MXPA97008482A - Asociati thickeners - Google Patents

Abstract

The associative thickeners of the present invention are water-soluble polymer compositions having a poly (acetal- or cheno-polyether) structure with ends limited by hydrophobic groups. They are prepared by the copolymerization of an alpha, omega-diol, -dithiol or diaminopolyether with a gem-dihalide compound in the presence of a base to form an alpha, omega-diol, -dithiol or -diaminopoly (acetal- or ketal) -polyter) which in turn reacts with hydro-bovine reagents to form the final product. These associative separators are used in film-forming coating compositions, such as, for example,

Description

"ASSOCIATIVE THICKENERS" This invention relates to water-soluble, hydrophobically modified, non-ionic synthetic polyethers with the ability to lend viscosity to water-based systems. Water soluble polymers (which are also commonly referred to as "thickeners" or "rheology modifiers") are widely used in many industrial waterborne systems as additives to modify their flow behavior. Thickeners increase and maintain viscosity at required levels under specified processing conditions and in end-use situations. Thickeners are useful, for example, in decorative and protective coatings, paper coatings, cosmetics and personal care articles, detergents, pharmaceuticals, adhesives and sealants, agricultural formulations and oil drilling fluids. One of these highly charged aqueous systems where the thickener is used in a decorative and protective coating is latex paint, which is composed of a dispersion of a polymeric latex, pigments, clays, and other additives in water.

Thickeners can be materials that either occur naturally or are manufactured synthetically. Natural thickeners, for example, include casein, alginates, tragacanth gum, guar, xanthan gum, locust bean gum and modified celluloses such as hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose. These natural products vary in their thickening efficiency. One of the drawbacks of thickeners based on the natural product is that they are subject to microbial attack and therefore the addition or formulation of antimicrobial agents is required. Synthetic thickeners include the various acrylic polymers, alkylene oxide polymers, amide polymers and maleic anhydride polymers. These synthetic thickeners can either be homopolymers or copolymers. The hydrolytic stability of some of these polymers depends on the pH of the solution and others are sensitive to the different components normally found in aqueous coatings. Regardless of whether the thickener is natural or synthetic, it is desirable that it be soluble in water to have optimum properties as a thickener in the various water-based systems. The term "water soluble polymer" refers to any polymeric substance that is soluble in water and, being soluble, produces a change in solution viscosity, refractive index or surface tension of water. Typically, a small amount (of about 0.1 to 5 weight percent) of water-soluble polymers is added to the latex paints to achieve the following performance characteristics during manufacture, storage and applications: a) Ease of formulation b) Prevention of sedimentation of suspended particles (latex, pigment, etc.) during storage, c) Good film formation during applications to achieve efficient coverage without resistance to excessive brush or roller drag, d) Good resistance to roller splashes, e) not excessive sagging after application on a vertical surface, and f) Good flow and leveling for the formation of a smooth and continuous film with good appearance. The above-mentioned natural and synthetic thickeners provide different degrees of thickening efficiency and application properties. However, they invariably fail to provide all the key operating properties in enamel paints. These key properties include film formation, flow and leveling and gloss that are generally offered by solvent based alkyd paints. Another incovenience of these thickeners is that they can have efficient compatibility with the various paint ingredients. To eliminate some of the storage deficiencies of conventional thickeners, a new class of thickeners has been designed and marketed which is commonly referred to as "associative thickeners" (see EJ Schaller and PR Sperry in "Manual Coating Additives"). , Editor LL Calbo, Volume 2, Page 105, 1992; Marcel De Ker, Inc. New York). These thickeners are water-soluble polymers hydrophobically modified. They experience intermolecular association in an aqueous solution in this way exhibit improved solution viscosity. They can also absorb the dispersed phase particles 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. Associative thickeners based on polysaccharide are manufactured by clinically inserting a small amount of a hydrophobic group (alkyl of 10 to 24 carbon atoms) into a modified polysaccharide. They are disclosed in US Patents Number 4, 228, 211, Number 4,243,802 and Patent Number EP 281,360. Among the commercial non-ionic synthetic associative thickeners, the hydrophobically modified ethoxylated urethane block copolymers (HEUR) constitute an important class. They are disclosed in U.S. Patent Nos. 4,079,028, Number 4,155,892 and Number 5,281,654. These are low molecular weight polyurethanes manufactured by condensing relatively low molecular weight polyethylene glycol (molecular weight ~ 10,000) with hydrophobic diisocyanates and blocking the end of the resulting copolymer 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 hydrophilic polyethylene oxide blocks through urethane bonds. The preparation of HEURs is also disclosed in US Patents Nos. 4,499,233 and Number 5,023,309. These HEURs are claimed as providing superior viscosity properties and improved flow and leveling in aqueous systems. Processes for the production of HEUR with hydrophobes suspended in groups are described in U.S. Patent Nos. 4,426,485 and 4,496,708. These HEUR are believed to provide enhanced thickening to aqueous systems through the micelle-like association. HEURs with terminal hydrophobic and branched structures are disclosed in U.S. Patent Number 4,327,008. They are manufactured by reacting polyalkylene oxides with a polyfunctional material, a diisocyanate and water and terminal blockage of the resulting product with a hydrophobic monofunctional active hydrogen-containing compound or a monoisocyanate. HEUR containing silicon having specific utility in paints and coatings are disclosed in European Patent Application Number 0 498 442 A1. They are the reaction products of an isocyanate functional material, a polyether polyol, a hydrophobic compound containing monofunctional active hydrogen, a functional material with silane and water. From the point of view of apolications and economic, the predominant inconveniences of HEUR thickeners are their high cost, difficulty of handling and tendency to destabilize the paint (separation of dispersed particles from the aqueous phase) (GD Shay and AF Rich, J. Coatings Technology, Volume 58, Number 7, Page 43, 1986).

Random copolymers of ethylene oxide and long chain alkyl epoxides are disclosed in U.S. Patent Number 4,304,902. These copolymers provide improved aqueous viscosity but do not provide good flow and leveling in the latex paint. U.S. Patent No. 4,411,819 describes the preparation of polyethers having a branched chain structure and characterized by having terminal hydrophobes. They are manufactured by reacting a low molecular weight polyol with a mixture of ethylene oxide and at least one inner alkylene oxide having from 3 to 4 carbon atoms. The polyethers are then blocked in the terminal with a mixture of alpha-olefin epoxide of 12 to 18 carbon atoms. The low molecular weight hydrophobically blocked terminal polyether (~ 9,000) is reported in PCT International Application WO 92 08753. These are manufactured by coupling a low molecular weight surfactant (~ 4,500) with m-dichloromethylbenzene. The preparation of hydrophobically blocked low molecular weight terminal polyethers (~ 9,000) is also disclosed in U.S. Patent No. 5,045,230. These are manufactured 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 PESO ~ 9,000). Since these hydrophobically terminal block polyesters are of low molecular weight, they do not lend efficient viscosity to aqueous systems including latex paints. Latex compositions containing low molecular weight (3,000-20,000) water soluble polyethers bearing terminal hydrophobes have been disclosed in US Patent Number 3,770,684. They were claimed as providing improved leveling in latex paints. However, these polyethers are not efficient to increase the viscosity of the water and did not provide the required biological properties in several highly charged aqueous systems. Therefore, they are not versatile or economical. Commercial non-ionic synthetic associative thickeners often exhibit poor and variable compatibility in paints, as exemplified by syneresis, poor color acceptance, variable paint viscosity over time, and inadequate coverage power. There is a need in the paint industry for a non-ionic synthetic associative thickener to correct these deficiencies at an effective dosage level in cost. No single thickener is known to provide 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 rheology of reference coating. Although this approach works in a limited manner, the mixing of the thickeners is often annoying and depending on the mutual interactions between the individual thickener, the stability and operation of the frequent coatings are at risk. The present invention relates to a water-soluble copolymer composition comprising a basic structure of polyether linked with acetal- or ketal having terminals that are blocked with hydrophobic groups. The present invention is also directed to a process for preparing a terminally hydrophobically blocked poly (acetal or ketal polyether) comprising a) reacting a polyether alpha, omega-dihydroxy with a gem-dihalide compound in the presence of a base to form a basic structure of poly [polyether of acetal- or ketal] of alpha, omega-dihydroxy, and b) to react the basic structure with a hydrophobic reagent to form the poly (hydrate-blocked acetal- or ketal polyether) hydrophobically in the terminal. The present invention furthermore relates to a film-forming coating composition comprising an aqueous solution of the hydrophobically blocked poly [polyether of acetal- or ketal] composition in the terminal mentioned above. The polymers of the present invention have been found to efficiently thicken the various water-based systems, including latex paints and provide an improved combination of paint properties (stability, flow and leveling, film formation, splash resistance and sagging resistance). The term "flow and leveling" as used in this invention refers to the degree to which a coating flows after the application in order to prevent any surface irregularities such as, for example, brush marks, a "rough" appearance. , crests or craters, which are produced by the mechanical process of applying a coating. "Film formation" means the formation of a continuous film to uniformly go over the surface of the substrate that is being coated.

"Splash resistance" means the ability of the coating formulation to coat the formation of tiny droplets flying during the application of the coating. "Stability" means the ability to maintain viscosity during aging and to prevent phase separation. "Combate" as used herein, refers to the downward movement of a coating on a vertical surface between the application time and the soling, resulting in 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 characteristic appearance of a hanging curtain. The warping is aesthetically undesirable. In addition, coatings that resist the tendency to sag will not easily peel off in a paint brush or paint roller and will not readily degrade on a horizontal surface such as a ceiling. According to the invention, the basic structure of the water soluble polymer can be a high molecular weight deformed polyether, such as polyalkylene glycol (also known as polyalkylene oxide) bearing terminal -OH groups. High molecular weight polyethylene glycols (molecular weight 17,000 to 35,000) can be obtained from Fluka Chemical Corporation, of Ronkonkoma, New York. Alternatively, a desired high molecular weight polyether precursor can be manufactured in situ by condensing the low molecular weight polyethers with a coupling agent such as a gem-dihalogen reagent or a mixture of gem-dihalogen reagents as shown below. Several classes of low molecular weight polyethylene glycols (MW ~ 4,000-8,000) are available from Union Carbide sold under the Carbowax brand.

Base (y + l) HO-PE-OH + and X-A-X > HO-PE-O- [-A-0-PE-] and -OH H20 wherein PE is a polyether; A is a residue that separates the halogen atoms (X). The terminal groups of PE can also be -SH and -NH2 groups. Note that if X-A-X is a geminal dihalogen reagent, then the polyether blocks are connected through acetal or ketal bonds that are stable in alkaline environments.

As soon as the type of hydrogen or terminal, R, is related, the polyether could carry either the same or different hydrophobes at its ends. The hydrophobically modified polyether can be manufactured by reacting the terminal groups of -OH, -SH or - H2 of the polyether with a suitable hydrophobic reagent in the presence of a base in an organic solvent. Base Y + 2 Z-R > R-0 O-R + Y - Z Solvent wherein, it is the basic structure of the water soluble polyether, Z is a functional group capable of reacting with the Y end groups (Y = -OH, -SH and -NH2) of the polyether, and R is a hydrophobic group. To carry out the process, any solvent or mixtures of solvent free of active hydrogens and stable to the bases could be used. However, tetrahydrofuran solvents, alkyl ethers of alkylene glycols or hydrocarbons are preferred. In spite of the foregoing, the process can also be carried out in the absence of a solvent. The polymer composition of the present invention has the following formula R2-R3 R2 III R1- (OCH2CH) and OCO- (CH2-CH-0) and -R5 I-R4 x wherein: R1 and R5 are independently selected from the group it consists of a hydrophobic group or H. The hydrophobic groups may be either the same or different in the same molecule, and are selected from hydrocarbyl, alkyl, aryl, alkylalkyl, cycloaliphatic, perfluoroalkyl, carbosilyl, polycyclic and complex dendritic hydrophobes groups. The preferred hydrophobic group is alkyl having a carbon atom scale of 8 to 22, preferably being 12 to 18 carbon atoms. These hydrophobic groups can either be saturated or unsaturated, branched or linear; the upper limit of the number of carbon atoms in the hydrophobic groups is 40 carbon atoms, preferably 27 carbon atoms and more preferably 22 carbon atoms; the lower limit of the number of carbon atoms in the hydrophobic groups is one carbon atom, preferably 4 carbon atoms, more preferably 8 carbon atoms. Specific examples of the hydrophobic groups are ethyl, dodecyl, hexadecyl and octadecyl groups. When the hydrophobic groups are independently selected from alkyl, perfluoroalkyl or carbosilyl, the scale of carbon atoms is from one to 40 carbon atoms. When the hydrophobic groups are aryl, arylalkyl, cycloaliphatic and polycyclic groups, on the scale of carbon atoms it is from 3 to 40 with the preferred scale being from 6 to 29 carbon atoms, and in the especially preferred scale being from 14 to 25 carbon atoms. R2 is selected from the group consisting of H, alkyl groups having from 1 to 3 carbon atoms or a combination thereof; R3 and R4 are independently selected from the group consisting of the groups of H, alkyl of 1 to 6 carbon atoms and phenyl; and is an integer having values from about 1 to about 500; and x is an integer having values from about 1 to about 50. The composition of the present invention has a basic structure of poly (acetal- or ketal polyether) which is either aligned or branched, with the linear being preferred. Polyethers that may be used in this invention include any water-soluble polyalkylene oxide or polyalkylene oxide copolymers; the preferred polyether basic structure is polyethylene oxide and the water-soluble copolymers of ethylene oxide and another comonomer such as propylene oxide and butylene oxide. The weight average molecular weight of the copolymer has an upper limit of 2,000,000, preferably, 500,000 and more preferably 100,000. The lower limit of the molecular weight of the polymer is 500, preferably 15,000, and especially preferably 20,000. In accordance with the present invention, a wide variety of hydrophobic terminal block acetal- or ketal- polyethers could be manufactured, by appropriately selecting the various reaction conditions and manipulating the stoichiometry and molecular weight of the reactants. Generally, any gem-dihalide can be used in the process to prepare the poly (acetal- or ketal- polyether) of the present invention. However, dihalogenomethanes such as dibromomethane and dichloromethane are preferred. Examples of other dihalides include: 1,1-dichlorotoluene (C6H5CHC1), 1,1-dichloroethane (CH3CHC12) and 1,1-dibromomethane (CH3CHBr2). When a solvent is used, any solvent free of active hydrogens in the process of this invention can be used. oxygenated hydrocarbon solvents carrying from 2 to 30 carbon atoms being preferred. Examples of solvents that can be used in the present invention are: toluene, xylene, aliphatic hydrocarbons, dialkyl ethers and alkylene glycols and diethoxymethane. Any concentrated base capable of reacting with the terminal active hydrogens of the acetal- or ketal- poly- polyether) to form the poly (acetal- or ketal-) dianon polyether could be used in the process. Examples of bases that can be used in this invention are alkali metal hydrides, alkali metal hydroxides, alkali metal carbonates and organic bases. The preferred process for making hydrophobically terminal block poly (acetal) polyethers comprises mixing the inhibited polyether with caustic soda at elevated temperatures, followed by copolymerization of the polyether with gem-dihalide and subsequently subjecting the poly (acetal polyether) to terminal blockage. with a hydrophobic reagent. In accordance with this invention, the poly (polyether acetal- or ketal-) compositions are terminally hydrophobically blocked and can be used in film-forming coating compositions such as latex paints, the pigment volume (PVC) concentration of the Latex paint may have a lower limit of 5, preferably 10 and an upper limit of 85, preferably 80. More particularly, when the latex paint is high gloss paint, the PVC is from about 15 to about 30; When the paint is a semi-gloss paint, the PVC is from about 20 to about 35; and when it is an opaque paint, the PVC is from about 40 to about 80. Likewise, for latex paints, the ICI viscosity should be greater than about 1.5 Pa. at 25 ° C for good performance. The following examples illustrate the preparation of the acetal poly) polyethers of the terminal block hydrophobe of the present invention. However, they should not be interpreted as being the only ones that limit the invention, since other variations of the process are possible.

EXAMPLE 1 Preparation of PEG-8000 / Methylene Copolymer In a three neck round bottom flask (1000 milliliters) equipped with a Dean-Stark separator (at the top of which was fixed a condenser whose upper part was connected to a nitrogen source, a magnetic stirrer and a thermometer were added polyethylene glycol (MW ~ 8000) (PEG- 8000) (45 grams) and toluene (100 milliliters) The moisture of the PEG-8000 was azeotropically removed by distilling the toluene.The residual toluene, which could be distilled in the reaction flask at atmospheric pressure, was removed by passing a stream of nitrogen to through the viscous PEG-8000 solution and holding one of the necks of the reaction flask open, then the flask containing dry PEG-8000 was cooled to room temperature and the Dean-Stark separator was removed. At room temperature, dry tetrahydrofuran (HPLC grade) (THF) (650 milliliters) and a dispersion of sodium hydride (60 percent in mineral oil) (0.85 gram) were added. e was heated to reflux for 0.5 hour. After this, a solution of dibromomethane (0.98 gram) in THF (50 milliliters) was added dropwise to the reaction mixture of PEG-8000 / NaH over a period of 2 hours under a nitrogen atmosphere through a addition funnel. The resulting reaction mixture was heated to reflux for 24 hours. After evaporation of the solvent, a fluffy white solid was isolated. The weight average molecular weight of the PEG-8000 / methylene copolymer was 53000 and the polydispersity index was 1.94. It was soluble in water to form a crystalline solution.

EXAMPLE 2 Preparation of the PEG-8000 Copolymer / Methylene Terminal Blocking of 18 Carbon Atoms in Tetrahydrofuran (THF) The PEG-8000 / methylene copolymer (described in Example 1) (13 grams) was dried by dissolving in boiling toluene (60 millimeters) and azeotropically distilling the toluene from the polymer solution. The "dry" PEG-8000 / methylene copolymer was heated to reflux in a dispersion of sodium hydride (60 percent in mineral oil) (0.25 gram) and 1-bromooctadecane (0.5 gram) in THF (150 milliliters), during 22 hours under a nitrogen atmosphere. After evaporation of the solvent from the reaction mixture, a beige solid was isolated. The PEG-8000 / terminal block methylene copolymer of 18 carbon atoms obtained in this way was soluble in water (2 percent solution, viscosity BF at 30 revolutions per minute ~ 1080 centipoise). The hydrophobic content of 18 carbon atoms of the product was 1.42 percent.

EXAMPLE 3 Preparation of PEG-8000 / Terminal Block Methylene Copolymer of 18 Carbon Atoms Using Dichloromethane To a three-necked round bottom flask (500 milliliters) equipped with a Dean-Stark separator (at the top of which was fixed a condenser whose upper part was connected to a nitrogen source), a magnetic stirrer and thermometer were added. PEG-8000 (18 grams) and toluene (70 milliliters). The moisture of PEG-8000 was removed azeotropically by distilling toluene. The residual toluene that could not be distilled from the reaction flask at atmospheric pressure was removed by passing a stream of nitrogen through the viscous solution of the PEG-8000 and keeping one of the necks of the reaction flask open. Then the flask containing the dried PEG-8000 was cooled to room temperature and the Dean-Stark separator was removed. To the dried PEG-8000 at room temperature dry tetrahydrofuran (HPLC grade) (THF) (170 milliliters) and a diprionsion of sodium hydride (60 percent in mineral oil) (0.4 gram) were added. The resulting reaction mixture was heated to reflux for 1.5 hours. After this, dichloromethane (0.15 gram) was added to the PEG-8000 / NaH reaction mixture and the resulting reaction mixture was refluxed for 18 hours to form the PEG-8000 / methylene copolymer. Then, sodium hydride (60 percent dispersion in mineral oil) (0.3 gram) and 1-bromooctadecane were added to the reaction mixture containing the PEG-8000 / methylene copolymer. After heating the resulting mixture to reflux for 8 hours, it was cooled to room temperature and transferred to a plastic tray. After evaporation of the solvent inside the canopy, a slightly brown solid was isolated. The weight average molecular weight of the PEG-8000 / terminal blockade methylene copolymer of 18 carbon atoms was 31,947 with a polydispersity index of 1.91. It was soluble in water to form a crystalline solution (2 percent solution of BF viscosity at 30 revolutions per minute ~ 1780 centipoises). The octadecyl (C18H37) content of the polymer was 2.02 weight percent.

EXAMPLE 4 Preparation of PEG-8000 Copolymer / Methylene Terminal Block Mixed of 12 Carbon Atoms / 16 Carbon Atoms In a stainless steel pressure reactor (Chemco type) were added PEG-8000 (750 grams), THF (750 milliliters) and sodium hydride (dispersion at 60 percent in mineral oil) (22 grams). After sealing the reactor, the resulting mixture was heated at 80 ° C for one hour and then cooled to 40 ° C. After this, dibromomethane (13 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 a mixture of 1-bromododecane (8 grams) and 1-bromohexadecane (15 grams). The resulting reaction mixture was heated to 120 ° C for 2 hours, cooled to room temperature and the reactor charge transferred to a plastic tray. After evaporation of the solvent, an ante-colored solid was isolated. The PEG-8000 / mixed terminal block copolymer of 12 carbon atoms / 16 carbon atoms formed in this manner was soluble in water (solution at 2 percent viscosity BF at 30 revolutions per minute ~ 60 centipoise).

EXAMPLE 5 Preparation of PEG-8000 Copolymer / Methylene Terminal Blocking of 16 Carbon Atoms The procedure described in Example 4 using the following reagents: 1. PEG-8000 - 750 grams 2. Tetrahydrofuran - 750 milliliters 3. Sodium hydride (60 percent dispersion in mineral oil) - 22 grams and 4. Dibromomethane - 11 grams, and 5. 1-Bromohexadecane (Fluka, 97 percent pure) - 42 grams. The PEG-8000 / methylene terminal block copolymer of 16 carbon atoms was soluble in water (solution at 2 percent BF viscosity at 30 revolutions per minute ~ 590 centipoise.) The cetyl content (C16H33) of the copolymer was 1.52 percent by weight.

EXAMPLE 6 Preparation of PEG-8000 Copolymer / Methylene Blocking Terminal 16 Carbon Atoms in Dimethyl Ether of Dipropylene Glycol Example 5 was repeated using dimethyl ether of Dipropylene glycol Proglyde® DMM (Dow Chemical) as the reaction solvent. The PEG-8000 / methylene terminal block copolymer of 16 carbon atoms was soluble in water (solution at 2 percent viscosity BF at 30 revolutions per minute ~ 120 centipoises).

EXAMPLE 7 Preparation of PEG-8000 Copolymer / Methylene Terminal Block of 16 Carbon Atoms in Diethymethane Example 5 was repeated using diethoxymethane (Eastman Chemical) as the reaction solvent. The PEG-8000 / methylene terminal block copolymer of 16 carbon atoms was soluble was water (solution at 2 percent viscosity BF at 30 revolutions per minute ~ 720 centipoises).

EXAMPLE 8 Preparation of Terpolymer of PEG-8000 / Jeffamine® ED-6000 / Terminal Block Methylene of 16 Carbon Atoms in THF A terpolymer of PEG-8000 / Jeffamine® ED 6000 / methylene was made by copolymerizing the PEG-8000 (600 grams ), Jeffamine® ED-6000 (a polyoxyalkylene amine obtainable from Hunstman Corporation) (150 grams) and dibromomethane (12 grams) in the presence of sodium hydride (60 percent dispersion, 22 grams) in tetrahydrofuran (750 milliliters) , in accordance with the procedure described in Example 4. This terpolymer was then reacted in situ with 1-bromohexadecane (42 grams) at 120 ° C for 2 hours. After evaporation of the solvent, a fluffy solid was isolated. The PEG-8000 / Jeffamine® ED-6000 / terminal block methylene copolymer of 16 carbon atoms was soluble in water (solution at 2 percent viscosity BF at 30 revolutions per minute ~ 300 centipoises). The cetyl content (C16H33) of the copolymer was 0.95 weight percent.

EXAMPLE 9 Preparation of Polyalkylene Glycol Copolymer EMKAROX HV 105 / Methylene Terminal Blocking of 18 Carbon Atoms Example 2 was repeated using the following reagents. to. EMKAROX HV 19 polyalkylene glycol (nominal molecular weight ~ 20,000, obtainable from ICI Americas) - 18 grams b. Toluene - 100 milliliters c. THF - 170 milliliters d. Sodium hydride (dispersion at 60 percent) - 0. 5 gram e. Dibromomethane - 0.2 gram f. 1-Bromooctadecane - 1.0 gram In the 10 percent BF viscosity solution of the EMKAROX HV 105 polyalkylene glycol copolymer of terminal blockage of 18 carbon atoms was 140 centipoise. Painting Properties of the Hydrothobic Terminal Blocking Polyethers. The following Examples illustrate the thickeners of the present invention being incorporated into an acrylic vinyl latex (UCAR 367 or POLYCO 2161) based on opaque paint (pigment volume concentration = 60 percent) and a fully acrylic semi-gloss paint (Rhoplex AC- 417 or 417M) (pigment volume concentration = 24 percent) to achieve an initial Stormer viscosity of 90-95 Kreb Units. The ingredients used in acrylic vinyl flat paint and fully acrylic semi-gloss paint are shown in Tables 1 and 2, respectively. The significance and scale of the different paint properties are as follows: a) The Stormer viscosity (initial storage and after fifteen days) was measured by a Stormer viscometer at a shear rate of 200 sec. expressed in Kreb Units (KU) b) ICI viscosity was measured by an ICI cone and plate viscometer at 12,000 sec-1 and expressed in poises c) Thickening efficiency (TE) measured as the weight percentage of the dry thickener and necessary in the paint to achieve the 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, bar of intermediate scale, wet film thickness (WFT) (in microns) above which warpage occurs f) Splash resistance by rolling through a black panel compared to a scale of 0-10; 0 = worse and 10 = better) g) 60 ° of brightness is the specular brightness seen at 60 ° Table 1 Base Opaque White and Light Dye Materials Kilograms Liters Water 90,800 90.84 Dispersant (potassium tripolyphosphate), 908 0.38 Ross & Rowe 551 908 0.87 Dispersant (Tamol 731) 2.270 2.12 Defoaming (defoaming of Hercules SGL) .908 1.02 Ethylene glycol 9.080 1.25 Carbitol acetate 4.540 4.50 Titanium Dioxide (Ti-Pure® R-901) 79,450 19.38 Calcium carbonate (Camel CARB) 68.100 25, .13 Iceberg Clay 56.750 21, .73 Silice 1160 11.350 4, .28 Grind a Hegman of 4 and dilute at slower speed as follows Materials Kilograms Liters Nonylphenol Epoxy (Makon 10) 1.362 1.29 Acrylic vinyl latex (Polyco 2161) 90,800 83.27 Biocide (Proxel GXL) 0.454 0.42 Water and / or thickener solution 113.730 113.81 Total 531,410 377.29 Constants of the Formula Weight / 3.785 liters, kilograms 5.33 Concentration of pigment volume,% 62.7 Volume of non-volatiles,% 31.3 Weight of non-volatile,% 49.9 Viscosity Stormer, KU (initial) 95 + 2 Table 2 Semi-gloss White Interior Materials Kilograms Liters Propylene glycol 36.320 35.20 Dispersant (Tamol® SG-1) 3.859 3.37 Defoamer (Hercules SGL defoamer) 0.908 0.98 Titanium dioxide (Ti-Pure® R-900) 108.960 26.21 Silice (Imsil A-15) 11,350 4.28 Crush a Hegman of 7+ and dilute at slower speed as follows: Materials Kilograms Liters Acrylic latex emulsion (Rhoplex AC-417M) (48 percent solids) 227,000 211.96 Antifoaming agent (Hercules SGL defoamer) 1.226 1.40 Propylene glycol 4.540 4.39 Biocide (Prolex GXL) 4.540 0.42 Coalescing (Texanol®) 9.806 10.33 Anionic Surfactant (Premix of Triton GR-7M) 0.227 0.23 Water 9.443 9.46 Water and / or thickener solution 69.780 69.87 Total 483,873 378.50 Constants of the Formula Weight / 3,785 liters, kilograms 4.840 Concentration of pigment volume,% 24.8 Volume of non-volatiles,% 32.9 Weight of non-volatiles,% 48.0 Viscosity Stormer, KU (initial) 90 + 2 Brightness 60 ° 40 +5 EXAMPLES 10-27 Preparation of Different Copolymers of PEG-8000 / Methylene Hydrophobic Terminal Blocking Following the procedures described in Examples 1 and 2, a series of PEG-8000 / methylene terminal block hydrophobe copolymers with different molecular weights (17,000-150,000) and carrying different amounts of different hydrophobes (Ci6-C22) were manufactured varying the amount of appropriate reagents and reaction conditions. The viscosity of the solution of a hydrophobic terminal blocking polyether depended on its molecular weight, hydrophobic type in the hydrophobic content. The properties of the paint of the different thickeners with different compositions are given in Tables 3 and 4. All the molecular weights (indicated in Tables 3 and 4) refer to the weight average molecular weight of the sample.

Methods for Determining the Average Molecular Weight in Weight of the Poly (Acetal Polyethers) The weight average molecular weights of the poly (acetal polyethers) were measured by size exclusion chromatography (SEC). SEC measurements were carried out on a 0.20M lithium acetate stabilizer (pH 4.8) plus 0.5 percent beta-cyclodextrin plus 0.1 percent N-methyl pyrrolidone (NMP) mobile phase with both columns and the refractive index detector graduated with thermostat at 40 ° C. The polymers were chromatographed through a set of Shodex PROTEIN® columns (2 KW-802.5 + 1 KW-803 + 1 KW-804) in series at a flow rate of 1.0 milliliter per minute. A sample concentration of 0.20 percent was used with an injection volume of 200 liters. The molecular weight distribution data are based on the polyethylene oxide / polyethylene glycol standards and are not absolute.

TABLE 3 PROPERTIES OF THE COMPLETELY ACRYLIC SEMIBRILLING PAINT (RHOPLEX AC-417M) OF THE METILEN / PEG-8000 COPOLYMERS OF TERMINAL BLOCKING Hydrophobic examples M? X Viscosity TE KU 10-4 (2%) (cps) (%) c18 62 3560 0.29 93/105 11 53 3800 0.33 90/104 12 '18 53 2120 0.36 90/101 13 74 600 0.55 89/105 14 '18 109 1720 0.29 88/102 67 1720 0.39 88/106 16 C18 71 4100 0.24 90/103 17 '18 74 4100 0.29 92/109 18 C18 59 3000 0.31 90/107 19 '18 57 2000 0.36 91/101 twenty - . 20 -18 56 1000 0.73 93/116 21 '18 410 0.47 88/101 22 '18 72 420 0.43 90/102 23 '16 53 280 0.58 90/102 24 '16 67 220 0.65 90/113 '16 48 180 0.73 90/106 26 '16 61 120 0.73 91/113 27 C16 35 30 1.16 90/101 twenty TABLE 3 (CONTINUED) Examples ICI Leveling Combo Splatter Glitter 60c 10 0.9 10 6 9 51.6 11 1.0 10 6 8 51.7 12 1.1 9 8 7 55.6 13 1.5 10 6 9 53.1 14 1.1 10 6 9 50.9 15 1.1 10 6 7 54.9 16 0.9 9 8 7 55.8 17 1.0 10 8 8 58.2 18 1.0 10 8 8 58.2 19 1.1 9 8 7 55.6 1.9 10 54.8 1. 9 54.2 1. 8 10 51.6 1. 8 10 51.6 2. 2 10 51.3 2. 4 10 51.3 2. 5 10 51.0 2. 7 10 55.4 TABLE 4 Properties of Opaque Vinyl-Acrylic Paint (UCAR 367) of the Methylene Copolymers / PEG-8000 of Bloquo Terminal Hydrophobic examples M? X Viscosity TE KU 10 ~ 4 (2%) (cps) (%) C18 62 3560 0.45 97/104 11 C18 53 3800 0.51 96/104 12 C18 53 2120 0.54 94/101 13 C18 74 600 0.98 95/110 14 C18 109 1720 0.81 97/108 C18 67 1720 0.63 93/106 16 C18 71 4100 0.48 96/109 17 C18 74 4100 0.47 96/112 18 C18 59 3000 0.50 93/106 19 -18 57 2000 0.55 94/102 '18 56 1000 0.89 97/113 21 '18 78 410 0.82 94/102 22 '18 72 420 0.62 93/107 23 '16 53 280 0.64 93/102 24 '16 67 220 0.75 94/109 '16 48 180 0.82 96/110 26 '16 61 120 0.86 97/115 twenty TABLE 4 (CONTINUED) Examples ICI Leveling Combo Splatter 10 1.5 8 12 9 11 1.8 10 9 9 12 1.5 7 11 7 13 2.3 8 12 9 14 1.9 8 12 9 15 1.6 7 10 8 16 1.5 8 8 8 17 1.5 7 8 8 18 1.3 7 8 8 19 1.4 8 11 7 20 2.2 12 21 1.7 12 22 2.8 10 23 2.9 24 3.0 8 10 25 3.3 7 12 26 3.5 8 11 As can be seen, the properties of the paint are controlled by the molecular weight, the type of hydrophobe and the viscosity of the solution. The data of the painting clearly show that by properly adjusting these molecular parameters, a balance of the properties of the paint can be achieved.

EXAMPLE 28 Preparation of PEG-8000 Copolymer / Methylene Terminal Blocking of 16 Carbon atoms in a Solvent-Free Process Using Sodium Hydroxide as the Base To an Abbe tape mixer were added PEG-8000 (1250 grams) and sodium hydroxide (37 grams). After sealing the reactor, the mixture was heated at 80 ° C for one hour. Then dibromomethane (18.5 grams) was added to the PEG-8000 / NaOH mixture and the resulting reaction mixture was heated at 80 ° C for 4 hours to form the PEG-8000 / methylene copolymer. The copolymer of PEG-8000 / methylene at 80 ° C was added 1-bromohexadecane (65 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. During cooling to room temperature, the reaction mixture solidified. The crude reaction mixture was soluble in water (solution at 2 percent BF viscosity at 30 revolutions per minute ~ 410 centipoise).

EXAMPLE 29 Preparation of PEG-8000 / Methylene Block Copolymer Terminal of 16 carbon atoms in an Exempt Process of Solvent Using Sodium Hydroxide as the Base with a Shorter Reaction Time.

To an Abbe tape mixer was added PEG-8000 (1250 grams) and sodium hydroxide (37 grams). After sealing the reactor, the mixture was heated at 80 ° C for 1 hour. Then dibromomethane (18.5 grams) was added to the PEG-8000 / NaOH mixture and the resulting reaction mixture was heated at 100 ° C for 2 hours to form the PEG-8000 / methylene copolymer. To the PEG-8000 / methylene copolymer was added 1-bromohexadecane (65 grams) and the resulting reaction mixture was heated at 120 ° C for 2 hours. After this, the reactor was opened and the melted reaction mixture was emptied in a plastic tray. Upon cooling to room temperature, the reaction mixture solidified. The Raw Reaction Mixture was Water Soluble (solution at 2 percent BF viscosity at 30 revolutions per minute ~ 410).

EXAMPLE 30 Preparation of PEG-8000 / Methylene Block Copolymer Terminal of 16 Carbon Atoms in an Solvent-Free Process Using Sodium Hydroxide as the Base Example 28 was repeated using less sodium hydroxide. The reagents used were: a. PEG-8000 - 1250 grams b. Sodium hydroxide - 25 grams c. Dibromomethane - 18.5 grams d. 1-Bromohexadecane - 65 grams The crude reaction mixture was soluble in water (solution at 2 percent BF viscosity at 30 revolutions per minute ~ 60 centipoises).

EXAMPLE 31 Preparation of PEG-8000 Copolymer / Methylene Terminal Blocking of 16 Carbon Atoms in an Solvent-Free Process Using Sodium Hydride as the Base Example 28 was repeated using the following reagents. to. PEG-8000 - 1250 grams b. Sodium hydride (60 percent dispersion in mineral oil) - 36.5 grams c. Dibromomethane - 18.5 grams d. 1-Bromohexadecane - 70 grams The water-soluble raw reaction mixture (2 percent solution of BF viscosity at 30 revolutions per minute ~ 620 centipoise).

EXAMPLE 32 Preparation of PEG-8000 Copolymer / Methylene Terminal Blocking of 12 Carbon Atoms in an Solvent-Free Process Using Sodium Hydroxide as the Base Example 28 was repeated using the following reagents. to. PEG-8000 - 1250 grams b. Sodium hydroxide 37 grams c. Dibromomethane - 17 grams d. 1-Bromododecane - 83 grams The water-soluble raw reaction mixture (solution at 20 percent BF viscosity at 30 revolutions or minute ~ 4400 centipoise). The dodecyl (C? 2H25) content of the copolymer was 1.75 weight percent.

EXAMPLE 33 Preparation of Copolymer PEG-8000 / Methylene Blocking Terminal of 12 carbon atoms / 16 carbon atoms in a Solvent-free Precess Using Sodium Hydroxide as the Base Example 28 was repeated using a mixture of 1-bromododecane and 1-bromohexadecane as the terminal blocking agents. The reagents used were: a. PEG-8000 - 1250 grams b. Sodium hydroxide - 37 grams c. Dibromomethane - 18.5 grams d. 1-Bromododecane - 20 grams e. 1-Bromohexadecane - 60 grams The water-soluble raw reaction mixture (solution at 2 percent BF viscosity at 30 revolutions per minute ~ 165 cetipoises).

EXAMPLE 34 Preparation of the Nonylphenyl / PEG / Terminal Block Methylene Copolymer of 16 C atoms in a Solvent-Free Process Using Sodium Hydroxide as the Base Example 28 was repeated using a mixture of PEG-8000 and ethoxylated nonylphenol, CgH? G -C6H4-0 (CH2CH20) 40-H (IGEPAL CO-890, obtainable from GAF Corporation) as polyethylene glycol substrates. The other reagents used are shown below. to. PEG-8000 - 1250 grams b. IGEPAL CO-890 - 25 grams c. Sodium hydroxide - 37 grams d. Dibromomethane - 18.5 grams e. 1-Bromohexadecane - 60 grams The water-soluble raw reaction mixture (solution at 12 percent BF viscosity at 30 revolutions per minute - 195 centipoise) Effect of the Degree of Hydrophobic Terminal Blocking on the properties of the Poly (Polyether Acetal) It was surprising to find that the degree of hydrophobic terminal block, that is, the fraction of chain terminals blocked with a hydrophobe, of poly (polyether of acetal) of a given molecular weight dramatically affected its key paint properties (Thickening efficiency, ICI viscosity, leveling and splash resistance). This is exemplified by comparing the paint properties of the various poly (acetal polyethers) of identical molecular weight (weight average molecular weight ~ 31,000) prepared according to the procedure described in Example 28 but containing different degrees of blocking 16 carbon atoms (see data in Table 5).

TABLE 5 Properties of Rhoplex AC-417M Semi-gloss Paint of 16 Terminal Carbon Terminal Poly (Acetal Polyethers) (MOLECULAR PESO ~ 31,000) with Different Hydrophobic Levels of 16 Carbon Atoms Mués- Content TE KU ICI Nive- Salted Combi- Gloss after 18 Atoms (%) side of 60 ° Carbon (% in Weight) 1. 45 0.73 91/105 2.0 10 47.0 b 1.90 0.51 90/104 1.6 9 8 9 45.8 c 2.00 0.30 88/96 1.0 6 9 8 47.5 d 2.28 0.32 90/105 1.1 6 12 9 46.4 The data in Table 5 show that the best balance of the properties of the paint is achieved at an intermediate level of hydrophobic content of approximately 1.9 percent by weight which corresponds to a degree terminal block of approximately 70 percent. The lower hydrophobic weight percentages provide good thickening efficiency and the higher levels lead to poor leveling and lower ICI viscosity. The optimum degree of terminal blockage to achieve a balance of paint properties would vary with the molecular weight of poly (polyether-acetal).

Claims (40)

CLAIMS;

1. A water soluble polymer composition comprising a basic structure of poly (acetal or ketal polyether) having terminals that are blocked with hydrophobic groups.

The polymer composition of claim 1, wherein the hydrophobic groups are independently selected from the group consisting of alkyl, aryl, arylalkyl, cycloaliphatic, perfluoroalkyl, carbosilyl, polycyclyl and complex dendritic groups.

3. The polymer composition of claim 2, wherein the hydrophobic alkyl, perfluoroalkyl and carbosilyl groups comprise from 1 to 40 carbon atoms.

4. The polymer composition of claim 2, wherein the hydrophobic aryl, arylalkyl, cycloaliphatic and polycyclic groups comprise from 3 to 40 carbon atoms.

5. The polymer composition of claim 3, wherein the hydrophobic group is an alkyl group of 8 to 22 carbon atoms.

6. The polymer composition of claim 5, wherein the hydrophobic group is an alkyl of 12 to 18 carbon atoms.

The polymer composition of claim 4, wherein the hydrophobic group is selected from the group consisting of aryl, arylalkyl, cycloaliphatic and polycyclic groups of 6 to 29 carbon atoms.

The polymer composition of claim 7, wherein the hydrophobic group is selected from the group consisting of aryl, arylalkyl, cycloaliphatic and polycyclic groups of 14 to 25 carbon atoms.

9. The polymer composition of claim 1, wherein the upper molecular weight limit of the polymer is about 2,000,000.

10. The polymer composition of claim 1, wherein the upper limit of the molecular weight is about 500,000.

11. The polymer composition of claim 1, wherein the upper limit of the molecular weight is about 100,000.

12. The polymer composition of claim 1, wherein the lower limit of the molecular weight is about 500.

13. The polymer composition of claim 1, wherein the lower limit of the molecular weight of the polymer is about 15,000.

14. The polymer composition of claim 1, wherein a lower limit of molecular weight is about 20,000.

15. A polymer composition having the following formula R2 R3 R2 I I Rl ~ - (OCH2CH) and O C O- (CH2-CH-0) and -R5 I R x wherein: R1 and R5 are independently selected from the group consisting of a hydrophobic group having 1 to 40 carbon atoms or H, R2 is selected from the group consisting of H, alkyl, having 1 to 3 carbon atoms, or a combination thereof. R3 and R4 are independently selected from the group consisting of H, alkyl of 1 to 6 carbon atoms and phenyl, and is an integer of about 5 to about 500, and x is an integer of about 1 to about 50.

16. The composition The polymer composition of claim 15, wherein R is H.

17. The polymer composition of claim 15, wherein R2 is an alkyl having 1 to 2 carbon atoms.

18. The polymer composition of claim 15, wherein R3 and R4 are both H.

19. The polymer composition of claim 16, wherein R3 and R4 are alkyl groups having 1 to 2 carbon atoms.

The polymer composition of claim 15, wherein and is about 180.

21. The polymer composition of claim 15, wherein and is about 100.

22. The polymer composition of claim 15, wherein x is about 15.

The polymer composition of claim 15, wherein x is about 5.

24. A process for preparing a hydrophobically terminal block poly (acetal or ketal) ether comprising a) reacting a polyether alpha , omega-dihydroxy, -dithiol or -diamino or a mixture thereof with a gem-dihalide compound in the presence of a base to form a basic structure of poly (polyether of acetal- or ketal) alpha, or ega-dihydroxy, and (b) reacting the basic structure with a hydrophobic reagent to form the hydrophobic terminal block poly (acetal or ketal).

The process of claim 24, wherein the hydrophobic groups are independently selected from the group consisting of alkyl, aryl, arylalkyl, cycloaliphatic, perfluoroalkyl, carbosilyl, polycyclyl, and dendritic groups.

26. The process of claim 25, wherein the hydrophobic alkyl, perfluoroalkyl and carbosilyl groups comprise from 1 to 40 carbon atoms.

The process of claim 25, wherein the hydrophobic aryl, arylalkyl, cycloaliphatic, and polycyclic groups comprise from 3 to 40 carbon atoms.

The process of claim 26, wherein the hydrophobic group is an alkyl of 8 to 22 carbon atoms.

29. The polymer composition of claim 28, wherein the hydrophobic group is alkyl of 12 to 18 carbon atoms.

30. The process of claim 27, wherein the hydrophobic group is selected from the group consisting of aryl, arylalkyl, cycloaliphatic, polycyclic and dendritic groups of 6 to 29 carbon atoms.

The process of claim 30, wherein the hydrophobic group is selected from the group consisting of aryl, arylalkyl, cycloaliphatic and polycyclic alkyl groups of 14 to 25 carbon atoms.

32. The process of claim 24, wherein the upper limit of the molecular weight of the polymer is about 2,000,000.

33. The process of claim 24, wherein the upper limit of the molecular weight is about 500,000.

34. The process of claim 24, wherein the upper limit of the molecular weight is about 100,000.

35. The process of claim 24, wherein the lower limit of the molecular weight is about 500.

36. The process of claim 24, wherein the lower limit of the molecular weight of the polymer is about 15,000.

37. The process of claim 24, wherein the lower limit of the molecular weight is about 20,000.

38. A film-forming coating composition comprising the poly (acetal or ketal polyether) composition of the hydrophobic terminal block of claim 1.

39. The film-forming coating composition of claim 38, wherein the composition is a latex paint.

40. The film-forming coating composition of claim 39, wherein the latex paint has a pigment volume concentration of about 15 to about 80.