CN103717556A - Aminoalcohol compounds and their use as zero or low voc additives for paints and coatings - Google Patents

Abstract

Provided are aminoalcohol compounds for use as additives in paints and coatings. The compounds are of the formula I:wherein p, m, n, R, R1, R2, R3, R4, R5, and R6 are as defined herein.

Description

The application of zero or low VOC additive of amino alcohol compound and conduct paint and coating

the cross reference of related application

The application requires the right of priority of India's application that the U.S. Provisional Application that the sequence number of submission on July 28th, 2011 is 61/512,628 and the sequence number of submitting on April 3rd, 2012 are 1342/CHE/2012, and described application is incorporated to herein by reference.

Technical field

The present invention relates in general to amino alcohol compound and they as the application of the low smell of paint and coating, zero or low content of volatile organic compounds (VOC) additive.

Background technology

Organic amine is used as neutralizing agent in water-based paints.In many areas, paint manufacturers is faced with the rules of volatile organic content (VOC) in the preparation that reduces them.The most frequently used neutralizing amine is 100% volatile, is therefore VOC contribution.In addition,, while using in the paint formulations at low VOC, the smell of these amine is more obvious.

Ammonia and inorganic hydroxide and carbonate are the possible alternatives as neutralizing agent, and it is defined as non-VOC contribution.Yet, although ammonia is effective neutralizing agent, there is very strong smell, and be not therefore suitable in low smell paint.Inorganic hydroxide and carbonate, have bad scrub resistance because they often cause coating, is therefore undesirable.

Paint and coating often stand the temperature significantly changing, for example, storing and In transit.The temperature so changing may cause paint or coating to experience one or more freeze-thaw cycle.Yet freezing and thawing has injurious effects to paint and coating, adversely affect their performance (for example, increasing viscosity), and sometimes make preparation not use.For freeze thawing (F/T) stability is provided, sometimes in paint and coating, comprise simple glycol (for example ethylene glycol).Yet these materials may be undesirable, because they may be high VOC, be not therefore conventionally suitable in low VOC preparation.

The problem that the present invention solves is to provide for painting the additive with coating, and it shows low or VOC free and can have low-down amine smell or there is no amine smell.

Summary of the invention

We have been found that the amino alcohol compound of the structure representing plays the effect of the efficient additive of paint and coating now below.For example, described compound plays the effect of efficient neutralizing agent and/or freeze-thaw stabiliser.In addition, described compound can have much other favourable character, has further strengthened their applicabilities in paint and coating.Advantageously, described compound shows low or VOC free, and in some embodiments, shows low-down amine smell.

In one aspect, provide the water-based paints or the coating that comprise additive, tackiness agent, carrier and pigment, wherein said additive is the compound of formula I:

Wherein p is 0 or 1, and m and n be from 0 to 8 integer independently, and condition is that at least one of p, m and n is not zero;

R, R ¹and R ²when occurring, be all H, alkyl, cycloalkyl, hydroxyalkyl, CH independently at every turn ₂cH ₂n(R ³) ₂, or R ⁴;

R ³when occurring, be H, alkyl, cycloalkyl, hydroxyalkyl or R independently at every turn ⁴;

R ⁴when occurring, be CH independently at every turn ₂cHR ⁷oH, wherein R ⁷be independently H, alkyl, cycloalkyl, phenyl, phenyl-alkyl-, alkoxyalkyl or hydroxyalkyl; With

R ⁵and R ⁶when occurring, be to form cycloalkyl together with H or alkyl or the carbon connected with them independently at every turn.

In yet another aspect, provide for reducing the water-based paints that contains neutralizing agent or freeze thawing additive, tackiness agent, carrier and pigment or the method for coating content of volatile organic compound, described method comprises utilizes as described herein formula I compound as neutralizing agent or freeze thawing additive.

The compound of formula II is provided in yet another aspect:

Wherein m and n are from 0 to 6 integer independently;

R, R ¹and R ²when occurring, (work as R at every turn ²while existing) be H, alkyl, cycloalkyl, hydroxyalkyl, CH independently ₂cH ₂n(R ³) ₂or R ⁴;

R ³when occurring, be H, alkyl, cycloalkyl, hydroxyalkyl or R independently at every turn ⁴;

R ⁴when occurring, be CH independently at every turn ₂cHR ⁷oH, wherein R ⁷be independently H, alkyl, cycloalkyl, phenyl, phenyl-alkyl-, alkoxyalkyl or hydroxyalkyl;

R ⁵and R ⁶when occurring, be to form cycloalkyl together with H or alkyl or the carbon connected with them independently at every turn.

Embodiment

Except as otherwise noted, numerical range, for example " from 2 to 10 ", comprise the numerical value (for example 2 and 10) that limits described scope.

Except as otherwise noted, ratio, percentage, umber etc. are by weight.

" low VOC preparation " and similarly term refer to for whole paint or coating formulation, and in every liter of paint, organic volatile content is 50 grams or still less (except water)." zero VOC preparation " and similar term refer to for whole paint or coating formulation, and in every liter of paint, organic volatile content is 5 grams or still less (except water).Total organic volatile content can utilize each raw-material information to calculate.The organic volatile content of starting material (except amino alcohol compound of the present invention) can utilize known test, for example EPA24 test method measuring.

" zero or low VOC compound " and similarly term refer to that specific amino alkylol cpd of the present invention has passed through the standard of being illustrated by one or more gas chromatographies, and described gas chromatography is ASTM D6886-rev method, ISO11890 or GB18581 for example.ASTM D6886-rev method is preferred.

When this specification sheets, no matter " alkyl " be separately or for example, as the part (in dialkyl amido) of another group, comprises straight chain and the branched-chain aliphatic group with 1-10 or 1-8 or 1-6 alkyl carbon atoms.Preferred alkyl includes but not limited to methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group and hexyl.Except as otherwise noted, described alkyl optional with 1,2 or 3, preferably 1 or 2, more preferably 1 synthesize compatible substituting group replacement with described herein.Such substituting group includes, but are not limited to nitro, halogen, ester, nitrile, acid amides, carboxylic acid (C for example ₀-C ₆-COOH) and C ₂-C ₆alkene.Except as otherwise noted, aforementioned substituting group is not further substituted itself.

" hydroxyalkyl " refers to that alkyl as defined above contains hydroxyl substituent, described carbon or end carbon or inner carbon on its carbon.Preferred hydroxyalkyl comprises 2-hydroxyethyl and methylol.Methylol is preferred.

Term " alkoxyl group " refers to the saturated straight chain that contains 1 to 6 carbon atom or branched alkoxy (methoxyl group for example, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, neopentyl oxygen, isopentyloxy, positive hexyloxy, or different hexyloxy), and preferably contain 1 to 4 carbon atom.The representative example of preferred alkoxyl group comprises methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert.-butoxy.

Term " alkoxyalkyl " refers to alkoxy replacement of hydrogen atom in alkyl as defined above.The example of alkoxyalkyl includes but not limited to, 3-methoxyl group-propyl group, methoxymethyl and 2-methoxyl group-ethyl.

Term " cycloalkyl " refers to the unsaturated cyclic hydrocarbon group of saturated and part with 3 to 12 ring carbon atoms or 3 to 8 ring carbon atoms or 3 to 7 ring carbon atoms.Preferred cycloalkyl includes but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, suberyl and ring octyl group.Except as otherwise noted, described cycloalkyl optionally by 1,2 or 3, preferably 1 or 2, more preferably 1 replace with synthetic compatible substituting group described herein.Such substituting group includes, but are not limited to alkyl, nitro, halogen, ester, nitrile, acid amides, carboxylic acid (C for example ₀-C ₆-COOH) and C ₂-C ₆alkene.Preferred substituting group is alkyl.

" aryl " is the C6-C14 aromatics part that comprises one to three aromatic ring.Preferably, described aryl is C6-C12 or C6-C10 aryl.Preferred aryl includes but not limited to phenyl, naphthyl, anthryl and fluorenyl.More preferably phenyl and naphthyl.Phenyl further preferably.Except as otherwise noted, described aryl optionally by 1,2 or 3, preferably 1 or 2, more preferably 1 replace with synthetic compatible substituting group described herein.Such substituting group includes, but are not limited to C ₁-C ₆alkyl, nitro, halogen, ester, nitrile, acid amides, carboxylic acid (C for example ₀-C ₆-COOH) and C ₂-C ₆alkene.Except as otherwise noted, aforementioned substituting group is not further substituted itself.

Term " aryl-alkyl-" refers to aryl-C ₁-C ₁₀alkyl-.Preferred aryl-alkyl is phenmethyl.

" containing glycol " and similar term refer to the weight based on lacquer formulations, and described lacquer formulations comprises and is less than 1wt%, is preferably less than 0.5wt% and is more preferably less than the glycol of 0.2wt%.For the object as beyond freeze thawing agent, paint of the present invention or coating formulation can comprise some minimum quantitys, be less than the glycol of 1wt%, thereby but this quantity not sufficient to give the sufficient freeze thawing character of described preparation, by the 5-cycle F/T describing in embodiment below, test.

" octanol-water partition coefficient (K _ow) " be a kind of zero dimension concentration ratio, it is measured and represents that compound is at isopyknic two kinds of miscible solvents of part---the distribution after reaching balance between n-Octanol and water.K _owhigher, compound is more nonpolar.Log K _owvalue is directly proportional to water-soluble retrocorrelation and to molecular weight substantially.

As mentioned above, in one aspect, the invention provides the amino alcohol compound of the additive that can be used as water-based paints and coating formulation.For example, described amino alcohol compound plays neutralizing agent in paint or coating in some embodiments.In such preparation, comprise neutralizing agent, so that pH is brought up to expected value, conventionally, between 7 and 13, be more typically between 8 and 10.The conventional neutralizing agent of major part using in current industrial is VOC contributor.In addition,, when when being the preparation of low VOC in other side, the smell of conventional neutralizing agent is more obvious.

By contrast, amino alcohol compound of the present invention is outstanding low odoring substance, has the benefit of zero or low VOC.Except their outstanding low VOC and low smell attribute, described amino alcohol compound can be given and the suitable attribute of performance providing by conventional neutralizing amine.Therefore, with amino alcohol compound of the present invention, reached the advantage of low smell and low VOC, and other attribute of paint or coating has not been had to obvious negative effect.

Alternately, or except the function as neutralizing agent, compound of the present invention can be used as F/T additive or agent.Freeze thawing additive (stablizer) adds paint and coating formulation to reduce zero pour, even and therefore allow described preparation being exposed to temperature variation, particularly by the character that still keeps their to expect after causing temperature freezing and that melt, comprise viscosity.When not there is not such additive, paint may flocculate and/or viscosity increases, and this may make them be difficult to use.In some cases, preparation may solidify, and causes them not use.Compound of the present invention provides freeze-thaw stability raising, also has additional benefits low or VOC free material.Therefore, described compound is the freeze thawing additive of higher VOC, effective substitute of for example glycol.

In addition, except neutralization and freeze-thaw stability, the character of various other expectations of (improve or provide and be comparable to for example attribute of 2-amino-2-methyl-1-propanol of commercial materials) paint and coating can be provided amino alcohol compound of the present invention, for example following one or more: erosion resistance, scrub resistance, resistance to blocking, help dispersiveness (codispersion), improve gloss, color acceptance and stability, reduce xanthochromia, stability to aging, water resisting property, washability, stain resistance, low temperature coalescence and microbial control synergetic property.

Amino alcohol compound of the present invention is the compound of formula I:

Wherein p, m, n, R, R ¹, R ², R ³, R ⁴, R ⁵and R ⁶as above definition.In the present invention, at least one of p, m and n is not zero.

In some embodiments, the amino alcohol compound of formula I is the compound of formula I-1, and it is that wherein R is the formula I compound of H.

In some embodiments, the compound of formula I and I-1 is the compound of formula I-2, and it is R wherein ³it is the formula I compound of H.

In some embodiments, the compound of formula I, I-1 and I-2 is the compound of formula I-3, and it is R wherein ¹formula I, I-1 or the I-2 compound of H.

In some embodiments, the compound of formula I, I-1 and I-2 is the compound of formula I-4, and it is R wherein ¹and R ⁴identical and the two be all CH ₂cHR ⁷the formula I of OH, I-1 or I-2 compound.In some embodiments, R7 is H, alkyl (preferably C1-C3 alkyl, more preferably ethyl or methyl) or alkoxyalkyl (preferably isopropoxy methyl).

In some embodiments, the compound of formula I, I-1, I-2, I-3 and I-4 is the compound of formula I-5, and it is R wherein ²when occurring, be H or R independently at every turn ⁴formula I, I-1, I-2, I-3 or I-4 compound.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4 and I-5 is the compound of formula I-6, and it is that wherein m is 1 formula I, I-1, I-2, I-3, I-4 or I-5 compound.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4 and I-5 is the compound of formula I-7, and it is that wherein m is 2 formula I, I-1, I-2, I-3, I-4 or I-5 compound.In some embodiments, when m is 2, R ²when once occurring, be CH ₂cH ₂n(R ³) ₂and be R when separately occurring again and again ⁴.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6 and I-7 is the compound of formula I-8, and it is that wherein n is 1 formula I, I-1, I-2, I-3, I-4, I-6 or I-7 compound.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7 and I-8 is the compound of formula I-9, and it is that wherein p is 0 formula I, I-1, I-2, I-3, I-4, I-6, I-7 or I-8 compound.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4, I-5, I-7, I-8 and I-9 is the compound of formula I-10, and it is that wherein m is 0 to 7 or 0 to 6 or 0 to 5 or 0 to 4 or 0 to 3 or 0 to 2 or 0 to 1 formula I, I-1, I-2, I-3, I-4, I-5, I-7, I-8 or I-9 compound.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-9 and I-10 is the compound of formula I-11, and it is that wherein n is 0 to 7 or 0 to 6 or 0 to 5 or 0 to 4 or 0 to 3 or 0 to 2 or 0 to 1 formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-9 or I-10 compound.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-10 and I-11 is the compound of formula II, and it is that wherein p is 1 formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-10 or I-11 compound.The compound of formula II can be expressed as follows:

Wherein p, m, n, R, R ¹, R ², R ³, R ⁴, R ⁵and R ⁶as above definition.

In some embodiments, the compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-9, I-10, I-11 and II is the compound of formula III, and it is that wherein n is 0 formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-9, I-10, I-11 or II compound.The compound of formula III can be expressed as follows:

Wherein p, m, R, R ¹, R ², R ³, R ⁴, R ⁵and R ⁶as above definition.

In some embodiments, described amino alcohol is compound or composition as shown in table 1.

Table 1.

The compound of formula I can easily be prepared.The example of exemplary program is presented in figure I.

Figure I

As shown in Figure 1, the amine that compound of the present invention can through type A reacts and prepares with one or more oxiranes or oxidation arylene compound.In typical program, described oxirane slowly adds in the formula A amine being stirred.Reaction can be carried out with pure state, or uses solvent for example water or alcohol (for example methyl alcohol), if reactive material thickness and can not stirring particularly.Reaction can be carried out at the temperature changing, for example, between room temperature and 100 ℃.In some embodiments, preferably maintain the temperature between approximately 40 and 60 ℃.After adding oxirane or oxidation arylidene, time enough can be at room temperature stirred in reaction, and for example 2 to 24 hours, until it reaches the level that completes of expectation.Product mixtures can be used as it is, if particularly reaction is pure state operation, or can be further purified by known method.

The amine of formula A is commercially available and/or can be easily synthetic by those skilled in the art.The example of suitable formula A amine includes but not limited to: diethylenetriamine, tetren, 2-methyl isophthalic acid, 2-propylene diamine, N-(2-amino-ethyl) piperazine, and Isosorbide-5-Nitrae-bis-(2-amino-2-methyl propyl group) piperazine.

Equally, oxirane is commercially available or can easily prepares.The non-limitative example of suitable oxirane comprises: oxyethane; Propylene oxide; Butylene oxide ring; (isopropoxy methyl) oxirane; Racemic glycidol; Styrene oxide 98min.; With epoxidation of cyclohexene thing.

Compound of the present invention can be used as the additive of water-based paints and coating formulation.Therefore in yet another aspect, the invention provides and wherein exist formula I compound as water-based paints or the coating of additive.In some embodiments, the paint that contains formula I compound or coating formulation are totally the preparations of low VOC or zero VOC.Described paint or coating be used to provide house and industrial surface for example floor, automobile, house is outside and protectiveness and/or the ornamental blocking layer of inner and other buildingss.Described paint or coating formulation, except the additive compound that comprises formula I, also comprise tackiness agent, pigment and carrier.

Comprising pigment is in order to provide opacifying power and desired color to final coated material, and is also used to paint or coating that the volume of increase is provided.Although may there is multiple pigment in the final paint using or coating, at the commitment that forms preparation, sometimes only add for example titanium dioxide of white pigment, and may with for example calcium carbonate and/or kaolin combination of pigment extender.Any other desired versicolor pigment (comprising more white pigment) can be optionally adds after late phase or preparation complete.

Pigment can be organic or inorganic.The example of pigment can include but not limited to that titanium dioxide, kaolin, calcined kaolin, carbon black, iron oxide black, iron oxide yellow, red iron oxide, iron oxide brown, organic red pigment comprise the red and metallization of quinacridone and non-metallic azo red pigment (such as Lithol, lithol rubine, toluidine red, naphthol red), phthalocyanine blue, phthalocyanine green, list or diaryl compound Huang, benzimidazolone yellow, heterocyclic yellows, quinacridone magenta, quinacridone violet etc., and any combination.In some embodiments, the gross weight of the amount of pigment based on described preparation can be 10-30 % by weight.

In paint and coating formulation, comprising tackiness agent is pigment particles to be disperseed and be suspended in network wherein in order to provide.Tackiness agent is bonded together pigment particles, and for paint or paint film integrity and tack are provided.In general, for water-based paints and coating, described tackiness agent is latex sill.

Prepared by the aqueous emulsion polymerization reaction of the monomer mixture that emulsion adhesive generally causes by free radical, the monomer that described monomer mixture contains alkyl acrylate (methyl acrylate, ethyl propenoate, butyl acrylate and/or 2-EHA), alkyl methacrylate, vinyl alcohol/acetic ester, vinylbenzene and/or vinyl cyanide and ethene type.Suitable tackiness agent comprises the adulterant of acrylic acid or the like, vinyl acetate-vinyl material or these materials of acrylic acid or the like, vinylacrylic acid class, vinylbenzene.In preparation of the present invention, the amount of tackiness agent can be conventional amount in paint and coating formulation, and due to desired glossiness/bright range and the solid content of specific lacquer formulations, described amount can extensively change.As limiting examples, in the gross weight of preparation, the amount of adhesive solids can be approximately 5% to approximately 35%.

Preparation also comprises carrier, and preparation composition dissolves, disperses and/or be suspended in wherein.In water-base preparation of the present invention, carrier is water normally, although other group water solutions such as water-alcohol mixture etc. also can be used.Aqueous carrier generally, after every other component has counted, is supplied the surplus of preparation.

Except additive discussed above, pigment, tackiness agent and carrier, other materials can be included in paint and coating formulation.They include but not limited to flow agent and tensio-active agent, thickening material, rheology modifier, solubility promoter for example glycols comprise propylene glycol or ethylene glycol, inhibiter, defoamer, dispersion aids, other amino alcohol compounds, alkali and biocide.

Paint of the present invention and coating formulation can be by well known to a person skilled in the art prepared by conventional paint production technology.Conventionally, preparation is prepared by two-step approach.First, by dry colour being ground to phase component with other, comprising that other solid powder preparation materials of great majority mix under constant high-shear is stirred, the mixture of high viscosity and high solid content to be provided, to prepare the disperse phase that is commonly called grinding phase.This part of design the method, for effective wetting dry colour, makes them remove caking, and makes them stable in aqueous dispersion.

Paint preparation method's second step is commonly called adjusts rare or dilution stage, this be because with viscosity generally the residue formulation component lower than grinding mixture dilute the abrasive material of thickness.Conventionally, any other paint material that mixes tackiness agent, any pigment disperseing in advance and only need mix and may need appropriateness to shear in dilution stage.Can be by dilution component be added in the container that contains grinding mixture in succession, or by grinding mixture being added in the container of the pre-composition that contains latex resin and other dilution components, then in succession add last dilution component, complete dilution stage.In any situation, all need constant stirring, although it is optional to apply high-shear.

The compound of formula I of the present invention common one or more places in 3 different opportunitys in preparation process add in preparation: add pigment dispersion to, add adhesive dispersion to and/or finally add lacquer formulations to.Usage quantity can easily be determined by those of ordinary skills.

For example, when existing as neutralizing agent, can preferably use the amount definite according to the expectation pH of described preparation.The amount of conventionally, adding described compound will make to provide final pH in 7 to 13, preferably 8 to 10, more preferably 8.5 to 9.5 scope.In some embodiments, can also use mineral alkali with together with the compound of formula I, sodium hydroxide for example, with in further promoting and character.

When the freeze thawing additive, described compound preferably adds (for example the tune of manufacture method as above rare during) in the later stage of described preparation.In some embodiments, compound of the present invention mainly plays freeze-thaw stabiliser.When mainly as freeze-thaw stabiliser, in some embodiments, the amount of described compound is approximately 0.2% to approximately 10% based on total formulation weight amount.

In yet another aspect, the invention provides for reducing the water-based paints that contains neutralizing agent and/or freeze-thaw stabiliser, tackiness agent, carrier and pigment or the method for coating content of volatile organic compound.Described method comprises utilizes formula (I) compound of significant quantity as neutralizing agent and/or freeze-thaw stabiliser.

As mentioned above, compound of the present invention plays the effect of zero or low VOC and low smell additive for water-based paints and coating formulation.For example, described compound can play the effect of neutralizing agent and/or freeze thawing (F/T) stablizer.Because they can play the effect of freeze-thaw stabiliser, known F/T stablizer for example glycol can be eliminated from paint and coating formulation.This has the advantage that possibility further reduces the VOC of preparation.

Therefore, of the present invention aspect another, provide to comprise formula I compound and containing low VOC paint or the coating formulation of glycol.For for F/T stablizer, preferred described formula I compound has lower Column Properties: (primary, secondary and tertiary) amido sum is 1 to 10; Hydroxyl (OH) number is 1 to 20;-10 to 10 with octanol-water partition coefficient.

In some embodiments, glycol, low VOC paint or the weight percent (wt%) of coating formulation based on weight of formulation of not containing of the present invention can not comprise: the tackiness agent of 5-35%; 10-30% pigment; 0.2 to 10% formula I compound; With 30-60% carrier.In some embodiments, the pH scope of described preparation is between 7 and 13.In some embodiments, formula III compound as above is preferred F/T stablizer.In another embodiment, 3,3'-((((2,3-dihydroxypropyl) azane two bases) two (second-2,1-bis-bases)) two (azane two bases)), two (propane-1,2-glycol) are preferred F/T stablizers.In another embodiment, 3,3', 3 ", 3 " '-((((2,3-dihydroxypropyl) azane two bases) two (ethane-2,1-bis-bases)) two (azane three bases)) four (propane-1,2-glycol) are preferred F/T stablizers.

Except neutralization and freeze-thaw stability, compound of the present invention can strengthen the character of various other expectations of described preparation, for example following one or more: erosion resistance, scrub resistance, resistance to blocking, helps dispersiveness, improve gloss, color acceptance and stability, reduce xanthochromia, stability to aging, water resisting property, washability, stain resistance, low temperature coalescence, with together with biocide with existing in preparation for the synergetic property of microbial control.

Some embodiments of the present invention will describe in detail now in the following embodiments.

Embodiment

synthetic (universal test)

The 3-neck round-bottomed flask that is equipped with magnetic stirrer, nitrogen protection, the controlled heating mantles of thermopair and interpolation funnel packs the amine (1.0 equivalent) of expectation into.Feed hopper packs the oxirane (1 or more equivalent) of expectation into.Reaction pure state operation, and if material thickness and can not stirring can be used solvent for example water or alcohol.During interpolation, temperature of reaction remains on about 25-100 ℃.Starting to add alkyl oxide for example when propylene oxide and butylene oxide ring, notice slight heat release.Yet, when Racemic glycidol is used as described epoxide, can observe a large amount of heat releases.Heat release is controlled by slow interpolation and/or ice bath.After completing interpolation, 2-24 hour is at room temperature stirred in reaction.Described material can former state be used for painting application.

Embodiment 1:3, two (propane-1,2-glycol) (DETA-Glyc) for 3'-((((2,3-dihydroxypropyl) azane two bases) two (ethane-2,1-bis-bases)) two (azane two bases))

In the 3-neck round-bottomed flask of outfit magnetic stirrer, nitrogen protection, the controlled heating mantles of thermopair and feed hopper, pack diethylenetriamine (103g, 1 mole, 1.0 equivalents) and 100mL water into.Between described amine and water mixing period, observe slight heat release.Once heat release is calmed down, described feed hopper just packs 96% pure Racemic glycidol (192.5g(174mL), 2.5 moles, 2.5 equivalents into) and be added into very lentamente described amine/aqueous solution.Described reaction is extremely heat release, therefore slowly adds described oxirane and will control temperature of reaction.Described reaction is in 25 ℃ (controlling temperature by slow interpolation and ice bath), 60 ℃ (controlling temperature by slow interpolation and ice bath) and 85 ℃ (controlling temperature by slow interpolation) lower operation.In all cases, reaction product is similar.To described amine, adding Racemic glycidol will change into and produce yellow color without tryptamines.Complete after interpolation, 2-3 hour is at room temperature stirred in reaction.Total thick yield is about 99%.The composition of mixture passes through

CI-LC/MS determines.Retention time 2.4min(main ingredient): 3,3'-((((2,3-dihydroxypropyl) azane two bases) two (ethane-2,1-bis-bases)) two (azane two bases)) two (propane-1,2-glycol)): [M+H]=326.2.Accessory constituent comprises: retention time 2.0min:3,3'-(azane two bases two (ethane-2,1-bis-bases)) two (azane two bases)) two (propane-1,2-glycol).[M+H]=252.2; Retention time 2.5min:3,3'-((2-((2,3-dihydroxypropyl) (2-((2,3-dihydroxypropyl) amino) ethyl) amino) ethyl) azane two bases) two (propane-1,2-glycol).[M+H]=400.3; Retention time 2.5min(acromion; Accessory constituent): 3,3', 3 ", 3 " '-((((2,3-dihydroxypropyl) azane two bases) two (ethane-2,1-bis-bases)) two (azane three bases)) four (propane-1,2-glycol).[M+H]=474.3。By Kugelrohr or scraped film type, distill, can from mixture, remove residual parent material and 3-((2-((2-aminoethyl) amino) ethyl) amino) propane-l, 2-glycol.

Embodiment 2:1, two (propane-2-alcohol) (TEPA-3PO) for 1'-((((2-hydroxypropyl) azane two bases) two (ethane-2,1-bis-bases)) two ((2-aminoethyl) azane two bases))

Utilize tetren (0.5mol) and propylene oxide (1.5mol) as parent material and according to above-described similar program, can prepare title compound.LC/MS analyzes and shows constituent mass scope from 363 to 537 dalton.IR shows OH and NH ₂at 3294cm ^-1, aliphatic CH is 2962 and 2815cm ^-1, aliphatic CH ₂and CH ₃1456,1370,1334,1293,1133,1061,1013,944 and 842cm- ¹. ¹h-NMR is presented at 3.836ppm(2.5Hs) locate wide unimodal, at 2.724-2.308ppm(22Hs) the complicated multiplet located, and at 1.168-1.092ppm(9Hs) the complicated multiplet located. ¹³h-NMR is presented at 13,77.175-73.531ppm place signal, 4,68.508-67.271ppm place signal, 7,65.667-62.911ppm place signal, 10,60.326-56.966ppm place signal, 51.935 and 50.255ppm place individual signals, and 6,31.960-30.842ppm place signal.

Embodiment 3:7,13-bis-(2-hydroxypropyl)-4,7,10,13,16-pentaaza nonadecane-2,18-glycol (TEPA-4PO)

Utilize tetren (0.5mol) and propylene oxide (2.0mol) as parent material and according to above-described similar program, can prepare title compound.IR is similar to the result obtaining for TEPA-3PO with NMR analytical results.

Embodiment 4:TEPA-2.5PO

Utilize tetren (0.5mol) and propylene oxide (1.25mol) as parent material and according to above-described similar program, can prepare title compound.IR is similar to the result obtaining for TEPA-3PO with NMR analytical results.

Embodiment 5: heavy polyamine X-propylene oxide (HPX-3PO)

Utilize the mixture of heavy polyamine X(ethyleneamines, can derive from The Dow ChemicalCompany) (0.5mol) and propylene oxide (1.5mol) as parent material and according to above-described similar program, can prepare title compound.Product pKa data: pKl=9.2; PK2=7.0; PK3=4.8.

Embodiment 6:7-(2-hydroxypropyl)-4,7,10,13-tetra-azepine n-Hexadecane-2,15-glycol (TETA-3PO)

Utilize Triethylenetetramine (TETA) (0.5mol) and propylene oxide (1.5mol) as parent material and according to above-described similar program, can prepare title compound.LC/MS analyzes and shows constituent mass scope from 277 to 473 dalton.The composition of mixture is determined by CI-LC/MS.Main ingredient is 7-(2-hydroxypropyl)-4,7,10,13-tetra-azepine n-Hexadecane-2,15-glycol, 7,10-bis-(2-hydroxypropyl)-4,7,10,13-, tetra-azepine n-Hexadecane-2,15-glycol and 4,7,10-tri-(2-hydroxypropyl)-4,7,10,13-tetra-azepine n-Hexadecane-2,15-glycol.Accessory constituent comprises: 1-((2-((2-((2-amino-ethyl) amino) ethyl) amino) ethyl) amino) propane-2-alcohol, 4,7,10,13-tetra-azepine n-Hexadecane-2,15-glycol and 4,7,10,13-tetra-(2-hydroxypropyl)-4,7,10,13-tetra-azepine n-Hexadecane-2,15-glycol.

Embodiment 7:VOC test and pKa

According to ASTM D6886-rev method test VOC character.The parameter following (table 2) of using:

Table 2

Parameter	ASTM6886-rev
		Post	DB-5,30mx0.25mm,1μm
Flow velocity (ml/min)	1.0ml/min
		Temperature in (C)	260
Detector temperature (C)	270
		Initial temperature (C)	50
Keep (min)	4
		Speed 1 (C/min)	20
Outlet temperature (C)	250
		Keep (min)	6
Speed 2 (C/min)	20
		Total time (min)	20
Mark	Nothing
		Column material	5% phenyl/95% methyl polysiloxane

The VOC of various compounds and pKa show in the following Table 3.

Table 3

¹according to ASTM D6886-rev method.GC condition is listed in table 2.

²the VOC being contributed by neutralizing agent in the lacquer formulations completing, and measure according to the program of summarizing in ASTM D6886 method.

Main ingredient in thick amine for example TEPA-4PO, HPX3PO and DETA-Glyc is ' zero ' VOC.According to ASTM D6886-method, their retention time is longer than 20 minutes.In ISO11890-2, SCAQMD M131-91 and GB18581, these materials are wash-out after specified sign thing also.

³eDBDA-bis--AMP=Ν 1, Ν 1'-((ethane-1,2-bis-bases two (oxygen)) two (ethane-2,1-bis-bases)) two (2-methylpropane-1,2-diamines).

Embodiment 8:

Prepare acrylic delustring paint (flat paint) preparation: preparation as shown in table 4 has the zero VOC delustring preparation of vinylacrylic acid ester latex.

Table 4

Utilize described in following method evaluation and paint:

PH, low shearing and shear viscosity.The pH of each preparation measures with the digital pH meter with the pH glass probe of combination.Krebs-unit (KU) viscosity apparatus statistics have shown that KU type Bu Shi (Brookfield) viscometer of device measures (ASTM D562) at 25 ℃.High-shear (" ICI ") viscosity according to ASTM D4287 utilize 0.45 ° of cone-plate that Brookfield CAP1000+ viscometer is 1.511cm with radius under 900rpm with 12,000s ^-1shearing rate measure, sample temperature is controlled at 25 ℃.

Glossiness, contrast ratio.By the excellent blade coating of filming, to the paint film of the 3-mil wet-film thickness of the opaque testing plate of Leneta Form3-B, measuring glossiness and opaqueness.Before measuring, plate is dried at least 16 hours under 25 ℃ and 50% relative humidity.

According to ASTM D523, use BYK-Gardner micro-TRI glarimeter measurement at the glossiness of 60 ° or the gloss (sheen) of 85 °.

With BYK-Gardner Color Guide Sphere colourimeter (D65 source/10 ° viewer), it measures reflectance spectrum according to ASTM E1164, carries out opacity measurement.Described colourimeter partly matches continuously measured according to ASTM D2805 from the black background of opaqueness testing plate and white background, carrys out measurements and calculations opaqueness.

Scrub resistance.D10 type Gardco scrubbing resistance tstr for wet scrub resistance, according to ASTMD2486 with 37 circles/minute fixed speed measure.By the 7-mil gap side of U-shaped coating device (Dow latex rod, can derive from Paul N.Gardner, Inc.), on Leneta P-121-10N black plastic plate, apply side by side scraping of two repetitions film (drawdowns).Described plate under 25 ℃ and 50% relative humidity dry 7 days.This plate is fixed on the platform of cleaning tstr, each has pad to produce the test site of raising under film side by side.Before every 400 circles of described test, grinding medium and the 5ml water of 10g regulation are placed in the path of washing scrubber.When brush wears away the continuous lines of removing completely across the coating of raising testing surface width described in whole, record the end points of each paint film.

Resistance to soiling.On Leneta P-12I-10N black plastic plate, apply the paint film of 3-mil wet-film thickness and under 25 ℃ and 50% relative humidity dry 7 days.Whole width across described film applies following contamination medium---pencil, pen, wax crayon, Sucus Vitis viniferae and coffee.Allow these media on each paint film, retain 30 minutes.Plate is fixed on the platform of D10 type scrubbing resistance tstr, and grinds boat (abrasion boat) test 200 circles with the 1-1b, the 2x4 inch that have soaked the cheese cloth parcel of 1% detergent for washing clothes solution.After dry, by plate: 0=described in the grading ranking of describing in ASTM D4828, do not remove initial spot; 3=slightly removes, and spot is easily seen; 5=moderate is removed, and spot is slightly visible; 7=spot almost be cannot see; 10=spot is removed completely.The result of more than testing on described lacquer formulations is listed in table 5.

Table 5.

In delustring preparation, compare with sodium hydroxide, TETA3PO demonstrates scrub resistance to be improved.

Embodiment 9:

Prepare acrylic semi-gloss paint preparation: there is zero-VOC semi-finished agent preparation as shown in table 6 of acrylic latex.

Table 6

The method that described paint is described according to embodiment 8 and following resistance to blocking are evaluated.The film that is coated on the 3-mil wet-film thickness of opaque testing plate was dried 1 and 3 day before test under 25 ℃ and 50% relative humidity.For each test, paint sheet is cut into 11/2 inch of square of triplicate pairing.Place on every pair of facing opposite, and then every pair covers with No. 8 rubber plugs.At 25 ℃, on described rubber plug, place 1kg counterweight 1 hour, or at 50 ℃, place 30 minutes.When each time period finishes, remove described counterweight and by slow stable power, the square of pairing peeled away.According to ASTM D4946 with 0(maximum adhesion) to 10(is minimum, adhere to) amount that adheres to of O&A.More than test the result of zero VOC semi-finished agent is listed in table 7.

Table 7

In zero VOC semi-finished agent, TEPA2.5PO and TETA3PO demonstrate scrub resistance slightly to be improved.

Embodiment 10

The lacquer formulations that preparation contains compound of the present invention: F/T agent 1 and 2 preparations of described lacquer formulations utilization as shown in structure below.The octanol water partition coefficient of these compounds utilizes Moriguchi etc., Chem.Pharm.Bull.40 (1), and the method in 127-130 (1992) is calculated.The F/T-1 calculating and the octanol-water partition coefficient of F/T-2 are respectively-2.59 and-3.99.Table 8 has shown the lacquer formulations for freezing and thawing test.Paint sample-18 ℃ freezing 17 hours, then at 25 ℃, melt 7 hours.This forms 1 complete freeze-thaw cycle.After each freeze-thaw cycle, utilize and at room temperature measure viscosity from the KrebsStormer viscometer of Sheen.Viscosity is measured with Krebs unit (KU).To containing zero VOC compound of the present invention, as the freeze-thaw cycle result of the paint sample of rear additive, in table 9, list.Described rear interpolation compound mixes with 2wt% in described paint sample.Use identical lacquer formulations to prepare all samples.Paint sample without any rear additive is named as " blank ".

Table 8

Composition	wt%
		Water	17
Kathon?LXE	0.1
		ROZONE2000	0.3
Tego?Foamex	0.02
		HEC	0.5
Orotan731A	0.6
		AMP95	0.1
Tergitol15S40	0.2
		TiO 2R706	18.00
Calcite?MF	4.00
		Omyacarb	3
ACRYSOL?RM5000	1
		AMP95	0.1
Water	16.16
		Tego?Foamex	0.02
Water	1.9
		ROPAQUE?ULTRA?E	7.00
PRIMAL TM?SF018	30.00
		Amount to	100

KATHON ^tMlXE is that it can derive from The Dow Chemical Company for preserving killing activity agent in the tank of latex enamel preparation.

ROZONE ^tMthe 2000th, for the liquid fungicides with wide spectrum anti-microbial effect and the algicide of water or solvent-based coating, it can derive from The Dow Chemical Company.

TEGO FOAMEX ^tMbe defoamer, can derive from Evonik Industries.

HEC is Natvosol (NATRASOL250HBR Aqualon), can derive from Ashland.

OROTAN ^tM731A is the pigment dispersing agent for various latex base coating.It is the sodium salt of carboxylate salt polyelectrolyte, can derive from The Dow Chemical Company.

AMP-95 is the 2-amino-2-methyl-1-propanol with 5% water.It is neutralizing agent and dispersion aids, can derive from The Dow Chemical Company.

TERGITOL ^tM15S40 is the nonionic surface active agent of secondary alcohol ethoxyl compound, can derive from The Dow Chemical Company.

TiO ₂r706 is multi-usage rutile titanium dioxide pigment, can derive from DuPont.

CALCITE MF has 10 micron granularities and can derive from 20MICRONS Ltd.

OMYACARB ^tMbe that granularity is the calcium carbonate of 2 microns, and can derive from OMYA.

ACRYSOL ^tMrM5000 does not have solvent, a non-ionic associative type thickening material for emulsion paint.It can derive from The Dow Chemical Company.

ROPAQUE ^tMuLTRA E is the Opacifying polymers that increases the locked-in-air voids ability of japanning, and it can derive from The Dow Chemical Company.

PRIMAL ^tMsF018 is the acrylic polymers of the wear-resisting scrubbing character for painting to provide good.It can derive from The Dow Chemical Company.

In table 9, the KU value lower than 150 of report is considered to acceptable, and all values (except blank value) are all considered to very acceptable.

Table 9

Described paint sample stands to paint performance test.Contain the F/T agent 1 that adds as rear additive and the paint sample of F/T agent 2 and withstand five freeze-thaw cycle.For the benchmark of described research, be to contain propylene glycol and Diethylene Glycol as the paint sample of freeze thawing additive.Paint sample without any rear additive is " blank ".This sample is not by first freeze-thaw cycle.

Performance characteristics with there is propylene glycol (PG) and compare to observe whether described performance is had to disadvantageous effect as the paint sample of described additive.Table 10 has reported that the result of opaqueness and table 11 reported whiteness correlated performance.

Yuan 10

Table 11

The paint film that coating device is used for applying 150 micron thickness is sheared in fixed interval (FI) from Sheen.That paints sample scrapes dried coating film 7 days.The measurement device of Sheen Micromatch Plus is come from opaqueness utilization.With Sheen Micromatch Plus, carry out colour measurement.Described instrument is according to CIE color space L, a*, b* system-computed colorimetric parameter.Yellow chromaticity is according to b* (yellow one blue mark) report, and whiteness is measured (red-green mark) report according to L and last a*.Chromatism measurement between reference and sample colourity is

$\mathrm{\ΔE}=\sqrt{{\left(\mathrm{\ΔL}\right)}^2+{\left(\mathrm{\Δa}\right)}^2+{\left(\mathrm{\Δb}\right)}^2}$

Wherein Δ L, Δ a, Δ b are respectively the poor of L, a and b value between sample (paint with rear additive) and reference (blank).Table 11 has been listed L, a, b and Δ Ε value.

The paint performance data of the compounds of this invention after 5 freeze-thaw cycle, obtain and with do not experience any freeze-thaw cycle described ' blank ' paint data comparison.

Claims (15)

1. the water-based paints or the coating that comprise tackiness agent, carrier, pigment and formula 1 additive:

Wherein p is 0 or 1, and m and n be from 0 to 8 integer independently, and condition is that at least one of p, m and n is not zero;

R, R ¹and R ²when occurring, be H, alkyl, cycloalkyl, hydroxyalkyl, CH independently at every turn ₂cH ₂n(R ³) ₂or R ⁴;

R ³when occurring, be H, alkyl, cycloalkyl, hydroxyalkyl or R independently at every turn ⁴;

R ⁴when occurring, be CH independently at every turn ₂cHR ⁷oH, wherein R ⁷be independently H, alkyl, cycloalkyl, phenyl, phenyl-alkyl-, alkoxyalkyl or hydroxyalkyl; With

R ⁵and R ⁶when occurring, be to form cycloalkyl together with H or alkyl or the carbon connected with them independently at every turn.

2. the water-based paints of claim 1 or coating, wherein R ²when occurring, be H or R independently at every turn ⁴.

3. the water-based paints of claim 1-2 any one or coating, wherein m is 1 or 2.

4. the water-based paints of claim 1-3 any one or coating, wherein n is 0 or 1.

5. the water-based paints of claim 1-4 any one or coating, wherein m is 2 and R ²when once occurring, be CH ₂cH ₂n(R ³) ₂with when another time occurs, be R ⁴.

6. the water-based paints of claim 1-5 any one or coating, it is containing glycol.

7. the water-based paints of claim 1-6 any one or coating, wherein said additive is the compound of formula III:

Wherein p, m, R, R ¹, R ², R ³, R ⁴, R ⁵and R ⁶as claim 1 defines.

8. the water-based paints of claim 7 or coating, wherein said additive contains: add up to (primary, secondary and tertiary) amido of 1 to 10; 1 to 20 hydroxyl; With octanol-water partition coefficient be-10 to 10.

9. the compound of formula II:

Wherein m and n are from 0 to 6 integer independently;

R, R ¹and R ²when occurring, (work as R at every turn ²while existing) be H, alkyl, cycloalkyl, hydroxyalkyl, CH independently ₂cH ₂n(R ³) ₂or R ⁴;

R ³when occurring, be H, alkyl, cycloalkyl, hydroxyalkyl or R independently at every turn ⁴;

R ⁴when occurring, be CH independently at every turn ₂cHR ⁷oH, wherein R ⁷be independently H, alkyl, cycloalkyl, phenyl, phenyl-alkyl-, alkoxyalkyl or hydroxyalkyl;

R ⁵and R ⁶when occurring, be to form cycloalkyl together with H or alkyl or the carbon connected with them independently at every turn.

10. the compound of claim 9, wherein R and R ³the two is all H.

The compound of 11. claim 9-10 any one, wherein R ¹h.

The compound of 12. claim 9-10 any one, wherein R ¹and R ⁴identical and the two be all CH ₂cHR ⁷oH.

The compound of 13. claim 9-12 any one, wherein R ²when occurring, be H or R independently at every turn ⁴.

The compound of 14. claim 9-13 any one, wherein m is 1 or 2.

The compound of 15. claim 9-14 any one, wherein m is 2 and R ²when once occurring, be CH ₂cH ₂n(R ³) ₂with when separately occurring again and again, be R ⁴.