MXPA01005442A

MXPA01005442A - Hydrophobically modified comb copolymers

Info

Publication number: MXPA01005442A
Application number: MXPA/A/2001/005442A
Authority: MX
Inventors: Arjun C Sau
Original assignee: Hercules Incorporated
Priority date: 1998-12-04
Filing date: 2001-05-31
Publication date: 2002-03-26

Abstract

A comb copolymer comprising a backbone comprising (a) hydrophilic units, (b) residues of dihalogeno compounds remaining after the halogen atoms have been removed and (c) moiety containing pendant hydrophobe, such copolymer being particularly well suited as thickener for latex paints.

Description

"HYDROPHOBICALLY MODIFIED COMINE COPOLYMERS" BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to hydrophobically modified polymers and more particularly relates to hydrophobically modified, water-soluble, water-soluble comb copolymers suitable for thickening systems carried in water.

DESCRIPTION OF THE PREVIOUS TECHNIQUE Water-soluble polymers (which are also commonly referred to as "thickeners" or "rheology modifiers") are widely used in many industrial systems carried in water as additives to modify their flow behavior. One of these highly filled aqueous systems is latex paint, which is composed of a dispersion of a polymeric latex, pigment and clays and other additives in water. Typically, a small amount (from 0.1 percent to 5 percent by weight) of the water-soluble polymer is added to the latex paints to achieve the following - - performance characteristics during manufacturing, storage and applications: a) Ease of formulation and ability to manufacture at least a fast rate, b) Prevention of solidification of suspended particles (latex, pigment, etc.) during storage, c) Good film construction during applications to achieve efficient hiding without excessive brush or roller drag, d) Good roll splatter resistance, c) No excessive bending after application on a vertical surface, and e) Good flow and leveling for the formation of a smooth and continuous film with good looks. Several water-soluble polymers currently used in latex paints are: i) natural polysaccharides, ii) chemically modified polysaccharides, and iii) synthetic polymers. Examples of polysaccharide-based thickeners include xanthan gum, locust bean gum and cellulosic materials such as hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose and ethylhydroxyethylcellulose. Synthetic thickeners are polyacrylates, oxides of - - polyalkylene and polyacrylaiuides which could be homopolymers or copolymers. Its properties of hydrolytic stability and operation, however, depend on the pH. The aforementioned natural and synthetic thickeners provide different degrees of thickening efficiency and application properties. However, they invariably fail to provide key performance properties in glossy paints. These include good film construction, flow and leveling, and gloss that are generally offered by solvent based alkyd paints. Another inconvenience of these thickeners is that they have poor compatibility with the different paint ingredients. To eliminate some of the operational deficiencies of conventional thickeners, a new class of thickeners has recently been designed and marketed, commonly referred to as "associative thickeners" (see EJ Schaller and PR Sperry, in "Handbook"). of Coatings Additives ", Ed. LJ Calbo, Volume 2, page 105, 1992, Marcel Dekker, Inc., New York). These thickeners are hydrophobically modified water-soluble polymers. They undergo intermolecular association in aqueous solution and thus exhibit improved solution viscosity. They can also be absorbed into the particles of the dispersed phase of an aqueous dispersion and thus form a "three-dimensional network." Since they provide improved paint properties not offered by conventional thickeners, they have gained commercial importance. they are manufactured by chemically grafting a small amount of a hydrophobic group (alkyl of 10 to 24 carbon atoms) into the polysaccharide backbone and are disclosed in U.S. Patent Nos. 4,228,277; 4,243,802 and EP 281,360. Among the commercial non-ionic synthetic associative thickeners, the hydrophobically modified ethylene oxide urethane block copolymers (HEUR) constitute an important class. Numbers 4,079,028, 4,155,892 and 5,281,654 are disclosed in US Pat. These are low molecular weight polyurethanes made by condensing polyethylene glycol of relatively low molecular weight (molecular weight ~ 10,000) with terminal blocking hydrophobic diisocyanates with hydrophobic alcohols or amines. They are characterized by having three or more hydrophobes - two of which are terminal and the rest are internal. The hydrophobic groups are connected to the hydrophobic polyethylene oxide blocks through urethane bonds. The preparation of HEURs dispersible in water is disclosed in US Pat. Nos. 4,499,233 and 5,023,309. These HEURs are alleged to provide superior viscosity properties and improved leveling in aqueous systems. Processes for the production of HEURs with hydrophobes suspended in bundles are described in U.S. Patent Nos. 4,426,485 and 4,496,708. These HEURs are believed to provide enhanced thickening to aqueous systems through micelle-like association. HEURs with the branched structure and the terminal hydrophobes are disclosed in U.S. Patent Number 4,327,008. They are made by reacting polyalkylene oxides with a polyfunctional material, a diisocyanate and water and terminal blocking of the resulting product with a hydrophobic monofunctional active hydrogen-containing compound or a monoisocyanate. HEURs containing silicon having specific utility in paints and coatings are disclosed in European Patent Application Number 0498,442 A1. They are reaction products of an isocyanate functional material, a polyether polyol, a hydrophobic compound containing monofunctional active hydrogen, a silane-functional material and water. One of the disadvantages of HEUR thickeners is that they are hydrolytically unstable under strongly acidic or alkaline conditions, particularly at elevated temperatures. Therefore, they can not be processed or used in these situations. From the points of view of applications and economic, the main disadvantages of HEUR thickeners are their high cost, difficulty in handling and tendency to destabilize the paint (separation of dispersed particles from the aqueous phase) (GD Shay and AF Rich, J of Coatings Technology, Volume 58, Number 7, page 43, 1986). The random copolymers of ethylene oxide and long chain alkyl epoxides are disclosed in US Patent No. 4,304,902. These copolymers provide improved aqueous viscosity, but do not provide good flow and leveling in latex paints. U.S. Patent No. 4,411,819 describes the preparation of polyethers having a branched chain structure and which are characterized as having terminal hydrophobes. They are made by reacting a low molecular weight polyol with a mixture - - of ethylene oxide and at least one lower alkylene oxide having from 3 to 4 carbon atoms. The polyethers are then terminally blocked with a mixture of alpha-olefin oxides of 12 to 18 carbon atoms. The hydrophobically low molecular weight terminal block polyether (~9,000) is disclosed in PCT Int. Appl. WO 92 08753. These are made by coupling a low molecular weight surfactant (~ 4,500) with m-dichloromethylbenzene. The preparation of low molecular weight hydrophobic terminal block polyethers (~ 9,000) is also disclosed in the Patent North American Number 5,045.23. These are prepared by reacting aliphatic alcohols of 8 to 22 carbon atoms with a mixture of ethylene oxide and propylene oxide and subsequently coupling the alkoxylated alcohols with a diepoxide to form a polyether (Molecular Weight ~ 9,000). Since these hydrophobically terminal block polyethers are low molecular weight, they do not efficiently viscosify aqueous systems including latex paints. U.S. Patent No. 5,574,127 discloses associative thickeners which are water soluble polymer compositions having a poly (acetal- or ketal-polyether) parent element with terminals that are blocked with. hydrophobic groups. They are prepared by copolymerization of a polyether of alpha, omega-diol, dithiol or -diamino with a gem-dihalide compound in the presence of a base to form a poly (acetal- or ketal-polyether of alpha, omega-diol, -diol or -diamino which in turn is reacted with hydrophobic reagents to form the final product.These associative thickeners are used in film-forming coating compositions such as latex paints.An alternative strategy to achieve better rheological properties for various systems carried in Water is dependent on the properties of associative thickeners with a comb architecture The comb-type polyurethane thickeners are described in US Patent Number 5,496,908.These polymers have moderate viscosities in an aqueous solution and are useful as thickeners for paints of alkyd or latex base The synthesis and viscoelastic properties of thickeners are also disclosed of comb type polyurethane (Xu, B, et al., Langmuir, 1997, 13, 6896; Xu, B. and others, Langmuir, 1997, 13, 6903). It is known in the art that currently there is not a single thickener that provides all the desired performance characteristics required in water borne coatings. Therefore, very often, attempts are made to use mixtures of two or more different thickeners to achieve the required coating rheology. Even when this approach works in a limited way, the mixing of the thickeners is often annoying and depending on the mutual interactions between the individual thickener, the stability and operation of the coatings could be at risk. Despite continued activity in the art, there has not been produced a hydrophobically modified synthetic water-soluble polymer that is hydrolytically stable through a wide pH range and at elevated temperatures and useful for viscosifying aqueous compositions in a cost-effective manner.

COMPENDIUM OF THE INVENTION In accordance with the present invention, there is provided a comb copolymer comprising a main element comprising (a) hydrophilic units, (b) at least one residue of a dihalogen compound after the removal of the halogen atoms and (c) at least one portion containing the suspended hydrophobe.

In addition, the ends of the chain of these comb copolymers can carry hydrophobes.

- Further provided in accordance with the present invention is a process for preparing a comb copolymer comprising a main element comprising (a) hydrophilic units, (b) at least one residue of a dihalogen compound after the removal of the halogen atoms and (c) at least one portion containing the suspended hydrophobe comprising: (1) copolymerizing the water-soluble polymer that carries alpha, omega-active hydrogen, (2) hydrophobic compounds that have hydrogen, alpha, omega-active atoms or their alkoxylated derivatives, and (3) dihalogen compounds or their derivatives in the presence of a base over a period of time enough to form the comb copolymer. Film-forming coating compositions comprising the comb copolymers of the present invention are provided according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION A peel copolymer comprising a main element comprising: (a) hydrophilic units, (b) at least one residue of a dihalogen compound after removal of the halogen atoms, and (c) at least a portion containing a suspended hydrophobe has been found to efficiently thicken various systems carried in the water including latex paints and provides the improved combination of paint properties (flow and leveling, film construction, splash resistance and sag resistance) in a manner efficient. The dihalogen compound that provides the residue (b) may or may not contain suspended hydrophobes. Dependent on its chemical composition, the comb copolymer can be nonionic, cationic or anionic. "Flow and leveling" as used in this invention refers to the degree to which a coating flows outward after application in a manner that overrides any surface irregularities such as brush marks, an "orange bark" appearance. , crests or craters, which are produced by the mechanical process of applying a coating. "Film construction" means the formation of a continuous film to uniformly cover the surface of the substrate that is being coated. "Splash resistance" means the ability of the coating formulation to withstand - _ the formation of small droplets during the application of the coating. "Stability" means the ability to maintain viscosity during aging and prevent phase separation. "Sag resistance", as used herein, refers to the resistance to downward movement of the coating on a vertical surface between the application time and the solidification. The warping leads to an uneven coating having a thick bottom edge. The resulting warp is usually restricted to a local area on a vertical surface and may have the characteristics of a hanging curtain. The warping is aesthetically undesirable. In addition, coatings with good sag resistance will not easily run off a paint brush or paint roller and will not easily peel off a horizontal surface such as, for example, a ceiling after it is applied. The water-soluble hydrophilic polymers from which the hydrophilic units can be derived are selected from the group consisting of polyalkylene oxide, polyalkylene oxide copolymer, poly (acrylic acid), poly (acrylic acid-co-methacrylic acid), poly ( acrylamide), poly (dialkyldiallylammonium salts), polyamido-polyamine, poly (ethyleneimine), poly (methyl-male-ether-co-maleic anhydride), polyvinylpyrrolidone, poly (2-ethyloxazoline) and polypeptides. The polyalkylene oxide units are derived from compounds selected from the group consisting of water-soluble polyalkylene oxides and copolymers thereof and are preferably derived from polyethylene oxide and water-soluble copolymers of polyethylene oxide. The polyalkylene oxides and copolymers of polyalkylene oxides generally have a weight average molecular weight (Mw) of at least about 200, preferably at least about 8,000. The polyalkylene oxides and copolymers of polyalkylene oxides generally have a molecular weight of up to about 35,000, preferably up to about 10,000. The residue of the dihalogen species can be any hydrocarbyl radical, preferably a hydrocarbyl radical having 1 to 20 carbon atoms. Residues of the dihalogen species can be derived from dihalogen compounds and their derivatives. In general, the dihalogen compounds can be dihalogenoalkanes, aromatic compounds substituted with dihalogen, dihaloorganometallic compounds and derivatives thereof. Preferably, the dihalogen compounds are gem-dihalometrenomethane and its derivatives, dihalogenoxylenes, and their derivatives, dihalogenoorganosilanes and the dihalogenoorganophosphorus compounds and their derivatives. Particularly preferred are the dihalogen compounds dibromo- and dichloromethane and their derivatives a, α-dichloro- and dibromoxylene and their derivatives and gem-dichloro and the dibromoorganosilane and organophosphorus compounds and their derivatives. The dihalogen can be an alkylene radical, such as a methylene radical, ethylene, etc., a xylenylene radical, or an organometallic radical, such as an organosilyl radical and / or an organophosphoryl radical.In the context of the present application , the term "derivatives" as referring to the dihalogen compounds and their derivatives means that these compounds are substituted with alkyl, aryl, and / or aralkyl groups The portion containing suspended hydrophobic groups is derived from the hydrophobic compounds they have alpha, omega-active hydrogen atoms and their alkoxylated derivatives, preferably fatty amines - - modified with alkylene oxide, and organophosphorus ethoxylated or organophosphorus compounds having hydrophobes attached thereto and fullerene compounds (carbon cage compounds containing from 60 to 90 carbon atoms) and especially preferably from ethoxylated fatty amine. The hydrophobe may be hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, cycloaliphatic, perfluoroalkyl, carboxylyl, frenrenyl, polycyclic and dendritic complexes, preferably it is an alkyl group. Generally, the hydrophobe has at least one carbon atom, preferably at least six carbon atoms. Generally, the hydrophobe has up to ninety carbon atoms, preferably up to twenty-two carbon atoms. Generally, the hydrophobes in the hydrophobic compounds have a molecular weight of at least about 15, preferably at least about 115. In general, the hydrophobes have a weight of up to about 1,100, preferably up to about 250. The geometry of the The main element of the comb copolymer may be linear, branched or star-like, preferably linear. Generally, the comb copolymer has a weight average molecular weight of at least about 6,000, preferably at least about 15,000. Generally, the comb copolymer has a weight average molecular weight of up to about 150,000, preferably up to about 100,000. In addition, of the suspended hydrophobes, the comb copolymers of the present invention can optionally have hydrophobes in the chain terminals of the comb copolymers as well. The hydrophobically-modified comb-type copolymers of the present invention are made by copolymerizing: (1) a water-soluble (hydrophilic) polymer, which carries hydrogen, alpha, omega-active atoms such as polyalkylene oxide, an oxide copolymer of polyalkylene, poly (acrylic acid), poly (acrylic acid-co-methacrylic acid), poly (acrylamide), poly (dialkyldiallylammonium salts), polyamidopolyamide, poly (ethyleneimine), poly (methyl vinyl ether) co-maleic anhydride ), polyvinylpyrrolidone, poly (2-ethyloxazoline) and polypeptides. (2) hydrophobic compounds having hydrogen, alpha, omega-active atoms or their alkoxylated derivatives, such as fatty amines modified with alkylene oxide and ethoxylated or organophosphorus organosilicon compounds having groups of hydrophobic compounds attached thereto , and (3) dihalogen compounds or their derivatives in the presence of a base, for a period of time sufficient to form the comb copolymer. In the context of the present application the term "hydrophobic compounds having hydrogen atoms, alpha, omega-active" means the hydrophobic compounds carrying more than one active hydrogen and the term - "their alkoxylated derivatives" means these compounds modified with oxide of alkylene. The comb-type copolymer formed in this manner in turn can be reacted with a hydrophobic compound capable of reacting with the active hydrogen atoms to form a hydrophobically terminal block copolymer. The hydrophobe can be hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, cycloaliphatic, perfluoroalkyl, carboxylyl, fulerenyl, polycyclic and complex dendritic groups, preferably it is an alkyl group. The process can be carried out in any solvent or solvent mixtures free of active hydrogens and stable to the bases. However, the solvents - preferred are oxygenated solvents such as tetrahydrofuran and alkyl ethers of alkylene glycols or hydrocarbon solvents. To carry out the process in a solvent, the base can be any strong base, preferably a sodium hydride base. In addition, the process can also be carried out in the absence of a solvent. In this case, the preferred base is an alkali metal hydroxide and that especially preferred is sodium hydroxide. The reaction project to form the comb copolymers of the present invention can be illustrated by the following: Base m H-A-H + n H (i) n-R2 (ID I comb copolymer with hydrophobes suspended II comb copolymer with suspended hydrophobes and terminals where H-A-H = a hydrophilic polymer that carries hydrogen atoms, alpha, omega-active, - HB (R) -H = a compound comprising a chemical entity "B", which may be an atom or a group of atoms, having a valence of at least three and having "B" hydrogen atoms attached , alpha, omega-active and a hydrophobic group suspended "R" or a mixture thereof; R] _ = hydrocarbyl, alkyl, alkenyl, aryl, arialkyl, arylalkenyl, cycloaliphatic, perfluoroalkyl, carbosilyl, fullerenyl, polycyclic groups and complex dendritic; X-D (R1) _) -X = a dihalogen compound wherein D is a hydrocarbon portion preferably having from 1 to 20 carbon atoms, or an organometallic radical, such as an organosilyl radical or a radical of .organophosphoryl or a mixture thereof, R-I 1 = H or a hydrophobic radical or an organometallic radical, X = halogen, such as Br, Cl, etc., R2-Y = a hydrophobic compound capable of react with the terminal active hydrogens of the comb copolymer (I) to tr through its functional group Y; R2 = hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, cycloaliphatic, perfluoroalkyl, carbosilyl, fullerenyl, polycyclic and dendritic complex groups; m, n and p represent the number of units of -A-, -B (R?) - and -D (RI) - in the comb copolymer (I) and the comb copolymer (II), preferably m = 1- fifty; n - 1-20; p = 1-10. Note that if X-D (Rl?) - X is a dihalogen or geminal compound, then blocks A and B in the comb copolymer (I) and the comb copolymer (II) are connected through acetal or ketal bonds that are stable in alkaline environments. The hydrogens active in H-A-H and H-B (R?) - H can form part of the functional groups such as -OH, -SH and -NH2. As regards what is related to the hydrophobic type, the suspended and terminal hydrophobes could be the same or different. Similarly, the terminal hydrophobes could be the same or different. As will be appreciated by a person skilled in the art, a wide variety of hydrophobically modified polyacetal- or poly-ketal-polyethers of the comb type could be made by appropriately selecting various reaction conditions and having the stoichiometry and structure of the reagents HAH, HB ( R?) - H, XD (RI; I _) - XYR ~ Y. The preferred process for making the comb copolymers of the present invention comprises suspending or dissolving HAH and HB (R?) - H in an inert solvent and copolymerizing them with X ~ D (RI) _) - X in the presence of a base suitable or a catalyst at elevated temperatures. The hydrophobically modified terminal block copolymer can be made in turn by reacting this comb copolymer with a hydrophobic reagent. Suitable solvents include toluene, xylene, aliphatic hydrocarbon solvents, tetrahydrofuran, alkylene glycol dialkyl ethers, diethoxymethane and the like. Suitable bases include finely divided sodium hydride, alkali metal hydroxides, and alkali metal carbonates. The organic bases could also be used. It is critical that the reaction solvent and reagents used in the process must be anhydrous or essentially moisture free. The scope of this invention as claimed is not intended to be limited by the following examples, which are provided by way of illustration only. All parts are by weight unless otherwise indicated. The hydrophobically modified comb copolymers of the present invention are suitable for use as rheology modifiers in paints, paper coatings, personal care products, textiles, adhesives, inks, oil well perforations, etc.

Process for determining the weight average molecular weight of the hydrophobically modified comb copolymers The weight average molecular weight of various hydrophobically modified comb copolymers was measured by size exclusion chromatography (SEC). The SEC measurements were carried out in a 0.20M lithium acetate buffer (pH 4.8) plus 1.0 percent methylated beta-cyclodextrin randomly substituted plus 0, 1 percent N-methyl pyrrolidone (NMP) mobile phwith both columns and the detector-refractive index subject to thermostat at 40 ° C. The polymers were chromatographed through a set of four SHODEX PROTEIN® Columns (KW804 + KW804 + KW803 + KW803) at a flow rate of 1.0 milliliter per minute. A sample concentration of 0.15 percent was used with one volume - of injection of 200 microliters. The molecular weight distribution data are based on polyethylene oxide / polyethylene glycol standards with critical molecular weight distributions and are not absolute.

EXAMPLE 1 Preparation of the terminal block comb copolymer of 16 carbon atoms containing suspended hydrophobes of 16/18 carbon atoms To a stainless steel pressure reactor (Chemco type) polyethylene glycol (Molecular Weight ~ 8,000) (PEG-8000) (563 grams) (as it stands, ie, containing approximately 2 percent moisture), was added RHODAMEEN® T-50 (ethoxylated tertiary amine based on a tallow radical (16/18 carbon atoms) and 50 moles of ethylene oxide) (obtainable from Rhodia, Inc.) (58 grams), tetrahydrofuran (THF) (750 milliliters) and sodium hydride (60 percent dispersion in mineral oil) (22 grams). After sealing the reactor, the contents of the reactor were heated to 80 ° C for 1 hour and then cooled to 40 ° C. After this, dibromo ethane (12 grams) was added to the reaction mixture at 40 ° C. and the resulting reaction mixture was heated at 80 ° C for 4 hours.

- - To this reaction mixture at 80 ° C was added cetyl bromide (65 grams) and the resulting reaction mixture was heated at 120 ° C for 2 hours. After this, the reaction mixture was cooled to room temperature and the reactor charge transferred to a polypropylene tray. After evaporation of the solvent, a foamy solid was obtained. The terminal block comb copolymer of 16 carbon atoms formed in this manner had a weight average molecular weight of 42.923 and the polydispersity index was 2.22. It was soluble in water (Brookfield viscosity in 2 percent solution at 30 revolutions per minute at 22 ° C ~ 510 centipoises). The cetyl and stearyl content of the copolymer were 1.67 and 0.05 weight percent, respectively.

EXAMPLE 2 Preparation of the terminal block comb copolymer of 16 carbon atoms containing suspended hydrophobes of 16/18 carbon atoms.

Example 1 was repeated using the following: a) PEG-8000 - 560 grams b) RHODAMEEN T-50 - 44 grams c) THF - 750 milliliters d) Sodium hydride (60 percent dispersion in mineral oil) - 22 grams e) Dibromomethane - 12 grams f) Cetyl bromide - 65 grams The terminal block comb copolymer of 16 carbon atoms formed in this manner had a weight average molecular weight of 52,154 and the polydispersity index was 2.26. The cetyl content of the copolymer was 1.3 weight percent. It was soluble in water (2 percent Brookfield viscosity solution at 30 revolutions per minute at 22 ° C - 335 centipoise).

EXAMPLE 3 Preparation of the terminal block comb copolymer of 16 carbon atoms containing suspended hydrobophones of 16/18 carbon atoms Example 1 was repeated using the following: a) PEG-8000 - 376 grams b) RHODAMEEN T-50 - 116 grams c) THF - 750 milliliters - - d) Sodium hydride (60 percent dispersion in mineral oil) - 22 grams e) Dibromomethane - 12 grams f) Cetyl bromide - 65 grams The terminal block comb copolymer of 16 carbon atoms formed in this manner had a weight average molecular weight of 48,919 and the polydispersity index was 2.14. It was capable of swelling as judged by phase separation of the swollen polymer when the polymer was suspended in water, stirred for 2 hours and allowed to stand overnight.

EXAMPLE 4 Preparation of the terminal block comb copolymer of 16 carbon atoms containing suspended hydrophobes of 16/18 carbon atoms.

Example 1 was repeated using the following: a) PEG-8000 - 654 grams b) RHODAMEEN T-50 - 29 grams c) THF - 750 milliliters d) Sodium hydride (60 percent dispersion in mineral oil) - 22 grams - - e) Dibromomethane - 12 grams f) Cetyl bromide - 65 grams The terminal block comb copolymer of 16 carbon atoms thus formed had a weight average molecular weight of 45.722 and the polydispersity index was 1.94. The cetyl content of the copolymer was 1.16 percent by weight. It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute at 22 ° C ~ 130 centipoises) EXAMPLE 5 Preparation of the 16-carbon terminal block comb copolymer containing suspended hydrophobes of 16/18 carbon atoms with 50 moles of ethylene oxide.

To an Abbe batten mixer were added PEG-8000 (1000 grams), RHODAMEEN T-50 (46 grams) and sodium hydroxide (34 grams). After sealing the reactor, the mixture was heated at 80 ° C for one hour. The dibromomethane (20 grams) was then added to the PEG-8000 / NaOH mixture and the resulting reaction mixture was heated at 80 ° C for 4 hours to form PEG-8000 / RHODAMEEN T-50 / methylene terpolymer. To this terpolymer at 80 ° C was added cetyl bromide (70 grams) and the resulting reaction mixture was- heated at 120 ° C for 2 hours. After this, the reactor was opened and the molten reaction mixture was emptied in a plastic tray. Upon cooling to room temperature, the reaction mixture solidified. The terminal block comb copolymer of 16 carbon atoms formed in this manner had a weight average molecular weight of 33.069 and the polydispersity index was 1.82. It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute at 22 ° C ~ 580 centipoises). The cetyl content of the copolymer was 2.2 weight percent. Paint Properties of Hydrophobic Terminal Blocking Comb Copolymers Properties of UCAR 367 Vinyl / Acrylic Plain Paint of Hydrophobic Terminal Blocking Comb Copolymers The comb copolymers of the present invention were incorporated into a plain vinyl-based paint / acrylic latex (UCAR 367) (pigment volume concentration = 60 percent) and a completely acrylic glossy i-gloss paint (Rhoplex AC-417M) to achieve an initial Stormer viscosity of 90-95 Kreb Units. The importance and scale of the different properties of the painting are the following. a) Viscosity Stormer (initial and after overnight storage) is measured by a Stormer viscometer at a rate of shear at 200 seconds - ^ - and expressed in Kreb Units (KU). b) The ICI viscosity is measured by an ICI plate and cone viscometer at 10, 000 seconds "and is expressed in poises c) Thickening efficiency (TE) measured as percentage by weight of the thickener required in the paint to achieve initial Stormer viscosity d) Leveling using the Leneta method (measured on a scale of 0-10, 0 = worst, and 10 = best) e) Bending resistance using the Leneta method, medium scale bar, thickness wet film (WFT, in thousandths of an inch) above which warping occurs f) Splash resistance by rolling through a black panel (compared on a scale of 0-10, 0 = worst and 10 = better g) The 60 ° brightness is the specular reflectance brightness seen at 60 ° C.

The properties of the paint of different hydrophobic terminal block comb copolymers are shown in Tables 1 and 2. TABLE 1 Properties of the Rhoplex AC-417M Acrylic Semi-gloss Paint of the 16-carbon Terminal Block Comb Copolymers.

Copolymer PEG-RT-5? (2) 2% TE (%) Viscosity of 8000 BFO) Stormer Comb of Example (g) (g) (centi (KU) poises) Example 3 376 116 Fan- 0.26 88/99 ble Example 1 563 58 510 0.25 92/102 Example 2 560 44 335 0.33 92/106 Example 4 654 29 130 0.55 88/101 Example C-1 - 410 0.36 90/106 Example 1: Example C-l d) 0.38 89/103 mixture 1: 3 Example 1: Example C-l 0.38 91/106 mixture 1: 1 - - Table 1 (continued) ICI Copolymer Combo Level Spray 60 ° Brush Comb of Example (poises! Example 3 0.7 2 18 8 45.4 Example 1 0.8 4 11 7 49.2 Example 2 1.1 6 10 9 49.0 Example 4 1.6 10 6 9 49.0 Example C-l 1.6 9 8 9 47.3 Example 1: Example C-ld) 1.2 47.7 mixture 1: 3 Example 1: Example C-l 1.2 10 47.0 mixture 1: 1 (!) Example C-l linear terminal block poly (acetal-polyethex) of 16 carbon atoms prepared in accordance with Example 28 of US Pat. No. 5,574,127; (2) RT-50 = Rhodameen® T-50 (3) BF = Brookfield viscosity measured at 30 revolutions per minute - - TABLE 2 Properties of the UCAR 367 Vinyl / Acrylic Plain Paint of the Terminal Coping Compounds of 16 Carbon Atoms.

Copolymer PEG-RT-50 (2) 2% TE (; Viscosity of 8000 BF (3) Stormer Comb of Example (g) (g) (centi¡KU) poises) Example 3 376 116 Fan- 0.59 94/108 ble Example 1 563 58 510 0.54 93/109 Example 2 560 44 335 0.58 97/113 Example 4 654 29 130 0.88 94/110 Example C-1 - 410 0.63 97/109 Example 1: Example C-l d) 0.64 96/114 mix 1: 3 Example 1: Example C-l 0.63 95/111 mixture 1: 1 - Table 2 (continued) ICI Copolymer Combo Level Spray 60 ° Brush Comb of Example (poises) Example 3 0.9 9 6 9 Example 1 1.4 9 6 9 Example 2 1.9 9 6 9 Example 4 2.5 9 6 9 Example C-l 2.2 9 6 9 Example 1: Example C-1 (D 2.3 mix 1: 3 Example 1: Example C-1 mix 1: 1 EXAMPLE 6 Preparation of the terminal block comb copolymer of 15 carbon atoms containing suspended hydrophobes of 16/18 carbon atoms.

- Example 5 was repeated using the following reagents. a) PEG-8000 - 1000 grams b) RHODAMEEN T-50 - 44.5 grams c) Sodium hydroxide - 35 grams d) Dibromomethane - 19 grams f) Cetyl bromide - 100 grams The terminal block comb copolymer of 16 carbon atoms formed in this manner had a weight average molecular weight of 25,672 (polydispersity index ~ 1.8). It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute at 22 ° C ~ 250 centipoises).

EXAMPLE 7 Preparation of the comb copolymer containing suspended hydrophobes of 16/18 carbon atoms.

Example 5 was repeated using the following reagents except that the terpolymer formed by copolymerization of PEG-8000, RHODAMEEN T-50 and dibromomethane was not reacted with cetyl bromide. - a) PEG-8000 - 750 grams b) RHODAMEEN T-50 - 154 grams c) Sodium hydroxide - 35 grams d) Dibromomethane - 20 grams The comb copolymer formed in this manner had a weight average molecular weight of 31,918 (polydispersity index ~ 1.79). It was soluble in water (solution at 6 percent Brookfield viscosity at 30 revolutions per minute at 22 ° C ~ 128 centipoises).

EXAMPLE 8 Preparation of the terminal block comb copolymer of 16 carbon atoms containing suspended hydrophobes of 16/18 carbon atoms.

Example 5 was repeated using the following reagents and the terpolymer formed by copolymerization of PEG 8000, RHODAMEEN T-50 and dibromomethane was subjected to terminal block with cetyl bromide a) PEG-8000-700 grams b) RHODAMEEN T-50 - 154 grams c) Sodium hydroxide - 35 grams d) Dibromomethane - 20 grams f) Cetyl bromide - 55 grams The carbon block 16 terminal block copolymer formed in this manner was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute at 22 ° C ~ 760 centipoises) EXAMPLE 9 Preparation of the comb copolymer containing suspended hydrophobes of 16/18 carbon atoms.

Example 7 was repeated using the following reagents. a) PEG-8000 - 751 grams b) RHODAMEEN T-50 - 232 grams c) Sodium hydroxide - 35 grams d) Dibromomethane - 22 grams The comb copolymer formed in this manner had a weight average molecular weight of 24,481 (polydispersity index ~ 1.93). It was soluble in water (solution at 6 percent Brookfield viscosity at 30 revolutions per minute at 22 ° C ~ 128 centipoises) - EXAMPLE 10 Preparation of PEG-8000 / bisphenol-A / terminal block methylene terpolymer of 16 carbon atoms Example 7 was repeated using the following reagents. a) PEG-8000 - 1000 grams b) Bisphenol-A polyethoxylate (0: MACOL RD 230E) (available from PPG Industries) - 27 grams c) Sodium hydroxide - 35 grams d) Dibromomethane - 22 grams f) Cetyl bromide - 100 grams The terpolymer formed in this way was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute at 22 ° C ~ 588 centipoises) EXAMPLE 11 Preparation of the terminal block comb copolymer of 16 carbon atoms using Rhodameen®. T-12/90 Example 5 was repeated using Rhodameen® T-12/90 instead of Rhodameen® T-50, Note: Rhodameen® T-12/90, - obtainable from Rhodia, Inc., is an ethoxylated tertiary amine based on the tallow radical (mixture of hydrophobes of 16 and 18 carbon atoms) and 20 moles of ethylene oxide. The various reagents used to make the comb copolymer are given below: a) PEG-8000 - 1000 grams b) RHODAMEEN T-12/90 - 40 grams c) Sodium hydroxide - 34 grams d) Dibromomethane - 20 grams f) Bromide of cetyl - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 19,000 and the polydispersity index was 1.49. It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute ~ 50 centipoise). The cetyl and octadecyl content of the copolymer were 2.3 percent and 0.03 percent by weight, respectively.

EXAMPLE 12 Preparation of the terminal block comb copolymer of 16 carbon atoms using 3-octadecyloxy-1,2-propanediol Example 5 was repeated using 3-octadecyloxy-1,2-propanediol instead of Rhodameen® T-50. 1. PEG-8000 - 1000 grams 2. DL-3-octadecyloxy-l, 2-propanoldiol - 11 grams 3. Sodium hydroxide - 34 grams 4. Dibromomethane - 20 grams 5. Cetyl bromide - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 58,969 and the polydispersity index was 1.99. It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute ~ 540 centipoises). The cetyl and octadecyl content of the copolymer were 1.26 and 0.14 weight percent, respectively.

EXAMPLE 13 Preparation of the polyacetal polyether polyether carrying copolymer carrying 18 carbon atoms Example 12 was repeated using cetyl bromide as the terminal blocking reagent - - 1. PEG-8000 - 820 grams 2. DL-3-octadecyloxy-l, 2-propanediol, 2 grams 3. Sodium hydroxide - 27 grams 4. Dibromomethane - 16.4 grams The comb copolymer carrying hydrophobes suspended from 18 carbon atoms had a weight average molecular weight of 47,381 and the polydispersity index was 1.72. It was soluble in water (solution at 7.3 percent Brookfield viscosity at 30 revolutions per minute ~ 25 centipoises). The cetyl content of the copolymer was 0.17 percent and 0.21 percent by weight, respectively.

EXAMPLE 14 Preparation of the terminal block comb polymer of 16 carbon atoms using 1-phenyl-1,2-ethanediol Example 12 was repeated using l-phenyl-1,2-ethanediol instead of 3-octadecyloxy-1,2-propanediol 1. PEG-8000 - 1000 grams 2. 1-Phenyl-1,2-ethanediol - 4.7 grams 3 Sodium hydroxide - 34 grams 4. Dibromomethane - 20 grams 5. Cetyl bromide - 70 grams - The carbon block 16 terminal block copolymer obtained in this manner had a weight average molecular weight of 34,772 and the polydispersity index was 1.57. It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute ~ 470 centipoises). The cetyl content of the copolymer was 1.95 percent.

EXAMPLE 15 Preparation of the terminal block comb copolymer of 16 carbon atoms carrying perfluoro-alkyl suspended hydrophobes Example 1 was repeated using 1H, 1H, 2H, 3H, 3H-pentafluoroundecane-1,2-diol instead of Rhodameen® T-50. The ingredients used were the following. 1. PEG-8000 - 100 grams 2. 1H, 1H, 2H, 3H, 3H-pentafluoroundecane-1,2-diol - 1.67 grams 3. Sodium hydride - (60 percent dispersion in mineral oil) - 4 grams 4 Tetrahydrofuran - 750 milliliters 5. Dibromomethane - 2.4 grams 6. Cetyl bromide - 11.5 grams The carbon block 16 terminal comb copolymer obtained in this way had a weight average molecular weight of 60,762 and the polydispersity index was of 3.6. It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute ~ 470 centipoises). The cetyl content of the copolymer was 0.5 weight percent.

EXAMPLE 16 Preparation of the terminal block comb copolymer of 16 carbon atoms using 1,3-dioxane-5,5-dimethanol Example 5 was repeated using 1,3-dioxane-5,5-dimethanol instead of Rhodameen® T-50. 1. PEG-8000 - 1000 grams 2. 1, 3-Dioxane-5, 5-dimethanol - 4.7 grams 3. Sodium hydroxide - 34 grams 4. Dibromomethane - 20 grams 5. Cetyl bromide - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 34.870 and the polydispersity index was 1.95. It was soluble in water (solution - - at 2.3 percent Brookfield viscosity at 30 revolutions per minute ~ 475 centipoise). The cetyl content of the copolymer was 1.95 weight percent.

EXAMPLE 17 Preparation of the terminal block comb copolymer of 16 carbon atoms carrying suspended fluorobenzal hydrophobes Example 1 was repeated using 3-fluorobenzal bromide instead of dibromomethane. The ingredients were the following. 1. PEG-8000 - 100 grams 2. Tetrahydrofuran - 750 milliliters 3. 3-Fluorobenzal bromide (obtainable from Lancaster Synthesis Inc.) - 3.8 grams 4. Sodium hydride (60 percent dispersion in mineral oil) - 4 grams 5. Cetyl bromide - 6 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 11.079 and the polydispersity index was 1.09. It was inflatable in water. The cetyl content of the copolymer was 0.9 weight percent.

EXAMPLE 18 Preparation of the terminal block comb copolymer of 16 carbon atoms using a mixture of polyethylene glycols with different molecular weight and Rhodameen® T-50 Example 5 was repeated using a mixture of polyethylene glycols and Rhodameen T-50. 1. Polyethylene glycol (Molecular Weight ~ 8000) - 980 g 2. Polyethylene glycol (Molecular Weight ~ 2000) - 30 g 3. Rhodameen® T-50 - 46 grams 4. Sodium hydroxide - 34 grams 5. Dibromomethane - 20 grams 6. Cetyl bromide - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 49.844 and the polydispersity index was 1.92. It was soluble in water (2 percent solution of Brookfield viscosity at 30 revolutions per minute ~ 600 centipoises). The cetyl content of the copolymer was 1.52 weight percent.

EXAMPLE 19 Preparation of the terminal block comb polymer of 16 carbon atoms containing hydrophobes of 16 carbon atoms suspended Example 5 was repeated using 1-hexadecylamine instead of Rhodameen® T-50. 1. PEG-8000 - 1000 grams 2. 1-Hexadecylamine - 8 grams 3. Sodium hydroxide - 34 grams 4. Dibromomethane - 20 grams 5. Cetyl bromide - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 45,842 and the polydispersity index was 1.74. It was soluble in water (2 percent Brookfield viscosity solution at 30 revolutions per minute ~ 520 centipoise). The cetyl content of the copolymer was 1.5 weight percent. The nitrogen content of the copolymer was 29 parts per million.

- EXAMPLE 20 Preparation of the terminal block comb copolymer of 16 carbon atoms carrying suspended (dimethyl-n-propyl) silyl groups Example 1 was repeated using a mixture of dibromomethane and (dichloromethyl) dimethyl-n-propylsilane instead of dibromomethane. 1. PEG-8000 - 100 g 2. Tetrahydrofuran - 750 milliliters 3. Sodium hydride (60 percent dispersion in mineral oil) - 4 grams 4. (Dichloromethyl) dimethyl-n-propylsilane (Lancaster Synthesis Inc.) - 0.5 gram 5. Dibromomethane - 2 grams 6. Cetyl bromide - 7 grams The 16-carbon terminal block silylated comb copolymer obtained in this way had a weight average molecular weight of 17.318 and the polydispersity index was 1.27. It was soluble in water (solution at 4 percent Brookfield viscosity at 30 revolutions per minute ~ 17 centipoises).

- EXAMPLE 21 Preparation of the terminal block comb copolymer of 16 carbon atoms containing boronatofluorophenyl hydrophobes suspended Example 5 was repeated using 4-fluorobenzeneboronic acid instead of Rhodameen T-50 1. PEG-8000 - 1250 grams 2. 4-Fluorobenzeneboronic acid - 3 grams 3. Sodium hydroxide - 34 grams 4. Dibromomethane - 20 grams 5. Cetyl bromide - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 31.007 and the polydispersity index was 1.6. It was soluble in water (solution at 1.7 percent by weight of Brookfield viscosity at 30 revolutions per minute ~ 220 centipoise). The cetyl content of the copolymer was 1.97 weight percent. The boron content of the copolymer was 164 parts per million.

EXAMPLE 22 Preparation of the 16-carbon terminal block comb copolymer containing suspended (dimethyl-n-propyl) silyl suspended hydrophobes Example 5 was repeated using a mixture of dibromomethane and (dichloromethyl) dimethyl-n-propylsilane instead of dibromomethane. 1. PEG-8000 - 1152 grams 2. Sodium hydroxide - 34 grams 3. (Dichloromethyl) dimethyl-n-propylsilane - 3.6 g 4. Dibromomethane - 17 grams 5. Cetyl bromide - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 30,176 and the polydispersity index was 1.5. It was soluble in water (2 percent by weight Brookfield viscosity solution at 30 revolutions per minute ~ 230 centipoise). The cetyl content of the copolymer was 1.86 weight percent.

EXAMPLE 23 - Preparation of the terminal block comb copolymer of 16 carbon atoms containing suspended fluorophenyl hydrophobes.

Example 5 was repeated using a mixture of dibromomethane and 3-fluorobenzal bromide instead of dibromomethane. 1. PEG-8000 - 1152 grams 2. Sodium hydroxide - 34 grams 3. Bromide of 3-fluorobenzal - 5 grams 4. Dibromomethane - 17 grams 5. Bromide of cetyl - 70 grams The carbon block 16 terminal block copolymer obtained in this way had a weight average molecular weight of 31,492 and the polydispersity index was 1.57. It was soluble in water (solution at 1.7 percent by weight of Brookfield viscosity at 30 revolutions per minute ~ 330 centipoises). The cetyl content of the copolymer was 1.92 weight percent.

Claims

- - CLAIMS:

1. A comb copolymer comprising a main element comprising (a) hydrophilic units, (b) at least one residue of a dihalogen compound after the removal of the halogen atoms and (c) at least one portion containing hydrophobic suspended.

2. The copolymer of claim 1, wherein the hydrophilic units are derived from water soluble polymers.

The copolymer of claim 1, wherein the hydrophilic units are derived from synthetic hydrophilic polymers which are selected from the group consisting of polyalkylene oxide, polyalkylene oxide copolymer, poly (acrylic acid), poly (dialkyldiallylammonium salts) , polyamido polyamine, poly (ethylene imine), poly (methyl vinyl ether co-maleic anhydride), polyvinyl pyrrolidone, poly (2-ethyloxazoline) and polypeptides.

4. The copolymer of claim 1 wherein the hydrophilic units are derived from compounds selected from the group consisting of water-soluble polyalkylene oxides and copolymers thereof. -

5. The copolymer of claim 1, wherein the residue of a dihalogen compound is a hydrocarbyl radical.

The copolymer of claim 1, wherein the residue of a dihalogen compound is derived from compounds selected from the group consisting of dihaloalkanes and their derivatives.

7. The copolymer of claim 1, wherein the residue of a dihalogen compound is an organometallic radical.

8. The copolymer of claim 1, wherein the residue of a dihalogen compound is an organosilyl radical.

9. The copolymer of claim 1, wherein the residue of a dihalogen compound is an organophosphoryl radical.

The copolymer of claim 1, wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of dihalogenoorganosilanes and their derivatives.

The copolymer of claim 1, wherein the residue of a dihalogen compound is derived from compounds that are selected from the group consisting of dihalogenoorgano-phosphorus compounds and their derivatives. -

12. The copolymer of claim 1, wherein the portion containing suspended hydrophobes is derived from compounds selected from the group consisting of hydrophobic compounds having hydrogen, alpha, omega-active atoms and their alkoxylated derivatives.

The copolymer of claim 1, wherein the suspended hydrophobic-containing portion is derived from compounds selected from the group consisting of hydrophobic compounds having hydrogen, alpha, omega-active atoms and their ethoxylated derivatives.

The copolymer of claim 1, wherein the portion containing suspended hydrophobes is derived from hydrophobic compounds having alpha, omega-halogen atoms.

The copolymer of claim 4, wherein the polyalkylene oxides and the copolymers of the polyalkylene oxides have a weight average molecular weight of at least about 200.

16. The copolymer of claim 4, wherein the oxides of polyalkylene and copolymers of polyalkylene oxides have a weight average molecular weight of up to about 35,000.

The copolymer of claim 12, wherein the hydrophobes of the hydrophobic compounds have a molecular weight of at least about 15.

18. The copolymer of claim 12, wherein the hydrophobes of the hydrophobic compounds have a molecular weight of up to about 1,100.

19. The copolymer of claim 1, wherein the geometry of the comb copolymer portion is of the linear, branched or star type.

The copolymer of claim 1, wherein the hydrophobe is selected from the group consisting of hydrocarbyl, alkyl, aryl, arylalkyl, cycloaliphatic, perfluoroalkyl, carbosilyl, fulerenyl, polycyclic and complex dendritic groups.

21. The copolymer of claim 1, wherein the hydrophobe has at least one carbon atom.

22. The copolymer of claim 1, wherein the hydrophobe has up to forty carbon atoms.

23. The copolymer of claim 1, which has a weight average molecular weight of at least about 6,000.

24. The copolymer of claim 1, which has a weight average molecular weight up to about 150,000.

25. The copolymer of claim 1, wherein the hydrophilic units are derived from water-swellable polymers. -

26. The copolymer of claim 1, wherein the portion containing suspended hydrophobes is derived from the hydrophobic compounds having alpha, omega-epoxy groups.

27. The copolymer of claim 1, wherein the portion containing suspended hydrophobes is derived from fullerene compounds.

The copolymer of claim 4, wherein the residue of a dihalogen compound is derived from compounds that are selected from the group consisting of dihaloalkands and their derivatives, the portion containing suspended hydrophobes is derived from compounds selected from the group which consists of hydrophobic compounds having alpha, omega-active hydrogen atoms and their ethoxylated derivatives, the polyalkylene oxides and the polyalkylene oxide copolymers have a molecular weight of from about 200 to about 35,000, the hydrophobes of the hydrophobic compounds have a molecular weight of about 15 to about 1,100, the geometry of the portion of the linear, branched or branched type comb copolymer, the hydrophobe is selected from the group consisting of hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, cycloaliphatic, perfluoroalkyl, carbosilyl, fullerenyl, polycyclic and dendr Ticos - complexes, the hydrophobe has from one to ninety carbon atoms, and the comb copolymer has a weight average molecular weight of from about 6,000 to about 150,000.

29. The copolymer of claim 28, wherein the polyalkylene oxide units are deferred from polyethylene oxide and the water soluble copolymers of polyethylene oxide.

30. The polymer of claim 28, wherein the residue of the dihalogen compound is derived from gem-dihalogenomethane and its derivatives.

31. The copolymer of claim 28, wherein the hydrophobic-containing portion is derived from fatty amines modified with alkylene oxide, and ethoxylated organophosphorus or organophosphorus compounds having hydrophobe attached thereto.

32. The copolymer of claim 28, wherein the polyethylene oxide and polyethylene oxide copolymers have a molecular weight of at least about 8,000.

33. The copolymer of claim 28, wherein the polyethylene oxide and the polyethylene oxide copolymers have a molecular weight of up to about 10,000. - 5

34. The copolymer of claim 28, wherein the hydrophobes of the hydrophobic compounds have a molecular weight of at least about 115.

The copolymer of claim 28, wherein the hydrophobes of the hydrophobic compounds have a molecular weight up to about 250.

36. The copolymer of claim 28, wherein the geometry of the comb copolymer portion is linear.

37. The copolymer of claim 28, wherein the hydrophobic group is an alkyl group.

38. The copolymer of claim 28, which has a weight average molecular weight of at least about 15,000.

39. The copolymer of claim 28, which has a weight average molecular weight of up to about 100,000.

40. The copolymer of claim 28, wherein the hydrophobe has at least six carbon atoms.

41. The copolymer of claim 28, wherein the hydrophobe has up to twenty-two carbon atoms.

42. The copolymer of claim 1, wherein the portion is subjected to hydrophobic terminal block.

43. The copolymer of claim 42, wherein the terminal blocking hydrophobes are selected from the group consisting of hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, cycloaliphatic, perfluoroalkyl, carbosilyl, fullerenyl, polycyclic, and complex dendritic groups.

44. The copolymer of claim 28, wherein the residue of the dihalogen compound is a hydrocarbyl radical having from 1 to 20 carbon atoms.

45. The copolymer of claim 29, wherein the residue of a dihalogen compound is derived from gem-dihalogenomethane and its derivatives, the portion containing the hydrophobes is derived from fatty amines modified with alkylene oxide and ethoxylated organophosphorus or organophosphorus compounds having hydrophobes attached to them. same, the polyethylene oxide and the polyethylene oxide copolymers have a molecular weight of about 8,000 to about 10,000, the hydrophobes of the hydrophobic compounds have a molecular weight of about 115 to about 250, the geometry of the copolymer portion of comb is linear, the hydrophobe is an alkyl group, the comb copolymer has a weight average molecular weight of about 15,000 to about 100,000 and the hydrophobe has six to twenty-two carbon atoms.

46. The copolymer of claim 45, wherein the hydrophobic portion is derived from fatty amine.

47. The copolymer of claim 45, wherein the hydrophobic portion is derived from alkoxylated fatty amine.

48. The copolymer of claim 45, wherein the hydrophobic portion is derived from ethoxylated fatty amine.

49. The copolymer of claim 45, wherein the residue of a dihalogen compound is derived from the group consisting of dibromomethane, dichloromethane and its derivatives.

50. The copolymer of claim 47, wherein the residue of a dihalogen compound is derived from the group consisting of dibromethane, diclomethane and its derivatives.

51. The copolymer of claim 28, wherein the portion is terminally blocked with hydrophobes.

52. The copolymer of claim 28, wherein the hydrophobe is an alkyl group.

53. The copolymer of claim 45, wherein the portion is terminally blocked with hydrophobes.

54. A process for preparing a comb copolymer comprising a portion consisting of (a) hydrophilic units, (b) at least one residue of a dihalogen compound after the removal of the halogen atoms and (c) by at least one suspended hydrophobic-containing portion comprising copolymerizing: (1) a water-soluble polymer carrying hydrogen, alpha-omega-active atoms that are selected from the group consisting of polyalkylene oxide, and polyalkylene oxide copolymers, poly (acrylic acid), poly (acrylic acid-co-methacrylic acid), poly (acrylamide), poly (dialkyldiallylammonium salts), polyamidopolyamine, poly (ethyleneimine), poly (methyl vinyl ether-co-maleic anhydride), polyvinylpyrrolidone, poly (2-ethyloxazoline) and polypeptides. (2) hydrophobic compounds having hydrogen, alpha, omega-active atoms or their ethoxylated derivatives, or having alpha, omega-halogen atoms or alpha, omega-epoxy groups, and (3) dihalogen compounds that are selected from the group consisting of dihalogenoalkanes and their - derivatives, aromatic compounds substituted with dihalogens and their derivatives, and the dihalogenoorganometal compounds and their derivatives in the presence of a base for a period of time sufficient to form the comb copolymer.

55. The process of claim 54, wherein the water soluble polymer is selected from the group consisting of polyalkylene oxides and copolymers thereof.

56. The process of claim 54, wherein the polyalkylene oxides and the polyalkylene oxide copolymers have a weight average molecular weight of at least about 200.

The process of claim 54, wherein the oxides of polyalkylene and the copolymers of polyalkylene oxides have a weight average molecular weight of up to about 35,000.

58. The process of claim 54, wherein the dihalogenoalkanes or their derivatives are selected from the group consisting of gem-dihalogenomethane and its derivatives, the aromatic compounds substituted with dihalogen and their derivatives are selected from the group consisting of dihaloxyxylenes and their derivatives and dihalogenic organotin compounds or their derivatives are selected from the group consisting of dihalogenoorganosilanes, dihalogenoorganophosphorus and its derivatives.

59. The process of claim 54, wherein the hydrophobic compounds are selected from the group consisting of fatty amines, fatty amines modified with alkylene oxide, alkoxylated organosilicon compounds, and alkoxylated organophosphorus compounds having hydrologics attached thereto.

60. The process of claim 54, wherein the hydrophobes of the hydrophobic compounds have a molecular weight of at least about 15.

61. The process of claim 54, wherein the hydrophobes of the hydrophobic compounds have a molecular weight up to approximately 1,100.

62. The process of claim 54, wherein the hydrophobic compound has a hydrophobe that is selected from the group consisting of hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl cycloaliphatic, perfluoroalkyl, carbosilyl, fullerenyl, polycyclic, and complex dendritic groups .

63. The process of claim 62, wherein the hydrophobe has at least one carbon atom.

64. The process of claim 62, wherein the hydrophobe has up to ninety carbon atoms.

65. The process of claim 54, wherein the comb copolymer has a weight average molecular weight of at least about 6,000.

66. The process of claim 54, wherein the comb copolymer has a weight average molecular weight up to about 150,000.

67. The process of claim 62, wherein the water soluble polymer is selected from the group consisting of polyalkylene oxides and copolymers thereof, the polyalkylene oxides and the polyalkylene oxide copolymers have a weight average molecular weight of from about 200 to about 35,000, the hydrophobic compounds have a molecular weight of from about 15 to about 1,100, the hydrophobe has from one to ninety atoms of carbon, and the comb copolymer has a weight average molecular weight of about 6,000 to about 150,000.

68. The process of claim 54, which comprises reacting the comb copolymer with a hydrophobic compound capable of reacting with the active hydrogen atoms.

69. The process of claim 54, wherein the hydrophobic compound has a hydrophobe that is selected from the group consisting of hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, - - cycloaliphatic, perfluoroalkyl, carbosilyl, fullerenyl, polycyclic and complex dendritic groups.

70. The process of claim 67, which comprises reacting the comb copolymer with the hydrophobic compound capable of reacting with the active hydrogen atoms.

71. The process of claim 70, wherein the hydrophobic compound has a hydrophobe that is selected from the group consisting of hydrocarbyl, alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, cycloaliphatic, perfluoroalkyl, carbosilyl, fullerenyl, polycyclic, and complex dendritic groups .

72. The process of claim 67, wherein the polyalkylene oxides and the polyalkylene oxide copolymers are selected from the group consisting of polyethylene oxide and the water-soluble polyethylene oxide copolymers.

73. The process of claim 67, wherein the dihalogenoalkanes and their derivatives are selected from the group consisting of dibromo- and dichloro-methane and its derivatives, the aromatic compounds substituted with dihalogen and its derivatives are selected from the group consisting of , -. ' -dichloro-, a'-dibromoxylene and its derivatives and the dihalogenoorganometal compounds and their derivatives are selected from the group consisting of gem-dichloro- and dibro or -organosilanes, gem-dichloro- and dibromo-organophosphorus compounds and their derivatives .

74. The process of claim 67, wherein the hydrophobic compounds having alpha, omega-active hydrogen atoms are selected from the group consisting of fatty amines modified with alkylene oxide, and the organophosphorus or organophosphorus ethoxylated compounds having hydrophobes attached to them.

75. The process of claim 72, wherein the polyethylene oxide and the polyethylene oxide copolymers have a molecular weight of at least about 8,000.

76. The process of claim 72, wherein the polyethylene oxide and the polyethylene oxide copolymers have a molecular weight of up to about 10,000.

77. The process of claim 72, wherein the hydrophobes of the hydrophobic compounds have a molecular weight of at least about 15.

78. The process of claim 67, wherein the hydrophobes of the hydrophobic compounds have a molecular weight of up to about 250.

79. The process of claim 67, wherein the hydrophobe is an alkyl group.

80. The process of claim 67, wherein the comb copolymer has a weight average molecular weight of at least about 15,000.

81. The process of claim 67, wherein the comb copolymer has a weight average molecular weight of up to about 100,000.

82. The process of claim 67, wherein the hydrophobe has at least six carbon atoms.

83. The process of claim 67, wherein the hydrophobe has up to twenty-two carbon atoms.

84. The process of claim 72, wherein the dihalogenoalkanes and their derivatives are selected from the group consisting of dibromo- and dichloromethane and their derivatives, the aromatic compounds substituted with dihalogen and their derivatives are selected from the group consisting of a, 'Dichloroamy, a'-dibromoxylene and its derivatives, and the dihalogenoorganometallic compounds and their derivatives are selected from the group consisting of gem-dichloro- and dibromo-organosilane, gem-dichloro- and dibromo-organophosphorus compounds and their derivatives, the hydrophobic compounds having alpha, omega-active hydrogen atoms are selected from the group consisting of fatty amines modified with alkylene oxide and ethoxylated organophosphorus or organophosphorus compounds having hydrophobes attached thereto, polyethylene oxide and the polyethylene oxide copolymers have a molecular weight of about 8,000 to about 10,000, the hydrophobic groups of the hydrophobic compounds have a molecular weight of from about 115 to about 250, the hydrophobe is an alkyl group, the comb copolymer has a weight average molecular weight of from about 15,000 to about 100,000, and the hydrophobe has from six to twenty-two carbon atoms.

85. The process of claim 67, which comprises reacting the comb copolymer with the hydrophobic compound capable of reacting with the active hydrogen atoms.

86. The process of claim 69, wherein the hydrophobic compound has a hydrophobe that is an alkyl group.

87. A film-forming coating composition comprising the comb copolymer of claim 1.

88. A film-forming coating composition comprising a comb copolymer of claim 3.

89. A film-forming coating composition that comprises the comb copolymer of claim 4.

90. A film-forming coating composition comprising the comb copolymer of claim 16.

91. A film-forming coating composition comprising the comb copolymer of claim 28.

92. A film-forming coating composition comprising the end lock comb copolymer of claim 42.

93. A film-forming coating composition comprising the terminal block comb copolymer of claim 43.

94. The film-forming coating composition of claim 87 wherein the composition is a latex paint.

95. The film-forming coating composition of claim 89, wherein the composition is a latex paint.

96. The film-forming coating composition of claim 90, wherein the composition is a latex paint.

97. The film-forming coating composition of claim 93, wherein the composition is a latex paint.

98. The copolymer of claim 1, wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of aromatic compounds substituted with dihalogen and its derivatives.

99. The copolymer of claim 28, wherein the residue of the dihalogen compound is derived from the compounds selected from the group consisting of aromatic compounds substituted with dihalogen and its derivatives.

100. The copolymer of claim 28 wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of organometallic dihalogen compounds and their derivatives.

101. The copolymer of claim 28, wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of dihaloxyxylenes and their derivatives.

102. The copolymer of claim 45, wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of dihaloxyxylenes and their derivatives.

103. The copolymer of claim 45, wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of dihalogenoorganosilanes, dihalogenoorganophosphorus compounds, and their derivatives.

104. The copolymer of claim 45, wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of dibromo- and dichloromethane and its derivatives.

105. The copolymer of claim 45, wherein the residue of a dihalogen compound is derived from the compounds selected from the group consisting of a, a'-dichloro- and a, -dibro-oxylene and its derivatives.