阅读说明：本技术 水溶性或水分散性组合物 (Water-soluble or water-dispersible compositions ) 是由 K·A·布拉什 V·克里希南 G·斯托克洛萨 Z·K·谢里安 于 2019-07-19 设计创作，主要内容包括：本公开通常涉及包含具有单-端和二-端封端的疏水基团的疏水改性的聚亚烷基二醇的水溶性或水分散性组合物。另外,本发明还涉及其在多种工业领域,例如涂料中的应用。(The present disclosure generally relates to water-soluble or water-dispersible compositions comprising hydrophobically modified polyalkylene glycols having both mono-and di-terminally terminated hydrophobic groups. In addition, the invention relates to its use in various industrial fields, such as coatings.)

1. A water-soluble or water-dispersible composition comprising a hydrophobically modified polyalkylene glycol having mono-and di-end capped hydrophobic groups, wherein the di-end capped hydrophobic groups comprise at least 50 weight percent based on the total weight of the capped hydrophobic groups.

2. The composition of claim 1, wherein the double-ended capped hydrophobic groups comprise at least 60 wt.%, based on the total weight of capped hydrophobic groups.

3. The composition of claim 2, wherein the double-ended capped hydrophobic groups comprise at least 65 wt.%, based on the total weight of capped hydrophobic groups.

4. The composition of claim 2, wherein the double-ended capped hydrophobic groups comprise about 70 wt% to about 98 wt% based on the total weight of capped hydrophobic groups.

5. The composition of any of claims 1-4, wherein the polyalkylene glycol is selected from the group consisting of polyethylene glycol, polypropylene glycol, poly (ethylene glycol-propylene glycol), polybutylene glycol, polytetrahydrofuran, and combinations thereof.

6. The composition of any of claims 1-5, wherein the hydrophobic group is selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, aryl, alkylaryl, arylalkyl, arylalkenyl, cyclic, cycloaliphatic, and polycyclic groups, the hydrophobic group optionally having at least one heteroatom.

7. The composition of claim 6, wherein the alkyl group is linear or branched and comprises from 4 to 24 carbon atoms.

8. The composition of claim 7, wherein the alkyl group comprises 6 to 20 carbon atoms.

9. The composition of claim 8, wherein the alkyl group comprises 8 to 16 carbon atoms.

10. The composition of any one of claims 1 to 9, wherein the polyalkylene glycol has a weight average molecular weight of from about 400 to 60,000 daltons.

11. The composition of claim 10, wherein the weight average molecular weight of the polyalkylene glycol is from 1,000 to 50,000 daltons.

12. The composition of claim 11, wherein the polyalkylene glycol has a weight average molecular weight of 3,000 to 35,000 daltons.

13. The composition of claim 12, wherein the weight average molecular weight of the polyalkylene glycol is from 6,000 to 30,000 daltons.

14. The composition of claim 13, wherein the polyalkylene glycol has a weight average molecular weight of from 9,000 to 30,000 daltons.

15. An aqueous protective coating composition comprising the composition of any one of claims 1 to 14.

16. The aqueous protective coating composition of claim 15, further comprising a latex polymer.

17. The aqueous protective coating composition of claim 16, wherein the latex polymer is selected from the group consisting of vinyl acetate ethylene polymers, acrylic polymers, vinyl-acrylic polymers, and styrene-acrylic polymers.

18. An aqueous protective coating composition according to any one of claims 15 to 17, further comprising a pigment.

19. The aqueous protective coating composition of claim 18 wherein the pigment is selected from the group consisting of hydrated alumina, barium sulfate, calcium silicate, clay, silica, talc, titanium dioxide, zinc oxide, and mixtures thereof.

20. An aqueous protective coating composition according to any one of claims 15 to 19, further comprising one or more of the following ingredients: a coagulant, solvent, wetting agent, defoamer, matting agent, dispersant, thickener, biocide, mildewcide, or surfactant.

21. An aqueous protective coating composition according to any one of claims 15 to 20, further comprising from about 0.5% to about 4% by weight of the composition of claim 1.

22. The aqueous protective coating composition of any one of claims 15 to 21, wherein the aqueous protective composition comprises a coating.

23. A method of preparing an aqueous protective coating composition comprising:

(a) adding a latex polymer to the aqueous solution; and

(b) adding the composition of any one of claims 1 to 14 to an aqueous solution to form the aqueous protective coating composition.

24. The method of claim 23, wherein the composition is added to the aqueous solution prior to adding the latex polymer to the aqueous solution.

25. The method of claim 23, wherein the composition is added to the aqueous solution after the latex polymer is added to the aqueous solution.

26. The method of claim 23, wherein the composition is added to the aqueous solution at the same time the latex polymer is added to the aqueous solution.

27. The method of any one of claims 23 to 26, wherein the aqueous protective composition comprises a coating.

1. Field of the invention

The processes, steps, methods, products, results and/or concepts disclosed herein (hereinafter collectively referred to as "the present disclosure") generally relate to water-soluble or water-dispersible compositions comprising hydrophobically modified polyalkylene glycols having both mono-and di-terminally terminated hydrophobic groups. In addition, the present disclosure relates to its use in various industrial fields such as coatings.

2. Background of the invention

Water-soluble polymers (also commonly referred to as "thickeners" or "rheology modifiers") are widely used as additives in many industrial aqueous systems to modify their flow properties. Thickeners will increase viscosity and maintain viscosity at a desired level under specified processing conditions and end use conditions. Thickeners are useful, for example, in decorative and protective coatings, paper coatings, cosmetic and personal care products, detergents, pharmaceuticals, adhesives and sealants, agricultural formulations, and petroleum drilling fluids.

In recent years, there has been an increase in the importance of SATs, particularly in controlling the rheology of aqueous coatings and latex paints. Since the SAT is prepared from alkaline chemicals, it can be prepared with certain characteristics in mind. In other words, synthetic associative thickeners can be tailored to desired and/or targeted properties from the beginning. SATs serve multiple functions in aqueous systems. For example, in latex paints and aqueous coatings, thickeners can provide improved stability and pigment suspension, as well as improved rheology and application properties. In personal care products, thickeners can improve the body, feel, smoothness, and richness of the product, making the product more aesthetically pleasing.

Rheology modifiers for aqueous coatings or paints can control viscosity over a wide range of shear rates. They are generally classified and referred to as low, medium and high shear rate tackifiers. The low shear rate adhesion promoter is used when the coating is stored in a tank and/or immediately after the coating is applied to a substrate. Sufficient low shear adhesion promoter is required to resist pigment settling and film sagging, but to provide the desired leveling of the applied film coating. Brookfield viscosity is a common measure of the low shear viscosity of a coating.

Medium shear tackifiers help to improve in-can appearance and handling properties as the coating is stirred, poured, and sometimes pumped, and can also affect spatter. Common measurements of medium shear viscosity include Stormer viscosity, brookfield viscosity at high rpm, and Rotothinner viscosity. Stormer viscosity is expressed in units of klebside (Kreb) (KU). Thus, rheology modifiers that provide moderate shear viscosity are commonly referred to as "KU tackifiers".

High shear adhesion promoters are used when the coatings are used for brushing, rolling and spraying. The high shear tackifier affects the resistance and film formation of the brush and roller, thereby contributing to hiding power. High shear viscosity is typically measured using a cone and plate viscometer including a standard ICI viscometer. Therefore, rheology modifiers that will provide good high shear viscosity are commonly referred to as "ICI tackifiers".

With each change in shear rate, the coating undergoes a viscosity change from low to medium shear, and finally to high shear, whereby a higher shear rate results in a low viscosity. Therefore, a rheology modifier must be developed to meet the varying shear rate of the coating to optimize sag resistance, flow and leveling over the entire range of shear rates.

Unfortunately, it is very challenging to use a rheology modifier to maintain sag resistance and good flow and leveling. As the sag resistance increases, the flow and leveling properties deteriorate. Although the paint does not drip, the workability is affected due to poor flow and leveling, thus leaving marks of the brush and roller. Coatings that flow and level well but resist sagging poorly can result in dripping. The paint formulator must optimize sag and flow properties and maintain or improve other paint properties such as hiding with minimum paint, extended open time, resistance to syneresis, roll and brush properties, and stain resistance. For example, it is difficult to use a rheology modifier in coating formulations to meet KU and ICI viscosity requirements. In certain applications, it is necessary to use a combination of KU and ICI viscosity rheology modifiers.

It is desirable to increase the ICI viscosity and efficiency of ICI architectural rheology modifiers without concomitant increase in KU viscosity because the increase in KU viscosity limits the ability of the formulator to add KU architectural rheology modifiers to the formulation. KU building rheology modifier formulations with insufficient addition can exhibit poor resistance to sagging and dripping when applied to a substrate. It is also desirable to use a rheology modifier to optimize coating performance over a range of shear rates.

Brief Description of Drawings

FIG. 1 is a graph of ICI viscosity for polymers A-N.

FIG. 2 is a graph of the Stormer viscosities of polymers A-N.

FIG. 3 is a plot of coating viscosity versus shear rate for polymers A-N.

Detailed Description

Before explaining at least one embodiment of the disclosure in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and to the arrangements of the components or steps or methods set forth in the following description or illustrated in the drawings. The disclosure is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings that are commonly understood by those of ordinary skill in the art. Furthermore, unless the context requires otherwise, singular terms shall include the plural and plural terms shall include the singular.

All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this disclosure pertains. All patents, published patent applications, and non-patent publications cited in any section of this application are expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication were specifically and individually indicated to be incorporated by reference.

All of the articles and/or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. Although the articles and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations may be applied to the articles and/or methods and in the steps or in the sequence of steps described herein without departing from the concept, spirit and scope of the disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the disclosure.

As used in accordance with this disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.

The words "a" or "an" when used in conjunction with the term "comprising" may mean "one," but are also consistent with the meaning of "one or more," at least one, "and" one or more than one. The use of the term "or" is used to mean "and/or" unless it is explicitly stated that alternatives are only meant to be mutually exclusive, although the present disclosure supports the definition of only alternatives and "and/or". Throughout this application, the term "about" is used to denote a value that includes the inherent variation in error of the quantifying device, the method used to determine the value, or the variation that exists between study objects. For example, and without limitation, when the term "about" is used, the specified value may vary by plus or minus twelve percent, eleven percent, or ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent. The use of the term "at least one" should be understood to include any number of one as well as more than one, including but not limited to 1,2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" may extend up to 100 or 1000 or more, depending on the term to which it is attached. In addition, the amount of 100/1000 should not be considered limiting, as lower or higher limits may also produce satisfactory results. In addition, use of the term "X, Y and at least one of Z" should be understood to include X alone, Y alone, and Z alone, and any combination of X, Y and Z. The use of ordinal number terms (i.e., "first," "second," "third," "fourth," etc.) is solely for the purpose of distinguishing between two or more items and, unless otherwise stated, is not intended to imply the order, sequence, or importance of one item to another or any order of addition.

As used herein, the words "comprising" (and any form of comprising, such as "comprises" and "comprising"), "having" (and any form of having, such as "has" and "having"), "including" (and any form of including, such as "includes" and "including") or "containing" (and any form of containing, such as "contains" and "containing") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. As used herein, the terms "or combinations thereof" and/or combinations thereof "refer to all permutations and combinations of the listed items preceding the term. For example, "A, B, C or a combination thereof" is intended to include at least one of: A. b, C, AB, AC, BC, or ABC, if the order is important in a particular situation, further including BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations containing one or more repetitions of the item or term, e.g., BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, and the like. It will be understood by those of skill in the art that there is generally no limitation on the number of items or terms in any combination, unless apparent from the context.

For the purposes of the following detailed description, other than in any operating examples or where otherwise indicated, numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". The numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the practice of the invention.

The term "alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to 50 carbons.

As used herein, the term "alkylene" refers to an unsaturated straight or branched hydrocarbon group having 1 to 50 carbon atoms with one or more carbon-carbon double bonds.

The term "aryl" refers to a mononuclear or polynuclear aromatic hydrocarbon group including carbocyclic and heterocyclic aromatic groups.

The term "monomer" refers to a small molecule that is chemically bonded to one or more monomers of the same or different species during polymerization to form a polymer.

The term "polymer" refers to a macromolecule comprising one or more types of monomeric residues (repeating units) linked by covalent chemical bonds. According to this definition, polymers include compounds in which the number of monomer units can range from very small, more commonly referred to as oligomers, to very large. Non-limiting examples of polymers include homopolymers and non-homopolymers, such as copolymers, terpolymers, tetrapolymers, and higher analogs.

All percentages, ratios and proportions used herein are by weight unless otherwise specified.

The present disclosure relates to water-soluble or water-dispersible compositions comprising hydrophobically modified polyalkylene glycols having mono-and di-terminated hydrophobic groups. The di-end-capped hydrophobic groups comprise at least 50 wt.%, or at least 55 wt.%, or at least 60 wt.%, or at least 65 wt.%, or at least 70 wt.%, or from about 70 wt.% to about 98 wt.%, based on the total weight of the capped hydrophobic groups.

The hydrophobically modified polyalkylene glycol may have a weight average molecular weight of from about 500 to about 2,000,000 daltons, or from about 500 to about 50,000 daltons, or from about 1,000 to about 1,500,000 daltons, or from about 1,000 to about 40,000 daltons, or from about 3,000 to about 30,000 daltons, or from about 5,000 to about 1,000,000 daltons, or from about 15,000 to about 500,000 daltons, or from about 20,000 to about 100,000 daltons.

Suitable polyalkylene glycols may include, but are not limited to, polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol, and polytetrahydrofuran. The polyalkylene glycol may also be a copolymer of at least two alkylene oxides, which may be selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. In one non-limiting embodiment, the copolymer may be polyethylene-polypropylene glycol.

In one non-limiting embodiment, the polyalkylene glycol is polyethylene glycol (PEG). PEG is prepared by polymerization of ethylene oxide and is commercially available in a wide range of number average molecular weights from about 300 to about 10,000,000 daltons. The molecular weight of the PEG used in the present disclosure may vary between about 1,000 to about 5,000,000 daltons, or about 2,000 to about 2,000,000 daltons, or about 3,000 to about 1,000,000 daltons, or about 5,000 to about 60,000 daltons.

Polyethylene glycol may include commercially available products such as, but not limited to, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1,000, polyethylene glycol 1,500, polyethylene glycol 2,000, polyethylene glycol 3,000, polyethylene glycol 3,350, polyethylene glycol 4,000, polyethylene glycol 4,600, polyethylene glycol 6,000, polyethylene glycol 8,000, polyethylene glycol 10,000, polyethylene glycol 12,000, polyethylene glycol 20,000, polyethylene glycol 35,000, and polyethylene glycol 40,000, polyethylene glycol (Polyglykol)400, polyethylene glycol 600, polyethylene glycol 4,000S, polyethylene glycol 8,000S, polyethylene glycol 9,000S, polyethylene glycol 20,000S, and polyethylene glycol 35,000S, which are commercially available from Sigma-Aldrich.

Examples of polypropylene glycol may include, but are not limited to, poly (propylene glycol) 425, poly (propylene glycol) 725, poly (propylene glycol) 1,000, poly (propylene glycol) 2,000, poly (propylene glycol) 2,700, and polypropylene glycol 4,000, all of which are commercially available from Sigma-Aldrich.

For polyethylene glycol-polypropylene glycol copolymers, the weight ratio of PPG/PEG may vary between about 80:20 to about 3:97, or about 70:30 to about 5:95, or about 50:50 to about 10: 90. Examples of polyethylene-polypropylene glycol may include, but are not limited to, M available from Sigma-Aldrich_nPoly (ethylene glycol) -block-poly- (propylene glycol) -block-poly- (ethylene glycol) of 8,400.

Examples of polytetrahydrofuran may include, but are not limited to, polytetrahydrofuran 250, polytetrahydrofuran 650, polytetrahydrofuran 1,000, polytetrahydrofuran 2,000, and polytetrahydrofuran 2,900, all of which are commercially available from Sigma-Aldrich.

The hydrophobic groups may be the same or different molecules and may be selected from the group consisting of hydrocarbyl, alkyl, aryl, arylalkyl, cycloaliphatic, perfluoroalkyl, carbosilane, polycyclic and complex dendritic groups. The hydrophobic group may contain at least one heteroatom, including nitrogen, oxygen, sulfur, and phosphorus. These hydrophobic groups may be saturated or unsaturated, branched or straight-chain. The upper limit of the number of carbon atoms in the hydrophobic group may be 40 carbons, or 27 carbons, or 22 carbons or 18 carbons; the lower limit of the number of carbon atoms in the hydrophobic group may be 1 carbon, or 4 carbons, or 8 carbons, or 10 carbons or 12 carbons. When the hydrophobic groups are independently selected from alkyl, perfluoroalkyl, and carbosilyl, the carbon range may vary from 1 to 40 carbons, or 4 to 24 carbons, or 6 to 20 carbons, or 8 to 16 carbons, or 10 to 16 carbons. When the hydrophobic groups are aryl, arylalkyl, cycloaliphatic, and polycyclic groups, the carbon ranges from 3 to 40, or 6 to 29 carbons, or 14 to 25 carbons.

In one non-limiting embodiment, the hydrophobic group can be an alkyl having from 1 to 40 carbons, or from 4 to 24 carbons, or from 6 to 20 carbons, or from 8 to 16 carbons, or from 10 to 16 carbons. Specific examples of the hydrophobic group may include, but are not limited to, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, and octadecyl.

The hydrophobically modified polyalkylene glycol may comprise from about 0.1% to about 10%, or from about 0.4% to about 8%, or from about 0.8% to about 5%, by weight of the hydrophobic groups, based on the total weight of the hydrophobically modified polyalkylene glycol.

The hydrophobically modified polyalkylene glycol can be prepared by mixing molten polyalkylene glycol with caustic at elevated temperature and then adding a hydrophobizing agent end-capped to the polyalkylene glycol.

The hydrophobizing agent may be an alkyl halide and/or a monoepoxide. Examples of the alkyl halide may include, but are not limited to, 1-bromobutane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromodecane, 1-bromododecane, 1-bromotetradecane, 1-bromohexadecane, 1-bromooctadecane and 1-bromodocosane. Examples of monoepoxides can include, but are not limited to, Allyl Glycidyl Ether (AGE), 2-ethylhexyl glycidyl ether (EHGE), hexadecyl glycidyl ether (HAGE-13, commercially available from Sachem), ethylene oxide [ [ behenyloxy ], methyl group](HAGE) -22, commercially available from Sachem), Naphthyl Glycidyl Ether (NGE), n-butyl glycidyl ether (n-BGE), isobutyl glycidyl ether (iso-BGE) and Cardura^TME10P glycidyl Ether and Versatic^TM 10(Hexion)。

Water-soluble or water-dispersible compositions comprising hydrophobically modified polyalkylene glycols can be used as rheology modifiers in coatings. The water-soluble or water-dispersible composition may also comprise other rheology modifiers for polysaccharides and derivatives thereof. The polysaccharide and its derivatives may be selected from cellulose, chitin, chitosan, starch, galactomannan and its derivatives. In one non-limiting embodiment, the cellulose derivative is a cellulose ether including hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methylhydroxypropyl cellulose, and carboxymethyl cellulose.

In another non-limiting embodiment, guar derivatives may include, but are not limited to, carboxymethyl guar, carboxymethyl hydroxypropyl guar, cationic hydroxypropyl guar, hydroxyalkyl guar such as hydroxyethyl guar, hydroxypropyl guar and hydroxybutyl guar, carboxyalkyl guar such as carboxymethyl guar, carboxypropyl guar, carboxybutyl guar, and the like.

The present disclosure also relates to aqueous protective coating compositions comprising hydrophobically modified polyalkylene glycols and latex polymers. The hydrophobically modified polyalkylene glycols are the same as those previously described. A variety of latex polymers can be used in the aqueous protective coating compositions of the present disclosure. They can be prepared by polymerization of various ethylenically unsaturated monomers, such as ethylene, vinyl and acrylic monomers. Latex polymers are typically prepared by copolymerizing more than one monomer to achieve several desired properties, particularly in the case of latex paints having little or no Volatile Organic Compounds (VOCs). Examples of latex polymers for use in the aqueous protective coating composition can include, but are not limited to, homopolymers or copolymers of vinyl acetate, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, styrene, ethylene, vinyl chloride, vinyl esters of versatic acid (VeoVa), vinyl propionate, butadiene, acrylonitrile, maleates, and fumarates. In one non-limiting embodiment, the latex polymer is selected from the group consisting of acrylic, vinyl-acrylic, and styrene-acrylic.

Other latex polymers may include, but are not limited to, alkyd resins, cellulose (nitrocellulose and cellulose esters), coumarone-indene, epoxy resins, esters, hydrocarbons, melamine, natural resins, oleoresins, phenolic resins, polyamides, polyesters, rosins, silicone resins, terpenes, ureas, urethanes, vinyl resins, and the like.

The aqueous protective coating composition may further comprise pigments, coalescents, solvents, wetting agents, defoamers, matting agents, dispersants, thickeners, biocides, mildewcides, and surfactants. The aqueous protective coating composition may optionally comprise other components, such as those typically used in such compositions. Typical components include, but are not limited to, one or more of the following: fillers, siccatives, leveling agents, plasticizers, stabilizers, tackifiers, suspending agents, flow control agents, anti-skinning agents, extenders, film forming aids, crosslinking agents, surface modifying agents, preservatives, leveling aids, surface modifying agents, wetting/wet edge agents (e.g., ethylene glycol, propylene glycol, and hexylene glycol), pH adjusting agents, and other ingredients useful in aqueous protective coating compositions.

Specific examples of the pigment may include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigment, diketopyrrolopyrrole red ("DPPBO red"), titanium dioxide, carbon black, barium sulfate, calcium silicate, zinc oxide, magnesium aluminum silicate, precipitated calcium carbonate, ground calcium carbonate, kaolin, talc, clay, barium sulfate, glass beads, calcium sulfate, barium sulfate, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal silica, and the like, Colloidal alumina, fumed silica, pseudoboehmite, aluminum hydroxide, alumina, modified alumina, lithopone, zeolite, halloysite hydrate, magnesium carbonate, magnesium hydroxide, lampblack, black iron oxide, red iron oxide, yellow iron oxide, brown iron oxide (a blend of red and yellow iron oxides with black), phthalocyanine green, phthalocyanine blue, organic reds (such as naphthol red, quinacridone red and toluidine red), quinacridone magenta, quinacridone violet, DNA orange and/or organic yellows (such as Hansa yellow).

Typically, the titanium dioxide grades used in aqueous protective coating compositions are surface modified by a variety of inorganic oxides such as silicates, aluminates, and zirconates. Aluminum silicate, perlite, feldspar, mica, calcium carbonate and/or diatomaceous earth may also be used.

In one non-limiting embodiment, the hydrophobically modified polyalkylene glycols of the present invention may be used as high shear rate tackifiers to increase ICI viscosity without an accompanying increase in KU viscosity. In the present application, the hydrophobically modified polyalkylene glycol may be characterized by the formula:

Ef＝(Dicap％)x(PEG M_n)³/10¹²

wherein Ef is the efficiency factor, Dicap% is the weight percentage of di-terminated hydrophobic groups based on the total terminated hydrophobic groups, and PEG M_nIs the number average molecular weight of the PEG used to prepare the hydrophobically modified polyalkylene glycol. Ef can vary from about 5 to about 15,000, or from about 25 to about 13,000, or from about 550 to about 13,000.

Mixtures of hydrophobically modified polyalkylene glycols containing different types of hydrophobic groups can also be used to adjust the viscosity to meet the requirements of the coating formulation. For example, it has surprisingly been found that by adding a mixture comprising at least two hydrophobically modified polyalkylene glycols having different types of hydrophobic groups to an aqueous coating material and independently adjusting the amount of hydrophobically modified polyalkylene glycol, the Stormer viscosity and ICI viscosity of the coating material can be greatly increased. By selecting the appropriate hydrophobic groups and the amount thereof grafted onto the polyalkylene glycol base polymer, a balance of Stormer viscosity and ICI viscosity can be achieved in the aqueous coating. These mixed hydrophobically modified polymer systems may comprise a blend of at least two hydrophobically modified polymers to allow the coating formulator to adjust the balance of Stormer and ICI viscosities as well as other rheological properties of the coating composition such as flow, leveling, anti-spattering and ability to suspend the dispersed phase.

In one non-limiting embodiment, the hydrophobically modified polyalkylene glycol may contain mixed alkyl and/or alkylene hydrophobic groups. The alkyl and/or alkylene groups may comprise from 4 to 22 carbons, or from 6 to 18 carbons, or from 8 to 16 carbons. In another non-limiting embodiment, the hydrophobically modified polyalkylene glycol may comprise mixed aryl, arylalkyl, cycloaliphatic and polycyclic hydrophobic groups, which may comprise from 3 to 40 carbons, or from 6 to 29 carbons, 14 to 25 carbons. In another non-limiting embodiment, the hydrophobically modified polyalkylene glycol may contain mixed alkyl, or alkylenearyl, arylalkyl, cycloaliphatic and polycyclic hydrophobic groups.

In one non-limiting embodiment, the weight ratio of the two different types of hydrophobic groups may be between about 25: 1 to about 1:25, or about 10: 1 to about 1:10, or about 5: 1 to about 1: 5, and is varied.

The amount of hydrophobically modified polyalkylene glycol employed in the aqueous protective coating compositions of the present invention is an effective amount to provide the desired thickening and rheological properties to the coating composition. In one non-limiting embodiment, the hydrophobically modified polyalkylene glycol may be used in an amount of from about 0.1 to about 5 weight percent, or from about 0.1 to about 3 weight percent, or from about 0.2 to about 3 weight percent, or from about 1 to about 3 weight percent of the aqueous protective composition.

The following examples illustrate the disclosure, parts and percentages being by weight unless otherwise indicated. The examples are provided to illustrate the disclosure and not to limit the disclosure. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present disclosure without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present disclosure cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Examples

Preparation of solid polymers

In the examples, the following abbreviations are used:

PEG: polyethylene glycol

NaOH: sodium hydroxide

C10 Br: 1-bromodecane

C12 Br: 1-bromododecane

C14 Br: 1-Bromopentadecalkyl

C16 Br: 1-bromohexadecane

M_n: number average molecular weight

M_w: weight average molecular weight

M_z: z-average molecular weight

Example 1: preparation of solid polymers A and C-N

PEG and NaOH were added to the reactor. The contents of the reactor were mixed under vacuum of 29 inches of mercury for time 1 while the temperature was raised to temperature 1 the vacuum was turned off and the temperature was adjusted to temperature 2. Water was added and the contents of the reactor were mixed for time 2. The temperature was adjusted to 3 deg.f and the alkyl halide was added in portions. The temperature was adjusted to 4 deg.f. Once temperature 4 is reached, the contents of the reactor are mixed for time 3. The contents of the reactor were mixed at a temperature of 4 deg.f at 29 inches of mercury for a time of 4 deg.f to produce polymer A, D and H-K. Polymers C, E, F, G and L-N were prepared without the application of vacuum. The contents of the reactor were discharged and allowed to cool to 20-25 ℃ to give solid polymers A and C-N. The amounts of reactants are given in table 1 and the reaction conditions for preparing solid polymers a and C-N are given in table 2, where time is given in minutes and temperature is given in degrees celsius.

TABLE 1 ingredients for solid Polymer preparation

TABLE 2 reaction conditions for Polymer preparation

Polymer and method of making same	Time 1	Time 2	Time 3	Time 4	Temperature 1	Temperature 2	Temperature 3	Temperature 4
									A	30	45	130	80	80.0	80.0	79.0	120.0
C	30	17	120	----	90.0	90.0	90.0	120.0
									D	30	35	65	70	80.0	80.0	80.0	120.0
E	30	35	60	30	95.0	95.0	96.0	120.0
									F	33	18	120	----	90.0	90.0	90.0	120.0
G	43	16	120	----	90.0	90.0	90.0	120.0
									H	40	20	90	60	90.0	91.0	91.0	120.0
I	40	15	90	75	90.0	90.0	90.0	120.0
									J	50	20	90	65	90.0	89.0	90.0	120.0
K	30	30	90	60	90.0	88.0	91.0	120.0
									L	50	20	120	----	91.0	91.0	91.0	120.0
M	48	15	120	----	90.0	92.0	91.0	120.0
									N	40	25	125	----	90.0	88.0	89.0	120.0
O	30	10	120	30	90.0-93.0	90.0	90.0	120.0
									P	40	10	120	30	90.0	90.0	90.0	120.0
Q	30	10	155	30	90.0-103.0	89.0	90.0	120.0-121.0
									R	40	20	150	----	91.0-93.0	93.0	92.0	120.0
S	45	20	150	----	89.0-92.0	92.0	92.0	119.0-121.0
									T	45	15	150	----	90.0-91.0	91.0	91.0	120.0

Example 2: preparation of solid Polymer B

2700g C129K PEG and 98g NaOH were added to the reactor. The contents of the reactor were mixed for about 37 minutes under a vacuum of 29 inches of mercury while the temperature was increased to about 90 ℃. The vacuum was turned off and the temperature was adjusted to about 90 ℃. 2.95g of water was added and the contents of the reactor were mixed for about 17 minutes. The temperature was adjusted to about 90 ℃ and 268.5g C12Br was added over 30 minutes while the temperature was adjusted to about 120 ℃. Once at 120 ℃, the contents of the reactor were mixed for about 60 minutes. The contents of the reactor were discharged and cooled to 20-25 ℃ to obtain a solid polymer B.

Example 3: of solid polymers O-T

PEG and NaOH were added to the reactor. The contents of the reactor were mixed under a vacuum of 29 inches of mercury for a time of 1 while the temperature was raised to temperature 1. The vacuum was turned off and the temperature was adjusted to temperature 2. Water was added and the contents of the reactor were mixed for time 2. The temperature was adjusted to 3 deg.f and the alkyl halide was added over 30-40 minutes. The temperature was adjusted to 4 deg.f. Once temperature 4 is reached, the contents of the reactor are mixed for time 3. The contents of the reactor were mixed at a temperature of 4 deg.f for a time of 4 at 29 inches of mercury to produce polymer O-Q. The polymer R-T was prepared without the application of vacuum. The contents of the reactor were discharged and allowed to cool to 20-25 ℃ to give a solid polymer O-T. The amounts of reactants are given in Table 1 and the reaction conditions for preparing the solid polymer O-T are given in Table 2, where time is given in minutes and temperature is given in degrees Celsius

Characterization of solid Polymer

High Pressure Liquid Chromatography (HPLC) measurements:

HPLC was used to determine the extent of hydrophobic blocking. The Agilent 1200 series quaternary liquid chromatography system and OpenLAB chromatographic data system, commercially available from Agilent Technologies (Santa Clara, Calif.) were used with a water/acetonitrile gradient and Evaporative Light Scattering Detection (ELSD) under reversed phase conditions. Polyethylene glycol (PEG), mono-capped PEG, and di-capped PEG were estimated by normalizing the area percentages.

Reagent:

1. deionized water, high purity-18 megaohms, from a laboratory water purification system.

Burdick & Jackson HPLC grade acetonitrile from Honeywell Burdick & Jackson, 101Columbia Road, Morristown, NJ 07962, Cat. No. 015-4.

3. Phosphoric acid, 85%, ACS reagent grade (H)₃PO₄CAS 7664-38-2) -www.sigmaaldrich.com, catalog No. 466123 or an equivalent.

Burdick & Jackson HPLC grade methanol, available from Honeywell Burdick & Jackson, 101Columbia Road, Morristown, NJ 07962, Cat. No. 230-4.

Sample preparation:

the samples were prepared by weighing approximately 100mg of polymer sample. HPLC methanol (nominally 10mL) and 2 drops of concentrated phosphoric acid were added. The sample was vortexed and/or heated slightly (-50 ℃) until dissolved in the solution.

All Agilent modules in the instrument setup-setup, including:

agilent G1322A 1200 series vacuum degasser

Agilent G1311A 1200 series quaternary pump

Agilent G1329A 1200 series standard automatic sample injector

Agilent G1316A 1200 Series constant temperature column oven

Agilent G7102A 1290Infinity II ELSD

Agilent OpenLAB chromatographic data system

The HPLC analysis conditions were as follows:

mobile phase-water/acetonitrile gradient

Flow rate-0.5 ml/min

Column-4.0 x50mm, 3 micron YMC-filled Ph, part number: PH12S03-0504WT (YMC America, Allentown, PA)

Column temperature-40 deg.C

The sample concentration-usually 10 mg/ml-is dissolved in acidified methanol

Injection volume-10. mu.l

End-capping is reported as normalized area percentage of the PEG, mono-capped PEG, and di-capped PEG peaks.

Size Exclusion Chromatography (SEC) measurements

SEC is used to measure the molecular weight distribution of a polymer. Alliance, commercially available from Waters corporation (Milford, MA)^TMHPLC System and Empower^TMChromatographic data systems are used to measure molecular weight. As used herein with respect to polymers, the terms molecular weight, average molecular weight, and apparent molecular weight refer to the arithmetic mean of the molecular weights of individual macromolecules as measured by SEC. Relative molecular weight averages of SEC were calculated relative to narrow molecular weight distribution poly (ethylene glycol/ethylene oxide) (PEG/PEO) standards.

All Waters modules in the instrument setup-setup, including:

waters M515 solvent delivery system

Waters M2707 autosampler

Waters M2414 differential refractive index Detector (DRI) for relative SEC

Column library-see section "analytical conditions" below

Waters Empower^TM3 software

RI range: 1.00 to 1.75RIU

Measurement range: 7x10^-7RIU

Drift-2 x10^-7RIU

SEC analysis conditions were as follows:

mobile phase-70% methanol/30% 0.6M lithium acetate (pH 4.8) (w/w)

Flow rate-1.0 ml/mi

Column-tandem of 1 Shodex KW-804 protein column (8 mm. times.300 mm) +1 Shodex KW-803 protein column (8 mm. times.300 mm) (Showa Denko America, Inc., 420Lexington Avenue, Suite 2335A, New York, NY 10170, USA)

Column temperature: 40 deg.C

DRI (differential refractive index) detector temperature: 40 deg.C

Calibration-narrow molecular weight distribution PEO/PEG standards (PSS-USA Inc. Amherst Fields Research Park, 160Old Farm Road, Amherst, MA 01002)

Sample concentration-typically 1.5mg/ml (unless otherwise indicated) -directly dissolved in the mobile phase for injection in a volume of 100. mu.l

Table 3 lists the characterization data for solid polymers A-N.

Table 4 shows the characterization data of the solid polymer O-T.

Table 3: summary of Polymer analysis

Table 4: summary of Polymer analysis

Aqueous polymer solutions

An aqueous polymer solution having 20.00 wt% of a solid polymer was prepared by neutralizing the polymer obtained from examples 1 and 2 in water with acetic acid. After neutralization, 0.50% by weight of a fungicide is addedBiocide (available from Thor Group Limited)A mixture of 1, 2-benzothiazol-3-one (2.50%) and 2-methyl-4-isothiazolin-3-one (2.50%), varying amounts of Sag 47 foam control agent from Momentiv Performance Materials and beta cyclodextrin (also known as Wacker Fine Chemicals) from Wacker Fine ChemicalsW7) was added to each aqueous polymer solution to provide an aqueous polymer solution having 20.00 wt.% solid polymer. The viscosity of an aqueous polymer solution having 20.00 wt.% solids polymer was measured using a Brookfield viscometer with LV spindle #4 at 30rpm and 25 ℃. Table 5 lists Sag 47, beta cyclodextrin amounts and brookfield viscosities.

An aqueous polymer solution having 20.00 wt% of a solid polymer was prepared by neutralizing the polymer obtained in example 3 in water with acetic acid. After neutralization, 0.50 wt.% of a fungicide is addedBiocides, or 0.10% Vantocil from Lonza GroupA composition of biocide and 0.02% Biosperse CN7539 biocide from Solenis. In addition, 0.04% by weight of Drewplus, commercially available from Ashland, was added^TML-1513 foam control agent or 0.04 wt% of Sag 47 foam control agent. In some cases, methyl β -cyclodextrin (also known as methyl β -cyclodextrin) from Wacker Fine ChemicalsW7M TL) was added to the aqueous polymer solution to provide an aqueous polymer solution having 20.00 wt.% solid polymer. The viscosity of an aqueous polymer solution having 20.00 wt.% solids polymer was measured using a Brookfield viscometer with LV spindle #3 or #4 at 30rpm and 25 ℃. Table 6 lists Sag 47, Drewplus^TML1513, methyl beta-cyclodextrin, and bactericideAmount of Biosperse CN7539, brookfield viscosity and LV axis used.

Table 5: aqueous polymer solutions

Table 6: aqueous polymer solutions

Coating applications

Table 7A and table 7B list the grinding formulation and the dilution formulation (letdown formulation), respectively.

Table 7A: grinding formulation

Nuosept^TM498G: 1, 2-benzisothiazol-3-one commercially available from Ashland inc.

Tamol^TM731A sodium salt of maleic anhydride copolymer, commercially available from Dow Chemical Company.

Dextrol^TMOC-180 HS: neutralized form of ethoxylated fatty alcohol phosphate ester (potassium salt), commercially available from Ashland inc.

Drewplus^TMT-4304: defoamers, commercially available from Ashland inc.

Strodex^TMPK-95G: neutralized form of the phosphoric acid co-ester of a fatty alcohol (potassium salt), commercially available from Ashland inc.

Ti-Pure^TMR-706: titanium dioxide, commercially available from Chemours Titanium Technologies.

7: micronized functional filler with median particle size of 3.5 micronsMaterials, commercially available from Cary Company.

400: hydrated magnesium aluminum silicate, commercially available from Active Minerals International, LLC.

Table 7B: dilute formulations

Rhoplex^TMVSR-105: acrylic emulsions, commercially available from the Dow Chemical Company.

Optifilm^TMEnhancer 400: a coagulant, commercially available from Eastman Chemical Company.

678: a bactericide, commercially available from Troy Corporation.

Measurement of thickening efficiency

Thickening efficiency was measured by adding 5.3g of water and 2.0g of the aqueous polymer solution listed in table 5 to 66.4g of the base paint obtained by mixing the formulations listed in tables 7A and 7B. The thickening efficiency is measured by brookfield viscosity, Stormer viscosity (KU) and ICI viscosity as described below. The results are shown in Table 8.

The Brookfield viscosity was measured using a Brookfield viscometer with a #5 spindle at 30RPM and 25 ℃. It is expressed in mpa.s.

Stormer viscosity was measured according to standard test method ASTM D562 using a Stormer viscometer. It is expressed in Kreb Units (KU).

ICI viscosity was measured using an ICI cone and plate viscometer according to standard test method ASTM D4287. It is expressed in mpa.s.

Table 8: thickening effect of aqueous Polymer solutions

Coating performance

Subjecting Aquaflow to^TMXLS 530 (a solventless, non-ionic synthetic association agent, commercially available from Ashland LLC) was added to the diluted formulations in table 7B along with water and each aqueous polymer solution having 20 wt% solids polymer listed in table 5. The coating is then prepared by mixing the milled and diluted formulation. Adjusting Aquaflow^TMXLS 530, aqueous polymer solutions each containing 20% by weight of solid polymer, and water were dosed to achieve Stormer viscosities of 100 to 125KU units and ICI viscosities of 95 to 150mpa.s, for the performance of the coatings to be measured as described below. The results are shown in Table 9.

The resistance was measured on a Leneta chart using a test strip according to the standard test method ASTM D4400Sagging property. Wet Film Thickness (WFT) in mils was measured, above which sagging occurred.

Measured on a scale of 0 to 10 according to standard test method ASTM D4062Leveling property(ii) a 0 is worst and 10 is best.

Gloss the gloss was measured according to ASTM D523 using a BYK Gardner Micro-Tri-gloss meter. Reported as 60 ° gloss.

The inherent hiding power (Intrisic Hide) of the coating was recorded as the Contrast Ratio (CR) measured on Leneta chart # 3B. A 3mil wet film thickness of the coating was applied on Leneta chart # 3B. The contrast is the ratio of the reflectance of the surface of a dry paint film coated on a black substrate (Yb) to a white substrate (Yw). Higher contrast indicates a coating with higher opacity and hiding.

Table 9: performance of coating application

Polymer solution	Sagging property	Leveling property	Gloss of 60 DEG	Inherent hiding power
					1	24	2	42.6	0.977
2	24	3	43.2	0.971
					3	24	5	43.9	0.980
4	18	9	45.2	0.981
					5	24	4	42.7	0.979
6	24	4	43.7	0.986
					7	24	4	44.6	0.980
8	24	3	51.9	0.975
					9	24	5	44.2	0.981
10	24	4	43.9	0.977
					11	16	9	42.3	0.979
12	18	9	48.5	0.978
					13	24	9	44.1	0.984
14	18	9	51.5	0.974