CN102633989B - Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method - Google Patents
Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method Download PDFInfo
- Publication number
- CN102633989B CN102633989B CN201210085185.1A CN201210085185A CN102633989B CN 102633989 B CN102633989 B CN 102633989B CN 201210085185 A CN201210085185 A CN 201210085185A CN 102633989 B CN102633989 B CN 102633989B
- Authority
- CN
- China
- Prior art keywords
- epoxy
- epoxy resin
- preparation
- emulsifying agent
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 58
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 57
- 239000004593 Epoxy Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229920000570 polyether Polymers 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 230000000694 effects Effects 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 229920003986 novolac Polymers 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000004843 novolac epoxy resin Substances 0.000 abstract 2
- 238000012856 packing Methods 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- -1 epoxy group compound Chemical class 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000004078 waterproofing Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 6
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 0 C*(C)(C)C(CNC)O Chemical compound C*(C)(C)C(CNC)O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention discloses a non-ionic active epoxy emulsifier preparation method and a waterborne epoxy resin preparation method. The non-ionic active epoxy emulsifier preparation method includes: firstly, using a single epoxy group compound to terminate alpha-methoxy-omega-alkyl polyether amine; and then adding novolac epoxy resin and a good amount of solvent in equimolar ratio, stirring the novolac epoxy resin and the solvent to homogeneous-phase solution prior to temperature rise reaction, and removing the solvent by means of reduced pressure distillation after reaction, so that non-ionic active epoxy emulsifier is prepared. The emulsifier and EP (epoxy resin) are added into a dispersing kettle according to different molar ratios to be evenly mixed, and deionized water is dropwise added to prepare epoxy resin aqueous emulsion with the solid content of 40-60% by means of phase inversion. The emulsion is high in storage stability, non-toxic and high in packing ratio of packing and can be cured at the room temperature, and a cured product has the advantages of high adhesive force and flexibility and is high in water proofing and solvent resistance.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the preparation method of a kind of non-ionic activity epoxy emulsifying agent and aqueous epoxy resins thereof.
Background technology
Solvent epoxy varnish brings harm because containing a large amount of organic solvents to ecotope, and the aqueous epoxy resins of environmental protection is more and more subject to people's favor.But epoxy resin itself is water insoluble, can not directly add water and carry out emulsification, must in its molecular chain, introduce hydrophilic radical or in system, add hydrophilic and oleophilic component.At present Waterborne Dispersions of Epoxy Resin be prepared with chemic modified method and phase inversion, wherein chemic modified method is mainly on epoxy resin molecular chain, to introduce carboxylic acid, sulfonic acid and hydroxyl isopolarity group by function monomer chain extension and free radical grafting modification, then in and salify prepare the aqueous epoxy resins of self-emulsifying.The ion that produces free state in N-process can be present in curing epoxy resin, therefore polymkeric substance water-intake rate is high, and the aqueous epoxy resins shock-resistance of grafting is poor, the randomness of grafting site in reaction, the response competition of graft reaction and properties-correcting agent autohemagglutination is difficult to control, and repeatability is poor.
Phase inversion is a kind of effective ways of preparing macromolecule resin water miscible liquid, and it is almost suitable for all macromolecule resins.Document " Chin.J.Polym.Sci. " [2007,25 (2): 137-143] prepared stable epoxy emulsion take PEG10000 as emulsifying agent by phase inversion, but due to the impact of emulsifying agent molecular migration, water tolerance and the solvent resistance of polymeric film are poor.Document " application chemical industry " [2006, 35 (10): 785-788] and " thermosetting resin " [2005, 20 (3): 20-22] chemical modification is combined with phase inversion, synthesize respectively end methoxy poly (ethylene glycol)-maleic anhydride-E44 and the ionic active emulsifier of non-ionic type and prepared epoxy resin water miscible liquid by means of phase inversion technique, emulsifying agent combines with chemical bond with macromolecular chain in curing polymkeric substance, reduce to a certain extent the water-intake rate of polymeric film, but the ester bond in emulsifying agent makes it still have the poor defect of stability to hydrolysis resistance.
The latest technology of aqueous epoxy coating is that the hydrophilic polyether segment of introducing nonionic in epoxy and solidifying agent molecular structure makes it obtain water-dispersion performance and prepares the epoxy emulsifying agent with reactive behavior at present.Its advantage is that this tensio-active agent has the function of tensio-active agent, can react with solidifying agent again and generate reticulated structure, prevents from dissociating out from paint film because the effect of water makes emulsifying agent.Adopt that the emulsion particle diameter prepared of phase inversion is little, good stability, and the emulsifying agent that additional emulsification formulation epoxy resin latex only need account for resin 1%～10% just can obtain desirable emulsion, epoxy resin latex cost with respect to other type is low, and tool has great advantage in actual applications.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the preparation method of a kind of non-ionic activity epoxy emulsifying agent and aqueous epoxy resins thereof is provided.The method does not need to add in organic acid and salify, and preparation technology is simple, reaction conditions gentleness.The film forming after the solidifying agent of preparation and curable epoxide has good water tolerance, snappiness and impact resistance.
The present invention proposes a kind of preparation method of non-ionic activity epoxy emulsifying agent, and this emulsifying agent can be used as active epoxy emulsifying agent and low molecular weight liquid epoxy is prepared epoxy resin latex by phase inversion, also can be mixed with separately epoxy resin latex.
The preparation method of the non-ionic activity epoxy emulsifying agent that the present invention proposes is: first fully react with monocycle oxycompound and α-methoxyl group-ω-alkyl, polyether amine the α-methoxyl group-ω-N-alkyl, polyether (being called for short MPE) that obtains end-blocking, then add novolac epoxy and the appropriate solvent of equimolar ratio, stir into after homogeneous phase solution at 15～50 ℃ of reaction 6～24h, more underpressure distillation makes non-ionic activity emulsifying agent (being called for short MPEF) except desolventizing.Wherein, monocycle oxycompound and α-methoxyl group-ω-alkyl, polyether amine fully react the product α-methoxyl group-ω-N-alkyl, polyether that carries out end-blocking and adopt general formula (1) below to represent:
In general formula (1): m, n, x, y are integer, and 4≤m≤30, and 0≤n≤2,0≤x≤1,0≤y≤2; Substituting group on phenyl ring be positioned at phenyl ring neighbour, or contraposition.
The present invention also proposes a kind of preparation method of aqueous epoxy resins, the method adopts multi-functional novolac epoxy to react with α-methoxyl group-ω-N-alkyl, polyether, the polyether segment with surface-active action is incorporated in epoxy resin molecular structure and has prepared non-ionic activity emulsifying agent, improved the consistency of emulsifying agent and epoxy resin.Emulsifying agent is mixed with epoxy resin, and having prepared Dispersed Phase Size by phase inversion is that nano level epoxy resin is with regard to water miscible liquid.Owing to containing dicyclo oxy functional groups in this emulsifying agent molecular structure, the preparation that also can directly add water can be carried out with solidifying agent the aqueous epoxy resin emulsion of crosslinking reaction.
The preparation method of described aqueous epoxy resins is made by following steps:
A. first adopt mono-epoxy compounds and α-methoxyl group-ω-alkyl, polyether amine fully to react the α-methoxyl group-ω-N-alkyl, polyether that obtains end-blocking, be called for short MPE;
B. then add novolac epoxy and the appropriate solvent of equimolar ratio, stir into after homogeneous phase solution at 15～50 ℃ of reaction 6～24h, reaction finishes rear underpressure distillation except desolventizing obtains non-ionic activity emulsifying agent, is called for short MPEF;
C. this emulsifying agent adds in Scattered Kettle and mixes by different mol ratio with epoxy resin (EP), and then dripping deionized water, to prepare solid content by phase inversion be 40～60% epoxy resin water miscible liquid (being called for short MPEF/EP water miscible liquid).
The aqueous epoxy resin emulsion preparation method that the present invention proposes adds after different fillers in the process of preparation emulsion, can form the environmental protection functional paint including electromagnetic screen coating and anti-corrosive and static conductive coating.
Tool of the present invention has the following advantages:
(1) the present invention has introduced the hydrophilic flexibility polyether segment of non-ionic type in the structure of emulsifying agent, make it have good snappiness and wetting ability, also the polyether segment containing in non-ionic type solidifying agent molecular structure, can play " bridged bond " effect, improve the consistency of epoxy resin and solidifying agent.
(2) preparation method's technique of the present invention is simple, reaction conditions gentleness.Phenolic hydroxyl group on α-methoxyl group-ω-alkyl, polyether amine phenyl ring can accelerate reactive behavior amino and epoxy group(ing), can under the reaction conditions of 15～50 ℃, prepare active epoxy emulsifying agent.
(3) adopt monocycle oxycompound (for example PO) to carry out after end-blocking α-methoxyl group-ω-alkyl, polyether amine, when α-methoxyl group-ω-N-the alkyl, polyether that contains secondary amino group simple function group reacts with multi-functional novolac epoxy, grafting site is determined, there is no chain extension side reaction, can obtain the active epoxy emulsifying agent of the controlled and stable performance of Stability Analysis of Structures, molecular weight.And in this active emulsifier, contain dicyclo oxy functional groups, and can carry out crosslinking reaction with solidifying agent, improve the cross-linking density of cured product.
(4) synthetic is non-ionic activity epoxy emulsifying agent, does not contain free ion after solidifying in film, has improved water tolerance and the pH value stabilization of film.Preparation process does not need to add organic acid (as acetic acid) neutralization can give the water-dispersion performance that emulsifying agent is good, and Soxylat A 25-7 in its molecular structure is natural materials, has the advantage of environmental protection.
Embodiment:
Embodiment 1:
(1) in reactor, add 0.1mol α-methoxyl group-ω-alkyl, polyether amine (MPE1) and 0.1mol propylene oxide (PO), at ambient temperature, stirring reaction 12h obtains α-methoxyl group-ω-N-isopropyl alcohol radical alkyl, polyether (being called for short PO-MPE1) of propylene oxide end-blocking.The molecular formula of this affixture is (2):
(2) then add 0.1mol novolac epoxy and appropriate tetrahydrofuran (THF), stir into after homogeneous phase solution at 50 ℃ of reaction 6h, reaction finishes rear underpressure distillation except desolventizing obtains non-ionic activity emulsifying agent, is called for short MPEF1.The molecular formula of this affixture is (3):
(3) this emulsifying agent can directly add deionized water to prepare solid content be 50% epoxy resin water miscible liquid (being called for short MPEF1 water miscible liquid).
Embodiment 2:
(1) in reactor, add 1mol α-methoxyl group-ω-alkyl, polyether amine (MPE2) and 1mol propylene oxide (PO), at ambient temperature, stirring reaction 18h obtains α-methoxyl group-ω-N-isopropyl alcohol radical alkyl, polyether (being called for short PO-MPE2) of propylene oxide end-blocking.The molecular formula of this affixture is (4):
(2) then add 1mol novolac epoxy and appropriate tetrahydrofuran (THF), stir into after homogeneous phase solution at 40 ℃ of reaction 16h, reaction finishes rear underpressure distillation except desolventizing obtains non-ionic activity emulsifying agent, is called for short MPEF2.The molecular formula of this affixture is (5):
(3) this emulsifying agent adds in Scattered Kettle and mixes with epoxy resin E44 for 1: 10 in molar ratio, and then dripping deionized water, to prepare solid content by phase inversion be 60% epoxy resin water miscible liquid (being called for short MPEF2/E44 water miscible liquid).
Embodiment 3:
(1) in reactor, add 1mol α-methoxyl group-ω-alkyl, polyether amine (MPE3) and 1mol propylene oxide (PO), at ambient temperature, stirring reaction 24h obtains α-methoxyl group-ω-N-isopropyl alcohol radical alkyl, polyether (being called for short PO-MPE3) of propylene oxide end-blocking.The molecular formula of this affixture is (6):
(2) then add 1mol novolac epoxy and proper amount of acetone, stir into after homogeneous phase solution at 30 ℃ of reaction 12h, reaction finishes rear underpressure distillation removes solvent acetone and obtains non-ionic activity emulsifying agent, is called for short MPEF3.The molecular formula of this affixture is (7):
(3) this emulsifying agent adds in Scattered Kettle and mixes with epoxy resin F44 for 1: 30 in molar ratio, and then dripping deionized water, to prepare solid content by phase inversion be 60% epoxy resin water miscible liquid (being called for short MPEF3/F44 water miscible liquid).
Embodiment 4:
(1) in reactor, add 0.5mol α-methoxyl group-ω-alkyl, polyether amine (MPE4) and 0.5mol propylene oxide (PO), at ambient temperature, stirring reaction 24h obtains α-methoxyl group-ω-N-isopropyl alcohol radical alkyl, polyether (being called for short PO-MPE4) of propylene oxide end-blocking.The molecular formula of this affixture is (8):
(2) then add 0.5mol novolac epoxy and appropriate tetrahydrofuran (THF), stir into after homogeneous phase solution at 30 ℃ of reaction 18h, reaction finishes rear underpressure distillation removes solvents tetrahydrofurane and obtains non-ionic activity emulsifying agent, is called for short MPEF4.The molecular formula of this affixture is (9):
(3) this emulsifying agent adds in Scattered Kettle and mixes with epoxy resin F51 for 1: 20 in molar ratio, and then dripping deionized water, to prepare solid content by phase inversion be 40% epoxy resin water miscible liquid (being called for short MPEF4/F51 water miscible liquid).
Embodiment 5:
(1) in reactor, add 0.3mol α-methoxyl group-ω-alkyl, polyether amine (MPE5) and 0.3mol butylene oxide ring (BO), at ambient temperature, stirring reaction 20h obtains α-methoxyl group-ω-N-isobutyl alcohol radical alkyl, polyether (being called for short BO-MPE5) of butylene oxide ring end-blocking.The molecular formula of this affixture is (10):
(2) then add 0.3mol novolac epoxy and appropriate tetrahydrofuran (THF) and dehydrated alcohol, stir into after homogeneous phase solution at 30 ℃ of reaction 24h, reaction finishes rear underpressure distillation except desolventizing obtains non-ionic activity emulsifying agent, is called for short MPEF5.The molecular formula of this affixture is (11):
(3) this emulsifying agent adds in Scattered Kettle and mixes with epoxy resin E44 for 1: 20 in molar ratio, and then dripping deionized water, to prepare solid content by phase inversion be 60% epoxy resin water miscible liquid (being called for short MPEF5/E44 water miscible liquid).
Embodiment 6:
(1) in reactor, add 0.8mol α-methoxyl group-ω-alkyl, polyether amine (MPE6) and 0.8mol butylene oxide ring (CO), at ambient temperature, stirring reaction 24h obtains α-methoxyl group-ω-N-isobutyl alcohol radical alkyl, polyether (being called for short CO-MPE6) of butylene oxide ring end-blocking.The molecular formula of this affixture is (12):
(2) then add 0.8mol novolac epoxy and appropriate tetrahydrofuran (THF) and acetone, stir into after homogeneous phase solution at 30 ℃ of reaction 24h, reaction finishes rear underpressure distillation except desolventizing obtains non-ionic activity emulsifying agent, is called for short MPEF6.The molecular formula of this affixture is (13):
(3) this emulsifying agent adds in Scattered Kettle and mixes with epoxy resin F44 for 1: 15 in molar ratio, and then dripping deionized water, to prepare solid content by phase inversion be 60% epoxy resin water miscible liquid (being called for short MPEF6/F44 water miscible liquid).
Embodiment 7:
(1) in reactor, add 0.6mol α-methoxyl group-ω-alkyl, polyether amine (MPE7) and 0.6mol epoxy pentane (CO), at ambient temperature, stirring reaction 24h obtains α-methoxyl group-ω-N-isoamyl alcohol radical alkyl, polyether (being called for short CO-MPE7) of epoxy pentane end-blocking.The molecular formula of this affixture is (14):
(2) then add 0.8mol novolac epoxy and appropriate tetrahydrofuran (THF) and acetone, stir into after homogeneous phase solution at 30 ℃ of reaction 16h, reaction finishes rear underpressure distillation except desolventizing obtains non-ionic activity emulsifying agent, is called for short MPEF7.The molecular formula of this affixture is (15):
(3) this emulsifying agent adds in Scattered Kettle and mixes with epoxy resin E44 for 1: 15 in molar ratio, and then dripping deionized water, to prepare solid content by phase inversion be 60% epoxy resin water miscible liquid (being called for short MPEF7/E44 water miscible liquid).
Embodiment 8:
(1) in reactor, add 0.4mol α-methoxyl group-ω-alkyl, polyether amine (MPE8) and 0.4mol epoxypropyl phenyl ether (EPE), at ambient temperature, stirring reaction 24h obtains α-methoxyl group-ω-N-propyl group phenyl ether alcohol base alkyl, polyether (being called for short EPE-MPE8) of epoxy pentane end-blocking.The molecular formula of this affixture is (16):
(2) then add 0.4mol novolac epoxy and appropriate tetrahydrofuran (THF), stir into after homogeneous phase solution at 20 ℃ of reaction 24h, reaction finishes rear underpressure distillation except desolventizing obtains non-ionic activity emulsifying agent, is called for short MPEF8.The molecular formula of this affixture is (17):
(3) this emulsifying agent adds in Scattered Kettle and mixes with epoxy resin F51 for 1: 10 in molar ratio, and then dripping deionized water, to prepare solid content by phase inversion be 50% epoxy resin water miscible liquid (being called for short MPEF8/F51 water miscible liquid).
The preparation and property of bi-component aqueous epoxy resin paint film:
First component: non-ion aqueous epoxy resin latex.
Second component: self-vulcanizing nonionic waterborne epoxy curing agent D230 or D400.
Mix in the ratio of first component (epoxy group(ing) mol/g) and second component (active hydrogen number mol/g)=1: 1, after being uniformly dispersed, be coated on tinplate sheet with brush, after moisture evaporation, form transparent paint film.In specific embodiment, adopt aqueous epoxy emulsion and the curing room temperature afterwards of self-vulcanizing nonionic waterborne epoxy curing agent (D230 or D400) prepared by different emulsifiers to test paint film property in table 1 after maintaining 7d.
The performance of the different waterborne curing agent cured paint films of table 1
Note: the H that acid solution is 10%
2sO
4, the NaOH that alkaline solution is 10%.
It is illustrative that embodiment in this specification sheets describes, and nonrestrictive.Protection scope of the present invention is limited by claim, and the art personnel conceive within variation, the restructuring etc. done all should be encompassed in protection domain of the present invention according to the present invention.
Claims (6)
1. the preparation method of a non-ionic activity epoxy emulsifying agent, it is characterized in that: first fully react with monocycle oxycompound and α-methoxyl group-ω-alkyl, polyether amine the α-methoxyl group-ω-N-alkyl, polyether that obtains end-blocking, then add novolac epoxy and the appropriate solvent of equimolar ratio, after stirring into homogeneous phase solution, react 6～24h at 15～50 ℃, underpressure distillation removes desolventizing and makes non-ionic activity emulsifying agent again
Wherein, monocycle oxycompound and α-methoxyl group-ω-alkyl, polyether amine fully react the product α-methoxyl group-ω-N-alkyl, polyether that carries out end-blocking and adopt general formula (1) below to represent:
In general formula (1): m, n, x, y are integer, and 4≤m≤30, and 0≤n≤2, x=1,0≤y≤2; Substituting group on phenyl ring be positioned at phenyl ring neighbour, or contraposition.
2. the preparation method of non-ionic activity epoxy emulsifying agent according to claim 1, is characterized in that: described novolac epoxy adopts low-molecular-weight polyfunctional group liquid epoxies F44, F51 or its mixture.
3. the preparation method of non-ionic activity epoxy emulsifying agent according to claim 1, is characterized in that: be propylene oxide, butylene oxide ring, epoxy pentane for the mono-epoxy compounds of end-blocking, or epoxypropyl phenyl ether.
4. a preparation method for aqueous epoxy resins, is characterized in that comprising the following steps:
A. first adopt mono-epoxy compounds and α-methoxyl group-ω-alkyl, polyether amine fully to react the α-methoxyl group-ω-N-alkyl, polyether that obtains end-blocking, α-methoxyl group-ω-N-alkyl, polyether adopts general formula (1) below to represent:
In general formula (1): m, n, x, y are integer, and 4≤m≤30, and 0≤n≤2, x=1,0≤y≤2; Substituting group on phenyl ring be positioned at phenyl ring neighbour, or contraposition;
B. then add novolac epoxy and the appropriate solvent of equimolar ratio, stir into after homogeneous phase solution at 15～50 ℃ of reaction 6～24h, reaction finishes rear underpressure distillation and obtains non-ionic activity emulsifying agent except desolventizing;
C. this non-ionic activity emulsifying agent adds in Scattered Kettle and mixes by different mol ratio with epoxy resin, and then dripping deionized water, to prepare solid content by phase inversion be 40～60% aqueous epoxy resins.
5. the preparation method of aqueous epoxy resins according to claim 4, is characterized in that: in step b, solvent used is one or more in acetone, tetrahydrofuran (THF), ethanol.
6. the preparation method of aqueous epoxy resins according to claim 4, it is characterized in that: in step c, the mol ratio of non-ionic activity emulsifying agent and epoxy resin is 1:(0～30), the molar content of epoxy resin is non-vanishing, and epoxy resin is low molecular weight liquid epoxy E44, E51, F44 or F51.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210085185.1A CN102633989B (en) | 2012-03-27 | 2012-03-27 | Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210085185.1A CN102633989B (en) | 2012-03-27 | 2012-03-27 | Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102633989A CN102633989A (en) | 2012-08-15 |
| CN102633989B true CN102633989B (en) | 2014-06-11 |
Family
ID=46618575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210085185.1A Expired - Fee Related CN102633989B (en) | 2012-03-27 | 2012-03-27 | Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633989B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262603A (en) * | 2014-10-10 | 2015-01-07 | 天津工业大学 | Polyether demulsifier taking polyether amine as initiator and preparation method of polyether demulsifier |
| CN109021213B (en) * | 2018-06-12 | 2020-12-15 | 瑞奇新材料(广州)有限公司 | Water-based epoxy resin and preparation method thereof |
| CN109627692A (en) * | 2018-12-14 | 2019-04-16 | 中国林业科学研究院林产化学工业研究所 | A kind of self-emulsifying, flexible fat-based aqueous epoxy resins and preparation method thereof |
| CN111171672B (en) * | 2019-12-31 | 2022-04-05 | 鲁东大学 | Preparation method of water-based anticorrosive epoxy coating |
| CN112625554A (en) * | 2020-12-17 | 2021-04-09 | 重庆海联水性涂料有限公司 | Water-based double-component environment-friendly insulating anticorrosive paint for inner wall of transformer and preparation method thereof |
| CN113755082A (en) * | 2021-10-18 | 2021-12-07 | 无锡市造漆厂有限公司 | High-flash-point safe alkyd anticorrosive paint and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003664A (en) * | 2006-01-16 | 2007-07-25 | 浙江安邦新材料发展有限公司 | Latex of epoxy resin of aqueous phenolic aldehyde, and preparation method |
| CN101955589A (en) * | 2010-08-31 | 2011-01-26 | 上海三瑞化学有限公司 | Diluent-free self-emulsifying waterborne epoxy resin emulsion and preparation method thereof |
-
2012
- 2012-03-27 CN CN201210085185.1A patent/CN102633989B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003664A (en) * | 2006-01-16 | 2007-07-25 | 浙江安邦新材料发展有限公司 | Latex of epoxy resin of aqueous phenolic aldehyde, and preparation method |
| CN101955589A (en) * | 2010-08-31 | 2011-01-26 | 上海三瑞化学有限公司 | Diluent-free self-emulsifying waterborne epoxy resin emulsion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102633989A (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102633989B (en) | Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method | |
| CN106987194B (en) | Nonionic waterborne epoxy resin emulsion, nonionic waterborne epoxy curing agent, preparation methods of nonionic waterborne epoxy resin emulsion and nonionic waterborne epoxy curing agent and waterborne epoxy resin varnish | |
| CN105315437B (en) | A kind of self-emulsifying aqueous epoxy hardener of nonionic and preparation method thereof | |
| CN104053723B (en) | Coating for the novel chemically-reactive surfactant of freeze-thaw stability emulsion polymer and comprising it | |
| CN103087611B (en) | A kind of aqueous epoxide resin paint and preparation method thereof | |
| CN102432830B (en) | Water-based epoxy resin curing agent emulsion and preparation method thereof | |
| CN102268214B (en) | Preparation method of aqueous epoxy resin paint | |
| CN102977376A (en) | Nonionic self-emulsifying waterborne epoxy resin and preparation method and application thereof | |
| CN101974162B (en) | Low-VOC (Volatile Organic Compound) self-emulsifying solid epoxy resin water-based emulsion and preparation method thereof | |
| CN106010161B (en) | A kind of water-based metal anti-corrosion material and preparation method thereof | |
| CN103497338A (en) | Preparation and application method of ionic emulsifier special for epoxy resin in waterborne epoxy coating | |
| CN109735193A (en) | Resistance to long-acting heavy-duty aqueous epoxy zinc-enriched paint based on graphene and preparation method thereof | |
| CN104558529A (en) | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent | |
| CN105367755A (en) | Epoxy hardener, antiseptic varnish and preparation method thereof | |
| CN106432706B (en) | A kind of self-emulsification aqueous polyester emulsion and preparation method thereof | |
| CN105907290A (en) | Environment-friendly emulsion type water-based ultraviolet-curing plastic coating and preparation method thereof | |
| CN108059900A (en) | A kind of water-based anticorrosive paint and preparation method thereof | |
| CN109647008B (en) | A kind of aqueous industrial coating mineral oil antifoam agent and preparation method thereof | |
| CN107083152A (en) | A kind of high solidification low viscosity hardware coating | |
| CN109971312A (en) | A kind of aqueous epoxy floor coating and preparation method thereof | |
| CN108003325B (en) | Preparation method of high-molecular water-based epoxy resin, resin prepared by preparation method and application of resin | |
| CN112851967B (en) | Preparation method of thermoplastic waterborne epoxy resin emulsion with high molecular weight and capable of being used in single component | |
| CN112341604B (en) | Emulsion type epoxy curing agent and preparation method thereof | |
| CN109266085A (en) | A kind of reductive modification sulfonated graphene and its preparation method and application | |
| CN109385180A (en) | A kind of aqueous long-acting electrostatic conductive anticorrosion paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 528216 Guangdong Province, Foshan City Hardware Industrial Zone, Danzao Town Nanhai District Bo Jin Road No. 6 Applicant after: Guangdong King-Strong Material Engineering Co., Ltd. Applicant after: Foshan Kangtaiwei New Material Co., Ltd. Address before: 528216 Guangdong Province, Foshan City Nanhai District Danzao Daikin Industrial Zone Applicant before: King-Strong Tools and moulds Co., Ltd. Applicant before: Foshan Kangtaiwei New Material Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: KING-STRONG TOOLS AND MOULDS CO., LTD. TO: GUANGDONG KING-STRONG MATERIAL ENGINEERING LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method Effective date of registration: 20150302 Granted publication date: 20140611 Pledgee: Shunde Guangdong rural commercial bank Nanhai Branch of Limited by Share Ltd Pledgor: Guangdong Xin Gang Xin new material Polytron Technologies Inc|Foshan Kangtai Granville New Material Co., Ltd. Registration number: 2015990000162 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20180510 Granted publication date: 20140611 Pledgee: Shunde Guangdong rural commercial bank Nanhai Branch of Limited by Share Ltd Pledgor: Guangdong King-Strong Material Engineering Co., Ltd.|Foshan Kangtaiwei New Material Co., Ltd. Registration number: 2015990000162 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140611 Termination date: 20200327 |