MXPA06007751A - Colorant compatible synthetic thickener for paint - Google Patents

Abstract

A synthetic polymer has a water-soluble or water-swellable polymer backbone and terminal groups and/or intermediate groups of blocks of hydrophobes of alkyl- or aryl compounds containing a polymerizable cyclic monomer or a polymerizable double bond (or alkene) group or derivatives thereof. The blocks of hydrophobes are composed two or more units of the same or different hydrophobes. These synthetic polymers are used as rheology modifiers, especially in latex paints.

Description

SYNTHETIC THICKENER COMPATIBLE WITH COLORING, FOR PAINTING This application claims the benefit of the Provisional Application of E. U.A. No. 60 / 534,873, filed on January 8, 2004.

CAM PO OF THE INVENTION This invention relates to paint compositions using synthetic thickeners compatible with colorants. More specifically, the invention relates to the use in paint compositions of a synthetic thickener with a water soluble or swellable polymer column having hydrophobic end groups of oligomers of alkyl or aryl compounds containing a monomer polymerizable cyclic (i.e., an epoxide, a giicidyl ether, a cyclic oxide, an oxazoline) or a polymerizable double bond (ie, styrene, vinyl ether, acrimalides, acrylates), or derivatives thereof. • BACKGROUND PE LA Í VENCIÓN Hydrophobically modified water-soluble polymers of various types have been used to thicken latex paints to provide some performance during manufacturing, storage and applications. Some of these properties include: ease of formulation, prevention of pigment fixation, film formation during application, splash resistance, low slippage, good flow, and leveling of the paint film. These water-soluble polymers can come from a natural source such as cellulose, starch, poiidextran, guar gum or their ionic and non-ionic derivatives (hydroxyethyl, hydroxyprapis). Some examples of synthetic water-soluble polymers are polyacrylamides, polyacrylates, polyvinyl alcohol, polyvinyl sulphopates, polyethylene imine, polysaccharide, polyamidezetidinium ion, polyvinylpyrrolidone, polyaspartates, polyacetalpolyether, polyalkyl ethers and polyvinylpyrrolidone. Most types of water soluble polymer are described in "Water soluble polymers" by Yale Meltzer (Noyes Data Corporation, Parkridge, New Jersey, USA, 1981). The hydrophobic fixation is usually done with a single alkyl group or an alkyl phenol ethoxylate carrying a halide or an epoxide. There are also examples where the hydrophobe is grouped before the fixation as in the U.A. Patent. 4,426,485, patent application of E. U.A. 0045724 A1 (2002), Patent of E.U.A. 5,292,828, and Patent of E. U.A. 6337366. In these patents, the hydrophobes are previously connected to each other by means of a linking reagent such as diisocyanate, diepoxide, epichlorohydrin and a primary amine.

BRIEF DESCRIPTION OF THE INVEN N ION The present invention is directed to a polymer composition comprising a water-soluble or swellable synthetic polymer column having covalently connected ends and / or intermediate blocks of oligomeric hydrophobes which are selected from the group which consists of i) alkyl and aryl portions containing a polymerizable cyclic monomer, ii) a psilimerizable double bond, and iii) derivatives of i) and ii), wherein the blocks are two or more units of the same or different hydrophobes. The present invention also comprises a process for preparing the water-soluble or swellable polymer composition mentioned above which comprises a) reacting a water-soluble or swellable column polymer in water with a catalyst agent at to activate the polymer column, b) water the oligomerizing hydrophobic monomer (s) to the reaction mass, and c) polymerize the reaction mass at sufficient temperature and for a sufficient time in order to add monomer (s) hid Rophobic oligomerizers to the column either as end groups or as intermediate groups. This invention also relates to an aqueous protective coating composition comprising (a) the aforementioned polymer composition, (b) a colorant, and (c) a film-forming latex, wherein the viscosity of the protective coating composition aqueous remains unchanged or has a negligible loss compared to when using conventional rheology modifiers when adding the dye.FJ.

DETAILED DESCRIPTION OF THE INVENTION A new class of hydrophobically modified water-dispersible / water-soluble polymers has been discovered that provides good thickness, leveling, and squeezing properties in aqueous solution coatings that can be used alone without other coating additives needed in the past to adapt the formulation to balance these properties. It has been found that all that is needed is to provide synthetic water soluble polymer column structures with the ability to dissolve in water or be able to swell in water to the extent necessary for close application that has been modified in accordance with the present invention. The new class of rheology modifiers is a hydrophobically modified polymer having a water-soluble or swellable column portion in water and oligomeric hydrophobic portion (s) in the form of unit blocks. The hydrophobic oligomeric block has the following chemical architecture: where: n is an integer from 1 - 100 R is an alkyl or aryl group having from 2 carbons to 100 carbons. The alkyl group can be saturated or unsaturated, cyclic or non-cyclic, linear or branched, or halogenated, i.e., fluorinated, chlorinated or brominated. The alkyl and aryl groups may be, substituted, such as alkylsiloxane, alkyl ether, arylalkyl ether, alkylarylene ether, alkylene ether, alkyl thioether, alkylene thioether, alkyl amine, dialkyl amine, dialkyl amine oxide, triacyl ammonium, diaryl amine, dialkyl phosphine, diaryl phosphine, dialkyl phosphine oxide, diaryl phosphine oxide, dialkyl phosphate and the like.

A is a diradical connector of -O-, -S-, -CH2-, -O-CH2-, -SC H2-, -N H-, -N R'-, -N H -CH2-, -NR- CH2-, -PR'-, -POR'- (wherein R '= 1 to 12 carbons), polyalkylene ether (molecular weight = 44 to 50000), polyalkylene isocyanate-HEUR (molecular weight = 100 to 50,000).

B is a linking group of: -CH2-, -CH2O-, CH2S-, -CH2-NH-, -CR "HO-, -CR" HS-, -CR "HN H-, and -CH2NR" - ( where R "= 1 -12 carbons).

C is a connecting end equal to A or a strict end equal to: -OH, SH, -NH R ", -OR '", -SR "\ and -H.

Various specific chemical structures are shown below to illustrate this hydrophobic architecture.

Structure 1 In this case, A = -OCH2-, B = -O-CH2-, R = -CH2O-C8H18 and C = -OH.

Structure 2 In this example, A = -NHCN2-, B = -O-CH2-, R = -CH2O-C8H18 and C Structure 3 In this structure, A = -OCH2-, B = -OCH2-, C = -C6H13 and R OC6H5.

Structure 4 In this structure, A = polyalkylene oxide-CH2-, B = -O-C H2-, C -OH, and R = nonylphenoxy.

Structure 5 In this structure, A = -CH2-, B = -CH2-, C = H and R = Ph. (Note, Ph is a phenyl portion).

Structure 6 In this structure, A = -CH2-, B = -CH2-, C = -H, and R = -O-C8H 1 7 - These hydrophobic blocks can be synthesized from corresponding alkyl glycidyl ether (or thio or amido) by heating with a base or nucleophile of their own choice. Structures 1-4 are products of alkyl glycidyl ethers. Control oligomerization such as atom transfer polymerization, living radical polymerization, cationic polymerization, anionic polymerization and group transfer polymerization with self-quenching reagent would yield desired hydrophobicity of reactive vinyl monomers such as styrene, vinyl ether, vinyl ester, acrylate esters, acrylamide ester. Structures 5 and 6 are examples of control radical oligonucleotide product and self-capped. The hydrophobic blocks can be connected to the water soluble / water dispersible polymer via an ether, ester, urethane, amide, amine, urea or urea, depending on the choice of one skilled in the art. The connection could be made via an epoxide, a diisocyanate, a dialkyl halide, diester, or a compound carrying reactive mixture groups (e.g., epoxyalkylhalide, alkylhalide isocyanate). The commonly practiced method for fixing a hydrophobe to a water soluble / water dispersible polymer carrying reactive hydroxyl groups such as cellulose derivatives is by heating the alkali cellulose derivative with a halide or hydrophobic epoxide. An example of this type of reaction is the synthesis of hydrophobically modified hydroxyethyl cellulose (H M H EC). Both an alkyl halide and an alkyl glycidyl ether can be used as a hydrophobe modifier. Therefore, it is possible to convert the hydrophobe of this invention to an epoxide (using epihalohydrin), or a halogenated reagent such as PBr3 or PCI5 to form a reactive hydrophobe. It is more convenient to incorporate this type of hydrophobe to an addition polymer (vinyl alcohol, acrylamide, acrylates ...) via a monomer carrying this hydrophobe. For example, acryloyl ester of this type of hydrophobe of structure 4 could be polymerized together with acrylic acid and acrylamide to give the corresponding hydrophobically modified alkaline soluble emulsions (HASE). It is also convenient to make tertiary polyurethane hydrophobically modified ethylene oxide urethane block copolymer (HEUR) using a previously made hydrophobe. The hydrophobe containing one or two hydroxyl groups could be added to a mixture of polyethylene oxide with reactive hydroxyl end group then allowed to react with diisocyanate. However, it is very convenient to make the H EU R column and heat the resulting oligomers with a alkyl glycidyl ether of choice. The glycidyl alkyl ether moiety oligomerizes at the end of the HEUR column to give the telechelic H EU R. It is very convenient to only heat a mixture of polyethylene glycol and an alkyl glycidyl ether in the presence of a base in order to make PEG hydrophobically modified. The polymer column could be pre-modified with one or more alkyl diols or alkyl triol to form a branched structure, or converted to an acetal polyether as described in the U.S. Patent. 5574127 or Patent of E.U.A. 6162877. The reaction scheme below illustrates the ease of synthesis of the teиlykelic polymer of this type.

Scheme 1 The present invention is an associative polymer having a water soluble or swellable column which is a synthetic polymer. This column can be derived from a wide selection of materials such as polyacrylamides, polyacrylates, polyvinyl alcohol, polyvinyl sulfonates, polyethylene. imine, polymax, polyamidezetidinium ion, polyvinylpyrrolidone, polyaspartates, or polyacetalpolyether, polyalkyl ethers and polyalkylthioethers. Most types of water soluble polymer are described in "Water soluble polymers" by Yale Meltzer (Noyes Data Corporation, Parkridge, New Jersey, USA, 1981). The column itself is not reactive and can be any of the 5"synthetic polymers mentioned above as long as the column polymer is water soluble or can swell in water.The column becomes a reactive site when the hydrophobes are connected The hydrophobes can also be terminal groups (also known as telechelic groups) in the column.The column polymer can be linear or branched or dendritic in shape (ie, a configuration where three branches are attached to a single atom such as a carbon atom.) When the hydrophobic blocks are alkyl and aryl portions containing a polymerizable cyclic monomer, the total number of carbon atoms in the alkyl or aryl portions of the oligomeric groups The hydrophobic blocks can be from 1 to 100. Oligomeric blocks of hydrophobic portions are the reactive sites. Hydrophobic products must have at least two units, preferably at least 3 units, more preferably at least 7 units, and very preferably 10 units. It should be noted that more than 10 units may be present in the hydrophobic portions and that the number of units is limited only by the feasibility and economy of making said portion based on the size, structure, steric hindrance and other chemical or physical forces that act about the proximity of the units fixed in the blocks. In accordance with this invention, the oligomeric hydrophobes may be an alkyl or aryl moiety containing a polymerizable cyclic monomer or a polymerizable double bond, or derivatives of these portions. When the hydrophobe is an alkyl portion containing a polymerizable cyclic monomer, the alkyl group may have 1 to 40 carbon atoms, preferably 3 to 24 carbons, and more preferably 6 to 18 carbons. When the hydrophobe is an aryl portion containing a palmerizable cyclic monomer, the aryl group may have 6 to 40 carbon atoms, preferably 6 to 29 carbons, and most preferably 7 to 15 carbons. Examples of the cyclic polymethyl monomers are alkyl glycidyl ethers, aryl glycidyl ethers, aryl alkylene glycols, alkyl oxazoline and aryl oxazoline. When the hydrophobe is a polymerizable double bond, it may be an alkene monomer tai such as styrene and strienic compounds, vinyl compounds, acrylates and derivatives thereof, norbornenes and derivatives thereof, and alkenes and derivatives thereof, alkenyl siloxanes and derivatives thereof, alkenyl siianos and derivatives thereof, fluorinated and perfluorinated alkenes. Examples of alkenes are ethylene, propylene, butylene, etc. In accordance with the present invention, the polymer composition has a weight average molecular weight (Mw) with the upper limit of the polymer being about 10,000,000, preferably about 1,000,000, and more preferably about 100,000. The lower limit of the weight average molecular weight of the polymer is about 400, preferably about 1,000, and more preferably about 4,000.

An application for this type of hydrophobically modified water soluble polymer is paint formulation. These paint formulations are latex based, such as based on acrylic, based on vinyl acrylic or styrene-based. It has been found that the techene polymers of the present invention provide equilibrium properties in various paint formulations. However, unexpectedly, for acrylic paint (SG 10 M), the resulting paint also showed excellent viscosity retention (VRT) and dyed with various colorants. This type of performance is not seen in regular hydrophobic polymers alone. In latex paint formulations, the polymer of the present invention can be used alone or in combination with other conventional prior art rheology modifiers (or thickeners) such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC) , carboxymethylcellulose (CMC), methylhydroxy ethylcellulose (MHEC), ethylphthoxyethylcellulose (EHEC), and hydrophobically modified hydroxyethylcellulose (HM H EC). Typical latex paint formulations of this invention are based on acrylic, vinyl acrylic based, or styrene based. These latex-based paints have a pigment volume concentration (PVC) of 15 to about 80. Following are a series of examples that show the synthesis of hydrophobically modified PEG and polyacetal ether and their performance in two paint formulations: SG 10 M and UCAR 379G (acrylic vinyl-based paint). All parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 (PEG 20K, 16.4% addition level of ether glyceryl 2 methyl phenyl) A mixture of 30 g of molecular weight PEG was heated in a 3-necked 250 ml L-bottom flask equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle. of 20,000 (0.0015 mol) and toluene (80 L) at 60 ° C. At this temperature, KOH (2.1 g, 0.06 mol, in 3 g of water) was added and the reaction mixture was stirred for 1 hour. Glycidyl 2-methyl phenyl ether (5.91 g, 0.036 mol) was added and the reaction temperature was maintained at 1 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 μL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (33.7 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1H NMR) showed 20% incorporation of hydrophobe. The Brookfield viscosity of an aqueous solution of 5% of this oligomer was 67,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG10 M (standard formulation) TE% = 0.1 1, Viscosity Loss during Tinting (VLT) = -4 KU. For UCAR 379 G, TE% = 0.54, VLT = -10 KU.

EXAMPLE 2 ÍPEG 35K.9.3% addition level of qcididyl phenyl ether) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 40 g of PEG of molecular weight was heated. 35,000 (0.0011 mol) and toluene (80 L) at 60 ° C. At this temperature, KOH (1.54 g, 0.0275 mol, in 10 g of water) was added and the reaction mixture was stirred for 1 hour. Glycidyl phenyl ether (4.12 g, 0.0275 mol) was added and the reaction temperature was maintained at 110 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (40.5 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1H NMR) showed 8% incorporation of hydrophobe. The Brookfield viscosity of a 5% aqueous solution of this oligomer was 124,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG10 M (standard formulation) TE% = 0.14, Viscosity Loss during Tinting (VLT) = -6 KU. For UCAR 379 G, TE% = 0.68, VLT = -13 KU.

EXAM PLO 3 (PEG 35K, 10.4% addition level of alicidyl 2 methyl phenyl ether) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 30 g of PEG molecular weight was heated. 35, 000 (0.0015 mol) and toluene (80 L) at 60 ° C. At this temperature, KOH (1.15 g, 0.02 mol, in 3 g of water) was added and the reaction mixture was stirred for 1 hour. Glycidyl 2-methyl ether was added | phenyl (3.38 g, 0.02 mol) and the reaction temperature was maintained at 1 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (31 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1 H N M R) showed 6.8% incorporation of hydrophobe. The Brookfield viscosity of a 5% aqueous solution of this oligomer was 184,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG10 M (standard formulation) TE% = 0.1 1, Viscosity Loss during Tinting (VLT) = -12 KU. For UCAR 379 G, TE% = 0.57, VLT = -1 1 KU.

EXAM PLO 4 (PEG 20K, 14% glycidyl ether 2 methyl phenyl) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating blanket, a mixture of 30 g of PEG of molecular weight of 20,000 (0.0015 mol) and toluene (80 mL) was heated at 6G ° C. At this temperature, KOH (3.37 g, 0.06 mol, in 3 g of water) was added and the reaction mixture was stirred for 1 hour. Glycidyl 2-methyl phenyl ether (4.93 g, 0.03 mol,) was added and the reaction temperature was maintained at 1 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (33 g) was obtained. The Brookfield viscosity of an aqueous solution of 5% of this oligomer was 37,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG10 M (standard formulation) TE% = 0.12, Viscosity Loss during Tinting (VLT) = -7 KU. For UCAR 379 G, TE% = 0.47, VLT = -8 KU.

EXAM PLO 5 (PEG 30K, 27% addition level of glycidyl ether 2 methyl phenyl) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 30 g of PEG molecular weight was heated. 12,000 (0.0015 mol) and toluene (80 mL) at 60 ° C. At this temperature, KOH (1.7 g, 0.03 mol, in 3 g of water) was added and the reaction mixture was stirred for 1 hour. Glycidyl 2-methyl phenyl ether (10.9 g, 0.02 mol) was added and the reaction temperature was maintained at 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 μL x 3X) and drying under vacuum, a white powder polymer (35 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1 H N M R) showed 20% incorporation of hydrophobe. The Brookfield viscosity of an aqueous solution of 5% of this oligomer was a gel. Paint performance: SG10 M (standard formulation): Not soluble in paint. For UCAR 379 G, TE% = 0.57, VLT = -1 KU.

EXAM PLO 6 (PAPE 35K 6.9% addition level of buty-glycidyl ether) A mixture of 30 g of PAPE of molecular weight was heated in a 3-necked round bottom flask of 250 μL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating blanket. of 35,000 and toluene (80 mL) at 60 ° C. At this temperature, KOH (0.95 g, 0.02 mol, in 1 g of water) was added and the reaction mixture was stirred for 1 hour. Butyl glycidyl ether (2.23 g, 0.02 mol) was added and the reaction temperature was maintained at 110 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (30 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (H N M R) showed 4.7% incorporation of hydrophobe. The viscosity of an aqueous solution of 5% of this oligomer was > 200,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG10 M (standard formulation) TE% = 0.1 1, Viscosity Loss during Tinting (VLT) = -30 KU. For UCAR 379 G, TE% = 0.47, VLT = -35 KU.

EXAMPLE 7 (PEG 20K, 16.3% addition level of butyl glycidyl ether) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 30 g of PEG molecular weight was heated. 20,000 (0.0015 mol) and toluene (80 mL) at 60 ° C. At this temperature, KOH (0.77 g, 0.015 mol, in 1 g of water) was added and the reaction mixture was stirred for 1 hour. Butyl glycidyl ether was added (5.86 g, 0.045 mol) and the reaction temperature was maintained at 110 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 L) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer was obtained (31 g). Nuclear magnetic resonance with hydrogen nucleus (1H NMR) showed 9.5% incorporation of hydrophobe. Paint performance: SG10 M (standard formulation) not dissolved in the paint.

For UCAR 379 G, TE% = 0.40, VLT = 3 KU.

EXAMPLE 8 (PEG 35K.8.2% addition level of butyl glycidyl ether) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 30 g of PEG molecular weight was heated. 35,000 and toluene (80 mL) at 60 ° C. At this temperature, KOH (0.77 g, 0.02 mol, in 1 g of water) was added and the reaction mixture was stirred for 1 hour. Butyl glycidyl ether (2.68 g) was added, 0.02 mol) and the reaction temperature was maintained at 110 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (33 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1H NMR) showed 7.3% incorporation of hydrophobe. The Brookfield viscosity of an aqueous solution of 5% of this oligomer was 836,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG10 M (standard formulation) TE% = 0.15, Viscosity Loss during Tinting (VLT) = -21 KU. For UCAR 379 G, TE% = 0.32, VLT = -37 KU.

EXAMPLE 9 (PEG 35K, 6% addition level of 2-ethyl hexyl glycidyl ether) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 30 g of PEG molecular weight was heated. 35,000 and toluene (80 mL) at 60 ° C. At this temperature, KOH (0.77 g, 0.02 mol, in 1 g of water) was added and the reaction mixture was stirred for 1 hour. 2-Ethyl hexyl glycidyl ether (1.91 g, 0.02 mol) was added and the reaction temperature was maintained at 110 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 L) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (31 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1H NMR) showed 5.2% incorporation of hydrophobe. The Brookfield viscosity of a 5% aqueous solution of this oligomer was > 200,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Ef paint performance: SG10 M (standard formulation) TE% - 0.11, Viscosity Loss during Tinting (VLT) = -24 KU. For UCAR 379 G, TE% = 0.28, VLT = -30 KU.

EXAMPLE 10 (PEG 10K, 16.2% addition level of glycidyl C12 ether) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 30 g of PEG molecular weight was heated. 10,000 and toluene (80 mL) at 60 ° C. At this temperature, KOH (1.52 g, 0.04 mol, in 1.5 g of water) was added and the reaction mixture was stirred for 1 hour. Dodecyl glycidyl ether (5.81 g, 0.024 mol) was added and the reaction temperature was maintained at 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (31.8 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1 H NMR) showed 1 1% incorporation of hydrophobe. The Brookfield viscosity of a 5% aqueous solution of this oligomer was > 400000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Painting performance: SG 10 M (standard formulation). The material was not soluble in this painting. For UCAR 379 G, TE% = 0.52, VLT = -17 KU.

EXAMPLE 11 (PEG 10K, 23% addition level of glycidyl C12 ether) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle, a mixture of 30 g of PEG molecular weight was heated. 10,000 and toluene (80 mL) at 60 ° C. At this temperature, KOH (2.19 g, 0.04 mol, in 2 g of water) was added and the reaction mixture was stirred for 1 hour. Dodecyl glycidyl ether (8.71 g, 0.04 mol) was added and the reaction temperature was maintained at 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (33 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1 H N M R) showed 1 1% incorporation of hydrophobe. The Brookfield viscosity of a 5% aqueous solution of this oligomer was > 200,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Painting performance: SG 10 M (standard formulation). The material was not soluble in this painting. For UCAR 379 G, TE% = 0.52, VLT = -6 KU.

EXAMPLE 1 2 (PEG 20K, 7.2% addition level of C12 epoxide) A mixture of 30 g of molecular weight PEG was heated in a 3-necked 250 ml L-bottom flask equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle. of 20,000 and toluene (80 mL) at 60 ° C. At this temperature, KOH (0.67 g, 0. 04 mol, in 1 g of water) and the reaction mixture was stirred for 1 hour. 1,2-epoxydodecane (2.33 g, 0.012 mol) was added and the reaction temperature was maintained at 110 ° C for 5 hours.

After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane.

After filtration and washing with ethyl acetate (100 μL x 3X) and drying under vacuum, a white powder polymer (31 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1 H N M R) showed 6% incorporation of hydrophobe. The Brookfield viscosity of a 5% aqueous solution of this oligomer was > 400,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Painting performance: SG 10 M (standard formulation). The material was not soluble in this painting. For UCAR 379 G, TE% = 0.38, VLT = -24 KU.

EXAMPLE 13 (PEG 12K, 8.4% addition level of C12 epoxide) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating blanket, a mixture of 30 g of PEG molecular weight was heated. 12,000 and toluene (80 mL) at 60 ° C. At this temperature, KOH (0.84 g, 0.015 mol, in 1 g of water) was added and the reaction mixture was stirred for 1 hour. 1, 2-epoxydecapo (2.33 g, 0.012 mol) was added and the reaction temperature was maintained at 1 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 mL) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (31.2 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1 H N M R) showed 7.3% incorporation of hydrophobe. The Brookfield viscosity of a 5% aqueous solution of this oligomer was > 400,000 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Painting performance: SG 10 M (standard formulation). The material was not soluble in this painting. For UCAR 379 G, TE% = 0.49, VLT = -4 KU.

EXAMPLE 14 (PAPE, 22% qicididyl 2 methyl phenyl ether) A mixture of 50 g of PEG of molecular weight was heated in a 3-necked 250 ml L-bottom flask equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating mantle. of 40,000 (0.012 mol) and NaOH granules (3 g) at 80 ° C for 1 hour. At this temperature, dibromo-methane (1.65 g, 9.4 mol) was added and the reaction mixture was stirred for 4 hours. Glycidyl 2-methyl phenyl ether (14.23 g, 0.09 mol) was added and the reaction temperature was maintained at 1 10 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (100 g) was further added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 mL x 3X) and drying under vacuum, a white powder polymer (50 g) was obtained. Nuclear magnetic resonance with hydrogen nucleus (1H NMR) showed 14.9% incorporation of hydrophobe. The Brookfield viscosity of an aqueous solution of 5% of this oligomer was 58.800 cps. The Brookfield viscosity of a 25% solution in 25% butyl carbitol was 1, 500 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG10 M (standard formulation). TE% = 0.30. Viscosity Loss during Tinting (VLT) = 3 KU.

EXAMPLE 15 (PAPE, 15% glycidyl ether, 2-methyl phenyl) In a 3-neck round bottom flask of 250 mL equipped with a condenser, a nitrogen inlet / outlet, a mechanical stirrer, a thermal clock and a heating blanket, a mixture of 20 g of PEG of molecular weight was heated. 20,000 (0.0015 mol) and toluene (120 g) at 60 ° C. At this temperature, KOH (3.4 g, 0.06 mol, in 3.4 g of water) was added and the reaction mixture was stirred for 1 hour. Glycidyl 2-methyl phenyl ether (9.12 g, 0.055 mol) was added and the reaction temperature was maintained at 110 ° C for 5 hours. After the reaction was cooled to 60 ° C, toluene (80 L) was also added. The solution was precipitated in 300 mL of hexane. After filtration and washing with ethyl acetate (100 μL x 3X) and drying under vacuum, a white powder polymer (56 g) was obtained. The viscosity of an aqueous solution of 5% of this oligomer was 21 1, 600 cps (BF LV, S-63, 0.3 rpm at 25 ° C). Paint performance: SG 10 M (standard formulation) TE% = 0.18, Viscosity Loss during Tinting (VLT) = -1 KU. For UCAR 379 G, TE% = 0.61, VLT = -5 KU.

The above examples are summarized in the following Table 1, and compared to the commercially available thickener control, NLS 200.

Table 1: Paint performance for some thickeners MPGE: Methyl genyl glycidyl ether BGE: Butyl glycidyl ether EHGE: Ethyl hexyl glycidyl ether C12GE: Glycidyl dodecyl ether C12E: 1,2 Epoxide dodecane PAPE: Polyacetal polyether PEG: Polyethylene glycol TE%: Thickening efficiency EXAMPLE 17 Hydrophobically modified polyurethane A mixture of PEG (40 g, molecular weight = 8,000), toluene (50 mL) and 4,4'-methylene bis (cyclohexy-isocyanate) (0.9 g) and dibutyltin-aurate (10 mg) were heated together at 80 ° C for 16 hours . Methylphenylglycidyl ether (8 g) and NaOH (0.4 g) were added to the mixture and the reaction was maintained at 120 ° C for 2 hours. The polymer was precipitated in hexane. After drying, 40 g of a polymer product was obtained (hydrophobic content = 2%, molecular weight = 15,000).

EXEM PLO 18 Hydrophobically modified branched paper A mixture of PEG (40 g, molecular weight of 4,000), trimethylolpropane ethoxylate (0.4 g), and NaOH (2.4 g) was maintained at 80 ° C for 1 hour. Dibromomethane (1.8 g) and toluene (30 μL) were added and the mixture was kept at 80 ° C for 4 hours. Methylphenylglycidyl ether (4.87 g) was added to the reaction and the temperature was raised to 1.200 ° C. After 4 hours, the reaction was stopped. Toluene (120 mL) was added to dilute the reaction content. The product was isolated by precipitation in hexane (300 mL) and washed with ethyl acetate. After drying, a polymer (46 g) was obtained. A solution of 5% of this material had a Brookfield viscosity of 22,000 cps. The thickening efficiency of this material in SG10M was 0.13. The loss of viscosity when dyeing was -23 KU.

EJ E M PLO 1 9 Modified hydrophobic diisocyanate A mixture of PEG (60 g, molecular weight = 4,000) was heated with isoferone diisocyanate (1.8 g) and 2 drops of dibutyltin aurate to 80 ° C for 6 hours; then NaOH (1 g) was added. After 1 hour, methylphenylglycidyl ether (6 g) was added. The mixture was heated at 120 ° C for 4 hours. A polymer was obtained. The telechelic dihydroxyl product of the above process can be further reacted to increase its molecular weight by the addition of coupling reagents by carrying two or more hydrous hydroxyl groups to make linear or branched polymers having multiple hydrophobic sections. Typically, the di-, tri- or tetra-functional compounds are dihaiuro, diepoxide, di-urethane, tri-halide, triepoxide, tri-isocyanate. The di-functional coupling molecules would give linear products and the polyfunctional coupling molecules would give branched or dendritic products. Each type of product can give advantage for a specific need.

EXEM PLO 20 Linear coupling using a diisocyanate A mixture of PEG (600 g, molecular weight = 8,000) was heated with N aOH (12 g) and dibromomethane (8.5 g) at 80 ° C for 1 hour; Methyl phenyl glycidyl ether (107 g) was then added and heated for 3 hours at 120 ° C. A polymer product (Mn = 22,000, hydrophobic content 8.2%) was obtained after purification by using toluene and hexane. A solution of this polymer (10 g) in toluene (100 mL) was heated with mutylene-bis-phenylisocyanate (1.1 g) at 60 ° C for 24 hours. A polymer was obtained after precipitation in hexane. The polymer has the average molecular weight number (Mn) of 53,000.

EXAMPLE 21 Linear coupling using dibromomethane A mixture of PEG (60 g, molecular weight = 8,000), NaOH (1.2 g) and methylphenylglycidyl ether (8 g) was heated at 120 ° C for 3 hours to give a telechelic oligomer of Mn = 9,000. To this oligomer reaction mixture, dibromomethane (1.6 g) was added at 80 ° C. After 1 hour, a polymer (62 g) of an average molecular weight number of 19,000 was obtained.

EXAMPLE 22 Linear coupling using PAPE A mixture of PEG (27 g, molecular weight = 4, 000), NaOH (0.7 g), and methylphenylglycidyl ether (6 g) was heated at 120 ° C for 2 hours. After the mixture was cooled to 80 ° C, NaOH (1.5 g), dibromomethane (1.1 g), and PEG (23 g, molecular weight = 4000) were added and stirred together for 2 hours. After coagulation in hexane and drying, a polymer of molecular weight = 13,000 (52 g) was collected. The hydrophobic content was 2%. In the above examples, the hydrophobes of this invention were constructed in the form of passages in the polymer column. It is also possible to pre-form the hydrophobes of this invention and link them to the polymer column of interest such as those of isocyanate (HEUR type), cellulosic, acrylate / acrylamide (HASE type), polyvinyl alcohol chemistries as described in the previous section. It is also possible to use a polymerizable monomer containing hydrophobes of this invention to make different products by polymerizing with other monomers. The polymerizable monomers could be double bond in nature (such as vinyl, maleate, acrylate, acrylamide ...) or open ring in nature (such as epoxide, oxazoline, cyclic oxide, cyclic carbonate ...). Also the polymerizable monomers could be monomers that could participate in a condensation polymerization such as a diacid, diester, diol, diamine, dialkylhalides.

EXEM PLO 23 PEG finished in polystyrene Polystyrene terminated PEG was synthesized by radical atom transfer polymerization (ATRP). Macroinitiators for ATRP were synthesized by reactions of PE.Gs (molecular weight of 8,000, 20,000, 35,000) and 2-cioro-2-phenylacetyl chloride. Then styrene was polymerized in the presence of the macroinitiator to produce PEG terminated in polystyrene, as shown in scheme 2. - ' Styrene, Cul / Bypyp'dine Scheme 2. Synthesis of PEG terminated in polystyrene from ATRP ATRP is a recently developed radical polymerization technique. In ATRP, a transition metal compound acts as a transporter of a halogen atom in a reversible redox process. Its living characteristics allow the incorporation of styrene increasing iineally with the time of polymerization. Several PEGs terminated in polystyrene were synthesized from PEG with different molecular weight and with different length of the polystyrene segment, as listed in table 2.

Table 2. Synthesis of PEG terminated in polystyrene 1 Repetition of B. 2 Brookfield viscosity was measured at 22 ° C. 1 H NMR was used to determine the phenyl incorporation at each end of these triple block polymers after recrystallization to remove a small amount of homopolystyrene. The triple block polymer with PEG of 8,000 and 9 phenyls at each end shows limited solubility. The triple block polymer with PEG of molecular weight of 20,000 and 4 phenyls at each end shows low viscosity at 5.0% solids. The paint evaluation of these triple-block polymers was carried out in both UCAR 379 G and semi-glossy SG 10M paints. The results are listed in Table 3 and Table 4.

Table 3. Evaluation of semi-gloss paint UCAR 379 of PEG finished in polystyrene 1 . The weight ratio of this mixture is 4/1.

Table 4. Evaluation of semi-briliant paint AG-10M of PEG finished in polystyrene The application of the product of this invention is not restricted for painting (as demonstrated), but could be in any application where two incompatible phases are encountered (such as oil / water, hydrophobic surface / hydrophilic surface, high surface tension contact / low surface tension). Typical applications may be dispersion stabilization, emulsion stabilization, emulsion polymerization, drainage auxiliary for making paper, paper coating, paper size, slope control in pulp making, degreasing formulation, hair care gel. skin care, oil field fluids, concrete rheology control, green ceramic body additive, thermoplastic blends and surface modification. Although the invention has been illustrated by the above examples, this should not be considered as being limited by them, but rather, the invention encompasses the generic area as described hereinabove. Various modifications and modalities can be made without departing from the spirit and scope of the invention.

Claims (10)

1. REIVI N DICACIONES 1 .- A polymer composition comprising a water soluble or swellable synthetic polymer column having covalently connected ends and / or intermediate blocks of oligomeric hydrophobes that are selected from the group consisting of i) portions of alkyl and aryl containing a polymerizable cyclic monomer or mixture thereof; ii) a poiimerizable alkene or mixture thereof, and iii) derivatives of i) and ii), wherein the blocks are composed of two or more units of the same or different hydrophobes.
2. 2. The polymer composition according to claim 1, wherein the hydrophobic group is alkyl portions containing a polymerizable cyclic monomer with the total number of carbons in the alkyl group being from 1 to 40 carbons.
3. 3. The polymer composition according to claim 1, wherein the hydrophobic group is alkyl portions containing a polymerizable cyclic monomer with the total number of carbons in the alkyl group being from 3 to 24 carbons.
4. 4. The polymer composition according to claim 1, wherein the hydrophobic group is alkyl portions containing a polymerizable cyclic monomer with the total number of carbons in the alkyl group being from 6 to 18 carbons.
5. 5. The polymer composition according to claim 1, wherein the hydrophobic group is aryl portions containing a polymerizable cyclic monomer with the total number of carbons in the aryl group being from 6 to 40 carbons.
6. 6. The polymer composition according to claim 1, wherein the hydrophobic group is aryl portions containing a polymerizable cyclic monomer with the total number of carbons in the aryl group being from 6 to 29 carbons.
7. 7. The polymer composition according to claim 1, wherein the hydrophobic group is aryl portions containing a polymerizable cyclic monomer with the total number of carbons in the ary group being from 7 to 15 carbons.
8. 8. The polymer composition according to claim 1, wherein the upper limit of the weight average molecular weight of the polymer is about 10,000,000.
9. 9. The polymer composition according to claim 1, wherein the upper limit of the weight average molecular weight of the polymer is about 1,000,000.
10. 10. The polymer composition according to claim 1, wherein the upper limit of the weight average molecular weight of the polymer is about 100,000. 1 - The polymer composition according to claim 1, wherein the lower limit of the weight average molecular weight of the polymer is about 400. 12. The polymer composition according to claim 1, wherein the The lower limit of the weight average molecular weight of the polymer is about 1,000. 13. The polymer composition according to claim 1, wherein the lower limit of the weight average molecular weight of the polymer is about 4000. 14. The polymer composition according to claim 1, wherein the blocks Oligomeric hydrophobic intermediates are present and are pending from the column. 15. The polymer composition according to claim 1, wherein the intermediate blocks of oligomeric hydrophobes are present and are internal to the column. 16. The polymer composition according to claim 1, wherein the column is selected from the group consisting of polyacrylamides, polyacrylates, polyvinyl alcohol, polyvinyl sulfonates, polyethylene imine, polyethylene oxide, polysaccharide, polyamidezetidinium, polyvinylpyrrolidone, polyaspartates, polyacetalpolyether, polyalkyl ethers and polyalkyl thioethers. 17. The polymer composition according to claim 1, wherein the column is polyacetalpolyether and the hydrophobe is the oligomer of a polymerizable cyclic monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. 1 8. - The polymer composition according to claim 1, wherein the column is polyethylene glycol and the hydrophobic hydrophobe is the oligomer of a polymerizable cyclic monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl groups or aryl being from 1 to 100. 19. The polymer composition according to claim 1, wherein the column is polyurethane and the hydrophobe is the oligomer of a polymerizable cyclic monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. 20. The polymer composition according to claim 1, wherein the umna is an acrylamide or acrylate and the hydrophobe is the oiigomer of a polymerizable cyclic monomer with a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 1 00. 21 .- The The polymer composition according to claim 1, wherein the polymerizable cyclic monomer is selected from the group consisting of alkyl glycol ethers, aryl glycidyl ethers, alkyl epoxide, aryl alkyl epoxide, alkyl oxazoline, aryl oxazoline. and mixtures thereof. 22. - The polymer composition according to claim 1, wherein the column is polyethylene glycol and the hydrophobe is the oligomer of an alkene monomer polymerizing or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. 23. The polymer composition according to claim 1, wherein the column is polyurethane and the hydrophobe is the oligomer of a polymerizable alkene monomer or a mixture thereof carrying alkyl groups or aryl with the total number of carbons in the alkyl or aryl groups being from 1 to 100. 24.- The polymer composition according to claim 1, wherein the column is an acrylamide or acrylate and the hydrophobe is the oligomer of a polymerizable alkene monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. 25 .- The comp polymer deposition according to claim 1, wherein the polymerizable alkene monomers are present and are selected from the group consisting of styrene and styrenic compounds, vinyl compounds, acrylates and derivatives, acrylamides and derivatives, norbornenes and derivatives, and alkenes and derivatives, alkepil siloxanes and derivatives, alkenyl silanes and derivatives, fluorinated and perfluorinated alkenes. 26. A polymer composition comprising a water-soluble and water-swellable synthetic polymer column having covalently connected ends and / or oyigomeric hydrophobic intermediate blocks having the following formula: where: a) n is an integer of 1-100 b) R is an alkyl or aryl group having 1 to 100 carbons. c) A is a diradical linker of -O-, -S-, -CH2-, -O-CH2-, -S- CH2-, -NH-, -NR'-, -NH-CH2-, -NR- CH2-, -PR'-, -POR'- wherein R 'has from 1 to 12 carbons, polyalkylene ether having a molecular weight = 44 to 50000, and polyalkylene isocyanate having a molecular weight = 100 to 50,000. d) B is a linking group selected from the class consisting of -CH2-, -CH2O-, CH2S-, -CH2-NH-, -CR "HO B-, -CR" HS-, -CR "H -NH-, and -CH2NR "- where R" has 1-12 carbons e) C is a connecting end equal to A or a terminus equal to: -OH, SH, -NHR "', -OR"' , -SR "', and -H. 27. The composition according to claim 26, wherein n has a lower limit of 3. 28. - The composition according to claim 26, wherein n has a lower limit of 7. The composition according to claim 26, wherein n has a lower limit of 10. 30.- The composition in accordance with claim 26, wherein n has an upper limit of 75. The composition according to claim 26, wherein n has an upper limit of 50. The composition according to claim 26, wherein n has an upper limit of 20. The composition according to claim 26, wherein R is an alkyl group that is saturated or unsaturated or cyclic or non-cyclic or linear or branched or halogenated. 34. The composition according to claim 26, wherein the alkyl is halogenated which is selected from the group consisting of fluorinated, chlorinated and brominated. 35.- The composition according to claim 26, wherein the alkyl and aryl groups are substituted and selected from the group consisting of alkylsiloxane, aiolic ether, arylalkyl ether, alkylene ether, alkyl thioether, alkylene thioether , alkyl amine, dialkyl amine, dialkyl amine oxide, triacyl ammonium, diarylamine, dialkyl phosphine, diaryl phosphine, dialkyl phosphine oxide, diaryl phosphine oxide and dialkyl phosphate. 36.- The composition according to claim 26, wherein A = -OCH2-, B = -OCH2-, R = -CH2O-C8H18 and C = -OH. 37. - The composition according to claim 26, wherein A = -N HCH2-, B = -O-CH2-, R = -CH2O-C8H 18 and C = -OC6H 13. 38.- The composition according to claim 26, wherein A = -OCH2 -, B = -OCH2-, C = -CSH13 and R = -OC6H5- 39.- The composition according to claim 26, wherein A = polyalkylene oxide -CH2-, B = -O-CH2-, C = -OH and R = nonylphenoxy. 40.- The composition according to claim 26, wherein A = -CH2-, B = -CH2-, C = H and R = Ph. 41 .- The composition according to claim 26, wherein A = -CH2-, B = -CH2-, C = -H and R = -O-C8H? 7. 42. A process for preparing the water-soluble polymer composition which can be swollen in water according to the claim comprising c) reacting a column polymer soluble in water or swelling in water with water. a catalyst agent for activating the polymer column, d) adding the oligomerizing hydrophobic monomer (s) to the reaction mass, and e) polymerizing the reaction mass at a sufficient temperature and for a sufficient time in order to irrigate the monomer (s). ) hydrophobic oligomerizing to the column as ends and / or intermediate groups. 43.- The process according to claim 42, wherein the hydrophobic groups are covalently connected ends and / or intermediate blocks of oligomeric hydrophobes that are selected from the group consisting of i) alkyl and aryl portions containing a monomer polymerizable cyclic, ii) a polymerizable double bond (or alkene), and iii) derivatives of i) and ii), wherein the blocks are two or more units of the same or different hydrophobes. 44. The process according to claim 43, wherein the hydrophobic group is selected from alkyl portions containing a polymerizable cyclic monomer wherein the alkyl group has 1 to 40 carbons. 45. The process according to claim 43, wherein the hydrophobic group is selected from alkyl portions containing a polymerizable cyclic monomer wherein the alkyl group has 3 to 24 carbons. 46. The process according to claim 43, wherein the hydrophobic group is selected from alkyl portions containing a polymerizable cyclic monomer wherein the alkyl group has 6 to 18 carbons. 47. The process according to claim 43, wherein the hydrophobic group is selected from aryl portions containing a polymerizable cyclic monomer wherein the alkyl group has 6 to 40 carbons. 48. The process according to claim 43, wherein the hydrophobic group is selected from aryl portions containing a polymerizable cyclic monomer wherein the alkyl group has 6 to 29 carbons. 49.- The process according to claim 43, wherein the hydrophobic group is selected from aryl portions containing a polymerizable cyclic monomer wherein the alkyl group has 7 to 15 carbons. 50.- The process according to claim 42, wherein the polymer prepared by the process has a weight average molecular weight with an upper limit of about 10,000,000. 51.- The process according to claim 42, wherein the polymer prepared by the process has a weight average molecular weight with an upper limit of about 1,000,000. The process according to claim 42 , wherein the polymer prepared by the process has a weight average molecular weight with an upper limit of about 100, 000. 53.- The process according to claim 42, wherein the polymer prepared by the process has a molecular weight Weight average with a lower limit of about 400. 54.- The process according to claim 42, wherein the polymer prepared by the process has a weight average molecular weight with a lower limit of about 1000. 55. - The process according to claim 42, wherein the polymer prepared by the process has a weight average molecular weight with a lower limit of about 4000. 56.- The process according to claim 42, wherein the polymer prepared by the process it has intermediate blocks of oligomeric hydrophobes that are pending from the column. 57.- The process according to claim 42, wherein the polymer prepared by the process has intermediate blocks of oligomeric hydrophobes that are internal to the column. 58.- The process according to claim 42, wherein the polymer prepared by the process has a column that is selected from the group consisting of polyacrylamides, polyacrylates, polyvinyl alcohol, polyvinyl sulfonates, polyethylene imine, polyethylene, polyhydroxy, polyamidezetidinium ion, polyvinylpyrrolidone, polyaspartates, polyacetalpolyether, polyalkyl ethers and polyalkyl thioethers. 59. The process according to claim 43, wherein the polymer prepared by the process has a column that is a polyacetalpolyether and the hydrophobe is the oligomer of a polymerizable cyclic monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. 60. - The process according to claim 43, wherein the polymer prepared by the process has a column that is a polyethylene glycol and the hydrophobe is the oligomer of a polymerizable cyclic monomer (or a mixture thereof) carrying alkyl or aryl groups with the Total number of carbons in the alkyl or aryl groups being from 1 to 100. The process according to claim 43, wherein the polymer prepared by the process has a column that is a polyurethane and the hydrophobe is the oligomer of a polymerizable cyclic monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. The process according to claim 43, wherein the polymer prepared by the process has a column which is an acrylamide or acrylate and the hydrophobe is the oligomer of a polymerizable cyclic monomer or a mixture thereof carrying alkyl or aryl groups n the total number of carbons in the alkyl or aryl groups being from 1 to 100. The process according to claim 43, wherein the cyclic polymerizable monomers are selected from the group consisting of alkyl glycidyl ethers, ethers glycidyl aryl, alkyl epoxide, aryl alkyl epoxide, alkyl oxazoline, aryl oxazoline and mixtures thereof. 64.- The process according to claim 43, wherein the polymer prepared by the process has a column that is polyethylene glycol and the hydrophobe is the oligomer of a polymerizable alkene monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. The process according to claim 43, wherein the polymer prepared by the process has a column that is a polyurethane and the hydrophobe is the oligomer of a polymerizable alkene monomer or a mixture thereof carrying alkyl or aryl groups with the total number of carbons in the alkyl or aryl groups being from 1 to 100. The process according to claim 43, wherein the polymer prepared by the process it has a column which is an acrylamide or acrylate and the hydrophobe is the oligomer of a polymerizable alkene monomer or a mixture thereof carrying alkyl or aryl groups or with the total number of carbons in the alkyl or aryl groups being from 1 to 100. The process according to claim 43, wherein the polymerized alkene monomers are selected from the group consisting of styrene and compounds styrenics, vinyl compounds. acrylates and derivatives, acrylamides and derivatives, norbornenes and derivatives, and alkenes and derivatives, alkenyl siloxanes and derivatives, alkenyl silanes and derivatives, fluorinated and perfluorinated alkenes. 68.- An aqueous protective coating composition comprising (a) the composition of claim 1, (b) a colorant and (c) a film-forming latex, wherein the viscosity of the aqueous protective coating composition remains unchanged or it has a negligible loss compared to when conventional rheology modifiers are used when adding the dye. 69.- The aqueous protective coating composition according to claim 68, wherein the composition is a latex paint. 70. The aqueous protective coating composition according to claim 68, wherein the latex is selected from the group consisting of acrylics, vinyl acrylics and styrene. 71.- The aqueous protective coating composition according to claim 70, wherein the latex paint has a pigment volume concentration of about 15 to about 80. 72.- An aqueous protective coating composition comprising a) the polymer composition of claim 1, b) at least one thickener selected from the group consisting of H EU R, HASE, cellulose derivative and polyacetal polyether, c) a dye and d) a film-forming latex. 73.- The aqueous protective coating composition according to claim 72, wherein the cellulose derivative is present and is selected from the group consisting of hydroxyethylcellulose (HEC), hydroxypropyl cellulose (H PC), methylcellulose (MC) , carboxymethylcellulose (CMC), methylhydroxy ethylcellulose (MHEC), ethylhydroxyethylcellulose (EH EC) and hydrophobically modified hydroxyethyl cellulose (H MH EC). RESU M IN OF THE I NVENTION A synthetic polymer has a column of water soluble or swellable polymer and terminal groups and / or intermediate groups of hydrophobic blocks of alkyl or aryl compounds containing a polymerizable cyclic monomer or a double bond group (or alkene) polymerizes or derivatives thereof. The hydrophobic blocks are composed of two or more hydrophobic or different units thereof. These synthetic polymers are used as rheology modifiers, especially in latex paints.