Hydrophobically modified associative thickener polymer and preparation method and use thereof

Abstract

A hydrophobically modified associative thickener polymer prepared from a reaction mixture comprising a) a poloxamer triblock copolymer of formula (I): b) at least one active hydrogen-containing compound; c) a geminal halide compound and an alkaline hydroxide; or d) a polyglycidyl ether and an alkaline hydroxide; e) optionally a compound containing a hydrophobic moiety; and an aqueous protective coating composition. A method for preparing the hydrophobically modified associative thickener polymer is also disclosed.

Description

Technical Field

[0001] The disclosed processes, procedures, methods, products, results and / or concepts (hereinafter collectively referred to as the "disclosure") generally relate to methods for preparing reaction products and aqueous protective coating compositions containing the reaction products. Background Art

[0002] Water-soluble polymers (also commonly referred to as "thickeners" or "rheology modifiers") are widely used as additives in many industrial aqueous systems to modify the flow behavior of the system. Thickeners increase and maintain the viscosity at a desired level under specific processing conditions and end-use situations. Thickeners are used, for example, in decorative and protective coatings, paper coatings, cosmetics and personal care products, detergents, pharmaceuticals, adhesives and sealants, agricultural formulations, and oil drilling fluids.

[0003] Thickeners can be natural products, directly derived from natural products, or artificially synthesized. Examples of natural thickeners may include, but are not limited to, casein, alginate, tragacanth gum, guar gum, xanthan gum, locust and bean gum. Examples of natural thickeners may include, but are not limited to, cellulose ethers derived from cellulose, such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC) and carboxymethyl cellulose (CMC). The thickening efficiency of these natural and natural products (collectively referred to as "natural products") is different. One disadvantage of natural products is that they are susceptible to microbial influences, so antimicrobial agents may need to be added to the formulation. Examples of synthetic thickeners (also referred to as "associative thickeners" or "associative polymers") may include, but are not limited to, various acrylic polymers, alkylene oxide polymers, amide polymers and maleic anhydride polymers. Synthetic thickeners may also include nonionic synthetic associative thickeners (NSAT) rheology modifiers such as hydrophobically modified ethoxylated urethanes (HEUR), hydrophobically modified polyethylene glycols (HmPEG), and hydrophobically modified polyacetal-polyethers (HmPAPE). These synthetic thickeners may be homopolymers or copolymers. The hydrolytic stability of some of these polymers depends on the pH of the solution, and other polymers are sensitive to various components commonly found in waterborne coatings.

[0004] In recent years, synthetic associative thickeners have been used in a variety of applications, including adhesives and personal care, as well as industrial applications such as construction, specialty coatings, waterborne coatings, and latex paints. Synthetic associative thickeners have a variety of roles in waterborne systems. For example, in latex and waterborne coatings, thickeners can provide improved stability and pigment / extender suspension, as well as improved rheological and application properties. In addition, synthetic associative thickeners can be prepared with certain properties because they are synthesized from basic chemicals. In other words, synthetic associative thickeners can be completely customized for desired and / or target properties.

[0005] It has been found that the novel polymers and compositions according to the present invention can provide the important benefit of improved rheological properties, among many other performance attributes. The polymers and compositions thereof can be advantageously used in a variety of industrial applications, including coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Figure 1 Various polyglycidyl ether components of embodiments of the hydrophobically modified associative thickener polymers are depicted. DETAILED DESCRIPTION

[0007] Before explaining at least one embodiment of the present disclosure in detail, it should be understood that the present disclosure is not limited in its application to the details of the construction and arrangement of the components or steps or methods set forth in the following description or shown in the accompanying drawings. The present disclosure can have other embodiments or can be practiced or executed in various ways. Moreover, it should be understood that the words and terms used herein are for descriptive purposes and should not be considered as limiting.

[0008] Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings commonly understood by those of ordinary skill in the art. In addition, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

[0009] All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the technical level of those skilled in the art to which the present disclosure pertains. All patents, published patent applications, and non-patent publications cited in any part of this application are incorporated herein by reference in their entirety, as if each individual patent or publication was expressly and individually indicated to be incorporated herein by reference.

[0010] According to the present disclosure, all products and / or methods disclosed herein can be made and performed without excessive experimentation. Although the products and methods of the present disclosure have been described according to preferred embodiments, it is obvious to those of ordinary skill in the art that the products and / or methods described herein and the steps or step sequences of the methods can be changed without departing from the concept, spirit and scope of the present disclosure. All such similar substitutions and modifications apparent to those skilled in the art are considered to be within the spirit, scope and concept of the present disclosure.

[0011] As used in accordance with the present disclosure, the following terms shall be understood to have the following meanings, unless otherwise indicated.

[0012] When used in conjunction with the term "comprising", the use of the words "a" or "an" can mean "one", but it is also consistent with the meaning of "one or more", "at least one" and "more than one". The use of the term "or" is used to mean "and / or", unless explicitly indicated to refer to alternatives only when the alternatives are mutually exclusive, although the present disclosure supports definitions that refer only to alternatives and "and / or". Throughout this application, the term "about" is used to indicate that a value includes the inherent variation of the error of the quantification device, the method used to determine the value, or the variation present in the research subject. For example, but not as a limitation, when the term "about" is used, the specified value can vary plus or minus 12%, or 11%, or 10%, or 9%, or 8%, or 7%, or 6%, or 5%, or 4%, or 3%, or 2%, or 1%. The use of the term "at least one" should be understood to include one and any number 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" can be extended to 100 or 1000 or more depending on the term it is connected to. In addition, the amount of 100 / 1000 is not considered to be restrictive, because lower or higher restrictions can also produce satisfactory results. In addition, the use of the term "at least one of X, Y and Z" will be understood to include independent X, independent Y and independent Z, and any combination of X, Y, and Z. The use of ordinal terms (i.e., "first", "second", "third", "fourth", etc.) is only for the purpose of distinguishing two or more items, and unless otherwise specified, is not meant to imply any order or sequence or importance of one item relative to another item or any order of addition.

[0013] As used herein, the words "comprise" (and any form of inclusion, such as "comprises" and "comprises"), "have" (and any form of having, such as "have" and "has"), "include" (and any form of inclusion, such as "includes" and "include"), or "contain" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended, and do not exclude additional, unrecited elements or method steps. As used herein, the terms "or combinations thereof" and "and / or combinations thereof" refer to all permutations and combinations of the items listed preceding the term. For example, "A, B, C, or combinations thereof" is intended to include at least one of the following: A, B, C, AB, AC, BC, or ABC, and if order is important in the particular context, BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations containing repetitions of one or more items or terms, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, etc. Those skilled in the art will understand that unless otherwise apparent from the context, there is generally no limit to the number of items or terms in any combination.

[0014] For purposes of the following detailed description, except 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 appended claims are approximations that may vary depending upon the desired properties to be obtained in practicing the invention.

[0015] The term "alkyl" refers to a saturated linear or branched hydrocarbon group of 1 to 50 carbons.

[0016] As used herein, the term "alkylene" refers to an unsaturated, linear or branched hydrocarbon group having one or more carbon-carbon double bonds and 1 to 50 carbon atoms.

[0017] As used herein, the term "alkylyne" refers to an unsaturated, linear or branched hydrocarbon group having one or more carbon-carbon triple bonds and 1 to 50 carbon atoms.

[0018] The term "aryl" refers to a mononuclear or polynuclear aromatic hydrocarbon group including carbocyclic and heterocyclic aromatic groups.

[0019] The term "monomer" refers to a molecule, typically of molecular weight less than or equal to about 1000 Daltons, which chemically bonds with one or more monomers of the same or different type during polymerization to form a polymer.

[0020] The term "polymer" refers to a macromolecular compound having a molecular weight of generally about 1000 to about 500000 daltons, which comprises one or more monomer residues (repeating units) connected by covalent chemical bonds. By this definition, polymers encompass compounds wherein the number of monomer units can be from very few (which can more generally be referred to as oligomers) to very many. Non-limiting examples of polymers include homopolymers and non-homopolymers such as copolymers, terpolymers, tetrapolymers and advanced analogs.

[0021] The term "pigment" refers to an organic or inorganic material used to provide hiding or color to a paint formulation. The term "extender" refers to an inorganic material used as a filler in a paint formulation.

[0022] All percentages, ratios and proportions used herein are by weight, unless otherwise specified.

[0023] The present disclosure relates to a hydrophobically modified associative thickener polymer prepared from a reaction mixture comprising:

[0024] a) Poloxamer triblock copolymers of formula (I):

[0025]

[0026] b) at least one active hydrogen-containing compound;

[0027] c) gem-polyhalide and alkaline hydroxide; or

[0028] d) polyglycidyl ethers and alkaline hydroxides;

[0029] e) optionally, a compound comprising a hydrophobic portion;

[0030] wherein k is an integer from 5 to 200, and m is an integer from 5 to 150.

[0031] In some embodiments, the method of preparing a hydrophobically modified associative thickener polymer comprises: (1) melt mixing at least one active hydrogen-containing component, a poloxamer component, and an alkaline hydroxide to form a first mixture; (2) adding water to the first mixture to dissolve the first molten alkaline hydroxide to form a second mixture; (3) reacting the second mixture with a halogen compound or a sulfonate for a sufficient time to form a reaction product. In a non-limiting embodiment, the reaction product can be a poly(acetal-polyether or ketal-polyether).

[0032] In a non-limiting embodiment, the method for preparing a hydrophobically modified associative thickener polymer further comprises step (4) reacting a hydrophobic component with the reaction product. In some non-limiting embodiments, step (4) can be repeated any number of times, such as 1 time, or 2 times, or 3 times, or 4 times, or 5 times, or more times, wherein the hydrophobic component can be changed between subsequent steps.

[0033] The active hydrogen-containing components may be the same or different. If two or more active hydrogen-containing components are used, one of them must be at least difunctional. The active hydrogen-containing component may be monofunctional, comprising a monofunctional group of OH, SH or NH2. The active hydrogen-containing component may comprise at least two functional groups of OH, SH or NH2. The term "at least difunctional" may include components containing difunctional, trifunctional and tetrafunctional active hydrogen. The active hydrogen-containing compound may be represented by formula (II):

[0034] DX n

[0035] (II)

[0036] wherein X is OH, SH or NH2; D is a substituted or unsubstituted compound containing a functional group selected from the group consisting of an alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, alicyclic or polycyclic moiety, optionally containing at least one heteroatom; and n is an integer from 1 to 4, wherein when n is 1, the active hydrogen-containing compound is 'monofunctional', when n is 2, the active hydrogen-containing compound is 'difunctional', when n is 3, the active hydrogen-containing compound is 'trifunctional', and when n is 4, the active hydrogen-containing compound is 'tetrafunctional'. For example, by way of example only, the monofunctional active hydrogen-containing component may be an alkoxylated or non-alkoxylated alcohol, each of which may be represented by formula (III):

[0037]

[0038] Where R 1 is H or an alkyl group (such as CH3); p is an integer from 1 to 3; q is an integer from 0 to 500; R 2 It is a linear, branched, substituted, unsubstituted compound containing a functional group selected from the group consisting of alkyl, alkylene, alkenyl, alkyne, alkynyl, aryl, arylalkylene, arylalkenyl, arylalkynyl, cyclic and alicyclic compounds, wherein the total number of carbon atoms is 1 to 30.

[0039] Substitution, branching, saturation, unsaturation or cyclization can occur at R 2 Any position between carbon 1 and carbon 30. 2One or more branched side chains containing 1 to 30 carbons can be found anywhere from carbon 1 to carbon 30. The one or more branched side chains can also be substituted or unsubstituted alkyl, alkylene, alkenyl, alkyne, alkynyl, aryl, arylalkylene, arylalkenyl, arylalkynyl, cyclic or alicyclic groups.

[0040] Examples of monofunctional active hydrogen-containing components can include, but are not limited to, the following alcohols and alkoxylated forms of the alcohols: methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-docosanol, 1-tricosanol, 1-tetracosanol, 1-hexacosanol, 1-heptacosanol, 1-octacosanol, 1-nonacosanol, 1-triacontanol, 3-methyl-3-butene-1-ol, 3-butene-1-ol, 2-butanol, 3-methyl-3-butene-1-ol, 3-butene-2-ol, 3-methyl- ... 1-Butanol, 2-Ethyl-1-pentanol, 2,4-Dimethyl-1-pentanol, 2,3-Dimethyl-1-pentanol, 2-Propyl-1-pentanol, 3-Ethyl-2-methyl-1-pentanol, 2,3,4-Trimethyl-1-pentanol, 2-(1-methylethyl)-1-pentanol, 4-methyl-2-propyl-1-pentanol, 3-Methyl-2-propyl-1-pentanol, 2,3-Diethyl-1-pentanol, 3-Ethyl-2,4-dimethyl-1-pentanol, 2,4,4-Trimethyl-1-pentanol, 3-Pentanol, 2-Pentanol, 2-Methyl-3-pentanol, 3-Methyl-2-pentanol, 4-Penten-2-ol, 3-Ethyl-2-pentanol, 3,4-Dimethyl-2-pentanol, 4-Methyl-3- (1-methylethyl)-2-pentanol, 4-methyl-4-penten-2-ol, 3-methyl-4-penten-2-ol, 3-methyl-2-pentyn-2-ol, 5-hexen-1-yn-ol (5-hexen-1-yn-ol), 1,5-hexane-3-ol, 1-heptene-4-ol, 2-methyl-1-hexanol, 2-ethyl-hexen-1-ol, 2-methyl-1-heptanol, 3-methyl-2-hexanol, 2-ethyl-1-heptanol, 4-methyl-3-heptanol, 3-methanol-2-heptanol, 2,4-dimethyl-1-hexanol, 2,5-dimethyl-1-hexanol, 2-ethyl-1-hexanol, 3-ethyl-2-hexanol, 2-butyl-1-hexanol, 2-ethyl-4-methyl-1- 2-(1-methylethyl)-1-hexanol, 2-ethyl-3-methyl-1-hexanol, 2-ethyl-5-methyl-1-hexanol, 3-ethyl-2-methyl-1-hexanol, 4-ethyl-2-methyl-2-hexanol, 4-methyl-2-propyl-1-hexanol, 5-methyl-2-propyl-1-hexanol, 4-methyl-2-hexanol, 4-methyl-3-hexanol, 2-methyl-3-hexanol, 5-methyl-3-hexanol, 3-hexanol, 5-hexen-3-ol, 5-methyl-2-hexanol, 2,6-dimethyl-1-heptanol, 2-propyl-1-heptanol, 3-ethyl-2-heptanol, 2,5-dimethyl-1-heptanol, 2,4-dimethyl-1-heptanol, 2,3-Dimethyl-1-heptanol, 4-ethyl-3-heptanol, 2-butyl-1-octanol, 2-methyl-1-octanol, 2-ethyl-1-octanol, 5-methyl-4-octanol, 3-methyl-2-octanol, 4-methyl-3-octanol, 4-octanol, 3-octanol, 2,7-dimethyl-1-octanol, 5-ethyl-4-octanol, 6-ethyl-4-octanol, 2-methyl-1-nonanol, 2-methyl-5-nonanol, 4-methyl-5-nonanol, 7-methyl-4-nonanol, 7-methyl-5-nonanol, 3-nonanol, 2-nonanol, 2-methyl-1-decanol, 2-decanol, 5-decanol, 6-ethyl-4-decanol, 2-ethyl-1-undecanol, 2-propyl-1-undecanol, 2-butyl-1-undecanol alcohol, 2-(1-methylethyl)-1-undecanol, 2-(2-methylpropyl)-1-undecanol, 2-heptyl-1-undecanol, 2-(1,1-dimethylethyl)-1-undecanol, 2-(2-propen-1-yl)-1-undecanol, 8-methyl-4-undecanol, 3-ethyl-2-dodecanol, 2-propyl-1-dodecanol, 2-ethyl-1-dodecanol, 2-butyl-1-dodecanol, 2-(1-methylethyl)-1-dodecanol, 2-(2-methylpropyl)-1-dodecanol, 2-hexyl-1-dodecanol, 2-(1-methylethyl)-2-dodecanol, 4-dodecanol, 5-dodecanol, 6-dodecanol, 2-octyl-1-dodecane Alcohol, 2-(1,1-dimethylethyl)-1-dodecanol, 3-(1-methylethyl)-2-tridecanol, 2-nonyl-1-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol, 7-tridecanol, 2-ethyl-1-tetradecanol, 2-propyl-1-tetradecanol, 2-(1-methylethyl)-1-tetradecanol, 2-octyl-1-tetradecanol, 2-(2-methylpropyl)-1-tetradecanol, 2-dodecyl-1-tetradecanol, 2-(1,1-dimethylethyl)-1-tetradecanol, 2-decyl-1-tetradecanol, 3-(1-methylethyl)-2-pentadecanol, 3-ethyl-2-pentanedecanol ecanol), poly(ethylene glycol) methyl ether, ethylene oxide / propylene oxide copolymer monobutyl ether, polyalkylene glycol monovinyl ether, polyethylene glycol monoallyl ether, tristyrylphenol polyethylene glycol ether, 2,3-di-1-naphthylphenol, 2,6-bis(1-phenylethyl)phenol, 2,4,6-tris(1-phenylethyl)-phenol, 2-(1-methyl-1-phenylethyl)phenol, 2-(2-phenylethyl)phenol, 2,6-bis(1-methyl-4-phenylethyl)phenol, 2,4-bis(phenylmethyl)phenol, 3-(phenylmethyl)phenol, (1,1'-biphenyl)-2-ol, 2,4,6-tris(phenylmethyl)phenol, 2-(phenylmethyl)phenol, 5'-phenyl-(1,1':3',1”-terphenyl)-2'-ol, 2,4-bis(1-phenylethyl)-phenol, (1,1':3',1"-terphenyl)-4'-ol, 2,4,6-tris(1-methyl-1-phenylethyl)phenol, 2-(1-phenylmethyl)phenol, 2,4-bis(1-methyl-1-phenylethyl)phenol, 2,6-bis(phenylmethyl)-phenol, 4-(phenylmethyl)-phenol, 4-(1-phenylethyl)phenol and 3-(1-methyl-4-phenylethyl)phenol.

[0041] By way of example only, the at least difunctional active hydrogen containing components may each be represented by formula (V):

[0042]

[0043] wherein X is OH, SH or NH2; and q is an integer from 0 to 500. For example, but not by way of limitation, the component containing at least difunctional active hydrogen may include a diol, a polyol or a polyetheramine.

[0044] The diol may be polyethylene glycol. Examples of polyethylene glycol may include, but are not limited to, commercial products commercially available from Clariant, such as Polyethylene Glycol 200, Polyethylene Glycol 300, Polyethylene Glycol 400, Polyethylene Glycol 600, Polyethylene Glycol 1000, Polyethylene Glycol 1500, Polyethylene Glycol 3350, Polyethylene Glycol 4000, Polyethylene Glycol 6000, Polyethylene Glycol 8000; and Polyglykol 400, Polyglykol 600, Polyglykol 4000S, Polyglykol 8000S, Polyglykol 9000S, Polyglykol 20000S, Polyglykol 35000S.

[0045] Other glycols may include, but are not limited to, aminoethyl polyethylene glycols such as O-(2-aminoethyl) polyethylene glycol 3000 and O-(2-aminoethyl) polyethylene glycol 5000.

[0046] The polyetheramine may be a dihydroxy polyetheramine containing a primary amino group attached to the end of the polyether backbone chain, such as but not limited to Polyetheramine.

[0047] Polyols are compounds having three or more hydroxyl groups. Examples of polyols used in the present disclosure may include, but are not limited to: Voranol TM Triol Polyether Polyols (commercially available from DowDuPont Inc.); glycerol initiated ethylene oxide trifunctional polyols, including G31-28 Polyol, G31-35 Polyol and G31-43 Polyol (commercially available from Huntsman Corporation); and a pentaerythritol initiated ethylene oxide tetrafunctional polyol.

[0048] The hydrophobic component may be monofunctional. For example, by way of example only, the hydrophobic component may each independently be an alkyl halide, a sulfonate, or a monoepoxide. In a non-limiting embodiment, the hydrophobic component may be a monofunctional hydrophobic compound having an epoxide functional group represented by formula (VI):

[0049]

[0050] Wherein AA is a substituted or unsubstituted compound containing a functional group selected from the group consisting of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, alicyclic and polycyclic moieties, optionally containing at least one heteroatom. Examples of monoepoxides may 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 [(docosyloxy), methyl] (HAGE-22, commercially available from Sachem), naphthyl glycidyl ether (NGE), n-butyl glycidyl ether (n-BGE), isobutyl glycidyl ether (iso-BGE), and Cardura TM E10P glycidyl ether, Ultra LITE 513 (glycidyl ether based on cashew nutshell liquid technology) and Versatic TM Glycidyl ester of acid 10 (Hexion).

[0051] In another non-limiting embodiment, the hydrophobic component may comprise a monofunctional group of Br, Cl, I or F represented by formula (VII):

[0052] ZG

[0053] (VII)

[0054] Wherein Z is Br, Cl, I or F; and G is a substituted or unsubstituted compound containing a functional group, the functional group being selected from the group consisting of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, alicyclic or polycyclic moiety, optionally containing at least one heteroatom. Examples of alkyl halides may include, but are not limited to, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromodencane ...

[0055] In another non-limiting embodiment, the monofunctional hydrophobic components can each independently be a sulfonate.

[0056] In certain non-limiting embodiments, the hydrophobic component may include an active hydrogen-containing component. For example, by way of example only, the hydrophobic component may independently include an active hydrogen-containing component, which may be substituted or unsubstituted, and / or pure or mixed cut alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, alicyclic or polycyclic moiety, optionally containing at least one heteroatom. Non-limiting examples of such hydrophobic components comprising an active hydrogen-containing component may include those hydrophobic components described above, and may also include tristyrylphenol-polyethylene glycol ether (commercially available as Emulsogen TS100 from Clariant); C12 ethoxylate (commercially available as Novel 12-10 ethoxylate from Sasol); C16 ethoxylate (commercially available as Novel 16-10 ethoxylate from Sasol); C16 ethoxylate (commercially available as Alkonat C 200 from Oxiteno); C16 / C18 ethoxylate (commercially available as Genapol O100 from Clariant); C18 ethoxylate (commercially available as Genapol HS200 from Clariant or commercially available as Novel 18-20 ethoxylate from Sasol); C22 ethoxylate (commercially available as Novel 22-25 ethoxylates), and GX-5170 (ethoxylated surfactant based on cashew nut shell liquid technology).

[0057] When the hydrophobic component comprises a component containing active hydrogen, the example of the hydrophobic component may also include, but is not limited to, polyethylene glycol monomethacrylate, alcohol, amine and thiol. The example of polyethylene glycol monomethacrylate may include Genangen M5000MA, which is commercially available from Clariant. The example of amine may include, but is not limited to, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanamine, octadecylamine and nonadecanamine. The example of thiol may include, but is not limited to, 1-octyl mercaptan, 1-decyl mercaptan, 1-dodecanethiol, 1-hexadecanethiol and 1-octadecyl mercaptan.

[0058] The halogen compound may be at least difunctional, comprising at least two functional groups of Br, Cl, I or F. The term "at least difunctional" may include difunctional, trifunctional and tetrafunctional hydrophobic components. Examples of halogen compounds may include, but are not limited to, dibromomethane, tetrabromopentaerythritol and 1,3,5-tris(bromomethyl)benzene.

[0059] In a non-limiting embodiment, the halogen compound is selected from the group consisting of dibromomethane, dichloromethane, 1,1-dichlorotoluene, 1,1-dichloroethane and 1,1-dibromoethane, pentaerythrityltetrabromide, 1,3-dibromo-2-(bromomethyl)-2-methylpropane, 1,3-dichloro-2-(chloromethyl)-2-methylpropane, 2,2-dimethyl-1,3-dichloropropane, 1,3-dibromo-2,2-dimethylpropane, 1,3-dibromo-2-(bromomethyl)-propane, 1,3,5-tri(chloromethyl)benzene, p-xylene dibromide, pentaerythritol tetrachloride, pentaerythritol tetrabromide, 1,3,5-tri(bromomethyl)benzene, 1-(bromomethyl)-4-(chloromethyl)-benzene, 1,3-dichloro-2-(chloromethyl)propane.

[0060] In another non-limiting embodiment, the geminal halide compound may be replaced with a sulfonate ester derived from a diol or polyol.

[0061] In some embodiments, a method of preparing a hydrophobically modified associative thickener polymer comprises: (1) melt mixing at least one active hydrogen-containing component, a poloxamer component, and an alkaline hydroxide to form a first mixture; (2) adding water to the first mixture to dissolve the first molten alkaline hydroxide to form a second mixture; and (3) reacting the second mixture with a polyglycidyl ether compound for a sufficient time to form a reaction product.

[0062] In non-limiting embodiments, the method further comprises step (4), reacting the hydrophobic component with the reaction product. In some non-limiting embodiments, step (4) can be repeated any number of times, for example 1 time, or 2 times, or 3 times, or 4 times, or 5 times, or more times, wherein the hydrophobic component can change between subsequent steps.

[0063] The active hydrogen-containing component and the hydrophobic component have been described previously.

[0064] The polyglycidyl ether is selected from difunctional, trifunctional and tetrafunctional polyglycidyl ethers of formula (VIII):

[0065]

[0066] Wherein A is a substituted or unsubstituted compound containing a functional group selected from the group consisting of: alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, alicyclic or polycyclic moiety, which optionally contains at least one heteroatom; and s is an integer from 2 to 4, wherein when s is 2, the polyglycidyl ether is 'difunctional', when s is 3, the polyglycidyl ether is 'trifunctional', and when s is 4, the polyglycidyl ether is 'tetrafunctional'.

[0067] A non-limiting example of a polyglycidyl ether is represented by formula (IX):

[0068]

[0069] Where R 1 is H or methyl, and t is an integer from 1 to 500.

[0070] Non-limiting examples of polyglycidyl ether components may include, but are not limited to Figure 1 Instances in .

[0071] The present disclosure also relates to an aqueous protective coating composition comprising the aforementioned hydrophobically modified associative thickener polymer. The aqueous protective coating composition may further comprise a substantially water-insoluble polymer, such as a latex polymer or other types of polymer dispersions. Latex polymers can be prepared by polymerization of various ethylenically unsaturated monomers, such as ethylene, vinyl, and acrylic monomers. Typically, latex polymers are prepared by copolymerizing more than one monomer to achieve several desired properties, particularly for use in latex paints with little or no volatile organic compounds (VOCs).

[0072] Examples of latex polymers for use in the aqueous protective coating composition may include, but are not limited to, homopolymers or copolymers of vinyl acetate, methacrylic acid, acrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, styrene, ethylene, vinyl chloride, vinyl ester of versatic acid (VeoVa), vinyl propionate, butadiene, acrylonitrile, maleate, and fumarate. In a non-limiting embodiment, the latex polymer is selected from the group consisting of acrylic resins, vinyl-acrylic resins, styrene-acrylic resins, and ethylene vinyl acetate resins (VAE).

[0073] Other types of polymer dispersions include, but are not limited to, those prepared usually by condensation or addition polymerization (usually in bulk or in the presence of a solvent). The polymer dispersion is then dispersed in water and the solvent is substantially removed. Dispersion in water is usually assisted by nonionic or anionic functional groups on the polymer backbone and / or by adding a surfactant. Examples of such polymers are epoxy resins, polyesters, polyamides, polyurethanes, phenolic resins, melamine urea-formaldehyde resins, silicones, acrylic resins, etc.

[0074] Other types of polymers that may be added may include, but are not limited to, cellulose (cellulose nitrate and cellulose esters), coumarone-indene, hydrocarbon resins, natural resins, oleoresins, rosins, terpenes, and the like.

[0075] The aqueous protective coating composition may further comprise pigments / extenders, coalescing agents, 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 commonly used in coatings. Typical components include, but are not limited to, fillers, levelers, plasticizers, stabilizers, tackifiers, suspending agents, flow control agents, anti-skinning agents, extenders, film-forming aids, crosslinking agents, surface modifiers, corrosion inhibitors, antifouling agents, leveling aids, moisturizers / wet edge agents (e.g., ethylene glycol, propylene glycol and hexylene glycol), pH adjusters and combinations thereof.

[0076] Pigments / extenders are used to provide hiding power, color, and as fillers. Specific examples of pigments / extenders may include, but are not limited to, carbazole dioxazine crude pigments; monoazo pigments (acetoacetarylide, benzimidazolone, naphthol AS, colored b-naphthol dyes), disazo pigments (azo condensation pigments, dipyrazolone), polycyclic pigments (quinacridone, dioxazine, perylene, diketopyrrolopyrrole, isoindoline), and metal complex pigments (copper phthalocyanine); isoindolinone; isoindoline; polycyclic phthalocyanine; quinacridone; perylene; perinone; diketopyrrolopyrrole; isoindolinone ... pyrrole; thioindigo; anthraquinone; indanthrone; anthrapyrimidine; flavanthrone; pyranthrone; anthranthrone; 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 white); aluminum silicate; diatomaceous earth; magnesium silicate; synthetic amorphous silica; colloidal silica; colloidal alumina; fumed alumina; fumed silica; pseudo-boehmite; aluminum hydroxide, alumina; modified alumina; mica; lithopone; zeolite; hydrohalogenite; magnesium carbonate; magnesium hydroxide; lamp black; black iron oxide; nepeline syenite; red iron oxide; yellow iron oxide; brown iron oxide (a blend of red and yellow oxides with black); phthalocyanine green; phthalocyanine blue; organic reds (such as naphthol red, quinacridone red and toulidine red); quinacridone magenta, quinacridone violet; DNA orange; and / or organic yellows (e.g., Hansa yellow). Typically, titanium dioxide grades used in aqueous protective coating compositions are surface-modified with various inorganic oxides (such as silicates, aluminates and zirconates).

[0077] The amount of the hydrophobically modified associative thickener polymer used in the aqueous protective coating composition of the present disclosure is an amount effective to provide the desired thickening and rheological properties to the coating composition. In a non-limiting embodiment, the reaction product may be used in the range of about 0.05 to about 10 wt %, 0.05 to about 5 wt %, or about 0.05 to about 4 wt %, or 0.05 to about 3 wt %, or 0.2 to about 4 wt %, or about 0.2 to about 3 wt %, or 1 to about 4 wt %, or about 1 to about 3 wt %, or about 1 to about 2 wt % of the total aqueous protective composition.

[0078] The following examples illustrate the present disclosure, and unless otherwise stated, parts and percentages are by weight. Each example is provided to illustrate the present disclosure, not to limit the present disclosure. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made in the present disclosure without departing from the scope or spirit of the present invention. For example, a feature shown or described as part of one embodiment may be used in another embodiment to produce yet another embodiment. Therefore, the present disclosure is intended to cover modifications and variations within the scope of the appended claims and their equivalents.

[0079] Example

[0080] Examples 1-4 describe the synthesis of polymer AM.

[0081] In the examples, the following abbreviations are used:

[0082] M n : Number average molecular weight

[0083] M w : Weight average molecular weight

[0084] M z : Z average molecular weight

[0085] NaOH: Sodium hydroxide

[0086] C12Br:1-bromodecane

[0087] C16Br:1-bromohexadecane

[0088] C18 EO: C18 ethoxylate ~ 20 moles EO

[0089] DGE PEG1:M n Polyethylene glycol diglycidyl ether at about 500 (available from Sigma Aldrich)

[0090] BHT: Butylated Hydroxytoluene

[0091] PEO: Polyethylene oxide

[0092] PPO: Polypropylene oxide

[0093] Poloxamers: Block copolymers of PEO and PPO. Examples include: F127Prill, F108NF Prill, F88 Prill, PE 10500

[0094] Poloxamer 1A: F88Prill,M n About 9360; Mw Approximately 10600

[0095] Poloxamer 1B: F88,M n About 9550; M w Approximately 10800

[0096] Poloxamer 2: F127Prill,M n About 9110; M w Approximately 10700

[0097] Poloxamer 3: F108NF Prill, M n About 11400M w Approximately 13,600

[0098] Poloxamer 4: PE 10500,M n About 4250; M w About 5350

[0099] PEG1: polyethylene glycol, M n About 8500; M w About 8860

[0100] PEG2: polyethylene glycol, M n About 8010;M w About 8330

[0101] PEG3: polyethylene glycol, M n About 7620; M w About 8140

[0102] PEG4: polyethylene glycol, M n About 8410;M w About 8880

[0103] Example 1: Synthesis of Polymer AC

[0104] PEG (optional), poloxamer, and NaOH were added to the reactor. The contents of the reactor were mixed under a vacuum of 29 inches Hg for time 1 while the temperature was raised to Temperature 1. The vacuum was turned off and water was added. The contents of the reactor were mixed at Temperature 1 for time 2. DBM was added all at once at Temperature 1 and the contents of the reactor were mixed for time 3. At the end of Time 3, the temperature was raised to Temperature 2. The contents of the reactor were drained and cooled to 20-25°C to obtain solid polymers A, B, and C. Table 1 lists the amounts of reagents and Table 2 lists the reaction conditions required to prepare polymers A, B, and C.

[0105] Table 1

[0106]

[0107] Table 2

[0108]

[0109] Example 2: Synthesis of polymer DI

[0110] PEG, poloxamer, and NaOH were added to the reactor. The contents of the reactor were mixed for time 1 under a vacuum of 29 inches Hg while the temperature was raised to Temperature 1. The vacuum was turned off and water was added. The contents of the reactor were mixed at Temperature 1 for time 2. DBM was added in a single portion at Temperature 1 and the contents of the reactor were mixed for time 3. At the end of Time 3, the temperature was raised to Temperature 2. When the temperature was raised to Temperature 3, the alkyl halide was added in a single portion. Once Temperature 3 was reached, the contents of the reactor were mixed for time 4. For Polymers D, E, F, G, and H, the contents of the reactor were mixed at Temperature 3 for time 5 under a vacuum of 29 inches Hg. Polymer I was prepared without applying vacuum. The contents of the reactor were drained and cooled to 20-25°C to obtain solid Polymers D, E, F, G, H, and I. Table 3 lists the amounts of reagents and Table 4 lists the reaction conditions required to prepare Polymers D, E, F, G, H, and I.

[0111] Example 3: Synthesis of Polymers J and K

[0112] PEG, poloxamer and NaOH are added to the reactor. The contents of the reactor are mixed for time 1 under a vacuum of 29 inches Hg while the temperature is raised to temperature 1. The vacuum is turned off and water and C18 ethoxylate are added. The contents of the reactor are subjected to 3-5 cycles of vacuum (~5-29 inches Hg) and then nitrogen pressurization (to ~5-10 pounds) to make the contents of the reactor inert. After the last pressurization, the contents of the reactor are placed under a static vacuum (~5-10 inches Hg) to facilitate the transfer of DBM in the next step. The contents of the reactor are mixed at temperature 1 for time 2. DBM is added at temperature 1 for time 3. At the end of the DBM addition, the contents of the reactor are heated to temperature 2. From the beginning of the DBM addition, the contents of the reactor are mixed for time 4. At time 4, the contents of the reactor are heated to temperature 3. From the beginning of the DBM addition, the contents of the reactor are mixed for time 5. At the end of time 5, the contents of the reactor are mixed at temperature 3 for time 6 under a vacuum of 29 inches Hg. The contents of the reactor were drained and cooled to 20-25°C to yield solid polymers J and K. Table 3 lists the amounts of reagents and Table 4 lists the reaction conditions required to prepare polymers J and K.

[0113] Table 3

[0114]

[0115] Table 4

[0116]

[0117]

[0118] Example 4: Synthesis of polymers L and M

[0119] PEG, poloxamer, and NaOH are added to the reactor. The contents of the reactor are mixed under a vacuum of 29 inches Hg for time 1 while the temperature is raised to Temperature 1. At Temperature 1, the contents of the reactor are held under a vacuum of 29 inches Hg for time 2. The vacuum is turned off and BHT is added. The contents of the reactor are subjected to nitrogen pressurization (to ~5-10 pounds) and then to a vacuum (not to exceed 20 inches Hg) to render the contents of the reactor inert. Water is added and the contents of the reactor are mixed for time 3. DGE PEG1 is added for time 4. At the end of time 4, the temperature is raised to Temperature 2. Once Temperature 2 is reached, the alkyl halide is added and the contents of the reactor are mixed for time 5. The contents of the reactor are discharged and cooled to 20-25°C to obtain solid polymers L and M. Table 5 lists the amounts of reagents and Table 6 lists the reaction conditions required to prepare polymers L and M.

[0120] Table 5

[0121]

[0122] Table 6

[0123]

[0124] Polymer characterization

[0125] The polymers of Examples 1, 2, 3 and 4 were characterized by SEC.

[0126] SEC measurements

[0127] SEC is used to measure polymer molecular weight distribution. Waters HPLC System and EmpowerTM Chromatography Data System (commercially available from Waters Corporation (Milford, MA)) are used to measure molecular weight. As used herein for polymers, the terms molecular weight, average molecular weight, mean molecular weight and apparent molecular weight refer to the arithmetic mean of the molecular weight of a single macromolecule measured by SEC. According to the polyethylene glycol / ethylene oxide (PEG / PEO) standard with narrow molecular weight distribution, the relative molecular weight mean of SEC is calculated.

[0128] Instrument Setup – All Waters modules in the setup include:

[0129] Waters M515 Solvent Delivery System

[0130] Waters M2707 Autosampler

[0131] Waters M2414 differential refractive index detector (DRI) for relative SEC

[0132] Column library - see the "Analysis Conditions" section below for details

[0133] Waters Empower TM 3. Software

[0134] RI range 1.00 to 1.75 RIU

[0135] Measuring range 7x 10 -7 RIU

[0136] Drift - 2x 10 -7 RIU

[0137] The analytical conditions for SEC are described as follows:

[0138] Mobile phase - 70% methanol / 30% 0.6M lithium acetate (pH 4.8) (w / w)

[0139] Flow rate - 0.5ml / mi

[0140] Column - 1 Shodex KW-804 Protein column (8 mm × 300 mm) + 1 Shodex KW-803 Protein column (8 mm × 300 mm) in series (Showa Denko America, Inc., 420 Lexington Avenue, Suite 2335A, New York, NY 10170, USA)

[0141] Column temperature 40℃

[0142] DRI (differential refractive index) detector temperature 40°C

[0143] Calibration - PEO / PEG standards with narrow molecular weight distribution (Agilent, Inc. 2850 Centerville Road Wilmington, De. 19808-1610)

[0144] Sample concentration - usually 1.5 mg / ml (unless otherwise specified) - is dissolved directly in the mobile phase.

[0145] Injection volume - 100 μl

[0146] Polymer Analysis Data

[0147] The analytical data for polymers A, B, C, D, E, F, G, H, I, J, K, L and M are listed in Table 7.

[0148] Table 7

[0149] polymer <![CDATA[SEC M n ]]> <![CDATA[SEC M w ]]> <![CDATA[Dispersion index (M w / M n )]]> A 24,300 45,300 1.87 B 20,900 36,400 1.74 C 20,400 34,500 1.64 D 23,200 39,000 1.68 E 22,300 37,800 1.69 F 22,100 37,100 1.68 G 22,000 38,900 1.77 H 23,400 39,900 1.71 I 24,400 41,100 1.69 J 23,800 38,300 1.61 K 23,900 38,200 1.60 L 11,000 14,500 1.31 M 11,200 14,600 1.30

[0150] Polymer solution data

[0151] Aqueous solutions containing 17.50 or 20.00 wt% solid polymer were prepared by dissolving solid polymer AM in water. Polymer solutions A1, B1, C1, D1, E1, F1, G1, H1, I1, J1, K1, L1, and M1 were neutralized with acetic acid. 0.10% Vantocil Antimicrobial agent (available from Lonza Group) and 0.02% of Biosperse CN7539 antimicrobial agent (available from Solenis) and 0.04% of Sag*47 foam control agent (available from Momentive Performance Materials) were added to each polymer solution. W7M TL) (available from Wacker Fine Chemicals) was added as a viscosity suppressant to polymer solutions I1, J1, K1, L1, and M1. The viscosity of the polymer solutions having 17.50 or 20.00 wt% solid polymer was measured at 25°C using a Brookfield viscometer with LV spindle #2 (S62), #3 (S63), or spindle #4 (S64). Table 8 lists the amounts of the ingredients described for the polymer solutions and their Brookfield viscosities.

[0152] Table 8

[0153]

[0154] Paint Application Data Summary

[0155] Primer preparation

[0156] A semi-gloss primer formulation was prepared by mixing the grind formulation given in Table 9A and the letdown formulation given in Table 9B. During the let-down stage, the low shear polymer solution, high shear polymer solution and water were withheld.

[0157] Table 9A

[0158]

[0159] Table 9B

[0160] Element raw material pound gallon Density (lbs / gallon) 11 Rhoplex VSR 1050 500.00 56.56 8.84 12 Optifilm Enhancer 400 8.00 0.99 8.07 13 Drewplus T-4304 2.00 0.25 7.93 14 Polyphase 678 3.00 0.31 9.68 (reserve) water (83.95) 10.08 8.33 (reserve) High shear polymer solutions (24.00) 2.77 8.66 (reserve) Low shear polymer solutions 5.00 0.57 8.70

[0161] Nuosept TM 498G: 1,2-Benzisothiazolin-3-one, purchased from Ashland Inc.

[0162] Tamol TM 731A: Maleic anhydride copolymer sodium salt, available from The Dow Chemical Company

[0163] Dextrol OC-180HS: Phosphate ester surfactant from Ashland Inc.

[0164] Drewplus TM T-4304: defoamer, purchased from Ashland Inc.

[0165] Strodex TM PK-95G: Neutralized form of aliphatic alcohol phosphate ester (coester), available from Ashland Inc.

[0166] Ti-Pure R-706: Titanium dioxide, purchased from Chemours company

[0167] Micronized functional filler with a median particle size of 3.5 microns, purchased from The Cary Company.

[0168] Min-U-Gel 400: Attapulgite mineral from Active Minerals International LLC.

[0169] Rhoplex VSR1050: Acrylic latex from Dow Chemicals

[0170] Optifilm TM Enhancer 400: A coalescing agent available from Eastman Chemical Company Polyphase 678: A water-based fungicide available from Troy Corporation

[0171] Thickening efficiency measurement

[0172] The thickening efficiency of the polymer solution examples in paint was measured at two dosage levels: 0.09 wt % and 0.54 wt %. The Brookfield viscosity, Stormer viscosity (KU) and ICI viscosity were measured as described below. The Brookfield viscosity was measured using a Brookfield viscometer with a #5 rotor at 25°C at 30 rpm. It is expressed in mPa.s. The Stormer viscosity was measured using a Stormer viscometer at 25°C according to standard test method ASTM D562. It is expressed in Kreb units (KU). The ICI viscosity was measured using an ICI cone and plate viscometer according to standard test method ASTM D4287. It is expressed in mPa·s. The thickening efficiency measurements at 0.09 wt % and 0.54 wt % are provided in Table 10.

[0173] Table 10

[0174]

[0175]

Claims

1. A hydrophobically modified associative thickener polymer prepared from a reaction mixture comprising: a) Poloxamer triblock copolymers of formula (I): b) at least one active hydrogen-containing compound, wherein the active hydrogen-containing compound is represented by formula (V): wherein X is OH; and q is an integer from 0 to 500; and wherein all of the active hydrogen-containing compounds are present in an amount from 50 wt% to 99 wt%; c) a halogen compound and an alkaline hydroxide, wherein the halogen compound is selected from dibromomethane, dichloromethane, 1,1-dichlorotoluene, 1,1-dichloroethane and 1,1-dibromoethane, pentaerythritol tetrabromide, 1,3-dibromo-2-(bromomethyl)-2-methylpropane, 1,3-dichloro-2-(chloromethyl)-2-methylpropane, 2,2-dimethyl-1,3-dichloropropane, 1,3 dibromo-2,2-dimethylpropane, 1,3-dibromo-2-(bromomethyl)-propane, 1,3,5-tri(chloromethyl)benzene, p-xylene dibromide, pentaerythritol tetrachloride, 1,3,5-tri(bromomethyl)benzene, 1-(bromomethyl)-4-(chloromethyl)-benzene, 1,3-dichloro-2-(chloromethyl)propane, pentaerythritol tetrabromide and 1,3,5-tri(bromomethyl)benzene; or Polyglycidyl ether and alkaline hydroxide, wherein the polyglycidyl ether is represented by formula (IX): Where R 1 is H or methyl; and t is an integer from 1 to 500; e) an optional hydrophobic moiety-containing compound, wherein the hydrophobic moiety-containing compound is a monofunctional hydrophobic moiety-containing component having a functional group selected from the group consisting of halides, sulfonates, and epoxides; wherein k is an integer from 5 to 200, and m is an integer from 5 to 150.

2. The hydrophobically modified associative thickener polymer of claim 1, wherein k is an integer from 15 to 150, and wherein m is an integer from 10 to 100.

3. The hydrophobically modified associative thickener polymer of claim 1 or 2, wherein the poloxamer triblock copolymer is present in an amount of 1% to 99.9% by weight of the mixture.

4. The hydrophobically modified associative thickener polymer of claim 1 or 2, wherein the component containing the monofunctional hydrophobic moiety having epoxy functional groups is represented by formula (VI): wherein AA is a substituted or unsubstituted compound containing a functional group selected from alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, alicyclic and polycyclic moieties, optionally containing at least one heteroatom.

5. The hydrophobically modified associative thickener polymer of claim 4, wherein the component containing a monofunctional hydrophobic moiety having epoxy functionality is selected from the group consisting of allyl glycidyl ether AGE, 2-ethylhexyl glycidyl ether EHGE, hexadecyl glycidyl ether HAGE-13, ethylene oxide [(docosyloxy), methyl] HAGE-22, naphthyl glycidyl ether NGE, n-butyl glycidyl ether n-BGE, isobutyl glycidyl ether iso-BGE, E10P glycidyl ether, cashew nut shell liquid based glycidyl ether and Cardura TM E10P Glycidyl Ester.

6. The hydrophobically modified associative thickener polymer of claim 1 or 2, wherein the component containing the monofunctional hydrophobic moiety having halide functionality is represented by formula (VII): ZG (VII) wherein Z is Br, Cl, I or F; and G is a substituted or unsubstituted compound containing a functional group selected from alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, alicyclic and polycyclic moieties, optionally containing at least one heteroatom.

7. The hydrophobically modified associative thickener polymer of claim 6, wherein the component containing a monofunctional hydrophobic moiety having halide functionality is selected from the group consisting of 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromodencane ...

8. The hydrophobically modified associative thickener polymer of claim 1 or 2, wherein the compound comprising a hydrophobic moiety is present in an amount of 1 wt% to 25 wt%.

9. The hydrophobically modified associative thickener polymer of claim 1 or 2, wherein the geminal halide compound is present in an amount of 0.1 wt% to 10.0 wt%.

10. The hydrophobically modified associative thickener polymer of claim 1 or 2, wherein the alkaline hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, and combinations thereof.

11. The hydrophobically modified associative thickener polymer of claim 1 or 2, wherein the alkali hydroxide is present in an amount of 1.0 wt% to 10.0 wt%.

12. An aqueous protective coating composition comprising the hydrophobically modified associative thickener polymer according to any one of claims 1 to 11.

13. The aqueous protective coating composition of claim 12, further comprising a substantially water-insoluble polymer, wherein the substantially water-insoluble polymer is selected from a latex polymer or a polymer dispersion.

14. The aqueous protective coating composition of claim 13, wherein the substantially water-insoluble polymer is selected from, but not limited to, ethylene vinyl acetate resins, acrylic resins, vinyl-acrylic resins, styrene-acrylic resins, styrene-butadiene copolymers, butadiene-acrylonitrile copolymers, epoxy resins, polyurethanes, polyamides, versatate VeoVa, and polyesters.

15. The aqueous protective coating composition according to any one of claims 12 to 14, further comprising a pigment / extender.

16. The aqueous protective coating composition of claim 15, wherein the pigment / extender is selected from, but not limited to, organic and inorganic materials selected from phthalocyanine, iron oxide, titanium dioxide, zinc oxide, indigo, hydrated aluminum oxide, barium sulfate, calcium silicate, clay, silicon dioxide, talc, and mixtures thereof.

17. The aqueous protective coating composition of any one of claims 12 to 14, further comprising one or more selected from the group consisting of coalescing agents, solvents / co-solvents, wetting agents, defoaming agents, matting agents, dispersants, biocides, secondary rheology modifiers, pH adjusters, flow control agents, gloss control agents, plasticizers, antioxidants, UV radiation absorbers, colorants, film formers, and combinations thereof.

18. The aqueous protective coating composition according to any one of claims 12 to 14, further comprising one or more selected from the group consisting of a mildewcide, a thixotropic agent, a crosslinking agent, a surfactant, a wax, an adhesion promoter, and combinations thereof.

19. An aqueous protective coating composition according to any one of claims 12 to 14 comprising 0.05% to 10% by weight of a hydrophobically modified associative thickener polymer according to any one of claims 1 to 11.

20. The aqueous protective coating composition of claim 19 comprising 0.5 to 7 wt% of the hydrophobically modified associative thickener polymer of any one of claims 1 to 11.

21. The aqueous protective coating composition of any one of claims 12 to 14, wherein the aqueous protective composition is an architectural or industrial paint.

22. A method for preparing a hydrophobically modified associative thickener polymer as claimed in any one of claims 1 to 11, comprising: i) adding a poloxamer triblock copolymer, at least one active hydrogen-containing compound, and an alkaline hydroxide to a reactor while heating the contents of the reactor to at least 70° C., ii) mixing the contents of the reactor under a vacuum of 29 inches Hg, iii) adding the geminal halogen compound to the reaction mixture of step ii) and mixing the contents of the reactor, iv) optionally increasing the temperature of the reaction mixture, v) optionally adding a compound comprising a hydrophobic moiety and further mixing the contents of the reactor, vi) The contents of the reactor were discharged and cooled to 20 to 25°C to obtain a solid polymer.

23. A method for preparing a hydrophobically modified associative thickener polymer as claimed in any one of claims 1 to 11, comprising: i) adding a poloxamer triblock copolymer, at least one active hydrogen-containing compound, and an alkaline hydroxide to a reactor while heating the contents of the reactor to at least 70° C., ii) mixing the contents of the reactor under a vacuum of 29 inches Hg, iii) adding polyglycidyl ether to the reaction mixture of step ii) and mixing the contents of the reactor, iv) optionally increasing the temperature of the reaction mixture, v) optionally adding a compound comprising a hydrophobic moiety and further mixing the contents of the reactor, vi) The contents of the reactor were discharged and cooled to 20 to 25°C to obtain a solid polymer.

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