LOW VOC ADDITIVES FOR PAINTS AND COATINGS

Cross-Reference to Related Applications

This application claims priority from U.S. provisional application serial number 61/512,628, filed July 28, 2011, and from Indian application serial number

1342/CHE/2012, filed April 3, 2012, which are incorporated herein by reference.

Background

This invention relates generally to aminoalcohol compounds and their use as low odor, zero or low volatile organic content (VOC) additives for paints and coatings.

Organic amines are used in aqueous based paints as neutralizing agents. In many geographies, paint manufacturers are facing regulations to reduce the volatile organic content (VOC) of their formulations. Most conventional neutralizing amines are 100% volatile and are therefore VOC contributors. In addition, when used in an otherwise low VOC paint formulation, the odor of such amines is more noticeable.

Ammonia and inorganic hydroxides and carbonates are potential alternatives for use as neutralizers, that are by definition non-VOC contributors. However, ammonia, while an efficient neutralizer, has a very strong odor and is therefore unsuitable for use in low odor paint. Inorganic hydroxides and carbonates are undesirable because they often result in coatings with poor scrub resistance.

Paints and coatings are often subjected to widely varying temperatures, for instance during storage and transportation. Such varying temperatures may result in the paint or coating undergoing one or more freeze-thaw cycles. Freezing and thawing, however, has a detrimental effect on paint and coatings, unfavorably affecting their performance (e.g., by increasing the viscosity), and sometimes rendering the

formulations unusable. Simple glycols (e.g., ethylene glycol) are sometimes included in paints and coatings with the purpose of providing freeze-thaw (F/T) stability. However, these materials may not be desirable because they may be of high VOC and therefore generally not suitable for use in low VOC formulations.

The problem addressed by this invention is the provision of additives for paints and coatings which exhibit low or no VOC and may further have very low or no amine odor. Statement of Invention

We have now found that aminoalcohol compounds of the structures represented below function as highly efficient additives for paints and coatings. For instance, the compounds function as highly efficient neutralizers, and/or as freeze thaw stabilizers. In addition, the compounds may possess a number of other favorable properties that further enhance their applicability in paints and coatings. Advantageously the compounds exhibit either low or no VOC and in some embodiments, very low amine odor.

In one aspect, there is provided an aqueous based paint or coating comprising an additive, a binder, a carrier, and a pigment, wherein the additive is a compound of formula I:

(I)

wherein p is 0 or 1, and m and n are independently integers from 0 to 8, provided that at least one of p, m, and n is not zero;

R, R 1 and R 2 at each occurrence are independently H, alkyl, cycloalkyl, hydroxyalkyl, CH ₂ CH ₂ N(R ³ ) ₂ , or R ⁴ ;

R ³ at each occurrence is independently H, alkyl, cycloalkyl, hydroxyalkyl, or R ⁴ ;

R 4 at each occurrence is independently CH ₂ CHR 7 OH, wherein R 7 is

independently H, alkyl, cycloalkyl, phenyl, phenyl-alkyl-, alkoxyalkyl, or hydroxyalkyl; and

R ⁵ and R ⁶ at each occurrence are independently H or alkyl, or together with the carbon to which they are attached form cycloalkyl.

In another aspect, there is provided a method for reducing the volatile organic compound content of an aqueous based paint or coating that contains a neutralizing agent or freeze-thaw additive, a binder, a carrier, and a pigment, the method comprising using as the neutralizing agent or the freeze-thaw additive a compound of formula I as described herein.

In a further aspect, there is provided a compound of formula II:

(II)

wherein m and n are independently integers from 0 to 6;

R, R 1 and R2 at each occurrence (when R 2 is present) are independently H, alkyl, cycloalkyl, hydroxyalkyl, CH ₂ CH ₂ N(R ³ ) ₂ , or R ⁴ ;

R ³ at each occurrence is independently H, alkyl, cycloalkyl, hydroxyalkyl, or R ⁴ ;

R 4 at each occurrence is independently CH ₂ CHR 7 OH, wherein R 7 is

independently H, alkyl, cycloalkyl, phenyl, phenyl-alkyl-, alkoxyalkyl, or hydroxyalkyl;

R ⁵ and R ⁶ at each occurrence are independently H or alkyl, or together with the carbon to which they are attached form cycloalkyl. Detailed Description

Unless otherwise indicated, numeric ranges, for instance as in "from 2 to 10," are inclusive of the numbers defining the range (e.g., 2 and 10).

Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.

"Low-VOC formulation" and like terms mean an organic volatile content of 50 grams or less per liter of paint (water excluded) for the entire paint or coating

formulation. "Zero-VOC formulation" and like terms mean an organic volatile content of 5 grams or less per liter of paint (water excluded) for the entire paint or coating formulation. Total organic volatile content may be calculated by using information for the individual raw materials. Organic volatile content of raw materials (other than the aminoalcohol compounds of the invention) may be measured using well known tests, such as the EPA24 test method.

"Zero or low VOC compound " and like terms mean that a particular

aminoalcohol compound of the invention passes the criteria set forth by one or more gas chromatography methods, such as ASTM D6886-rev method, ISO 11890 or GB 18581. ASTM D6886-rev method is preferred.

"Alkyl," as used in this specification, whether alone or as part of another group (e.g., in dialkylamino), encompasses straight and branched chain aliphatic groups having 1-10, alternatively 1-8, or alternatively 1-6 alkyl carbon atoms. Preferred alkyl groups include, without limitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl. Unless otherwise indicated, the alkyl group is optionally substituted with 1, 2, or 3, preferably 1 or 2, more preferably 1, substituents that are compatible with the syntheses described herein. Such substituents include, but are not limited to, nitro, halogen, ester, nitrile, amide, carboxylic acids (e.g., C ₀ -C ₆ -COOH), and C ₂ -C ₆ alkene. Unless otherwise indicated, the foregoing substituent groups are not themselves further substituted.

"Hydroxyalkyl" refers to an alkyl group, as defined above, that contains a hydroxy substituent on one of its carbons, either a terminal or an internal carbon.

Preferred hydroxyalkyl include 2-hydroxyethyl-, and hydroxymethyl. Hydroxymethyl is more preferred.

The term "alkoxy" refers to a saturated straight or branched chain alkoxy group containing 1 to 6 carbon atoms (e.g. methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentyloxy, iso-pentyloxy, n-hexyloxy or iso-hexyloxy), and preferably 1 to 4 carbon atoms. Representative examples of preferred alkoxy groups include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso- butoxy, sec-butoxy and tert-butoxy.

The term "alkoxyalkyl" refers to an alkyl group, as defined above, wherein one hydrogen atom has been replaced by an alkoxy group. Examples of alkoxyalkyl groups include, but are not limited to, 3-methoxy-propyl, methoxymethyl and 2-methoxy-ethyl.

The term "cycloalkyl" refers to saturated and partially unsaturated cyclic hydrocarbon groups having 3 to 12 ring carbon atoms, alternatively 3 to 8 ring carbon atoms, or alternatively 3 to 7 ring carbon atoms. Preferred cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, and cyclooctyl. Unless otherwise indicated, the cycloalkyl group is optionally substituted with 1, 2, or 3, preferably 1 or 2, more preferably 1, substituents that are compatible with the syntheses described herein. Such substituents include, but are not limited to, alkyl, nitro, halogen, ester, nitrile, amide, carboxylic acids (e.g., C ₀ -C ₆ -COOH), and C ₂ -C ₆ alkene. A preferred substituent is alkyl.

An "aryl" group is a C6-C14 aromatic moiety comprising one to three aromatic rings. Preferably, the aryl group is a C6-C12, alternatively C6-C10 aryl group. Preferred aryl include, without limitation, phenyl, naphthyl, anthracenyl, and fluorenyl. More preferred are phenyl and naphthyl. Further preferred is phenyl. Unless otherwise indicated, the aryl group is optionally substituted with 1, 2, or 3, preferably 1 or 2, more preferably 1, substituents that are compatible with the syntheses described herein. Such substituents include, but are not limited to, C -C alkyl, nitro, halogen, ester, nitrile, amide, carboxylic acids (e.g., C ₀ -C ₆ -COOH), and C ₂ -C ₆ alkene. Unless otherwise indicated, the foregoing substituent groups are not themselves further substituted.

The term "aryl-alkyl-" refers to aryl-CrQo alkyl-. A preferred aryl-alkyl group is benzyl.

"Glycol-free" and like terms mean that a paint formulation comprises less than 1 wt , preferably less than 0.5 wt and more preferably less than 0.2 wt , of a glycol based on the weight of the formulation. The paint or coating formulation of this invention can comprise some minimal amount, i.e., less than 1 wt , of glycol for purposes other than as a freeze-thaw agent, but this amount is insufficient to impart to the formulation sufficient freeze-thaw properties so as to pass the 5-cycle F/T test described in the Examples, infra.

"Octanol- water partition coefficient (K ₀ w)" is a dimensionless concentration ratio whose magnitude expresses the distribution of a compound between equal volumes of two partially miscible solvents, n-octanol and water after they have reached equilibrium. The higher the K ₀ w, the more non-polar the compound. Log K ₀ w values are generally inversely related to aqueous solubility and directly proportional to molecular weight.

As noted above, in one aspect the invention provides aminoalcohol compounds that are useful as additives for aqueous-based paint and coating formulations. For instance, in some embodiments, the aminoalcohol compounds function as neutralizing agents in paints or coatings. Neutralizing agents are included in such formulations to raise the pH to a desired value, typically between 7 and 13, more typically between 8 and 10. Most conventional neutralizing agents currently used in the industry are VOC contributors. In addition, when used in an otherwise low VOC formulation, the odor of conventional neutralizing agents is more noticeable.

In contrast, the aminoalcohol compounds of the invention are excellent low odor materials with the benefit of having zero or low VOC. In addition to their excellent low VOC and low odor attributes, the aminoalcohol compounds may impart comparable performance properties to those provided by conventional neutralizing amines.

Consequently, the advantages of low odor and low VOC are achieved with the aminoalcohol compounds of the invention, without significant negative impact on other attributes of the paint or coating.

Alternatively, or in addition, to functioning as neutralizing agents, compounds of the invention are useful as F/T additives or agents. Freeze thaw additives (stabilizers) are added to paint and coating formulations to depress the freezing point and therefore to allow the formulations to maintain their desired properties, including viscosity, even after exposure to temperature variation, particularly temperatures that would cause freezing and thawing. When such additives are absent, the paint may flocculate and/or have increased viscosity which may make them difficult to use. In some cases, formulations may solidify, rendering them unusable. The compounds of the invention provide freeze- thaw stability enhancement with the added benefit of being low or no VOC materials. Thus, the compounds are effective replacements for higher VOC freeze-thaw additives, such as glycols.

Further, the aminoalcohol compounds of the invention may enhance (improve or provide attributes comparable to commercial materials such as 2-amino-2-methyl-l- propanol) various other desirable properties to paints and coatings, in addition to neutralization and freeze thaw stabilization, such as one or more of the following:

corrosion resistance, scrub resistance, blocking resistance, codispersion, gloss enhancement, color acceptance and stability, reduced yellowing, aging stability, water resistance, washability, stain resistance, low temperature coalescence and synergy for microbial control.

The aminoalcohol compounds of the invention are of the formula I:

(0

wherein p, m, n, R, R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are as defined above. In the invention, at least one of p, m, and n is not zero.

In some embodiments, the aminoalcohol compounds of formula I are of the formula 1-1, which are compounds of formula I wherein R is H.

In some embodiments, the compounds of formula I and 1-1 are of the formula 1-2, which are compounds of formula I or 1-1 wherein R is H. In some embodiments, the compounds of formula I, I-l, and 1-2 are of the formula 1-3, which are compounds of formula I, I-l, or 1-2 wherein R ¹ is H.

In some embodiments, the compounds of formula I, I-l, and 1-2 are of the formula 1-4, which are compounds of formula I, I-l, or 1-2 wherein R ¹ and R ⁴ are the same and are both CH ₂ CHR'OH. In some embodiments, R7 is H, alkyl (preferably Cl- C3 alkyl, more preferably ethyl or methyl), or alkoxylakyl (preferably

isopropoxymethyl) .

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, and 1-4 are of the formula 1-5, which are compounds of formula I, I-l, 1-2, 1-3, or 1-4 wherein R at each occurrence is independently H or R ⁴ .

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, and 1-5 are of the formula 1-6, which are compounds of formula I, I-l, 1-2, 1-3, 1-4, or 1-5 wherein m is 1.

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, and 1-5 are of the formula 1-7, which are compounds of formula I, I-l, 1-2, 1-3, 1-4, or 1-5 wherein m is 2. In some embodiments, when m is 2, R 2" at one occurrence is CH ₂ CH ₂ N(R 3 ^J ) ₂ and at the other occurrence is R ⁴ .

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-6, and 1-7 are of the formula 1-8, which are compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-6, or 1-7 wherein n is i.

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, and 1-8 are of the formula 1-9, which are compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1- 6, 1-7, or 1-8 wherein p is 0.

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-7, 1-8, and 1-9 are of the formula 1-10, which are compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-7, 1-8, or 1-9 wherein m is an integer from 0 to 7, alternatively 0 to 6, alternatively 0 to 5, alternatively 0 to 4, alternatively 0 to 3, alternatively 0 to 2, or alternatively 0 to 1.

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-9, and I- 10 are of the formula I-l l, which are compounds of formula I, I- l, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-9, or I- 10 wherein n is an integer from 0 to 7, alternatively 0 to 6, alternatively 0 to 5, alternatively 0 to 4, alternatively 0 to 3, alternatively 0 to 2, or alternatively 0 to 1. In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1- 10, and I-l l are of the formula II, which are compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1- 10, or I-l 1 wherein p is 1. Compounds of formula II may be represented as follows:

(II)

wherein p, m, n, R, R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are as defined above.

In some embodiments, the compounds of formula I, I-l, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-9, 1- 10, I-l 1, and II are of the formula III, which are compounds of formula I, I-l, 1-2, 1- 3, 1-4, 1-5, 1-6, 1-7, 1-9, 1- 10, I-l l, or II wherein n is 0. Compounds of formula III may be represented as follows:

(HI)

wherein p, m, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are as defined above.

In some embodiments, the aminoalcohols are compounds or compositions as shown in Table 1.

Table 1.

yl)ethyl)azanediyl)bis(propane- 1 ,2-diol) tetraaza exa ecane- , - o

(azanetriyl))tetrakis(propane- 1 ,2-diol)

The compounds of formula I may be readily prepared. An example of a typical procedure is shown in Scheme I.

SCHEME I

R R ⁵ R ⁶

R = H, alkyl, cycloalkyl or hydroxyalkyl;

R ⁵ R ⁶ P _R 9 ^m ' R ⁵ _R 6 n R ⁹ independently - H, alkyl, cycloalkyl,

hydroxyalkyl, or CH ₂ CH ₂ N(R ¹⁰ ) ₂ ,

(A)

where R ¹⁰ is H, alkyl, cycloalkyl, or hydroxyalkyl

(I)

As shown in Scheme 1, compounds of the invention may be prepared by reacting an amine of formula A with one or more alkylene or arylene oxide compounds. In a typical procedure, the alkylene oxide is slowly added to the to the stirred formula A amine. The reaction may be conducted neat, or using a solvent, such as water or alcohol (e.g., methanol), particularly if the reaction material is viscous and unable to stir. The reaction may be carried out at varying temperatures, such as between room temperature and 100°C. In some embodiments, it is preferred to maintain the temperature between about 40 and 60°C. After addition of the alkylene or arylene oxide, the reaction may be stirred at room temperature for sufficient time until it reaches the desired level of completion, such as 2 to 24 hours. The product mixture may be used as is, particularly if the reaction is run neat, or may be further purified by known methods.

Formula A amines are commercially available and/or may be readily synthesized by those skilled in the art. Examples of suitable formula A amines include, without limitation: diethylene triamine, tetraethylene pentamine, 2-methyl-l,2-propanediamine, N-(2-aminoethyl)piperazine, and 1 ,4-bis(2-amino-2-methylpropyl)piperazine.

Similarly, alkylene oxides are commercially available or may be easily prepared. Non-limiting examples of suitable alkylene oxides include: ethylene oxide; propylene oxide; butylene oxide; (isopropoxymethyl)oxirane; glycidol; styrene oxide; and cyclohexene epoxide.

The compounds of the invention are useful as additives for aqueous-based paint and coating formulations. Thus in a further aspect, the invention provides an aqueous based paint or coating in which a compound of formula I is present as an additive. In some embodiments, the paint or coating formulation containing the compound of formula I is overall a low VOC, alternatively a zero VOC, formulation. The paint or coating is used to provide a protective and/or decorative barrier for residential and industrial surfaces, such as for floors, automobiles, exteriors and interiors of houses, and other buildings. The paint or coating formulation, in addition to comprising an additive compound of formula I, also comprises a binder, a pigment, and a carrier.

Pigments are included to provide hiding power and the desired color to the final coated material and may also be used to provide bulk to the paint or coating. While multiple pigments may be present in end-use paints or coatings, sometimes only white pigment, such as titanium oxide, perhaps in combination with extender pigments such as calcium carbonate and/or kaolin clay, is added in the early stages of the formation of the formulation. Any other desired pigments of various colors (including more white pigment) can optionally be added at the later stages of, or after, the formulation is completed.

Pigments may be organic or inorganic. Examples of pigments can include, but are not limited to, titanium dioxide, kaolin clay, calcined kaolin clay, carbon black, iron oxide black, iron oxide yellow, iron oxide red, iron oxide brown, organic red pigments, including quinacridone red and metallized and non-metallized azo reds (e.g., lithols, lithol rubine, toluidine red, naphthol red), phthalocyanine blue, phthalocyanine green, mono- or di-arylide yellow, benzimidazolone yellow, heterocyclic yellow, quinacridone magenta, quinacridone violet, and the like, and any combination thereof. In some embodiments, the amount of pigment may be from 10 to 30% by weight based on the total weight of the formulation.

Binders are included in the paint and coating formulations to provide a network in which the pigment particles are dispersed and suspended. Binders bind the pigment particles together and provide integrity and adhesion for the paint or coating film.

Generally, for aqueous based paints and coatings, the binders are latex based materials.

Latex binders are typically prepared by free radical initiated aqueous emulsion polymerization of a monomer mixture containing alkyl acrylate (methyl acrylate, ethyl acrylate, butyl acrylate and/or 2-ethylhexylacrylate), alkyl methacrylate, vinyl alcohol/acetate, styrene, and/or acrylonitrile and ethylene type monomers. Suitable binders include acrylic, vinyl acrylic, styrenated-acrylic, vinyl acetate ethylene based materials, or blends of these materials. The amount of the binder in the formulations of the invention can be the amount conventionally used in paint and coating formulations, which can vary widely due to the desired gloss/sheen range, and also the solids concentration, of a specific paint formulation. By way of non-limiting example, the amount of binder solids can be from about 5% to about 35% by weight of the total formulation weight.

The formulations also contain a carrier in which the formulation ingredients are dissolved, dispersed, and/or suspended. In the aqueous based formulations of the invention, the carrier is usually water, although other water-based solutions such as water-alcohol mixtures and the like may be used. The aqueous carrier generally makes up the balance of the formulation, after all the other ingredients have been accounted for.

Other materials may be included in the paint and coating formulations besides the additives, pigments, binders, and carriers discussed above. These include, but are not limited to, leveling agents and surfactants, thickeners, rheology modifiers, co-solvents such as glycols, including propylene glycol or ethylene glycol, corrosion inhibitors, defoamers, co-dispersants, additional aminoalcohol compounds, bases, and biocides.

The paint and coating formulations of the invention may be manufactured by conventional paint manufacturing techniques, which are well known to those skilled in the art. Typically, the formulations are manufactured by a two-step process. First, a dispersion phase, commonly referred to as the grind phase, is prepared by mixing the dry pigments with other grind phase components, including most other solid powder formulation materials, under constant high shear agitation to provide a high viscosity and high solids mixture. This part of the process is designed to effectively wet and dis- agglomerate the dry pigments and stabilize them in an aqueous dispersion.

The second step of the paint manufacturing process is commonly referred to as the letdown or thindown phase, because the viscous grind is diluted with the remaining formulation components, which are generally less viscous than the grind mix. Typically, the binders, any predispersed pigments, and any other paint materials that only require mixing and perhaps moderate shear, are incorporated during the letdown phase. The letdown phase may be done either by sequentially adding the letdown components into a vessel containing the grind mix, or by adding the grind mix into a vessel containing a premix of the latex resins and other letdown components, followed by sequential addition of the final letdown components. In either case, constant agitation is needed, although application of high shear is not required.

The compounds of formula I of the invention are typically added to the formulation at one or more of three different places in the manufacturing process: to the pigment dispersion, to the binder dispersion, and/or in a final addition to the paint formulation. The amount used may be readily determined by person of ordinary skill in the art.

For instance, when present as a neutralizer, it may be preferable to use an amount that is determined based on the desired pH of the formulation. Typically, an amount of the compound is added so as to provide a final pH in the range of 7 to 13, preferably 8 to 10, more preferably 8.5 to 9.5. In some embodiments, inorganic bases, such as sodium hydroxide, may also be used, together with the compounds of formula I, to further facilitate the neutralization properties.

When used as a freeze-thaw additive, the compounds are preferably added late in the formulation (e.g., during the letdown phase of the manufacturing process, as described above). In some embodiments, the compounds of the invention function primarily as a freeze-thaw stabilizer. When used primarily as a freeze-thaw stabilizer, the amount of the compound is, in some embodiments, from about 0.2% to about 10%, based on total weight of the formulation. In a further aspect, the invention provides a method for reducing the volatile organic compound content of an aqueous based paint or coating that contains a neutralizing agent and/or freeze-thaw stabilizer, a binder, a carrier, and a pigment. The method comprises using as the neutralizing agent and/or freeze thaw stabilizer an effective amount of a compound of formula (I).

As noted above, the compounds of the invention function as zero or low VOC and low odor additives for aqueous based paints and coating formulations. For instance, the compounds may function as neutralizers and/or as freeze-thaw (F/T) stabilizers. Because of their ability to function as freeze thaw stabilizers, known F/T stabilizers, such as glycols, may be eliminated from paints and coating formulations. This has the advantage of potentially further reducing the VOC of a formulation.

Thus, in a still further aspect the invention provides a glycol-free, low VOC paint or coating formulation comprising a compound of formula I. For use as a F/T stabilizer, it is preferred for the compound of formula I to have the following attributes: the total number of amine groups (primary, secondary and tertiary) is 1 to 10; the number of hydroxy groups (-OH) is of 1 to 20; and the octanol-water partition coefficient is from -10 to 10.

In some embodiments, a glycol-free, low VOC paint or coating formulation of the invention may comprise in weight percent (wt%) based on the weight of the formulation: 5 to 35% of a binder; 10 to 30% pigment; 0.2 to 10% compound of formula I; and 30 to 60% carrier. In some embodiments, the pH of the formulation is in a range between 7 and 13. In some embodiments, compounds of formula III as described above are preferred F/T stabilizers. In further embodiments, 3,3'-((((2,3- dihydroxypropyl)azanediyl)bis(ethane-2,l-diyl))bis(azanediyl ))bis(propane-l,2-diol) is a preferred F/T stabilizer. In still further embodiments, 3,3',3",3"'-((((2,3-dihydroxypropyl) azanediyl)bis(ethane-2,l-diyl))bis (azanetriyl))tetrakis(propane-l,2-diol) is a preferred F/T stabilizer.

In addition to neutralization and freeze-thaw stabilization, the compounds of the invention may enhance various other desirable properties to the formulation, such as one or more of the following: corrosion resistance, scrub resistance, blocking resistance, codispersion, gloss enhancement, color acceptance and stability, reduced yellowing, aging stability, water resistance, washability, stain resistance, low temperature coalescence, and synergy with biocides present in the formulation for microbial control.

Some embodiments of the invention will now be described in detail in the following Examples.

EXAMPLES

Synthesis (Generic Experimental)

A 3-neck round bottom flask equipped with a magnetic stirrer, nitrogen blanket, thermocouple controlled heating mantle and addition funnel is charged with desired amine (1.0 equivalent). The addition funnel is charged with desired alkylene oxides (1 or more equivalents). The reaction is run neat and if the material is viscous and unable to stir, solvent such as water or alcohol can be used. During the addition, the reaction temperature is maintained at ca. 25-100°C. A mild exotherm is noted at the beginning of the addition for alkyl oxides such as propylene oxide and butylene oxide. However, a large exotherm may be observed when glycidol is used as the epoxide. The exotherm is controlled by slow addition and/or ice bath. After completing the addition, the reaction is stirred at room temperature for 2-24 hrs. The material may be used as-is in the paint application.

Example 1 : 3,3'-((((2,3-dihydroxypropyl)azanediyl)bis(ethane-2, 1 - diyl))bis(azanediyl))bis(propane- 1 ,2-diol) (DETA-Glyc)

A 3-neck round bottom flask equipped with a magnetic stirrer, nitrogen blanket, thermocouple controlled heating mantle and addition funnel is charged with diethylene triamine (103 g, 1 mole, 1.0 equivalent) and 100 mL of water. A slight exotherm is observed during the mixing of the amine and water. Once the exotherm subsides, the addition funnel is charged with 96% pure Glycidol (192.5 g (174 mL), 2.5 moles, 2.5 equivalent) and added very slowly to the amine/water solution. The reaction is extremely exothermic and therefore, slow addition of the alkylene oxide will control the reaction temperature. The reaction has been run at 25°C (control temperature by slow addition and ice-bath), 60°C (control temperature by slow addition and ice-bath) and at 85°C (control temperature by slow addition). In all cases, the reaction products are similar. Addition of Glycidol to the amine turns the colorless amine to develop a yellow color. After complete addition, the reaction is stirred at room temperature for 2-3 hrs. The overall crude yield is approximately 99%. The composition of the mixture was determined by CI - LC/MS. Retention time 2.4 min (major component): 3,3'-((((2,3- dihydroxypropyl)azanediyl)bis(ethane-2,l-diyl))bis(azanediyl ))bis(propane-l,2-diol). ): [M+H] = 326.2. Minor components include: retention time 2.0 min: 3,3'- ((azanediylbis(ethane-2,l-diyl))bis(azanediyl))bis(propane-l ,2-diol). [M+H] =

252.2;Retention time 2.5 min: 3,3'-((2-((2,3-dihydroxypropyl)(2-

((2,3dihydroxypropyl)amino)ethyl)amino)ethyl)azanediyl)bi s(propane- 1 ,2-diol). [M+H] = 400.3; Retention time 2.5 min (shoulder; Minor component): 3,3',3",3"'-((((2,3- dihydroxypropyl)azanediyl)bis(ethane-2, 1 -diyl))bis(azanetriyl))tetrakis(propane- 1 ,2- diol). [M+H] = 474.3. The residual starting material and 3-((2-((2- aminoethyl)amino)ethyl)amino)propane-l,2-diol can be removed from the mixture by Kugelrohr or wiped film distillation.

Example 2: l,l'-((((2-hydroxypropyl)azanediyl)bis(ethane-2,l-diyl))bis( (2- aminoethyl)azanediyl))bis(propan-2-ol) (TEPA-3PO)

Using tetraethylene pentamine (0.5 mol) and propylene oxide (1.5 mol) as starting materials and following analogous procedures to those described above, the title compound may be prepared. LC / MS analyses show component masses ranging from 363 to 537 daltons. IR shows OH and NH ₂ at 3294 cm ^"1 , aliphatic CH at 2962 and 2815 cm ^"1 , and aliphatic CH ₂ and CH ₃ at 1456, 1370, 1334, 1293, 1133, 1061, 1013, 944, and 842 cm ^"1 1H-NMR shows a broad singlet at 3.836 ppm (2.5 Hs), a complex multiplet at 2.724 - 2.308 ppm (22 Hs), and a complex multiplet at 1.168 - 1.092 ppm (9 Hs). ¹³ H- NMR showed 13 signals at 77.175 - 73.531 ppm, 4 signals at 68.508 - 67.271 ppm, 7 signals at 65.667 - 62.911 ppm, 10 signals at 60.326 - 56.966 ppm, single signals at 51.935 and 50.255 ppm, and 6 signals at 31.960 - 30.842 ppm.

Example 3: 7,13-bis(2-hydroxypropyl)-4,7,10,13,16-pentaazanonadecane-2, 18-diol (TEPA-4PO)

Using tetraethylene pentamine (0.5 mol) and propylene oxide (2.0 mol) as starting materials and following analogous procedures to those described above, the title compound may be prepared. The IR and NMR analysis results are similar to those obtained for TEPA-3PO. Example 4: TEPA-2.5PO

Using tetraethylene pentamine (0.5 mol) and propylene oxide (1.25 mol) as starting materials and following analogous procedures to those described above, the title compound may be prepared. The IR and NMR analysis results are similar to those obtained for TEPA-3PO.

Example 5: Heavy Polyamine X-propylene oxide (HPX-3PO)

HPX-3PO

Using Heavy Polyamine X (a mixture of ethyleneamines available from The Dow Chemical Company) (0.5 mol) and propylene oxide (1.5 mol) as starting materials and following analogous procedures to those described above, the title compound may be prepared. Product pKa data: pKl = 9.2; pK2 = 7.0; pK3 = 4.8.

Example 6: 7-(2-hydroxypropyl)-4,7,10,13-tetraazahexadecane-2,15-diol (TETA-3PO) Using Triethylenetetramine (0.5 mol) and propylene oxide (1.5 mol) as starting materials and following analogous procedures to those described above, the title compound may be prepared. LC / MS analyses show component masses ranging from 277 to 473 daltons. The composition of the mixture is determined by CI - LC/MS. The major components is 7-(2-hydroxypropyl)-4,7,10,13-tetraazahexadecane-2,15-diol, 7,10- bis(2-hydroxypropyl)-4,7,10,13-tetraazahexadecane-2,15-diol and 4,7,10-tris(2- hydroxypropyl)-4,7,10,13-tetraazahexadecane-2,15-diol. The Minor components include: l-((2-((2-((2-aminoethyl)amino)ethyl)amino)ethyl)amino)propa n-2-ol, 4,7,10,13- tetraazahexadecane-2,15-diol and 4,7, 10, 13-tetrakis(2-hydroxypropyl)-4,7, 10,13- tetraazahexadecane-2, 15-diol.

Example 7: VOC Testing and pKa

VOC properties are tested according to the ASTM D6886-rev method. The parameters used are as follows (Table 2): Table 2

VOC and pKa data for various compounds are shown in the following Table 3.

Table 3

According to ASTM D6886 -rev method. GC conditions listed in Table 2.

The VOC contributed by the neutralizer in a finished paint formulation and measured according to the procedure outlined in the ASTM D6886 method.

The main components in the crude amine such as TEPA-4PO, HPX 3PO and DETA- Glyc are 'zero' VOC. Their retention time is longer than 20 minutes according to the ASTM D6886- method. These materials also elute after the designated markers in the ISO 11890-2, SCAQMD M131-91 and GB 18581.

³ EDBDA-bis-AMP = ΝΙ,ΝΙ '-((ethane- l,2-diylbis(oxy))bis(ethane-2,l-diyl))bis(2- methylpropane- 1 ,2-diamine) . Example 8:

Preparation of acrylic -based flat paint formulation: Zero-VOC flat formulation with vinyl acrylic latex are prepared as shown in Table 4.

Table 4

The paints are evaluated using the following methods:

pH, Low Shear and High Shear Viscosity. The pH of each formulation is measured with a digital pH meter with a glass combination pH probe. Krebs-units (KU) viscosity is measured with Brookfield model KU viscometer with digital display (ASTM D562), at 25°C. The high shear ("ICI") viscosity is measured according to ASTM D 4287 using a Brookfield CAP 1000+ viscometer at a shear rate of 12,000 s ^"1 at 900 rpm, with a 0.45° cone of radius 1.511 cm, and a sample temperature controlled at 25°C.

Gloss, contrast ratio. Gloss and opacity measurements are done on films applied with a 3-mil wet-film drawdown bar to Leneta Form 3-B opacity charts. Panels are dried at least 16 hours at 25°C and 50% relative humidity before measurement.

Gloss at 60° or sheen at 85° is measured with a BYK-Gardner micro-TRI-gloss meter in accordance with ASTM D 523.

Opacity measurements are done with a BYK-Gardner Color Guide Sphere color meter (D65 source / 10° observer), which measures reflectance spectra in conformity to ASTM E 1164. The meter measures and calculates opacity according to ASTM D 2805 from pairs of successive measurements over the black-background and white-background sections of the opacity charts.

Scrub Resistance. Wet-scrub resistance is measured with a Gardco Model D10 scrub resistance tester, with a fixed speed of 37 cycles / minute according to ASTM D 2486. Replicate side-by-side drawdowns are drawn on Leneta P-121-10N black plastic panels with the 7-mil gap side of a U-shaped applicator bar (the Dow latex bar, available from Paul N. Gardner, Inc.). The panels are dried 7 days at 50% relative humidity at 25°C. The panels are secured to the stage of the scrub tester with shims under each of the side-by- side films to give a raised test area. Before each 400 cycles of the test, lOg of the specified abrasive medium and 5 mL of water are placed in the path of the scrub brush. The end point for each paint film is recorded when the brush wears a continuous line of complete paint removal across the width of the raised test surface.

Stain resistance. Paint films of 3-mil wet-film thickness are applied on Leneta P-121-10N black plastic panels and dried 7 days at 50% relative humidity at 25°C. The following staining media are applied across the width of the film - pencil, pen, crayon, grape juice, and coffee. These media are allowed to remain on each paint film for 30 minutes. Panels are secured to the stage of the Model D10 scrub resistance tester, and tested 200 cycles with a 1-lb, 2-by-4-inch abrasion boat wrapped with cheesecloth soaked with a 1% solution of laundry detergent. After drying, panels are rated by the rating scale described in ASTM D 4828: 0 = no removal of original stain; 3 = slight removal, stain readily visible; 5 = moderate removal, stain slightly visible; 7 = stain barely visible; 10 = complete removal of stain. The results of the above tests on the paint formulations are listed in Table 5.

Table 5.

In a flat formulation, TETA 3PO showed improvement in scrub resistance, compared to sodium hydroxide.

Example 9:

Preparation of acrylic -based semi-gloss paint Formulation: Zero- VOC semi-gloss formulation with acrylic latex is prepared as shown in Table 6.

Table 6

The paints are evaluated according to the methods described in Example 8, and also for blocking resistance as follows. Films of 3-mil wet-film thickness applied to opacity charts are dried for 1 and 3 days at 50% relative humidity at 25°C before testing. For each test, coated panels are cut into triplicate pairs of 1 ½ inch squares. Each pair of squares is placed face to face, then each pair is covered with a No. 8 rubber stopper. A 1 kg weight is placed on the rubber stopper for 1 hour at 25°C, or for 30 ,minutes at 50°C. At the end of each time period, the weights are removed and the pairs of squares are peeled apart with slow, steady force. The amount of adhesion is observed and evaluated according to ASTM D 4946 on a scale of 0 (greatest adhesion) to 10 (least adhesion). The results of the above tests on zero-VOC semi-gloss formulation is listed in Table 7.

Table 7

In a zero VOC Semi Gloss Formulation, TEPA 2.5PO and TETA 3PO show slight improvement in scrub resistance.

Example 10

Preparation of paint formulations containing compounds of the invention: The paint formulations are prepared using F/T agent 1 and 2 as shown by structures below. The octanol water partition coefficients are calculated for these compounds using the method of Moriguchi et al., Chem. Pharm. Bull. 40(1), 127-130 (1992). The calculated octanol- water partition coefficients for F/T-l and F/T-2 are -2.59, and -3.99, respectively. Table 8 shows the paint formulations used for the freeze-thaw experiments. Paint samples are frozen at -18°C for 17 hours and then thawed at 25°C for 7 hours. This constitutes 1 complete freeze-thaw cycle. Viscosities are measured after each freeze- thaw cycle using a Krebs Stormer Viscometer from Sheen at room temperature. The viscosity is measured in Krebs unit (KU). The results of freeze-thaw cycles on paint samples that contain zero-VOC compounds of the invention as post-adds are listed in the Table 9. The post-add compounds are mixed at 2 wt in the paint samples. The same paint formulation is used in preparing all the samples. The paint sample without any

Table 8

Ingredient % by wt

Water 17

Kathon LXE 0.1

ROZONE 2000 0.3

Tego Foamex 0.02

HEC 0.5

Orotan 731 A 0.6

AMP95 0.1

Tergitol 15S40 0.2

Ti0 ₂ R 706 18.00

Calcite MF 4.00

Omyacarb 3

ACRYSOL RM 5000 1

AMP95 0.1

Water 16.16

Tego Foamex 0.02

Water 1.9

ROPAQUE ULTRA E 7.00

PRIMAL ^1M SF 018 30.00

Total 100 KATHON™ LXE is an in-can, active biocide for preserving latex enamel paint formulations, and it is available from The Dow Chemical Company.

ROZONE™ 2000 is a liquid fungicide and algaecide with broad-spectrum antimicrobial action for water- or solvent-based coatings, and it is available from The Dow Chemical Company.

TEGO FOAMEX™ is a defoamer available from Evonik Industries.

HEC is hydroxy ethyl cellulose (NATRASOL 250 HBR Aqualon ) available from Ashland.

OROTAN™ 731 A is pigment dispersant for various latex based coatings. It is a sodium salt of a carboxylate polyelectrolyte, and it is available from The Dow Chemical Company.

AMP-95 is 2-amino-2-methyl-l-propanol with 5% water. It is a neutralizer and co-dispersant available from The Dow Chemical Company.

TERGrrOL™ 15S40 is a nonionic surfactant of a secondary alcohol ethoxylate available from The Dow Chemical Company.

Ti0 ₂ R 706 is a multipurpose rutile titanium dioxide pigment available from DuPont.

CALCITE MF is of 10 micron particle size and available from 20MICRONS Ltd. OMYACARB™ is calcium carbonate is of particle size 2 microns and available from OMYA.

ACRYSOL™ RM 5000 is a solvent-free, non-ionic associative thickening agent for use with latex paints. It is available from The Dow Chemical Company.

ROPAQUE™ ULTRA E is an opaque polymer that increases the dry hiding capability of paint coatings, and it is available from The Dow Chemical Company.

PRIMAL™ SF 018 is an acrylic polymer for use in paints to afford good abrasive scrub resistance. It is available from The Dow Chemical Company.

The KU values below 150 as reported in Table 9 are considered acceptable, and all the values (other than that for the Blank) reported are considered very acceptable. Table 9

The paint samples are subjected to paint performance testing. The paint samples that contain F/T Agent 1, and F/T Agent 2 when added as post-add survive five freeze- thaw cycles. The benchmarks used for the study are paint samples that contained propylene glycol and diethylene glycol as freeze-thaw additives. The paint sample without any post-add is the "Blank." This sample fails the first cycle of freeze-thaw.

The performance properties are compared to the paint sample with propylene glycol (PG) as the additive to see if there is a detrimental effect on the properties. Table 10 reports the findings for opacity and Table 11 reports the whiteness related properties.

Table 10

Tab e 11

A fixed gap shearing applicator from Sheen is used to draw paint films of thickness 150 microns. The draw-downs of paint samples are dried for 7 days. The opacity is measured using the device from Sheen Micromatch Plus. Color measurements are done with Sheen Micromatch Plus. The instrument calculates color parameters according to CIE color space L, a*, b* system. Yellowness is reported in terms of b* (yellow-blue scale), whiteness is reported in terms of L and finally a* measures (red- green scale). The color difference between the reference and the sample colors is measured as

AE = V(AL) ² + (Δ ) ² + (Δδ) ²

where AL, Aa, Ab are the differences between the sample (paint with post-additive) and reference (blank) for L, a and b values, respectively. Table 11 lists the L, a, b and ΔΕ values.

The paint performance data with the compounds of the invention are taken after 5 freeze-thaw cycles and compared to the data with the 'Blank' paint, which has not gone through any freeze-thaw cycles.