediate then with many epoxide groups resin reaction, become salt solution dilution preparation aqueous latex of epoxy hardener by mono-epoxy compounds end-blocking acetate at last.
Yet the preparation that has the solidifying agent of emulsification and curing function concurrently but rarely has report.The commercialization of water corrosion-resistant epoxy paint progress is slower simultaneously, and its cost is too high, at present the large-scale commercial production of the domestic water borne epoxy resin anticorrosive paint of also being unrealized.This is the gap of home and overseas just, and the aqueous epoxide resin paint that how to prepare high-performance and low-cost is to put a research institution and a numerous researchists very urgent urgent problem in front at home.
Summary of the invention
The objective of the invention is to propose a kind of non-environmental-pollution and do not contain high-performance water-based epoxy cold coating of VOC or low VOC and preparation method thereof.
The aqueous epoxide resin paint that the present invention proposes is a high-performance dual-component coating, form with two components of aqueous epoxy resin curing agent by a kind of in liquid epoxies, Resins, epoxy ethereal solution or the epoxy resin latex, the Resins, epoxy ethereal solution is by adding cosolvent in the Resins, epoxy, the Resins, epoxy dissolving is obtained, and the add-on of cosolvent is the 1%-10% of weight epoxy; Epoxy resin latex is obtained by the emulsifying agent emulsification of Resins, epoxy through Resins, epoxy and polyether Glycols reaction acquisition, and the add-on of emulsifying agent is the 5%-15% of weight epoxy; Aqueous epoxy resin curing agent be by polyamines class solidifying agent through end-blocking, addition, salify process modification and the water soluble solid agent that obtains, existing hydrophilic radical in this emulsifying agent molecule segment has lipophilic group again, directly emulsion epoxy resin; Resins, epoxy wherein is the bisphenol A-type low-molecular-weight epoxy resin.
Among the present invention, above-mentioned aqueous epoxy resin curing agent (first component) and liquid epoxies or Resins, epoxy ethereal solution or epoxy resin latex (second component) are 1.2 by the mol ratio of amine hydrogen and epoxy group(ing): 1-1: 1.2, aqueous epoxide resin paint varnish.
Among the present invention, described polyether Glycols is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or a kind of in any two monomeric multipolymers etc. among them.
Two-Component Waterborne Epoxy Resin Coating requires at room temperature to solidify.Polyamines class solidifying agent and adduct thereof are the self-vulcanizing epoxy curing agents of using always, it is applicable to the solvent-borne type system and is not suitable for the water-base epoxy system, because it can not be dispersed in and form stable dispersion in the epoxy resin latex, cause the destruction of emulsion on the contrary, two are separated, coating curing is bad, even can not solidify.And the solidifying agent that uses in the water-base epoxy system must satisfy following condition:
(1) compatible with epoxy resin latex, can be evenly dispersed in the emulsion that form uniformly can be in room temperature film-forming solidified dispersion.
(2) there is consistency preferably the volatilization of the moisture content in emulsion back with Resins, epoxy, can form the homogeneous wet film, thereby can fully and fully solidify, and obtains filming of excellent property.
(3) speed of response with Resins, epoxy is moderate, to guarantee enough working lives.
Satisfy above requirement, need solidifying agent is carried out modification.
The present invention proposes a kind of preparation method of aqueous epoxide resin paint, water miscible epoxy hardener polyamine compounds falls primary amine hydrogen through the addition reaction of mono-epoxy compounds, then, the product that reaction obtains and the Resins, epoxy addition reaction of various molecular weight, in the hope of improving the lipophilicity of polyamines class solidifying agent, its after product makes aqueous epoxy curing agent by steps such as salify and dilutions.This kind solidifying agent is because existing hydrophilic radical in the molecule segment has lipophilic group again, so have emulsifying effect, direct emulsion epoxy resin and need not add emulsifying agent again.Like this, the aqueous epoxy coating of preparation is neither contained add emulsifying agent, do not contain organic solvent again or contain seldom organic solvent, can effectively protect environment.Its concrete steps are:
(1) aqueous epoxy resin curing agent is synthetic
(a) end-blocking
Adopt the reaction of polyethylene polyamine and mono-epoxy compounds, temperature of reaction is controlled at 55-65 ℃, and the time was controlled at 100-150 minute, and the mol ratio of polyethylene polyamine and mono-epoxy compounds is 1: 1.2-1.2: 1; Because reaction should add mono-epoxy compounds for thermopositive reaction in polyethylene polyamine in batches, prevent temperature too high cause sudden and violent poly-.
(b) addition
To through end capped polyethylene polyamine and diepoxides addition reaction, the mol ratio of end-blocking product and epoxy compounds is 1.8: 1-2.2: 1, and temperature of reaction is controlled at 90-100 ℃, and the time was controlled at 1-2 hour; Polyethylene polyamine and epoxy resin compatibility are bad, by with it and diepoxides addition, introduce the Resins, epoxy segment in molecule, can improve the consistency with Resins, epoxy.
Do not contained primary amine hydrogen in the solidifying agent that makes thus, but still had reactive hydrogen to exist, be secondary amine hydrogen, thereby its reactive behavior is reduced, helped prolonging working life.Simultaneously owing in molecule, introduced the Resins, epoxy segment, the consistency of it and Resins, epoxy is improved.
(c) salify
Adopt the organic acid salify, the equivalence ratio of remaining amine hydrogen is 1 after organic acid and end-blocking and the addition: 3.5-1: 4.5, and temperature of reaction is 85-95 ℃, and the time is 50-70 minute, and reaction adds entry after finishing, and gets solidifying agent, and solid content can be 30-50%.Adopt the organic acid salify, can reach hydrophilic-lipophilic balance preferably, make it that consistency preferably can be arranged with the resin in Resins, epoxy or the epoxy resin latex.Salt-forming reaction adds entry after finishing, and regulates the solid content of solidifying agent, obtains water miscible solidifying agent, and it is the faint yellow viscous liquid of solid content at 30-50%.
(2) mix
With a kind of mixing in the solidifying agent of gained and liquid epoxies, Resins, epoxy ethereal solution or the epoxy resin latex, promptly get aqueous epoxide resin paint.
Among the present invention, described polyethylene polyamine can adopt a kind of in diethylenetriamine, triethylene tetramine, tetrem alkene hexamine or the different Fu Er ketone diamines etc.Because the end group of this class polyethylene polyamine contains primary amine hydrogen, they are higher than secondary amine hydrogen with the reactive behavior of epoxy group(ing), so will prolong working life, primary amine hydrogen are sealed with mono-epoxy compounds.
Among the present invention, described mono-epoxy compounds can adopt the mixture of aliphatic group glycidyl ether (as butylglycidyl ether, alkyl glycidyl ether), arylolycidyl ethers (as phenyl glycidyl ether, benzyl glycidyl ether) or aliphatic group glycidyl ether and arylolycidyl ethers.
Among the present invention, described diepoxides can adopt bisphenol A type epoxy resin, as Resins, epoxy such as 601,6101 and 618.
Among the present invention, described organic acid is Glacial acetic acid or formic acid etc.
Among the present invention, for reducing the viscosity of reactant, can add cosolvent in the addition reaction system, the add-on of cosolvent is the 2%-10% of weight epoxy.
Among the present invention, can be ether solvent, a kind of as in ethylene glycol monoethyl ether, dihydroxypropane single-ether or the propylene glycol monomethyl ether etc. to Resins, epoxy dissolved cosolvent.
Among the present invention, the preparation of epoxy resin latex can obtain by prior art, being about to Resins, epoxy and polyether Glycols reacts in the presence of lewis acid catalyst, temperature of reaction is 90-110 ℃, reaction times is 6-8 hour, generate emulsifying agent, the mol ratio of Resins, epoxy and polyether Glycols is 1.2: 1-1: 1.2; Add cosolvent in the Resins, epoxy, make the Resins, epoxy dissolving, the consumption of cosolvent is the 2%-10% that Resins, epoxy adds weight; The emulsifying agent and the epoxy resin solution that obtain are adopted phase inversion technique, obtain epoxy resin latex.The add-on of emulsifying agent is the 5%-15% of used weight epoxy.Described polyether Glycols is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or a kind of in any two monomeric multipolymers etc. among them.
Among the present invention, the preparation of Resins, epoxy ethereal solution can obtain by prior art, promptly is to add cosolvent in Resins, epoxy, makes the Resins, epoxy dissolving, and to reduce the viscosity of Resins, epoxy, the add-on of cosolvent is the 1%-10% of weight epoxy.
Preparation aqueous epoxide resin paint varnish
First component: aqueous epoxy resin curing agent
Second component: low molecular weight liquid epoxy or Resins, epoxy ethereal solution or epoxy resin latex
The preparation of varnish: the mol ratio of amine hydrogen and epoxy group(ing) is 1.2 in first component and the second component: 1-1: 1.2.
The performance of gained coating:
The median size of emulsive Resins, epoxy:＜1 μ m;
Surface drying time (fingers-touch method): about 1 hour (GB/T 1728-79);
Working life: 6 hours (glossiness drop to original 75%);
Hardness of film (fork method):＞0.7 (GB/T 1730-93);
Sticking power (drawing the circle method): 1 grade;
Glossiness: 90%;
Water tolerance: 25 ℃, distilled water immersion, 10 days, non-foaming, (GB/T 1733-99) do not come off;
Acid resistance: 25 ℃, 5%H
2SO
4Solution soaking, 4 days, non-foaming, (GB 1763-79) do not come off;
Alkali resistance: 25 ℃, the 5%NaOH solution soaking, 4 days, non-foaming, (GB 1763-79) do not come off.
Embodiment
Embodiment 1
(1) aqueous epoxy curing agent is synthetic
(a) end-blocking
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, add the 130g butylglycidyl ether more in batches, control reaction temperature is 60 ℃, and in 2 hours reaction times, product is light yellow viscous liquid.
(b) addition
In four-necked bottle, add 601 Resins, epoxy 42g, add the 30g ethylene glycol monoethyl ether again, be heated to 80 ℃, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 23g again, slowly heat up, control and maintenance temperature of reaction are about 90 ℃, react 2 hours.
(c) salify
5g acetic acid is joined in the reactant, and holding temperature was reacted 1 hour about 90 ℃ again.
(d) dissolving
In the time of 90 ℃, add 175g water, be stirred to the formation yellow solution.
Solid content: about 30%
Viscosity: about 3,000mPa.s
Amine hydrogen equivalent: 800
(2) preparation of bi-component aqueous epoxy resinous varnish
The first component:: aqueous epoxy resin curing agent
Second component: low molecular weight liquid epoxy
With the first component: the mixed of second component=4: 1 (weight ratio), stir by hand, be coated on sheet glass and the tinplate sheet with brush. form transparent wet film behind the moisture evaporation, surface drying time is 60 minutes, film performance:
Hardness (fork method) 0.5
Glossiness 60%
Sticking power 4
25 ℃ of water tolerance, 72 hours, distilled water immersion, non-foaming, do not peel off.
25 ℃ of acid resistances, 4 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off
25 ℃ of alkali resistances, 2 days, the 5%NaOH solution soaking, non-foaming, do not come off.
Embodiment 2
(1) aqueous epoxy curing agent is synthetic
(a) end-blocking
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, add the 150g phenyl glycidyl ether more in batches, control reaction temperature is 55 ℃, and in 150 minutes reaction times, product is light yellow viscous liquid.
(b) addition
In four-necked bottle, add 601 Resins, epoxy 42g, add the 30g ethylene glycol monoethyl ether again, be heated to 80 ℃, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 24.7g again, slowly heat up, control and maintenance temperature of reaction are about 90 ℃, react 2 hours.
(c) salify
10g acetic acid is joined in the reactant, and holding temperature was reacted 1 hour about 90 ℃ again.
(d) dissolving
In the time of 90 ℃, add 150g water, be stirred to the formation yellow solution.
Solid content: about 30%
Viscosity: about 18600mpa.s
Amine hydrogen equivalent: 711
(2) preparation of bi-component aqueous epoxy resinous varnish
First component: aqueous epoxy resin curing agent
Second component: low molecular weight liquid epoxy
With the first component: the mixed of second component=3.5: 1 (weight ratio), stir by hand, be coated on sheet glass and the tinplate sheet with brush. form transparent wet film behind the moisture evaporation, surface drying time is 60 minutes, film performance:
Hardness (fork method) 0.80
Glossiness 70%
1 grade of sticking power
25 ℃ of water tolerance, 96 hours, distilled water immersion, non-foaming, do not peel off.
25 ℃ of acid resistances, 4 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off
25 ℃ of alkali resistances, 2 days, the 5%NaOH solution soaking, non-foaming, do not come off.
Embodiment 3
(1) aqueous epoxy curing agent is synthetic
(a) end-blocking
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, add the 306g alkyl glycidyl ether more in batches, control reaction temperature is 65 ℃, and in 100 minutes reaction times, product is light yellow viscous liquid.
(b) addition
In three-necked bottle, add 618 Resins, epoxy 16g, add the 8g ethylene glycol monoethyl ether again, be heated to 80 ℃, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 38g again, slowly heat up, control and maintenance temperature of reaction are about 95 ℃, react 1.5 hours.
(c) salify
5g acetic acid is joined in the reactant, and holding temperature was reacted 50 minutes at 95 ℃ again.
(d) dissolving
In the time of 90 ℃, add 150g water, be stirred to the formation yellow solution.
Solid content: about 41.8%
Viscosity: about 14800mPa.s
Amine hydrogen equivalent: 382.4
(2) preparation of bi-component aqueous epoxy resinous varnish
First component: aqueous epoxy resin curing agent
Second component: low molecular weight liquid epoxy
With the first component: the mixed of second component=2: 1 (weight ratio), stir by hand, be coated on sheet glass and the tinplate sheet with brush. form transparent wet film behind the moisture evaporation, surface drying time is 60 minutes, film performance:
Hardness (fork method) 0.70
Glossiness 60%
Sticking power 3
25 ℃ of water tolerance, 72 hours, distilled water immersion, non-foaming, do not peel off.
25 ℃ of acid resistances, 3 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off
25 ℃ of alkali resistances, 1 day, the 5%NaOH solution soaking, non-foaming, do not come off.
Embodiment 4
(1) aqueous epoxy curing agent is synthetic
(a) end-blocking
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, add the 256g benzyl glycidyl ether more in batches, control reaction temperature is 60 ℃, and in 2 hours reaction times, product is light yellow viscous liquid.
(b) addition
In three-necked bottle, add 6101 Resins, epoxy 42g, add the 14g dihydroxypropane single-ether again, be heated to 80 ℃, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 33.5g again, slowly heat up, control and maintenance temperature of reaction are about 90 ℃, react 2 hours.
(c) salify
5g acetic acid is joined in the reactant, and holding temperature was reacted 1 hour about 90 ℃ again.
(d) dissolving
In the time of 90 ℃, add 175g water, be stirred to the formation yellow solution.
Solid content: about 30%
Viscosity: about 4000mPa.s
Amine hydrogen equivalent: 700
(2) preparation Resins, epoxy ethereal solution
Add cosolvent dihydroxypropane single-ether 5g in 100g Resins, epoxy 618, make the Resins, epoxy dissolving, to reduce the viscosity of Resins, epoxy, the add-on of cosolvent dihydroxypropane single-ether is 5% of a weight epoxy.
(3) preparation of bi-component aqueous epoxy resinous varnish
First component: aqueous epoxy resin curing agent
Second component: Resins, epoxy ethereal solution
With the first component: the mixed of second component=3.5: 1 (weight ratio), stir by hand, be coated on sheet glass and the tinplate sheet with brush. form transparent wet film behind the moisture evaporation, surface drying time is 60 minutes, film performance:
Hardness (fork method) 0.70
Glossiness 90%
Sticking power 1
25 ℃ of water tolerance, 72 hours, distilled water immersion, non-foaming, do not peel off.
25 ℃ of acid resistances, 5 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off
25 ℃ of alkali resistances, 2 days, the 5%NaOH solution soaking, non-foaming, do not come off.
Embodiment 5
(1) aqueous epoxy curing agent is synthetic
(a) end-blocking
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, add the 256g benzyl glycidyl ether more in batches, control reaction temperature is 65 ℃, and in 100 minutes reaction times, product is light yellow viscous liquid.
(b) addition
In three-necked bottle, add 6101 Resins, epoxy 42g, add the 14g dihydroxypropane single-ether again, be heated to 80 ℃, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 33.5g again, slowly heat up, control and maintenance temperature of reaction are about 100 ℃, react 1 hour.
(c) salify
5g acetic acid is joined in the reactant, and holding temperature was reacted 1 hour at 100 ℃ again.
(d) dissolving
In the time of 90 ℃, add 175g water, be stirred to the formation yellow solution.
Solid content: about 30%
Viscosity: about 4000mPa.s
Amine hydrogen equivalent: 700
(2) preparation epoxy resin latex
Resins, epoxy 618 and polypropylene glycol are reacted in the presence of lewis acid catalyst, and temperature of reaction is 90-110 ℃, and the reaction times is 6-8 hour, generates emulsifying agent, and the mol ratio of Resins, epoxy and polyether Glycols is 1.2: 1-1: 1.2; 100g Resins, epoxy 618 is dissolved in the 30g ethylene glycol ethyl ether, adds emulsifying agent 30g again, be stirred to Resins, epoxy and dissolve fully.Use homogenizer to be 3000 rev/mins then and stir down, stir and drip water 70g simultaneously, continue to stir 10min after water droplet is intact, obtain epoxy resin latex at rotating speed.Particle size of emulsion is 0.086 μ m.
(3) preparation of bi-component aqueous epoxy resinous varnish
First component: the aqueous epoxy resin curing agent of self-emulsifying type
Second component: epoxy resin latex
With the first component: the mixed of second component=3.5: 2 (weight ratio), stir by hand, be coated on sheet glass and the tinplate sheet with brush. form transparent wet film behind the moisture evaporation, surface drying time is 60 minutes, film performance:
Hardness (fork method) 0.70
Glossiness 90%
Sticking power 1
25 ℃ of water tolerance, 98 hours, distilled water immersion, non-foaming, do not peel off.
25 ℃ of acid resistances, 6 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off
25 ℃ of alkali resistances, 4 days, the 5%NaOH solution soaking, non-foaming, do not come off.
Claims (10)
1, a kind of aqueous epoxide resin paint, it is characterized in that forming with two components of aqueous epoxy resin curing agent by a kind of in liquid epoxies, Resins, epoxy ethereal solution or the epoxy resin latex, the Resins, epoxy ethereal solution is by adding cosolvent in the Resins, epoxy, the Resins, epoxy dissolving is obtained, and the add-on of cosolvent is the 1%-10% of weight epoxy; Epoxy resin latex is obtained by the emulsifying agent emulsification of Resins, epoxy through Resins, epoxy and polyether Glycols reaction acquisition, and the add-on of emulsifying agent is the 5%-15% of weight epoxy; Aqueous epoxy resin curing agent be by polyamines class solidifying agent through end-blocking, addition, salify process modification and the water soluble solid agent that obtains, existing hydrophilic radical in this emulsifying agent molecule segment has lipophilic group again, directly emulsion epoxy resin; Resins, epoxy wherein is the bisphenol A-type low-molecular-weight epoxy resin.
2, aqueous epoxide resin paint according to claim 1, it is characterized in that aqueous epoxy resin curing agent and liquid epoxies or Resins, epoxy ethereal solution or epoxy resin latex, mol ratio by amine hydrogen and epoxy group(ing) is 1.2: 1-1: 1.2, get aqueous epoxide resin paint varnish.
3, aqueous epoxide resin paint according to claim 1 is characterized in that described polyether Glycols is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or any two monomeric multipolymers a kind of among them.
4, a kind of preparation method of aqueous epoxide resin paint is characterized in that concrete steps are:
(1) aqueous epoxy resin curing agent is synthetic:
(a) end-blocking
Adopt the reaction of polyethylene polyamine and mono-epoxy compounds, temperature of reaction is 55-65 ℃, and the time is 100-150 minute, and the mol ratio of polyethylene polyamine and mono-epoxy compounds is 1: 1.2-1.2: 1;
(b) addition
To through end capped polyethylene polyamine and diepoxides addition reaction, the mol ratio of end-blocking product and epoxy compounds is 1.8: 1-2.2: 1, and temperature of reaction is 90-100 ℃, the time is 1-2 hour;
(c) salify
Adopt the organic acid salify, the equivalence ratio of remaining amine hydrogen is 1 after organic acid and end-blocking and the addition: 3.5-1: 4.5, and temperature of reaction is 85-95 ℃, and the time is 50-70 minute, and reaction adds entry after finishing, and gets solidifying agent, and solid content is 30-50%;
(2) mix
With a kind of mixing in the solidifying agent of gained and liquid epoxies, Resins, epoxy ethereal solution or the epoxy resin latex, promptly get aqueous epoxide resin paint.
5, the preparation method of aqueous epoxide resin paint according to claim 4 is characterized in that described polyethylene polyamine is a kind of in diethylenetriamine, triethylene tetramine, tetrem alkene hexamine or the different Fu Er ketone diamines.
6, the preparation method of aqueous epoxide resin paint according to claim 4 is characterized in that described mono-epoxy compounds is the mixture of aliphatic group glycidyl ether, arylolycidyl ethers or aliphatic group glycidyl ether and arylolycidyl ethers.
7, the preparation method of aqueous epoxide resin paint according to claim 4 is characterized in that described diepoxides is a bisphenol A type epoxy resin.
8, the preparation method of the described aqueous epoxide resin paint of root pick claim 4 is characterized in that described organic acid is Glacial acetic acid or formic acid.
9, the preparation method of aqueous epoxide resin paint according to claim 4 is characterized in that adding cosolvent in the addition reaction system, and the add-on of cosolvent is the 2%-10% of weight epoxy.
10, the preparation method of aqueous epoxide resin paint according to claim 9 is characterized in that described cosolvent is an ether solvent.
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