CN1121437C - In situ emulsified reactive epoxy polymer compositions - Google Patents

Abstract

An emulsified reactive epoxy polymer composition which is readily dispersed in water and is particularly suited for use in a coating composition which may be cured at ambient temperatures. The emulsifiable epoxy composition incorporates a hydrophilic polyoxyalkylene segment.

Description

Emulsive reactive epoxy polymer compositions on the spot

The present invention relates to contain the emulsive reactive epoxy polymer compositions in water of a kind of poly-epoxy emulsion and a kind of emulsive reactive polymer curing composition.On the other hand, the present invention relates to a kind of method for preparing the active polymer compositions of this emulsifying water.The present invention also relates to the cured coating that is formed at an enterprising single step reaction of substrate that is fit to by the active polymer compositions of emulsifying water on the other hand.

The coating system of two portions epoxy resin-matrix generally contains a kind of curable Resins, epoxy and a kind of this curing agent for epoxy resin that is used for, it is dispersed or dissolved in a kind of solvent usually, and---mainly being organic solvent---makes coating composition, for example pigment and floor sealing agent.Based on the reason of environment, it is disadvantageous using the organic solvent based coating composition of this class.On the other hand, the coating of this class solidified epoxy resin-matrix provides hard and wear-resisting and has been the coating of anti-hydro carbons and aqueous medium.

Developed dissolving or the emulsive water-based resin system in water that contain a kind of Resins, epoxy and a kind of solidifying agent, and less to environment and health affected.The exploitation of this class system see the polymkeric substance of Chou tint magazine (Polymers Paint C0lour J0urnal, Vol.184,1994, pp413-417).The water-based resin system has been described in US 4289826, GB-A-1533825 and GB-A-1380108.Described as Chou, known two portions water-based epoxy resin milk sap coating composition has significant disadvantages.Particularly clearly described and lacked in use the amidoamines adducts of dispersion liquid Resins, epoxy or the polyamines of modification: these solidifying agent generally have water-dispersible by making with the salifiable form of VFA.These acid often produce stinks, get rusty and the water sensitive problem fast.Get rusty fast and the water based epoxy priming paint preparation introduction (" Guidelines to Formulation of Waterborne Epoxy Primers ") of corrosive problem at M.A.Jackson, the polymkeric substance magazine (Polymers Paint Colour Journal) of tinting, Oct, 1990, Vol.180, No4270, PP 608-621 and H.Leidheiser, Jr. in organic coating, suppress Corrosion Mechanism (" Mechanism of Corrosion Inhibition with Special Attentionto Inhibitors in Organic Coatings ") about inhibitor, coating technology magazine (Journal of CoatingsTechnology), Oct.1988 has detailed discussion among the pp 97-106.

Thereby be difficult to the milk sap of the stable highly filled low viscosity good fluidity of exploitation usually.In addition, the coating performance that many known architectures show is poor, because in the time of on it being coated in a substrate, there is not its difficult combination of solvent, cause cured coating mechanical flexibility and poor adhesion, porousness height and too high for finishing the required film-forming temperature of ambient cure effect.This class system limited balance between wetting ability and hydrophobicity causes the flexible limited of formulation for coating material.This class system also be subjected to can not be effectively in coating composition in conjunction with the puzzlement of pigment.Therefore, pigment generally mixes with solidifying agent by grinding or stirring.

US 5118729 has described by the reactive grafting on the end-rings oxygen activity group of epoxy molecule before dispersion and has contained the improved waterborne epoxy dispersion that the emulsifying agent of polyethylene oxide residue obtains.

US 5344856 has described a kind of emulsible composition epoxy resin, and the milk sap that it forms a kind of water stability contains a kind of polyepoxide type compound and nominal difunctionality C _12-36The reaction product of lipid acid, by adding a kind of surfactant-dispersed, wherein this tensio-active agent contains poly-(oxyethane) ethanol of a kind of alkyl-aryloxy poly-(propylene oxide) or a kind of C _12-36Poly-(oxyethane) ethanol of-oxyl poly-(propylene oxide), wherein-oxyl partly is C _12-36Fatty Alcohol(C12-C14 and C12-C18) or C _12-36The residue of lipid acid: the chain terminator that can use standard.

US 3297519 has described the Resins, epoxy that need not dispersing auxiliary can self-dispersed concentration in water be up to 10%wt: described resin be select based on the glycidyl ether that contains the bisphenol-A of two bisphenol-A residues in the customized poly-ethylene oxide block bridging molecules.These products are as the composition of paper modifier.

US 5319004 has described water dispersible stiffening agent, and it is used for the Resins, epoxy by the affixture prepared in reaction of specific polyamidoamines acid amides and specific polyamines and specific polyepoxides and polyolefine polyether glycol.

WO-A-9501387 has described the preparation that can disperse the solidified epoxy composite certainly, and by the prepared in reaction of a kind of Resins, epoxy and a kind of polyphenol and a kind of amine-epoxy adduct: amine-epoxy adduct is the reaction product of a kind of aliphatic polyepoxide and a kind of poly suboxygen alkyl amine.Described product must need the amine of a kind of catalyzer promotion and polyphenol and Resins, epoxy-epoxy adduct reaction, and this can disperse the dispersion of solidified Resins, epoxy to require high shear force in specially designed equipment certainly.The back addition of amine-epoxy adduct to Resins, epoxy---this addition produces unsettled aqueous dispersion, and specific reaction sequence is necessary in order to avoid.

DE-A-4405148 has described the water dispersible epoxy composite by the reaction generation of aromatic epoxy resin, bisphenol-A and polyglycidyl ether polyepoxide, and wherein resin can be used to the amine hardener curing of the routine of Aquo System.The dispersion of the epoxy composite that this is water dispersible needs high shear force.

JP-A-H6-179801 has described water base curable composition epoxy resin, but is prepared by the active organic amine curing agent and the water of a kind of Resins, epoxy, a kind of self-emulsifying.Disperse easily by selecting solidifying agent to make.Claim and used the technology of describing of having: claim to have obtained good all being coated with and film forming character less than two kinds of Resins, epoxy of 200 epoxy equivalent (weight)s.

EP-A-EP 0617726 has described and has made the end capped resin of the mixable or soluble amine of water be used for water dispersible Resins, epoxy as solidifying agent, the end capped resin of amine is the reaction product of following material: a 1) polyamine species composition, contain the end capped polyalkylene glycol of one or more wetting ability amine and one or more hydrophobicity polyamines arbitrarily; 2) a kind of polyepoxide is by polyalkylene glycol or poly-(ring alkylidene group) two pure and mild polyglycidyl ethers of hydrophobicity arbitrarily and there are the amine supplement of two active amine hydrogens atoms to derive arbitrarily; 3) a kind of arbitrarily reactive thinner; With 4) be used for amine and Resins, epoxy catalyst for reaction arbitrarily.

No matter the improvement of being done so far, general be difficult to form the emulsive active polymer compositions---by epoxy equivalent (weight) greater than 350 Resins, epoxy and water-dispersion or dispersible solidifying agent derive---stable water dispersion: the dispersion of this based composition does not contain solvent, the height that the viscosity ratio that shows is suitable.Particularly need two kinds of compositions dispersive composition in advance, it obtains the final coating of good mechanical property at low ambient temperature curing.

The emulsive reactive epoxy polymer compositions that need provide present available industrial reactor to produce.Be the character of the final coating of optimization, wish that also this class reactive epoxy polymer compositions does not add acid or a large amount of organic solvent just can be stablized.The hydrophobicity solidifying agent that needs this class reactive epoxy polymer compositions can accept and disperse to use always in addition, may need these hydrophobicity solidifying agent to reach attractive economically low ambient temperature in some applications and solidify, the final coating with excellent mechanical properties still is provided simultaneously.

The invention provides a kind of reactive polymer milk sap, through the following steps preparation:

(i) at least a polyepoxide (II) and at least a polyether polyols diglycidylether (III), a kind of poly-hydroxy hydrocarbon (IX) and a kind of arbitrarily promotion catalyzer (XI) reaction arbitrarily prepare first reaction product;

(ii) first reaction product and polyoxy alkylidene diamines and at least a arbitrarily other amine (V) reaction prepare second reaction product (VIII);

(iii) emulsification second reaction product in water obtains a kind of moisture polyepoxide milk sap (VII);

(iv) in the moisture polyepoxide milk sap (VII) of reaction product (VIII), disperse or dissolve a kind of solidifying agent (XII), obtain emulsive active polymer compositions (I), wherein composition (I) if organic solvent composition---existence---be not more than 1.5%.

Described at least a other amine preferably includes two or more mixture of monofunctional amines, polyamines or its.

The present invention also provides the method for a kind of reactive polymer milk sap of preparation (I), comprising:

(i) at least a polyepoxide (II) and at least a polyether polyols diglycidylether (III), a kind of poly-hydroxy hydrocarbon (IX) and a kind of arbitrarily promotion catalyzer (XI) reaction arbitrarily prepare first reaction product;

(ii) first reaction product and polyoxy alkylidene diamines and at least a arbitrarily other amine (V) reaction prepare second reaction product (VIII);

(iii) emulsification second reaction product (VIII) in water obtains a kind of moisture polyepoxide milk sap (VII);

(iv) in polyepoxide milk sap (VII), disperse or dissolve a kind of solidifying agent (XII), obtain emulsive active polymer compositions (I), wherein composition (I) if organic solvent composition---existence---be not more than 1.5%.

On the other hand, the invention provides a kind of coating composition, contain by solidifying the solidified product that emulsive reactive epoxy polymer compositions (I) obtains.

Stability, wettability and viscometric properties that emulsive active polymer compositions (I) shows.In addition, bonding cohesiveness, flexibility, elasticity and the toughness that shows by the coating of emulsive reactive epoxy polymer compositions (I) preparation.

A kind of stable mixture represented in term " milk sap " as used herein, and wherein in polyepoxide milk sap (VII) or solidifying agent (XII) dispersion, external phase is water, and disperse phase is emulsive reactive epoxy polymer compositions or solidifying agent (XII).Term " emulsible " is described material and can be formed stable water external emulsion as used herein.Term " emulsive " shows that material is present in the disperse phase as used herein.Term " stable milk sap " refers to a kind of milk sap as used herein, does not wherein sink to the bottom in envrionment temperature at 23 ℃ of 6 months by a definite date dispersed compositions and forms solids cake compresses.Term " stable milk sap " does not get rid of in time that some particles settlings are easy to the composition of the soft stores of dispersive again after forming a kind of shaking as used herein.Can in a test, simulate at 23 ℃ of 6 months emulsion-stabilizing degree, wherein observe the emulsion-stabilizing degree that surpassed for 4 weeks at 40 ℃.

Term " reactive polymer " refers to make a further base polymer of chemical reaction of polymkeric substance owing to exist in main polymer chain, chain side or polymer chain terminated active functional group group in polymer backbone as used herein.

A kind of compound represented in term " polyepoxide " as used herein, and its average per molecule contains the epoxy moieties more than.Also comprise partially modified Resins, epoxy, that is, the reaction product of a kind of polyepoxide and a kind of poly-hydroxy hydrocarbon compound, wherein this reaction product average per molecule has the unreacted epoxide unit more than.Can prepare polyepoxide (polyglycidyl ether of poly-hydroxy hydrocarbon) by a kind of epihalohydrin and a kind of poly-hydroxy hydrocarbon or a kind of halo poly-hydroxy hydrocarbon reaction.This class preparation is well known in the art.See Kirk-Othmer chemical technology complete works (Encyclopedia of Chemical Technology) 3rd Ed.Vol.9 pp.267-289.

Epihalohydrin is corresponding to formula 1, wherein

Y is a halogen, preferred chlorine or bromine, most preferably chlorine; R is hydrogen or C _1-14Alkyl, more preferably methyl.

The poly-hydroxy hydrocarbon is represented a kind of compound at this, and it has hydrocarbon skeleton and average primary hydroxyl or secondary hydroxyl part more than, preferably average two or more hydroxylic moieties of each hydrocarbon molecule.The poly-hydroxy hydrocarbon that halogenated poly-hydroxy hydrocarbon is replaced by one or more halogen atoms in this expression.Hydroxylic moiety can be combined in aromatics part, aliphatic series part or alicyclic part.Wherein preferred poly-hydroxy hydrocarbon and halogenated poly-hydroxy hydrocarbon are bis-phenol, halogenated bisphenol, A Hydrogenated Bisphenol A and resol, that is, and and the reaction product of phenol and simple aldehyde---preferred formaldehyde---.The reaction product of phenol and aldehyde---preferred formaldehyde---is a known products, and its preparation method is as the same.This class product is commonly referred to resol.Be preferred for polyol of the present invention (IX) corresponding to formula 2 Wherein:

A is an aryl; By the aryl of an alkyl or halogen replacement; Polyaryl---wherein aryl moiety is by directly key, alkylidene group, halo alkylidene group, cycloalkylidene, carbonyl, alkylsulfonyl, sulfinyl, oxygen or sulphur connection, and this class polyaryl is replaced arbitrarily by one or more alkyl or halogen atom; Or the oligomeric reaction product of a kind of aldehyde and phenol;

U is greater than 1.Preferred u is from greater than 1 to 10, more preferably from greater than 1 to 3, and most preferably from 1.9 to 2.1.

More preferably poly-hydroxy hydrocarbon and halogenated poly-hydroxy hydrocarbon comprise corresponding to those of formula 3-6: R wherein ¹Be respectively C in each case _1-10Alkylidene group, C _1-10Halo alkylidene group, C _4-10Cycloalkylidene, carbonyl, alkylsulfonyl, sulfinyl, oxygen, sulphur, direct key or corresponding to the part of formula 7

R ²Be respectively C in each case _1-3Alkylidene group or halogen;

R ³Be respectively C in each case _1-10Alkylidene group or C _5-60Cycloalkylidene;

Q is respectively tetravalence C in each case _1-10Alkyl;

Q is respectively hydrogen, cyano group or C in each case _1-14Alkyl;

A is 0 or 1 in each case;

M is 0-4 in each case independently;

M ' is respectively 0-3 in each case; S is 0-4;

T is 1-5.

More preferably formula 3,4 and 5 the expression those poly-hydroxy hydrocarbon.

R ¹Preferred C _1-3Alkylidene group, C _1-3Halo alkylidene group, carbonyl, sulphur or a direct key; More preferably direct key, propylidene or a fluoro propylidene (C (CF ₃) ₂-); Propylidene most preferably.R ²Preferable methyl, bromine or chlorine; Most preferable or bromine.R ³Preferred C _1-3Alkylidene group or corresponding to many loop sections of formula 8 Wherein:

T is 1-5, preferred 1-3, most preferably 1.Preferred m ' is 0-2.Preferred m is 0-2.Preferred s is 0-8; More preferably 0-4.

In preferred poly-hydroxy hydrocarbon is dihydric phenol.Preferred dihydric phenol comprise contain not with the phenolic group reaction substituent those.The example of this class phenol is 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane; 2,2-two (4-hydroxy phenyl) propane; 2,2-two (3,5-two chloro-4-hydroxy phenyls) propane; Two (4-hydroxy phenyl) methane; 1,1-two (4-hydroxy phenyl)-1-diphenylphosphino ethane; 1,1 '-two (2,6-two bromo-3,5-dimethyl-4-hydroxy phenyl) propane; Two (4-hydroxy phenyl) sulfone; Two (4-hydroxy phenyl) thioether; Resorcinol and Resorcinol.Preferred dialkyl phenol is 2,2-two (4-hydroxy phenyl) propane (bisphenol-A), 2,2-two (4-hydroxy phenyl) methane (bisphenol-f) and 2,2-two (4-hydroxyl-3,5-dibromo phenyl) propane.

Cycloalkylidene refers to monocycle and polynuclear hydrocarbon part as used herein.Haloalkyl refers to a kind of compound as used herein, and it has the halogen atom of a carbochain and one or more replacement hydrogen.Haloalkyl also refers to the compound that all hydrogen atoms are replaced by halogen atom.Alkylidene group refers to the divalent alkyl part as used herein.

The polyepoxide of Shi Yonging is preferably corresponding to formula 9 in the present invention

Wherein, A, u and R are as defined above.

Select polyepoxide, preferably make reaction product (VIII) not by obviously crosslinked.This highly cross-linked reaction product forms gel and the coating that can not form.When reaction product does not form gel, may there be some branching.

Preferred polyepoxide is corresponding to formula 10-13

Wherein R, R ¹, R ², R ³, a, m, m ', s and t as defined above; R is 0-40.Preferred r is 0-10, most preferably is 1-5.Preferred s is 0-8; 0-4 most preferably.Symbol a, m, m ', r, s and t can represent mean number, because the compound of indication generally is the mixture that the indication unit has the compound of certain distribution.

If in the preparation of reaction product (VIII), use polyepoxide, then should select s to make reaction product not be linked to the stage that generates gel corresponding to formula 12.Preferred s is 0-3.

Polyoxy alkylidene dibasic alcohol diglycidylether (III) refers to the mixture of a kind of compound or compound as used herein, its per molecule contains on average the epoxy moieties more than, it can be by a kind of epihalohydrin and one or more polyol or halogenated polyol prepared in reaction corresponding to formula (14) corresponding to formula (1) R wherein ⁴Be respectively hydrogen, methyl, halogenated methyl or ethyl in each case, condition is if a R on oxyalkyl units ⁴Be ethyl, then another must be a hydrogen; Q is 1-400.Preferred q is 20-350, more preferably 40-300.Symbol q represents mean number, because the compound of indication generally is the mixture that q indication unit has the compound of certain distribution.

Polyoxy alkylidene dibasic alcohol diglycidylether (III) is corresponding to formula 15

Wherein R, R ⁴With q as defined above.

The polyepoxide (II) that uses in reaction product (VIII) is preferably corresponding to formula 10,11 or 12, and polyoxy alkylidene dibasic alcohol diglycidylether (III) is corresponding to formula 15.In another preferred embodiment, the polyepoxide (II) that uses in reaction product (VIII) is corresponding to the polyepoxide of formula 10,11 and 12, and 0.5-15%wt is corresponding to the polyoxy alkylidene diglycidylether (III) of formula 15.In a more preferred embodiment, the polyepoxide that 85-99.5%wt uses in reaction product (VIII) is corresponding to formula 10, and 0.5-15%wt is corresponding to the polyoxy alkylidene diglycidylether (III) of formula 15.

Amine component (V) exists with q.s, and making with the poly-epoxy reaction product (I) of polyoxy alkylidene diglycidylether (III) bonded has enough hydrophil lipophil balances, thereby poly-epoxy reaction product (I) is water dispersible property.Hydrophilic (gathering) amine or hydrophobic (gathering) amine can be present in the amine component.Polyoxy alkylidene diamines (V) is by primary amine or the end capped polyalkylene glycol of secondary amine group.Polyalkylene glycol chain can comprise from C as used herein _2-8Oxide compound or C _2-8Glycol ethylene oxide, third alkylene oxide, fourth alkylene oxide, ethylene glycol, propylene glycol, butyleneglycol, butanediol (such as 1, the 4-butanediol), tetrahydrofuran (THF), propane diol (such as 1,2-or 1,3-propane diol) or its mixture deutero-unit.Preferably, the polyether polyols chain comprises from the mixture of ethylene oxide, third alkylene oxide, ethylene oxide and third alkylene oxide or tetrahydrofuran (THF) deutero-unit, more preferably from ethylene oxide or ethylene oxide and the unitary mixture deutero-of third alkylene oxide deutero-unit.Comprise from the embodiment of the mixture of different alkylene oxide units that at those polyether polyols chains it can be random or with the block form of identical alkylene oxide that different alkylene oxide units is arranged.The polyoxy alkylidene diamines requires enough alkylene oxide deutero-unit, makes polyoxy alkylidene diamines and wetting ability polyepoxide obtain the end capped resin of final amine and has water-soluble or water miscibility.Preferred polyoxy alkylidene diamines molecular-weight average is 200-4000, more preferably 300-3000.The polyoxy alkylidene diamines that the present invention preferably uses is corresponding to formula 16

Wherein:

R ¹⁰Be hydrogen, methyl or ethyl in each case independently;

R ¹¹Be C in each case independently _1-10The alkylidene group of straight or branched, C _1-10The alkenylene of straight or branched or C _5-12The divalence cycloaliphatic groups;

R ¹³Be C in each case independently _1-10The alkyl of straight or branched or hydrogen; Z be independently in each case oxygen or X is C in each case independently _1-8The alkyl of straight or branched; C is 1 or bigger in each case independently; B is 2 or 3 in each case independently; F is 2-4 in each case independently; H is 0 or 1 in each case independently; Precondition is each

If unit f is 2 and R ¹⁰Be ethyl, another R then ¹⁰Must be hydrogen, if f is 3 or 4, R then ¹⁰Be hydrogen.

Preferred Z is an oxygen.Preferred X is C _2-4Alkylidene group.Preferred R ¹⁰Be hydrogen or methyl, be more preferably hydrogen.Preferred R ¹¹Be C _1-10The alkylidene group of straight or branched is more preferably C _2-4Alkylidene group.Preferred c is 2-6, is more preferably 2.6-3.Preferred b is 2.Preferred h is 0.

This class polyoxy alkylidene diamines is well known in the art.The example of preferred polyoxy alkylidene diamines is can be from Texaco Chemicals Company (Houston, Tx, the polyamines of the trade mark JEFFAMINE that USA) buys, for example JEFFAMINE D 400, JEFFAMINE D2000.

Other the amine of can be arbitrarily or optionally existing comprises the amine that contains at least one primary amine or secondary amine part, and it can react with Resins, epoxy; Preferred this compounds is that solid is obstructed.Term " solid is obstructed " about polyamines refers to amino on secondary carbon or tertiary carbon atom, that is, and and the position that solid is obstructed.Preferred this class polyamines is corresponding to formula 17 or 18 R ¹⁴-NH ₂18 R wherein ¹³As defined above, R ¹²Be the cyclohexyl or the C of cyclohexyl, replacement in each case independently _1-50Alkylene, it can be replaced by the substituting group of non-obstruction and can contain one or more secondary amine, ether, amine or thioether part on skeleton.R ¹²Preferred cyclohexyl or C _2-8The alkylene part contains acid amides or secondary amine arbitrarily on skeleton.R ¹³Preferred hydrogen or C _1-4The straight or branched alkylene moiety.In formula 16, R ¹³Hydrogen most preferably.In formula 18, R ¹⁴C most preferably _1-25Linear, side chain, alicyclic ring or greasiness loop section.The example of preferred amine comprises tert-Octylamine, N, N '-di-t-butyl ethylene diamine and 2,6-dimethylcyclohexylam,ne.

These polyamines that comprise q.s in composition are to improve the final mechanical property of the coating of solidifying preparation.If this class polyamines that uses is too much, final resin just can not be fully emulsified in water.

The poly-as used herein end capped molecule of epoxy milk sap (VII) finger ring oxygen as particle with the dispersion of representational size range in water, as the milk sap of preparation as described herein.Generally, the about 1.5 microns resin emulsion of the intermediate value of preferred preparation droplet diameter.Usually obtain the distribution of the droplet diameter of poly-epoxy milk sap particle 0.8-0.7 micron.For leaving standstill for a long time or some sedimentations may taking place during by high dilution when milk sap: stir by low-shearing power and be easy to overcome this sedimentation, for example manually stir the amount that is enough to be used in up to 20 liters.

The compound that poly-hydroxy hydrocarbon (IX) refers to have hydrocarbon skeleton and on average more than one primary hydroxyl or secondary hydroxyl part at this---preferably two or more---.Halogenated poly-hydroxy hydrocarbon refers to the poly-hydroxy hydrocarbon that replaced by one or more halogen atoms at this.Hydroxylic moiety can be connected aromatics aliphatic series part or alicyclic moiety.Wherein preferred poly-hydroxy hydrocarbon and halo poly-hydroxy hydrocarbon are bis-phenols; Halogenated bis-phenol; The hydrogenant bis-phenol; Resol, that is, and the reaction product of phenol and aldehyde---preferred formaldehyde---; And polyalkylene glycol.The reaction product of phenol and aldehyde---preferred formaldehyde---is known product, and its preparation method is as the same.This class product is commonly referred to resol.

At random, the emulsible composition that contains reaction product (VIII) can further contain a kind of organic solvent (X), and it exists with competent amount, stablizes epoxy milk sap in water.At random, this kind solvent is with the amount existence of the reaction product of per 100 weight parts (VIII) 10 parts by weight solvent at the most, preferred 0-5 weight part, most preferably 0-1.5 weight part.Preferred solvent comprises benzene, low-grade alkane alcohol, gamma-butyrolactone, γ-Ji Neizhi and the n-methyl-2-pyrrolidone based on the dibasic alcohol of aklylene glycol and its ether, alkyl or hydroxyalkyl replacement.Preferred aklylene glycol is based on those of ethylene oxide, third alkylene oxide and fourth alkylene oxide.Glycol ether is the alkyl oxide of this class dibasic alcohol.Preferred dibasic alcohol is based on those of third alkylene oxide and fourth alkylene oxide, and preferred glycol ether is the C of propylene glycol and butyleneglycol _1-4Alkyl oxide.Most preferred glycol ether is the C of propylene glycol _1-4Alkyl oxide.The example of preferred solvent is methyl ether, benzylalcohol, Virahol, butyrolactone, γ-Ji Neizhi, n-methyl-2-pyrrolidone and the dimethylbenzene of propylene glycol.

The catalyzer (XI) of preparation that can be used for promoting the reaction product (VIII) of polyepoxides and one or more poly-hydroxy hydrocarbon is those of the reaction that is used for epoxide group and the compound that contains reactive hydrogen well known by persons skilled in the art.The example of the catalyzer that uses comprises zinc carboxylate, organic zinc chelate compound, trialkylaluminium, quaternary alkylphosphonium salt and ammonium salt, tertiary amine and imidazolium compounds.Based on the gross weight of polyepoxides (II) and arbitrarily used poly-hydroxy hydrocarbon (IX), the general consumption of catalyzer is 0.01-2wt%; Preferred 0.02-1wt%, most preferably 0.02-0.1wt%.

The preferred solidifying agent (XII) that can use in the present invention be in poly-epoxy milk sap reaction product (VIII) soluble or dispersible those, its per molecule contains more than 2 reactive hydrogen atoms.Solidifying agent (XII) comprises the affixture of diamines and polyamines or this class polyamines and Resins, epoxy, and such as the reaction product of the diglycidylether of super normal isophorone diamine and dihydroxyphenyl propane, wherein this class reaction product preferably contains 115 normal amine; The polyamines of modification and amido amine and aromatics acid anhydride.Preferred polyamines.The multipolymer and the salt thereof that also can be used as the aminoalkyl groupization that vinyl carboxylic acid is arranged of solidifying agent---as described in US 4227621---and the self-dispersed solidifying agent of in the common co-pending application GB 9604297.3 that proposed on February 29th, 1996, describing.Preferred solidifying agent comprises aliphatic polyamines, the polyglycol diamines, Polypropylene oxide diamine, the poly(propylene oxide) triamine, amido amine, tetrahydroglyoxaline, active polymeric amide, many ring polyamines, ketoimine, (araliphatic) polyamines (promptly, xylylene amine), cycloaliphatic amine (promptly, isophorone diamine or diamines basic ring hexane), the methane diamines, 3,3-dimethyl-4,4-diamino bicyclohexane methylmethane, heterocyclic amine (aminoethylpiperazine), aromatic polyamine (methylene dianiline (MDA)), diamino diphenyl sulfone, mannich base, phenylalkylamine and N, N ', N "-three (the amino hexyl of 6-) melamine.The example of preferred solidifying agent comprises the polyamine curing agent of modification, as Casamid ^TM360 (Anchor Chemicals Ltd., Manchester, United Kingdom) or a kind of amine-epoxy adduct Epilink ^TMDP 660 (Akzo, Deventer, TheNetherlands).Other useful stiffening agent can be the mannich base class, that is, and and the reaction product of nonyl phenol, formaldehyde and a polyamine species---for example xylylene amine---.Akzo is with trade name Epilink ^TMDP 500 sells this class product.

Composition epoxy resin of the present invention contacts with cured resin with the solidifying agent of capacity.Preferably (epoxy glycidyl ether) equivalent is 0.5: 1 and 2: 1 with the normal ratio of solidifying agent; More preferably 0.6: 1.4-1.4-0.6; Even more preferably 0.8: 1.2-1.2: 0.8; Most preferably 0.9: 1.1-1.1: 0.9.

Milk sap of the present invention can comprise pigment, dyestuff, stablizer, softening agent and other conventional additives.Preferably dispersion in water or milk sap prescription have the solid content of 40-80%, most preferably 50-70%.

When being used to form coating, emulsive active polymer compositions of the present invention contacts with a kind of substrate.Coating is left in the cosolvent of water and any use evaporation subsequently.Coating was solidified in several days under envrionment conditions.Elevated temperature can be used for quickening the curing of coating composition.This condition of cure is known for those skilled in the art.Coating composition can contact with any methods known in the art with substrate, comprises spraying, inclining is coated with or roller coat.

In this case, carry out epoxy and improve reaction to prepare a kind of improved polyepoxide, the technology of carrying out this class reaction is well known to a person skilled in the art: see " Resins, epoxy handbook (TheHandbook of Epoxy Resins) ", H.Lee and K.Neville (1967), McGraw Hill, New York and US 2633458; 3477990; 3821243; 3907719; 3975397; 4071477.Can use conventional catalyst and conventional chain regulator and the chain terminator that epoxy improves reaction that be used for well known in the art.

Be the preparation coating composition, use pigment, slip additive, filler, dispersing auxiliary, defoamer, levelling agent, air-release agents and other additive commonly used in industry. The character of epoxy milk sap

The character with the two composition epoxy adhesive systems of solidified emulsification that applies depends primarily on the character of milk sap, especially depends on droplet size and distribution.Milk sap character partly influences formation, time of drying, water tolerance, gloss, pigment binding ability, productive rate, flexibility, associativity and the hardness of film.

Compare preparation and be easier to foaming when using the resin of water-dispersion with conventional solvent system.It is because in the especially impact of the mechanical energy when technological process is not carried out under vacuum during the emulsion process that this unfavorable foamy forms.Foam can cause apparent defective, such as hole, bubble and flake.The selection of the nonionic emulsifying agent in the Resins, epoxy of experiment also provides the ability of low bubble milk sap according to it.But (additive Germany) can join before emulsification in the epoxy-capped material for Byk Chemie, Wesel such as BYK 023 defoamer.The concentration of the defoamer that adds should be 0.04-0.5%.

The flocculation of resin droplet or assembly can cause inhomogeneous and coarse surface.The size of the droplet of milk sap has different influences to the different properties of film.

The increase of droplet particle size can reduce the character that resembles gloss, water tolerance, stability and pigment associativity, and the increase of droplet particle size can improve time of drying, bonding force and brushability.Obviously should find the balance of character.

General preferred preparation droplet dia little, the about 1.5 microns resin emulsion of its intermediate value.Usually obtain the experimental ring epoxy resins droplet dia be distributed as 0.8 and 7 micron.But, prolong when leaving standstill some sedimentations may take place with high dilution milk sap.Therefore take out from container when a small amount of need be by stirring that milk sap is avoided because that concentration difference causes is inconsistent.

In one embodiment, the invention provides mixture as the end capped poly-amino of a kind of waterborne epoxy of water dispersion-epoxy adduct milk sap (VII) and a kind of solidifying agent (XII), the end capped poly-amino of waterborne epoxy-epoxy adduct milk sap (VII) contains the reaction product of following material: the 30-90 weight part, preferred 50-85 weight part, more preferably one or more molecular-weight average of 60-80 weight part are greater than 300 aromatic polyepoxide (II), the 2-50 weight part, preferred 5-30 weight part, the poly(propylene oxide) diglycidylether (III) of the molecular-weight average 250-12000 of 10-20 weight part most preferably, and 2-50 weight part, preferred 5-30 weight part, the compound of 10-20 weight part (V) most preferably, the end capped poly-amino of waterborne epoxy-epoxy adduct milk sap (VII) is 178-1000 based on solid epoxy equivalent (weight) (EEW), preferred 250-750, most preferably 400-650.The end capped poly-amino of waterborne epoxy-epoxy adduct milk sap and a kind of solidifying agent are mixed with moisture emulsive active polymer compositions (I), solidifying agent (XII) exists with aqueous solution or dispersion form, or this solidifying agent can disperse in the end capped poly-amino of waterborne epoxy-epoxy adduct milk sap.

In another embodiment, before reacting with amine compound, by well known to a person skilled in the art standard method, can make aromatic polyepoxide and poly(propylene oxide) diglycidylether collaborative mutually or with a kind of polyphenol or a kind of alcohol reaction, the epoxy-capped compound of higher molecular weight is provided.

Another embodiment is the method for the moisture emulsive active polymer compositions of preparation.In the method, polyepoxide and amine 70-135 ℃, more preferably 80-130 ℃, most preferably 85-125 ℃ in liquid-phase mixing.Polyepoxide and amine be reflected at 80-200 ℃, more preferably 80-180 ℃, most preferably 80-160 ℃ carry out.The product that generates in water be emulsified in 50-110 ℃, more preferably 50-100 ℃, most preferably 50-90 ℃ carry out.Be the end capped poly-amino of preparation waterborne epoxy-epoxy adduct milk sap, the end capped poly-amino of waterborne epoxy-epoxy adduct milk sap and solidifying agent mix under the condition of low-shearing power stirring action in envrionment temperature.General use in the art be lower than 100rpm (rev/min) manually stir or the mixing in conventional equipment is enough to the emulsification in water with amino-epoxy adduct and solidifying agent.Can use higher stirring velocity, but not require.

Other embodiment is the cured coating that this moisture emulsive active polymer compositions ambient cure forms.Above-mentioned epoxy-capped stable milk sap provides stable emulsive active polymer compositions, temperature at 5-35 ℃, preferred 10-30 ℃, through 5-75 hour, preferred 10-50 hour time, relative humidity at 10-100%, preferred 25-60%, its curing provides the glossy cured film, the curing properties that shows, good anti-pendulum hardness and chemical resistant properties.

With conventional in the industry and be to well known to a person skilled in the art that method prepares clarifying formulation for coating material and painted pharmaceutical formulation.

The test method that is used for evaluate cure characteristic and coating performance also be industry conventional and be well known to a person skilled in the art.The special test method of using is now described.Other embodiment is the cured coating that this moisture emulsive active polymer compositions ambient cure forms.Above-mentioned epoxy-capped stable milk sap provides stable emulsive active polymer compositions, temperature at 5-35 ℃, preferred 10-30 ℃, through 5-75 hour, preferred 10-50 hour time, relative humidity at 10-100%, preferred 25-60%, its curing provides the glossy cured film, the curing properties that shows, good anti-pendulum hardness and chemical resistant properties.

Other embodiment is the cured coating that this moisture emulsive active polymer compositions ambient cure forms.Above-mentioned epoxy-capped stable milk sap provides stable emulsive active polymer compositions, temperature at 5-35 ℃, preferred 10-30 ℃, through 5-75 hour, preferred 10-50 hour time, relative humidity at 10-100%, preferred 25-60%, its curing provides the glossy cured film, the curing properties that shows, good anti-pendulum hardness and chemical resistant properties.

With conventional in the industry and be to well known to a person skilled in the art that method prepares clarifying formulation for coating material and painted pharmaceutical formulation.

The test method that is used for evaluate cure characteristic and coating performance also be industry conventional and be well known to a person skilled in the art.The special test method of using is now described. Painted prescription

The research to painted coating for described in the present invention has prepared different paint.

At first, (Germany) middle mixing is 5 minutes for VMA Getzmann, Reichshof at Dispermat FT at 2500 rpm for solidifying agent and pigment.The granulated glass sphere that in pigment paste, has added diameter 2mm, thus the weight ratio of pigment paste and granulated glass sphere is 1: 1.Under water cooling, carry out grinding in 25 minutes then with 2500rpm.After this in grinding base, add grinding water and defoamer, at 1000rpm with painted mixture restir 5 minutes.Grind the back and read the Grindometer reading, also read reading to confirm numerical value again in afterwards one day from pigment paste.In some cases, existing air bubble to hinder immediately in cream measures.The average particle size particle size of pigment paste is about 10 microns. Coating is used

Be used for using of physical test (solidification rate and gloss, flexibility) at single coating, coating with the Erichsen applicator (Erichsen, Hemer-Sundwig, Germany) or air-spraying make the film of a pre-determined thickness 50-60 micron.In using, the single coating of about 90 microns builds carries out all chemical resistant properties tests. Substrate

Use in test three kinds of substrates:

1. there is the sand blasting cold-rolled steel of 40 microns peak valley external forms to be used for salt tolerant spray test.Carry out two application that are coated with.The about 50-60 micron thickness of the coating of each formation, under envrionment conditions each coating at interval 1 day in order to solidify.

2. (190mm * 105mm * 0.75mm) is used for physical test to bonded steel 26-60-0C.

3. sheet glass is used for subsequently gloss and clarity test during working life and film formation. The condition of cure that is used to study

Before test according to following timetable under envrionment conditions (23 ℃/45-55%RH) solidity test sheet:

1. physical properties: 7 days

2. tolerance: in 3 weeks (minimum), these conditions and timetable exception show in data sheet and indicate.

3. the curing under improved condition is at the humidity check curing performance of 10 ℃ and very high about 80%RH (relative humidity).In this case, from measuring any long-term disadvantageous effect---as getting rusty fast---testing circumstance measure after shifting out test film. Physical test The time of drying of whole film (TFDT)

Be in the organic coating drying or solidify to form each stage of film and the module of degree that the type that is used for comparison coating is or/and the composition variation time of drying of whole film.Following process is that ASTM D 1640-83 is generalized basically, still, this use the Erichsen drying time recorder (509 types, Erichsen, Hemer-Sundwig, Germany).This is that a kind of register scribbles with constant speed a pin the glass stick of coating and pulls out above one. Methyl ethyl ketone (MEK) tolerance/pair friction

This test monitoring is solidifying its conduct of starting stage coating in the tolerance of the function of using the back time in the past to MEK.Prepare coating on steel, after coating was not sticking, the thickness of the desciccator diaphragm of test system was also determined reference frame.The difference of the thickness of desciccator diaphragm should be greater than 10%.It is as follows to carry out actual test: the flat end of 500g hammer is wrapped up with a slice cotton-wool fabric.Cotton-wool fabric has soaked into MEK, hammer is moved on to one side of panel.Move hammer front and back on whole coating is once two frictions.Careful operation does not apply any pressure on hammer.After per 20 two frictions, cotton-wool fabric soaks into again with MEK.Repeating this process is become visible by the panel that rubs or produces the degree of other shortcoming up to coating.Repeating this test every day can stand 100 two frictions and not have the visible influence to take place up to applying thing.The different table of the two friction development of MEK is sensible to crosslinked degree. Gloss

(Berlin Germany) reads reading and the measurement reflection at 20 °, 60 ° and 80 ° angles for Type L, Dr.Lange with the gloss gauger. Pendulum hardness forms

This test method is with pendulum damping test device, by being applied to hardness of organic coating progress on the acceptable crust as the tolerance of state of cure.Experimental evidence ASTM D 4366-84 method B: " pendulum of organic coating hardness (Persoz) damping test " carries out. Anti-abrupt impact

Carry out shock test with Gardner Heavy Duty Variable Impact Tester.Carry out oppositely (matrix is between knocker and test coating) and directly (knocker acts on coating) shock test.The result is with power (joule) expression of destruction (cracking) needs that cause film; Therefore, reading is high more, and the flexibility of film is good more. Film thickness

According to ASTM D 1186-81: " being applied to the non-destroyed measurement of the desciccator diaphragm thickness of the non magnetic coating on the iron-based material " (11) carry out this test. Clinging power

Cross cut test is to measure one or more coating systems to the clinging power of its matrix and the simple empirical experiment of inter coat clinging power.According to ASTM D 3359-83: " measuring clinging power by tape test " method B carries out this test.This method comprises by add and remove the clinging power of adhesive tape evaluation coated membrane to metal matrix on the otch of film.In the described embodiment of this report, use TESAPACK 4124 adhesive tapes. Tolerance to slow destruction/Erichsen rag

This empirical experiment explanation coating system is to because cracking that the destruction of matrix causes and/or the tolerance that loses clinging power.According to DIN/ISO 1520 in February nineteen eighty-two: " Tiefungspruefung " carries out this test. Chemical resistant properties

This test shows chemical resistant properties rapidly, only uses based on relevant rudimentary.

The cotton of the about 1cm of a slice diameter-wool fabric is with waiting that the chemical of testing coating soaks into.The chemical that is used for this purpose is: deionized water, ethanol, dimethylbenzene, toluene, gasoline, aqueous sodium hydroxide solution (10wt%), acetic acid aqueous solution (10wt%), aqueous hydrochloric acid (10wt%) and aqueous sulfuric acid (10wt%).Cotton-wool fabric is covered on the coating by silicone grease sealed glass lid with a diameter 50mm, 30mm height.Per hour or every day by measure bubbling and the outward appearance of the degree evaluation coating of variable color.This test carried out for 1 week.Monitor and bubble and the surperficial result who tests of visible, as variable color or softening, with 0 (the poorest)-10 (best) rating. The salt spray

In the saturated salt fog cabinet of the mist of 5% salts solution, test.55 ℃ of test temperatures.With epsilon lambda notation panel up to matrix.Expose and check panel after 500,750 and 1000 hours.Think and surpass the 6mm foaming or wrinklingly can not protect matrix exactly from line. Wet fastness

In the cabinet of 40 ℃ and 100% humidity, test.Expose and check after 550,750 and 1000 hours.The generation foaming is just thought can not protect matrix.

The following example is used herein to the purpose of detailed description, and does not think the restriction to the claim scope.Except as otherwise noted, umber described herein and percentage ratio are all based on weight.

Embodiment 1

1 liter of five neck round bottom glass reactor of nitrogen inlet, water condenser and electronic metal anchors agitator is equipped with in use.Use the 250ml dropping funnel.With thermocouple, heat cover and temperature regulator controlled temperature.

Diglycidylether (the A of the bisphenol-A of epoxy equivalent (weight) (EEW) 180,360g) with epoxy equivalent (weight) 5450,5: 1 polyoxy alkylidene diglycidylether (B of ethylene oxide/propylene oxide mol ratio, 60g) place reactor, in 30 minutes, in nitrogen atmosphere, be heated to 100 ℃.Use agitator after the B fusion, under agitation add 2, and the 6-dimethylcyclohexylam,ne (C, 80g).Reaction mixture is heated to 120 ℃, so thermopositive reaction takes place subsequently, peak value is at about 160 ℃.Reaction mixture reaction 2 hours.The Resins, epoxy that generates is the semisolid of non-sticky, the solubility that shows in acetone.Resin is cooled to 100 ℃, continues to add entry (500g) at 90 ℃, keeps 85-95 ℃ temperature simultaneously during first batch of 250ml water adds, and keeps 70-75 ℃ during second batch of 250ml water adds.The milk sap that generates kept 2 hours at 60 ℃ again, was cooled to bottling below 30 ℃.This epoxy milk sap solids content 50%, at the about 7500mPa.s of 23 ℃ viscosity, EEW about 1250.

(Ancamine 2280, and Anchor Chemicals UK is 8.4g) by manually being stirred in emulsification in the epoxy milk sap (100g) for preparing above with amino hydrogen equivalent (AHEW) 108 for poly-(methylene radical cyclo-hexylamine) in benzyl alcohol.Adding water (15 milliliters) alkene then releases.With this mixture on Bonder 26 60 0C steel plates with 200 microns drawing-offs rod casting film-formings.Coating becomes not sticking after 1 hour, stands the two frictions of 100 MEK after 24 hours 23 ℃ of curing, stands 200 MEK pairs after 7 days 23 ℃ of curing and rubs.Water droplet does not damage after last 7 hour or dissolves this film in this coating: the clinging power of this coating is fabulous.After 7 days, the coating of formation forms 17 joules impact resistance in self-vulcanizing, and Erichsen indentation value is 9.

Embodiment 2

Reaction sequence, reactant and equipment and in embodiment 1, use similar.Diglycidylether (the A of the bisphenol-A of epoxy equivalent (weight) (EEW) 180,387g) with epoxy equivalent (weight) 5450,5: 1 polyoxy alkylidene diglycidylether (B of ethylene oxide/propylene oxide mol ratio, 63g) place reactor, in 30 minutes, in nitrogen atmosphere, be heated to 100 ℃.Use agitator after the B fusion, under agitation add uncle's octyl amine (C, 80g).Reaction mixture is heated to 120 ℃, so thermopositive reaction takes place subsequently, peak value is at about 145 ℃.Reaction mixture reaction 2 hours.Resin was cooled to 70 ℃, added entry (470g) when keeping 50-70 ℃ at 1 hour.The milk sap solids content 52.5% that generates, at 23 ℃ viscosity 10000-15000mPa.s, EEW about 1075.

As shown in table 1 that this improved epoxy milk sap is painted, (AHEW 125 with hydrophobic relatively solidifying agent polyamidoamines acid amides Versamid 140, Cray Valley, Newport, Wales, United Kingdom) and 1: 1 the mixture solidified of weight ratio of the Polypropylene oxide diamine of molecular weight 400 (Jeffamine 400, Texaco Chemicals Company).The painted system water of describing in table 1 further dilutes, and is sprayed on the Bonder 26 60 0C plates.23 ℃ of color compositions dryings in 30 minutes: 23 ℃ solidify 7 days after the plates of coating stand the two frictions of 200 MEK and the performances (exposing 7 days in 55 ℃ of high humidity environments) of fabulous anti-water of condensation arranged.

Table 1

The contrast of the reactive epoxy polymer of painted emulsifying water

Technology/component	Coating 1 *	Coating 2 *
			Under agitation mix	Weight	Weight
Epoxy milk sap (EEW 1075, involatile constituent 52.5%)-embodiment 2	49.78	41.82
			Deionized water	10.23	16.10
Red iron oxide (Bayferrox 130M/Bayer AG, Leverkusen, Germany)	-	0.81
			Fe 2O 3And Mn 2O 3Pigment composition (Bayferrox 303T/ Bayer AG)	1.14	-
Iron oxide yellow (Bayferrox 920/Bayer AG)	-	0.81
			Titanium dioxide (Finntitan RR2/Kemira, Pori, Finland)	3.73	11.53
Contain magnesite MgCO 3Talcum powder (Talcum AT Extra/ Norwegian Talc Deutschland GmbH, Bad Soeden-Salmuenster, Germany)	1.82	-
			Lime carbonate (Dureal 10/OMYA GmbH, Koeln, Germany)	17.54	-
Moscow mica (Micro Mica W 1/Norwegian Talc Deutschland GmbH)	9.37	-
			Process white (Blanc Fix N/Sabed, Massa, Italy)	-	11.53
Zinc phosphate (Sicor ZNP/S/BASF AG, Ludwigshafen, Germany)	-	11.53
			The milk sap of non-volatile emulsifying agent of hydrophobicity and froth breaking polysiloxane (BYK 203/Byk-Chemie GmbH, Wesel, Germany)	0.60	0.59
(＜40 ℃) are distributed to＜10 μ m with the horizontal ball mill under cooling
			Under agitation add

Polyaminoamide (Versamid 140/Cray Valley) Polypropylene oxide diamine (Ancamine 480/Anchor Chemical) is at about 124 mixed catalysts of AHEW (Ancamine K 54/ Anchor Chemical)	0.79	54.40
			Equal paint (BYK S 715/Byk-Chemie GmbH)		-81
Polyether-modified methyl alkyl polysiloxane copolymer (BYK A 525/Byk-Chemie GmbH)		-81
			Total amount	00.00	1100.00

^*Coating 1=grey paint ^*Coating 2=rose coating embodiment 3

Method according to embodiment 1, diglycidylether (the A of the bisphenol-A of epoxy equivalent (weight) (EEW) 180,141.6g), bisphenol-A (B, 44.5g), epoxy equivalent (weight) 5450,5: 1 polyoxy alkylidene diglycidylether (C of ethylene oxide/propylene oxide mol ratio, 64.7g), p-tert-butylphenol (D, 7.6g) and methoxypropanol (E 4.2g) places reactor, is heated to 80 ℃ in 30 minutes in nitrogen atmosphere.Stir, mixture heating up to 90 ℃, under agitation add 70% active in methyl alcohol Yi base triphenyl phosphonium acid acetate (F, 0.4g).Reaction mixture is heated to 115 ℃, therefore thermopositive reaction takes place subsequently, and peak value is at about 140 ℃.With reaction mixture further be heated to 145 ℃ 2 hours, generate improved Resins, epoxy, epoxy equivalent (weight) is 760.

This resin is cooled to 90 ℃, under agitation add molecular weight 400 Polypropylene oxide diamine (Jeffamine D400, G, 163.6g) and isophorone diamine (H, 67.4g).Stop all heating, before 86 ℃ of generations of peak value, reacted constituent is cooled to about 70 ℃ in thermopositive reaction.At 45 minutes reaction mixture slowly is heated to 120 ℃, remained on this temperature 1.5 hours, be cooled to 99 ℃ at 15 minutes.Added entry (404.0g) continuously at 35 minutes when maintaining the temperature at least 65 ℃, before being cooled to be lower than 30 ℃ of bottlings, the milk sap of generation stirred 30 minutes at 60 ℃.

The milk sap solids content 55% that generates, at 23 ℃ viscosity 5000mPa.s, amino hydrogen equivalent (AHEW) is about 315, and pH is 11.4.

Embodiment 4

Poly-(the methylene basic ring is amine) (Ancamine X2280/Anchor Chemical, 85g) fully (BYK Chemie is 10.5g) with three-2,4 with dispersing auxiliary Disperbyk 182 in room temperature, (Ancamine K54/Anchor Chemical 4.5g) mixes 6-dimethylaminomethyl phenol.

Embodiment 5

Reaction sequence, reactant and equipment and in embodiment 1, use similar.Diglycidylether (the A of the bisphenol-A of epoxy equivalent (weight) (EEW) 180,235g), the polyglycidyl ether (B of the bisphenol-f of functionality 2.2 and epoxy equivalent (weight) (EEW) 168,100g), epoxy equivalent (weight) 5450,5: 1 polyoxy alkylidene diglycidylether (C of ethylene oxide/propylene oxide mol ratio, 60g) and bisphenol-A (D, 42.5g) place reactor, in 30 minutes, in nitrogen atmosphere, be heated to 80 ℃.Stir, mixture heating up to 90 ℃, under agitation add 70% active in methyl alcohol Yi base triphenyl phosphonium acid acetate (E, 0.6g).Reaction mixture is heated to 115 ℃, so thermopositive reaction takes place subsequently, peak value is at about 165 ℃.Reaction mixture further is heated to 145 ℃ of reactions 1.5 hours, generates the improved Resins, epoxy of epoxy equivalent (weight) 288.This resin is cooled to 100 ℃, under agitation add molecular weight 2000 Polypropylene oxide diamine (Jeffamine D2000, F, 62.5g).Reaction mixture was 92-95 ℃ of reaction 1 hour.

Added entry (500.0g) continuously at 1 hour when maintaining the temperature at least 70 ℃, before being cooled to be lower than 30 ℃ of bottlings, the milk sap of generation stirred 1 hour at 60 ℃.

Milk sap (embodiment 5) solids content 50% that generates, at 23 ℃ viscosity 2000-8000mPa.s, about 718 (based on the milk sap) of EEW.

In Table II the prescription of Clear paint that preparation as system 1-3 contains the epoxy resin emulsion of above-mentioned preparation has been described respectively, it has three kinds of stiffening agents respectively: the solution of (embodiment 5.1) a kind of poly-amino epoxy adduct in water is as solution, have 70% solid and AHEW 200 (Anquamine 401/Anchor Chemical), (embodiment 5.2) preparation method has described the character of the Clear coating that obtains 23 ℃ of these systems of curing at amine hardener and the amine hardener of (embodiment 5.3) preparation method in embodiment 4 descriptions that embodiment 3 describes in Table III.In Table IV, V and VI, describe based on painted formulation for coating material at this resin described in the embodiment 5 and hardener component, in Table VII, described by respectively 23 ℃ and 10 ℃ of curing by the comparison of the coating of these formulation to its general character.The erosion resistance that is obtained by the coating of these formulation by 23 ℃ of curing has been described in Table X III.

Table II

The Clear paint prescription

Component (weight part)	System 1	System 2	System 3
				Under agitation mixed 15 minutes
Epoxy milk sap-embodiment 5	721.7	618.1	716.0
				Solidifying agent 5 (1)	198.8	-	-
Solidifying agent 5 (2)	-	267.7	-
				Solidifying agent 5 (3)	-	-	142.0
Three-2,4,6-dimethylamino phenol (Catalyst Ancamine K54/Anchor Chemicals)	-	13.9	-
				Dilute with deionized water	79.5	100.3	142.0
At 23 ℃ viscosity (mPa.s)	About 3000	About 4500	About 2500
				Applying solid, %	50.0	50.0	50.0
The weight ratio of amino-H and epoxy equivalent (weight)	1∶1	1∶1	1∶0.9

Table III

The character of Clear paint

Character	System 1	System 2	System 3
				I) wet varnish uses the % benzylalcohol under the viscosity	0	0	About 7
Working life [hour]	Maximum 3	1.5	Maximum 2.5
				The time of drying of whole film (TFDT) [hour]	-6	-8	-6
II) desciccator diaphragm (on Bonder 26-60-0C) film thickness [μ m]	43	57	45
				Persoz hardness [s] was solidified under the envrionment temperature and was solidified under the envrionment temperature in 7 days in 1 day	40 90	60 159	90 236
The film outward appearance	Mist is arranged	Mist is slightly arranged	Transparent
				Draw lattice cohesive [% is residual] and solidified Erichsen indentation[mm under the environment temperature in 7 days] solidify 7 days resistance to water under the environment temperature and solidified the frictional property of anti-MEK in 1 day under the environment temperature and solidified under the environment temperature in 1 day	100＞10 poor＞100	100 9 100	100 9 fabulous＞150

Table IV

Formulation for coating material 1

Technology/component	Weight
		Under agitation mix
The aqueous solution of comparing embodiment 5	312.70
		Finntitan RR2 (titanium dioxide of Kemira)	101.72
Sicor ZNP/S (zinc phosphate of BASF)	101.72
		Blanc fix N (S0lvay SA, B-1050 Brussels, Belgian barium sulfate)	101.72
Bayferrox 130 M (ferric oxide of Bayer AG, redness)	7.13
		Bayferrox 920 (ferric oxide of Bayer AG, yellow)	7.13
Deionized water	86.36
		Byk 023 (defoamer of Byk Chemie GmbH)	4.81
(＜40 ℃) are distributed to＜10 μ m with the horizontal ball mill under cooling
		Under agitation add ready-formed solution, it contains:
The epoxy hardener that is used for embodiment 5 (1)	87.57
		Deionized water	189.13
The adding deionized water reaches the viscosity of application requiring	1000.00
		Parameter
Solids content:	53.7
		The pigment/binder ratio:	1: 0.7 (solid)
Pigment volume concentration (PVC) (PVC)	30.0％

Table V

Formulation for coating material 2

Technology/component	Weight
		Under agitation mix
The solidifying agent that is used for embodiment 5 (2)	124.77
		Catalyst A ncamine K54 (Anchor chemicals Ltd.)	8.76
Finntitan RR2 (titanium dioxide)	112.77
		Sicor ZNP/S (zinc phosphate)	112.77
Blanc fix N (barium sulfate)	112.77
		Bayferrox 130 M (ferric oxide, redness)	7.90
Bayferrox 920 (ferric oxide, yellow)	7.90
		Deionized water	65.32
Byk 033 (defoamer)	2.22
		(＜40 ℃) are distributed to＜10 μ m with the horizontal ball mill under cooling
Under agitation add
		Be used for the embodiment 5 epoxy aqueous solution relatively	287.92
Deionized water	156.90
		The adding deionized water reaches the viscosity of application requiring	1000.00
Parameter
		Solids content:	57.6
The pigment/binder ratio:	1: 0.7 (solid)
		PVC	30％

Table VI

Formulation for coating material 3

Technology/component	Weight
		Under agitation mix
The embodiment 5 epoxy aqueous solution relatively	443.66
		Finntitan RR2 (titanium dioxide)	76.01
Sicor ZNP/S (zinc phosphate)	76.01
		Blanc fix N (barium sulfate)	76.01
Bayferrox 130 M (ferric oxide, redness)	5.32
		Bayferrox 920 (ferric oxide, yellow)	5.32
Deionized water	31.14
		Byk 023 (defoamer)	4.65
(＜40 ℃) are distributed to＜10 μ m with the horizontal ball mill under cooling
		Under agitation add
The solidifying agent that is used for embodiment 5.3	88.98
		Add deionized water then	192.90
The adding deionized water reaches the viscosity of application requiring	1000.0
		Parameter
Solids content:	55.0
		The pigment/binder ratio:	1∶1.3
PVC	20％

Table VII

Water-based paint 1,2 and 3---the contrast of general aspects

(23 ℃ of curing)

General aspects	Coating 1	Coating 2	Coating 3
				Contain epoxy curing agent	5.1	5.2	5.3
The pigment volume concentration (PVC) of coating [%]	30	30	20
				Coat-thickness [μ m]	About 55	About 55	About 55
Time of drying, not sticking [hour]	1.8	2.5	2.8
				20 °/60 °/80 ° of gloss	1/2/33	1/6/27	9/50/86
MEK tolerance [DR] solidified in 1 day	＞100	80	＞100
				Fork (Pendulum) hardness is according to Persoz[s]	133	137	198
Draw lattice sticking power tape test surplus [%]	100	100	100
				Erichsen penetration hardness (indentation) [mm]
Solidified in 7 days	5.5	3.5	5.0
				Solidified in 14 days	3.3	3.4	4.5

Water-based paint 1,2 and 3---the contrast of general aspects

(solidifying) at 10 ℃/80%RH

General aspects	Coating 1	Coating 2	Coating 3
				Contain epoxy curing agent	5.1	5.2	5.3
The PVC[% of coating]	30	30	20
				Coat-thickness [μ m]	About 55	About 55	About 55
20 °/60 °/80 ° of gloss	1/3/36	3/22/50	14/62/91
				MEK tolerance [DR] solidified in 7 days	＞100	＞100	＞100
Fork (Pendulum) hardness is according to Persoz[s]	68	76	111
				Draw lattice sticking power tape test surplus [%]	100	100	100
Erichsen penetration hardness (indentation) [mm]	6.1	3.9	8.7

Table VIII

Coating 1,2 and 3 erosion resistance

Character	Coating 1	Coating 2	Coating 3
				Humidity ASTMD 4885-86A 7 days is constant in 55 ℃ of foamings [10=is best]	0	5	7
Clinging power after 24 hours in 23 ℃/50%RH pull-up adhesive tape, residual quantity [%]	0	99	99
				Salt spray-ASTM (B-117-730 *)[H]	350	500	1000
Scripe degree of wriggling [mm]	About 2	0	0
				Scripe bubble [10=is best]	4	4	9
Surface blistering [10=is best]	4	4	9
				Surface corrosion	Do not have	Do not have	Do not have

^*Have 50 μ m, first coating and 60 μ m, second coating, 40 μ m to sandblast to test on the steel at the maximum 40 μ m of peak-to-valley ratio.

Embodiment 6

Reaction sequence, reactant and equipment and in embodiment 1, use similar.Functionality 3.6, EEW are the polyglycidyl ether (A of 178 phenolic aldehyde, 390g) with epoxy equivalent (weight) 5450,5: 1 polyoxy alkylidene diglycidylether (B of ethylene oxide/propylene oxide mol ratio, 60g) place reactor, in nitrogen atmosphere, be heated to 90 ℃.Use agitator, reactant is 90 ℃ of reheat 15 minutes, under agitation add molecular weight 2000 Polypropylene oxide diamine (Jeffamine 2000, C, 50.0g).Temperature is reduced to 84 ℃, and it is muddy that mixture becomes.Reaction mixture carries out thermopositive reaction at 90 ℃, generates transparent solution.Mixture heating up to 100 ℃ remained on this temperature 15 minutes, under agitation water (250.0g) was added continuously at 30 minutes subsequently, maintained the temperature at 85-95 ℃ simultaneously.Mixture remain on 90 ℃ 15 minutes, under agitation water (118.0g) was added continuously at 15 minutes subsequently, maintain the temperature at 70-80 ℃ simultaneously.Cooling mixture to 50 ℃ kept 90 minutes in this temperature, was cooled to bottling below 30 ℃ then.

The milk sap solids content 57.5% that generates, at 23 ℃ viscosity 2500mPa.s, EEW about 415.

By the amine hardener (13g) and the epoxy functionalized emulsifying agent (42g) of above-mentioned preparation being disperseed the active polymer compositions of preparation emulsifying water, the preparation of amine hardener is described at embodiment 4.

The coating that will wet is applied on glass disc, Bonder steel plate 26 60 0C, and wet thickness is 200 microns.When solidifying for 23 ℃, about 2 hours of the time of drying of whole film.The film film of routine that the tolerance of water, acid and solvent is obtained than the active polymer compositions by the emulsifying water of the Resins, epoxy of water-dispersion and amine hardener preparation of this solidified is much better.Particularly compare with about 12 hours of general water-dispersion bisphenol-A type liquid epoxies system, these films show about 3 hours set time faster: compare with general water-dispersion bisphenol-A type liquid epoxies system, the solvent resistance of embodiment 8 described these films also will well about 2-3 doubly, its water tolerance will be got well about 4 times.

Embodiment 7

Diglycidylether (the A of the bisphenol-A of epoxy equivalent (weight) (EEW) 510,174g), the diglycidylether (B of the bisphenol-A of epoxy equivalent (weight) (EEW) 182,126g) and the poly(propylene oxide) diglycidylether of EEW 328 (trade mark of Dow Chemical Company is D.E.R.TM 732, C, 300g) in 1 liter of container, mix, in 80 ℃ stove, kept 1 hour, mix fully up to generating transparent uniform mixture.

Embodiment 8

Reaction sequence and equipment and in embodiment 1, use similar.Epoxy equivalent (weight) 5450,5: 1 polyoxy alkylidene diglycidylether of ethylene oxide/propylene oxide mol ratio (A, 71.5g) and isophorone diamine (B 187g) places reactor, is heated to 75 ℃ at 20 minutes.Begin to stir mixture heating up to 90 ℃ and kept 15 minutes in this temperature.Added the polyepoxide mixture (291.5g) that embodiment 7 prepares at 40 minutes 90-95 ℃ temperature, mixture kept 90 minutes at 90 ℃ again.Component is cooled to 80 ℃, under agitation added entry (450g) at 45 minutes, the temperature that keeps mixture simultaneously is more than 50 ℃.After adding water and finishing, the milk sap restir of generation 1 hour keeps 45-50 ℃ temperature simultaneously, is cooled to 30 ℃ of bottlings subsequently.The moisture dispersive solidifying agent of this polymerization shows the AHEW of 285-315.

Embodiment 9

Reaction sequence and equipment and in embodiment 1, use similar.(A, 65g) and N, (B 84g) places reactor to N '-di-t-butyl ethylene diamine, is heated to 75 ℃ in nitrogen atmosphere for epoxy equivalent (weight) 5450,5: 1 polyoxy alkylidene diglycidylether of ethylene oxide/propylene oxide mol ratio.Begin to stir, mixture was heated to 135 ℃ and kept 15 minutes in this temperature again at 30 minutes.Under agitation add EEW 328 the poly(propylene oxide) diglycidylether (D.E.R.TM732, C, 35g) and the diglycidylether of the bisphenol-A of EEW 180 (D, 316g), temperature is raised to 145 ℃ and kept 2 hours in this temperature.Mixture is cooled to 90 ℃, under agitation added entry (500.0g) continuously, keep at least 50 ℃ temperature simultaneously at 45-60 minute.Mixture kept 30 minutes 50 ℃ temperature again, was cooled to 30 ℃ of bottlings subsequently.The milk sap solids content 50% that generates, at 23 ℃ viscosity 500-1000mPa.s, the about 1000-1200 of EEW.This milk sap mixes with stoichiometry with the amino affixture milk sap of embodiment 8 described poly-epoxies at 1: 1,10 ℃ and higher temperature curing, coating Pa Sazi (Persoz) hardness 90 that generates, 23 ℃ solidify 24 hours after binding property be 100%, 23 ℃ solidify 7 days after, Erichsen penetration hardness (indentation) is 6, has anti-ability greater than the two frictions of 100 MEK.A feature of the system of embodiment 9 described epoxy milk sap preparations is that whole film is quick time of drying.Comparing embodiment 10

The polyoxyethylene glycol of weight-average molecular weight (Mw) 3000 (technical grade, 150g) and the polyglycidyl ether (18.5g) of the bisphenol-A base of epoxy equivalent (weight) 185 be heated to 100 ℃, under agitation use trifluoro boron etherate (0.9g) dilution that is diluted to 5%wt by dioxan.Mixture heating up to 130 ℃ remains on this temperature up to confirming that by the growth of epoxy equivalent (weight) reaction has stopped.The epoxy equivalent (weight) of product A about 360000.The polyglycidyl ether (325g) of the bisphenol-A base of epoxy equivalent (weight) 183, bisphenol-A (98g), affixture A (27g) and triphenylphosphine (750mg) mix in having equipped 2 liters of three-necked flasks of thermocouple, agitator, reflux exchanger and dropping funnel and are heated to 150-160 ℃, up to the epoxy equivalent (weight) that obtains 490-500.Cooling mixture is also used benzylalcohol (27g) and methoxypropanol (60g) dilution.Temperature is reduced to below 100 ℃, adds entry (105g) in 5-30 minute continuously, keeps agitator speed 800rpm simultaneously and makes temperature drop to 70-60 ℃.Further water (173g) dilution obtains aqueous dispersion.The solids content of this dispersion is 55.7%, viscosity 11700mPa.s.Can prepare the reactive epoxy polymer compositions of emulsifying water by this dispersion liquid by the amine hardener that solidifies Aquo System that is applicable to that under agitation adds any routine.Comparing embodiment 11

Isophorone diamine (26g) adds have been equipped in the three neck glass flask of thermocouple, agitator and condenser, fully stirs content, maintains the temperature at 40-50 ℃ simultaneously.Slowly add that (EEW 182 by the polyglycidyl ether of propylene oxide/epoxy equivalent (weight) 1980 that oxyethane unregulated polymer type polyether glycol PR-3009 (Asahi Denka Kogyo K.K.) obtains of 1 mole 3000, ethylene oxide content 85%wt and 2.2 moles of Epicholorohydrins (13g) and hydrophobicity epoxy compounds EP-4901, Asahi Denka Kogyo K.K., 12g), the generation of monitoring heat simultaneously.Be reflected at 90 ℃ and carried out 2 hours, add entry (13g), obtain self-emulsifying activated firming agent (X).(10g) self-emulsifying activated firming agent X (7g) and water (10g) mix and solidify Adeka resin EP-4200 for Asahi Denka Kogyo K.K., EEW190.The character of experimental film obtains following result.The condition of 24 hours caudacorias is " good ", and pencil hardness is " H ", soaks into that water tolerance is " good " after 7 days, and degree of adhesion (mortar board checkerboard test) is 100/100.Comparing embodiment 12 Preparation amine-epoxide affixture (66% end-blocking)

485g (0.4 equivalent) Jeffamine 2000 (Texaco Chemical Company packs in having equipped 1 liter of reaction flask of agitator, hot jacket, nitrogen tube, condenser and thermocouple, Houston, Texas) and polyepoxide (the Henkel Corporation of 142.2g (0.61 equivalent) propenoxylated (5PO) tetramethylolmethane, Ambler, PA).Reaction mixture under agitation slowly is heated to 125-130 ℃ and kept about 2.5 hours in this temperature.Reaction mixture is cooled to 70 ℃ then, analyzes epoxide and amine content.Product amine polyepoxide affixture has the total amine of 0.4meq/gm and the epoxide of 0.33meq/gm, shows that about 66% initial free ring oxygen groups reacts with amine. Preparation from dispersion resin

In having equipped 250 milliliters of reaction flasks of hot jacket, nitrogen tube, condenser, thermocouple and agitator, pack into the diglycidylether and 19.6g (0.172 equivalent) bisphenol-A of 66.4g (0.348 equivalent) bisphenol-A.Reactant is heated to 95 ℃, adds the amine-epoxide affixture and the 0.15g triphenylphosphine of the above-mentioned preparation of 12.0g (0.004 equivalent) then.Reaction mixture under agitation slowly is heated to 150 ℃, observes thermopositive reaction has taken place.Cool off immediately, keep temperature of reaction at 150-160 ℃.After thermopositive reaction finishes, reaction mixture remain on again 160 ℃ 1 hour, kept 15 minutes at 190 ℃ subsequently.Reaction mixture is cooled to 160 ℃ then, adds 14gpropyl Cellosolve ^TM(trade mark of Union Ca rbide Corporation) refluxes immediately.Reaction mixture is cooled to 100 ℃ and analysis.Generate from dispersion resin at propylCellosolve ^TMIn have 87.5% solid, total amine of 0.07meq/gm is arranged, based on resin solid, its epoxy equivalent (weight) is 552. The preparation aqueous dispersion

In having equipped 500 milliliters of reaction flasks of agitator, hot jacket, nitrogen tube, condenser and thermocouple, pack into the above-mentioned preparation of 112g from dispersion resin (SDR).Resin is heated to 100 ℃, progressively adds 16.5g water under stirring in 30 minutes, and simultaneous temperature is reduced to about 55 ℃.And then adding 48g water, simultaneous temperature was raised to 70 ℃ at 20 minutes.At 70 ℃, under agitation added 2g water at 20 minutes, add 3g water then.The water-in-oil dispersion that generates stirred 45 minutes, was cooled to 45 ℃ simultaneously, became oil-in-water dispersion subsequently.After reversing is finished, add the C of 2.0g CVC SpecialtyChemicals Corp. _6-10The single glyceryl ether of alcohol is as reactive thinner.Then at 50 ℃ of 1 hour adding 36.3g water.The aqueous dispersion that generates is at water/propyl Cellosolve ^TM(82/18) contains 56% resin solid in the solvent. The preparation of coating composition

The aqueous dispersion that adds the above-mentioned preparation of 12.4g (56% solid) in 250 milliliters of plastic cups adds 8290 epoxy hardeners of being buied by HiTech (diethylenetriamine of modification, hydrogen equivalent 163) that can be used as of equivalent (2g) subsequently.The water that adds capacity then makes mixture reach diffusible denseness.Aging 10 minutes of this epoxy dispersion/curing agent mixture uses #34 wire-wound rod iron that mixture is gone up casting film-forming at the TRU of frosted in advance COLD cold-rolled steel sheet (3 * 6 * 0.32 inch) then.Caudacoria was not sticking in 45 minutes.Film is measured the physical properties of coating composition in room temperature at air drying after 28 days, be assessed as " qualified (PASS) ".

Claims (21)

1. a moisture polyepoxide milk sap, preparation through the following steps:

(i) make a) a kind of polyoxy alkylidene diamines of a kind of being selected from (1) or (2) corresponding to the amine of following formula or the amine of polyamines:

And R ¹⁴-NH ₂

R in the formula ¹³Be C in each case independently _1-10The alkyl of straight or branched or hydrogen; R ¹²Be the cyclohexyl or the C of cyclohexyl, replacement in each case independently _1-50Alkylene, it can be replaced by the substituting group of non-obstruction and can contain one or more secondary amine, ether, amine or thioether part on skeleton; And R ¹⁴Be C _1-25Linear, side chain, alicyclic ring or greasiness loop section

B) at least a polyepoxide and

C) at least a polyoxy alkylidene diglycidylether,

Reaction generate epoxy-capped reaction product and

(ii) the epoxy-capped reaction product of emulsification in water provides a kind of aqueous poly-epoxy milk sap, and its epoxy equivalent (weight) is 375 or bigger.

2. a reactive polymer milk sap, preparation through the following steps:

(i) make a) a kind of polyoxy alkylidene diamines or corresponding to the polyamines of following formula: And R ¹⁴-NH ₂

R in the formula ¹³Be C in each case independently _1-10The alkyl of straight or branched or hydrogen; R ¹²Be the cyclohexyl or the C of cyclohexyl, replacement in each case independently _1-50Alkylene, it can be replaced by the substituting group of non-obstruction and can contain one or more secondary amine, ether, amine or thioether part on skeleton; And R ¹⁴Be C _1-25Prop up shape, side chain, alicyclic ring or greasiness loop section

B) at least a polyepoxide and

C) at least a polyoxy alkylidene diglycidylether,

Reaction generates epoxy-capped reaction product,

The (ii) epoxy-capped reaction product of emulsification in water, provide a kind of aqueous poly-epoxy milk sap and

(iii) in moisture poly-epoxy milk sap reaction product, disperse or dissolve solidifying agent, obtain the emulsive active polymer compositions.

3. claim 1 or 2 milk sap comprise at least a other amine in reaction mixture (i).

4. claim 1 or 2 milk sap comprise a kind of poly-hydroxy hydrocarbon in reaction mixture (i).

5. claim 1 or 2 milk sap comprise a kind of useful catalyzer in reaction mixture (i).

6. claim 1 or 2 milk sap comprise a kind of organic solvent.

7. the milk sap of claim 4, wherein said poly-hydroxy hydrocarbon is a polyhydroxy phenol.

8. the milk sap of claim 6, the consumption of wherein said organic solvent is no more than 1.5%.

9. the milk sap of claim 3, wherein said at least a other amine comprise two or more mixture of monofunctional amines, polyamines or its.

10. method for preparing moisture polyepoxide milk sap comprises:

(i) make a) a kind of polyoxy alkylidene diamines or corresponding to the polyamines of following formula:

And R ¹⁴-NH ₂

R in the formula ¹³Be C in each case independently _1-10The alkyl of straight or branched or hydrogen; R ¹²Be the cyclohexyl or the C of cyclohexyl, replacement in each case independently _1-50Alkylene, it can be replaced by the substituting group of non-obstruction and can contain one or more secondary amine, ether, amine or thioether part on skeleton; And R ¹⁴Be C _1-25Linear, side chain, alicyclic ring or greasiness loop section

B) at least a polyepoxide and

C) at least a polyoxy alkylidene diglycidylether,

Reaction generate epoxy-capped reaction product and

(ii) the epoxy-capped reaction product of emulsification in water provides a kind of aqueous poly-epoxy milk sap, and its epoxy equivalent (weight) is 375 or bigger.

11. a method for preparing reactive polymer milk sap comprises:

(i) make a) a kind of polyoxy alkylidene diamines or corresponding to the polyamines of following formula:

And R ¹⁴-NH ₂

R in the formula ¹³Be C in each case independently _1-10The alkyl of straight or branched or hydrogen; R ¹²Be the cyclohexyl or the C of cyclohexyl, replacement in each case independently _1-50Alkylene, it can be replaced by the substituting group of non-obstruction and can contain one or more secondary amine, ether, amine or thioether part on skeleton; And R ¹⁴Be C _1-25Linear, side chain, alicyclic ring or greasiness loop section

B) at least a polyepoxide and

C) at least a polyoxy alkylidene diglycidylether,

Reaction generates epoxy-capped reaction product,

The (ii) epoxy-capped reaction product of emulsification in water, provide a kind of aqueous poly-epoxy milk sap and

(iii) in moisture poly-epoxy milk sap reaction product, disperse or dissolve solidifying agent, obtain the emulsive active polymer compositions.

12. the method for claim 10 or 11 comprises at least a other amine in reaction mixture (i).

13. the method for claim 10 or 11 comprises the poly-hydroxy hydrocarbon in reaction mixture (i).

14. the method for claim 10 or 11 comprises a kind of useful catalyzer in reaction mixture (i).

15. the method for claim 10 or 11 comprises a kind of organic solvent.

16. the method for claim 13, wherein the poly-hydroxy hydrocarbon is a polyhydroxy phenol.

17. the method for claim 12, wherein said at least a other amine comprise two or more mixture of monofunctional amines, polyamines or its.

18. the method for claim 15, wherein with an organic solvent amount is no more than 1.5% in the amine.

19. the method for claim 11, wherein solidifying agent is added in the poly-epoxy milk sap reaction product continuously.

20. a coating contains the reactive polymer milk sap of claim 2, has cured.

21. the moisture poly-epoxy milk sap of claim 1 or the reactive polymer milk sap of claim 2 application in a kind of coating composition of preparation.