WO1999047578A1 - Surface active polyesters - Google Patents

Surface active polyesters Download PDF

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Publication number
WO1999047578A1
WO1999047578A1 PCT/US1999/005594 US9905594W WO9947578A1 WO 1999047578 A1 WO1999047578 A1 WO 1999047578A1 US 9905594 W US9905594 W US 9905594W WO 9947578 A1 WO9947578 A1 WO 9947578A1
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Prior art keywords
group
polymer
integer ranging
formula
mixtures
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PCT/US1999/005594
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French (fr)
Inventor
Venkataram Krishnan
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Reichhold, Inc.
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Priority to AU30047/99A priority Critical patent/AU3004799A/en
Publication of WO1999047578A1 publication Critical patent/WO1999047578A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34Higher-molecular-weight carboxylic acid esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/20Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6888Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

Definitions

  • the invention generally relates to polymers having specifically designed hydrophobicity and hydrophilicity properties.
  • the polymers themselves can be used in a number of areas such as aids in dispersion or suspension polymerization, low profile additives, sizing and coating applications, hot melt adhesives, powder coatings, and emulsifiers/dispersants for pigment dispersions and hydrophobic polymers (e.g., alkyds).
  • the polymers can also be used in applications where low molecular weight surfactants have traditionally been used.
  • Latices are typically made by an emulsion polymerization process involving the use of monomers, e.g., styrene, acrylates, etc., in an aqueous medium in the presence of free radical initiators, surfactants, and chain transfer agents.
  • the surfactants are responsible to a great extent in providing stability to the emulsion, and they can be anionic, cationic, or nonionic in nature. While these surfactants have been known to be essential for stabilization of the latex, they can be detrimental to the application performance of the polymer. For example, upon film formation of the latex, these surfactants can migrate to the polymer/air interface
  • the surfactants can concentrate at the polymer/substrate interface and contribute adversely to properties such as adhesion and corrosion resistance. Hence, it would be desirable to avoid using conventional surfactants in many applications.
  • the invention provides a polymer having specifically designed hydrophobic and hydrophilic properties.
  • the polymer is comprised of (a) at least one monomer residue of an aromatic dicarboxylic acid, wherein a side chain is attached from the aromatic ring and is described by the formula:
  • Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof; (b) at least one monomer residue of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or mixtures thereof; and (c) at least one monomer residue of an aliphatic alcohol, an aromatic alcohol, or mixtures thereof.
  • the monomer residues of (a), (b), and (c) are arranged to form the backbone of the polymer, and wherein the side chain of formula (I) is a pendant group extending from the polymer backbone.
  • the polymer when employed as a surfactant, the polymer is water dispersible.
  • the invention in another aspect, relates to a latex emulsion composition.
  • the composition comprises the polymer described hereinabove and a latex emulsion polymer.
  • the polymer interacts with the latex emulsion polymer so as to stabilize the latex emulsion polymer.
  • the polymers of the invention are highly advantageous. These polymers can serve as a very valuable aid to polymer design and performance. These multifunctional polymers can be permanently incorporated into the latex particle by grafting reactions and hence cannot be leached out and give rise to foaming, lack of adhesion, and water sensitivity. Being tailor-made polymers instead of low molecular weight surfactants, they can thus be designed to modify the required end properties of the polymer made by emulsion polymerization, such that the polymer is more desirable in its specific end use.
  • FIGS. 1 through 5 illustrate examples of structures of polymers encompassed by the scope of the invention
  • FIG. 6 illustrates a graph of surface tension versus concentration for the polymer of FIG. 1;
  • FIG. 7 illustrates a graph of surface tension versus concentration for the polymer of FIG. 2;
  • FIG. 8 illustrates a graph of surface tension versus concentration for the polymer of FIG. 3
  • FIG. 9 illustrates a graph of surface tension versus concentration for the polymer of FIG. 4;
  • FIG. 10 illustrates a graph of surface tension versus concentration for the polymer of FIG. 5.
  • FIG. 11 illustrates hydrolysis stability of a polymer when employed as a surfactant of the invention versus time.
  • the invention provides a polymer having specified hydrophobic and hydrophilic properties.
  • the polymer may be used as a surfactant to stabilize latex emulsion polymers.
  • the polymer is comprised of (a) at least one monomer residue of an aromatic dicarboxylic acid, wherein a side chain is attached from the aromatic ring and is described by the formula:
  • Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof; (b) at least one monomer residue of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or mixtures thereof; and (c) at least one monomer residue of an aliphatic alcohol, an aromatic alcohol, or mixtures thereof.
  • the monomer residues of (a), (b), and (c) are arranged to form the backbone of the polymer, and wherein the side chain of formula (I) is a pendant group extending from the polymer backbone.
  • the polymer is capable of displaying surface activity.
  • the polymer preferably has a number average molecular weight ranging from about 900 to about 10,000.
  • Q may represent various substituents that are capable of imparting hydrophobic and/or hydrophilic properties to the polymer.
  • the selection of these groups are known to one skilled in the art.
  • Q is represented by the formula:
  • R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof;
  • Y is selected from the group consisting of-O-, and -NH-;
  • Z may be selected from the group consisting of-(CH 2 ) n -; -(CH 2 CH 2 O) n -, and
  • R 51 is H or alkyl, preferably CH 3 ; and n is an integer ranging from 1 to 50.
  • Q may also be described by the following formulas:
  • the polymer may be described by the formula
  • R 12 , R 2 folk and R u are each independently selected from the group consisting of a saturated hydrocarbon group and an unsaturated hydrocarbon group.
  • X may be selected from H or halogen.
  • Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof.
  • R ⁇ , R, 2 , R 21 , and R 13 may be the same or different and can be selected from various saturated or unsaturated hydrocarbon groups such as, for example, aliphatic-containing groups, as well as aromatic-containing groups such as benzene and various derivatives thereof. These groups may be substituted with various substituents and functional groups if so desired. Examples of functional groups include, but are not limited to, hydroxyl, carboxyl, halogen, and amino. These groups may also be branched.
  • these groups include, but are not limited to, polyols such as ethylene glycol; propylene glycol; 1.3-propanediol; 2,4-dimethyl-2ethyl-hexane-l ,3-diol; 2,2-dimethyl-l ,3-propanediol; 2-ethyl-2- butyl-l,3-propanediol; 2-ethyl-2-isobutyl-l,3-propanediol; 1,3-butanediol; 1,4- butanediol; 1,5-pentanediol; 1,6-hexanediol; 2,2,4-trimethyl-l,3-pentanediol; thiodiethanol; 1,2-cyclohexanedimethanol; 2,2,4,4,-tetramethy 1-1,3 - cyclobutanediol; and p-xylyl
  • Polyethylene glycols may also be used such as, but not limited to, diethylene glycol, triethylene glycol, tetraethylene glycol; pentaethylene, hexaethylene, heptaethylene, octaethylene, nonaethylene, and decaethylene glycol. Additionally, bis-(2-hydroxyethoxy)-phenol A; trimethylolpropane; trimethylolethane; glycerol, 2,2-bis(hydroxymethyl)-l,3- propanediol, 1,2,3,4,5,6-hexahydroxy hexane, and the like may be employed. Mixtures of any of the above may be used.
  • ethoxylated amines include, but are not limited to, ethoxylated amines; and polyalcohols derived from ethylene oxide and propylene oxide.
  • Poly(ethylene/butylene) diol such as Kraton LiquidTM L-2203 polymer , hydroxy functional polybutadienes, aromatic and cycloaliphatic epoxies, and the like can also be employed. Additionally, it should be emphasized that amines having structures similar to the polyols mentioned above can be used.
  • R, relief R 12 , R 21 , and R 13 include substituents that are derived from various acids and anhydrides.
  • These acids or anhydrides include, but are not limited to, anhydrides and acids such as isophathahc, phthalic, terepthalic, acetylated hydroxy aromatic acids (e.g., acetoxy benzoic acid); diphenic, 4,4-oxydibenzoic, 4,4'-sulfonyldibenzoic, 4,4'-biphenyl- dicarboxylic and naphthalenedicarboxylic acids.
  • Linear or branched-chain saturated aliphatic diacids including oxalic, malonic, dimethylmalonic, succinic, glutaric, adipic, trimethyladipic, pimelic, 2,2-dimethylglutaric, azelaic and sebacic acids may be used.
  • Unsaturated aliphatic diacids including fumaric acid, maleic acid and itaconic acid can be employed.
  • Unsaturated aromatic acids can also be used such as, but not limited to, phenylene diacrylic acid and bis-cinnamic acids.
  • Cycloaliphatic diacids which may be used include 1 ,2-cyclohexane dicarboxylic acid and anhydride thereof; 1 ,3-cyclohexane dicarboxylic acid; 1 ,4-cyclohexane
  • Q may be represented by the formula:
  • R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof;
  • Y is selected from the group consisting of-O-, and -NH-; and
  • Z may be selected from the group consisting of-(CH 2 ) protest-, -(CH 2 CH 2 O) seldom-, and
  • R 51 is H or CH 3 .
  • the alkyl substituent may be substituted or unsubstituted.
  • An example of a substituted alkyl that may be employed for R is CH 2 C1.
  • the variable "n" is independently selected for each of the various substituents and encompasses integers ranging from 1 to 50.
  • Substituents which may be employed for R described above include, for example, alkyl groups such as CH 3 , and (CH 2 ) n wherein n ranges from 0 to 18,
  • R' can be, for example, -H, CH 3 , -CH 2 C1, and the like, and n ranges from 1 to 50.
  • R' and R" include, but are not limited to, hydrogen and straight or branched alkyl chains having 6 to 12 carbon atoms.
  • variables x, y, and z described in formula (II) preferably are integers ranging from 0 to 20, and more preferably 0 to 15. It is especially preferred that the x, y, and z be chosen such that the sum x+y+z ranges from 1 to 40. More preferably, the sum ranges from 5 to 25.
  • the above polymer described in formula (II) may be end-capped by use of a number of different components such as, for example, mono-functional alcohols, amines, or acids.
  • Preferred alcohols include those in the Igepal® CO and CA series, fatty alcohols, ethoxylated fatty alcohols, as well as others which are structurally similar. Components having isocyanate functionality may be employed if desired. Mixtures of the above may also be used.
  • a preferred acid includes, for example, benzoic acid.
  • the variable X contained in the polymer of formula II may be selected from a number of substituents such as, but not limited to, hydrogen, chlorine, fluorine, bromine, and the like.
  • side chains which include Z and R on the polymers represented by the formula II may be either hydrophobic, hydrophilic, or a combination of the two. These side chains may contain various substituents and functional groups known in the art.
  • An example of hydrophilic side chains may be represented by the formulae:
  • R is CH 3
  • Y is -O-
  • Z is -(CH 2 CH 2 O) m - wherein m is an integer ranging from 1 to 50.
  • hydrophobic side chain may be represented by the formula:
  • R is CH 3 , Z is -(CH 2 ) p -, Y is -O-, and p is an integer ranging from 1 to 50.
  • a side chain which may be used is represented by the formula:
  • R is CH 3 (CH 2 ) p C 6 H 4 , Z is -(CH 2 CH 2 O) n -, Y is -O-, n is an integer ranging from 1 to 30, and p' is an integer ranging from 1 to 50.
  • r may be an integer ranging from 1 to 50.
  • Groups which may also be used for Y include -O-, -NH-, and the like.
  • Substituents which can be also used for Z include -(CH 2 CH 2 O) n ,-;
  • n and n' may be the same or different and range from 0 to 50; and R' ' ' may be, for example, -H, -CH 3 , -CH 2 C1, and the like.
  • polymers that are preferably used as surfactants and encompassed by the invention are:
  • s is an integer ranging from 1 to 50
  • t is an integer ranging from 1 to 50
  • Z and R are defined herein;
  • u is an integer ranging from 1 to 50
  • v is an integer ranging from 1 to 50
  • R is defined herein;
  • the polymers of the invention are made according to known and accepted techniques. Examples of techniques that may be followed in making these materials are provided in U.S. Patent Nos. 3,787,526; 4,588,668; 4,933,252;
  • the polymers are formed from the reaction between a polyfunctional organic acid or anhydride and a polyhydric alcohol under specified conditions.
  • the polyfunctional organic acid or anhydride which may be employed are numerous.
  • Suitable polyfunctional acids or anhydrides thereof include, but are not limited to, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexane dicarboxylic acid, succinic anhydride, adipic acid, sebacic acid, azealic acid, malonic acid, alkenyl succinic acids such as n-dodecenylsuccinic acid, docecylsuccinic acid, octadecenylsuccinic acid, and anhydrides thereof. Lower alkyl esters of any of the above may also be employed. Mixtures of any of the above are suitable.
  • Suitable polyhydric alcohols which may be used in forming the polymers include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1 ,4-butanediol, 1,3 hexanediol, neopentyl glycol, 2-methyl-l,3-propanediol, 1,3-butylene glycol, 1 ,6-hexanediol, hydrogeneated bisphenol "A", cyclohexane dimethanol, 1,4-cyclohexanol, ethylene oxide adducts of bisphenols, propylene oxide adducts of bisphenols, sorbitol, 1,4- sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4- butanetriol, 1,2,5-pentanetriol,
  • the invention in another aspect, relates to a latex emulsion composition.
  • the composition comprises a polymer typically in the form of a surfactant described hereinabove and a latex emulsion polymer.
  • a surfactant described hereinabove and a latex emulsion polymer.
  • latex emulsion polymers acts as a surfactant and interacts with the latex emulsion polymer so as to stabilize the latex emulsion polymer.
  • the polymers can be used to stabilize various latex emulsion polymers without employing conventional surfactants.
  • latex emulsion polymers is to be construed broadly to include all of those which are typically stabilized by conventional cationic, anionic, and nonionic surfactants.
  • emulsion polymers include those made from a number of monomers including, but not limited to, aliphatic conjugated diene monomers, non-aromatic unsaturated ester monomers, aromatic unsaturated monomers, monomers based on the half ester of an unsaturated dicarboxylic acid monomer, unsaturated mono- or dicarboxylic acid monomers, unsaturated nitrogen containing monomers, monoethylenically unsaturated aliphatic hydrocarbons, and vinyl ester monomers.
  • Emulsion polymers which are formed from the above monomers are made in accordance with known and suitable techniques. The polymers of the invention may also be used in conjunction with conventional surfactants if so desired.
  • surfactants are typically those of the anionic, cationic, or nonionic type.
  • examples of surfactants are set forth in U.S. Patent Application Serial No. 08/856,789 filed 15 May 1997 and U.S. Patent No. 5,296,627 to Tang et al., the disclosures of which are incorporated herein by reference in their entirety. The selection of these surfactants is known to one skilled in the art.
  • the polymer interacts with the latex emulsion polymer by either being grafted or adsorbed onto the latex emulsion polymer to stabilize the latex emulsion polymer.
  • the process for making these latices can be either batch or semicontinuous.
  • the levels of polymers that may be employed in the latex emulsion composition may range from about 0.1 to about 10 percent based on 100 parts of monomer, and more preferably between about 1 and 7 percent based on 100 parts of monomer.
  • the polymers can also be used to make hybrid emulsions where the level of usage of the polymers may range from 10 to 80 percent based on
  • Example 1 Polymer Synthesis 150 g (0.2 mol) of poly(ethylene glycol) mono-methyl ether with an average molecular weight of 750 (MPEG 750) was charged with 39.62 g (0.2 mol) of trimellitic anhydride in a 1000 mL four-neck round bottomed flash. The flask was purged with nitrogen and maintained at 80°C for 30 min. Thereafter, 49.92 g of neopentyl glycol, 17.94 g of phthallic anhydride, 7.92 g of maleic anhydride, and 0.5 g of Fascat 2001 were added. The esterification reaction proceeded at 232°C and was monitored by acid value titration. The polymer thus synthesized possessed an acid value of 2.5 (PS-3412-67),
  • the flask was purged with nitrogen and maintained at 80°C for 30 min.
  • the mixture was agitated and then exposed to a inert nitrogen atmosphere.
  • the mixture was heated to 70°C, and then 5 ml of initiator solution including lpart of APS and 50 parts of water was added.
  • the resulting mixture was held for 10 minutes.
  • a seeding composition was subsequently added to the above mixture.
  • the seeding composition was as follows:
  • the pre-emulsion had the following composition:
  • the seeding took place for 45 minutes. After seeding, the temperature was raised to 75°C and a remaining amount of pre-emulsion was fed to the mixture at a rate of 0.5 g/min. Initiator solution was fed to this mixture at a rate of 4 ml/hr. Subsequently, the polymerization continued for about 1 hour. The solids content of the resulting latex was 37.7 percent. The latex particle size was 143 ⁇ m.
  • Examples 4-23 listed in Tables 2-6 represent molecular weight data of polymers described herein.
  • the polymers in each of the tables correspond in structure to the figure referred to by each table. As can be seen, a wide variety of polymers can be made.
  • Example 7 Lgepal CO- MPEG 750 Neopentyl 2370 2.1 17.5 210 glycol
  • Example 8 Lgepal CO- MPEG 750 PEG 200 2720 2.3 14.2 210
  • Example 9 Lgepal CO- MPEG 750 PEG 400 2280 2.8 14.8 210
  • Example 10 Lgepal CO- MPEG 750 PEG 600 2330 2.1 17.7 210
  • Example 11 Lgepal CO-210 PEG 200 1500 3.5 22
  • Example 12 Lgepal CO-210 PEG 600 1240 2.6 18.99
  • Example 13 Lgepal CO-210 PEG 1000 1270 2.6 16.7
  • Example 14 Lgepal CO-210 PEG 1450 1900 2.8 16
  • Example 15 Lgepal CO-210 PEG 200 900 2.4 19.62
  • Example 16 Lgepal CO-210 PEG 600 670 2.2 25.04
  • Example 17 Lgepal CO-210 PEG 1000 1560 2.6 16.78
  • Example 19 MPEG 750 1 2800 1.9 0.6
  • Example 21 MPEG 750 3 2650 2.5 1.2
  • the latex emulsion polymers which contain the polymers of the invention are useful in a number of applications.
  • the latex emulsion polymers may be used in printing inks, slasher dyeing, toner applications, sizing applications for use with glass or other fibers to improve strength, pigment encapsulation for imaging applications, coatings, and the like.
  • the applications for which the polymers can be used are many in number.
  • the polymers themselves can be used as aids in dispersion or suspension polymerization, low profile additives, sizing and coating applications, hot melt adhesives, powder coatings, emulsifiers/dispersants for pigment dispersions and hydrophobic polymers (e.g., alkyds), and in general applications where low molecular weight surfactants have traditionally been used.
  • the polymers can be used in non-aqueous (i.e., organic) solutions if so desired by the end user.

Abstract

A polymer comprises: (a) at least one monomer residue of an aromatic dicarboxylic acid, wherein a side chain is attached from the aromatic ring and is described by formula (I) wherein Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures of; (b) at least one monomer residue of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or mixtures thereof; and (c) at least one monomer residue of an aromatic alcohol, an aliphatic alcohol, or mixtures thereof; wherein the monomer residues of (a), (b), and (c) are arranged to form the backbone of the polymer, and wherein the side chain of formula (I) is a pendant group extending from the polymer backbone. Preferably the polymers are polyesters containing trimellitic acid having pendant polyoxyethylene side chains. They are used as surfactants in emulsion polymerizations.

Description

SURFACE ACTIVE POLYESTERS
Cross-Reference to Related Applications The instant application claims priority to U.S. Provisional Patent
Application No. 60/078,156 filed 16 March 1998, the disclosure of which is incorporated herein by reference in its entirety.
Field of the Invention The invention generally relates to polymers having specifically designed hydrophobicity and hydrophilicity properties. The polymers themselves can be used in a number of areas such as aids in dispersion or suspension polymerization, low profile additives, sizing and coating applications, hot melt adhesives, powder coatings, and emulsifiers/dispersants for pigment dispersions and hydrophobic polymers (e.g., alkyds). The polymers can also be used in applications where low molecular weight surfactants have traditionally been used.
Background of the Invention Latices are typically made by an emulsion polymerization process involving the use of monomers, e.g., styrene, acrylates, etc., in an aqueous medium in the presence of free radical initiators, surfactants, and chain transfer agents. The surfactants are responsible to a great extent in providing stability to the emulsion, and they can be anionic, cationic, or nonionic in nature. While these surfactants have been known to be essential for stabilization of the latex, they can be detrimental to the application performance of the polymer. For example, upon film formation of the latex, these surfactants can migrate to the polymer/air interface
-1- and can be leached out, thereby making the film water sensitive. Another possibility is that the surfactants can concentrate at the polymer/substrate interface and contribute adversely to properties such as adhesion and corrosion resistance. Hence, it would be desirable to avoid using conventional surfactants in many applications.
Summary of the Invention It is an object of the invention to provide materials that address the problems noted above. In addition, it would be desirable if these materials were able to perform other functions upon film formation of the latex such as, for example, coalescing aids, adhesion promotion, and the like.
In one example, it has been attempted to design polymers by introducing functionality that would promote steric and/or electrostatic mechanisms of emulsion stabilization. This can be accomplished by introducing hydrophilic (e.g., ethylene oxide) and /or hydrophobic (e.g., alkyl) groups as pendant chains connected to a polymer main chain which may or may not have ionic functionality such as, for example sulfonate, phosphate esters, sulfates, and the like. Thus, in one aspect, the invention provides a polymer having specifically designed hydrophobic and hydrophilic properties. The polymer is comprised of (a) at least one monomer residue of an aromatic dicarboxylic acid, wherein a side chain is attached from the aromatic ring and is described by the formula:
Q
I
-c=o (i)
wherein Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof; (b) at least one monomer residue of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or mixtures thereof; and (c) at least one monomer residue of an aliphatic alcohol, an aromatic alcohol, or mixtures thereof. The monomer residues of (a), (b), and (c) are arranged to form the backbone of the polymer, and wherein the side chain of formula (I) is a pendant group extending from the polymer backbone. Advantageously, when employed as a surfactant, the polymer is water dispersible.
In another aspect, the invention relates to a latex emulsion composition. The composition comprises the polymer described hereinabove and a latex emulsion polymer. The polymer interacts with the latex emulsion polymer so as to stabilize the latex emulsion polymer.
The polymers of the invention are highly advantageous. These polymers can serve as a very valuable aid to polymer design and performance. These multifunctional polymers can be permanently incorporated into the latex particle by grafting reactions and hence cannot be leached out and give rise to foaming, lack of adhesion, and water sensitivity. Being tailor-made polymers instead of low molecular weight surfactants, they can thus be designed to modify the required end properties of the polymer made by emulsion polymerization, such that the polymer is more desirable in its specific end use.
Brief Description of the Drawings FIGS. 1 through 5 illustrate examples of structures of polymers encompassed by the scope of the invention;
FIG. 6 illustrates a graph of surface tension versus concentration for the polymer of FIG. 1;
FIG. 7 illustrates a graph of surface tension versus concentration for the polymer of FIG. 2;
FIG. 8 illustrates a graph of surface tension versus concentration for the polymer of FIG. 3; FIG. 9 illustrates a graph of surface tension versus concentration for the polymer of FIG. 4;
FIG. 10 illustrates a graph of surface tension versus concentration for the polymer of FIG. 5; and
FIG. 11 illustrates hydrolysis stability of a polymer when employed as a surfactant of the invention versus time.
-3- Detailed Description of the Preferred Embodiments The invention will now be described in greater detail with respect to the preferred embodiments with reference to the detailed description and drawings. It should be appreciated however that these embodiments are for illustrative purposes, and do not limit the scope of the invention which is defined by the claims.
In one aspect, the invention provides a polymer having specified hydrophobic and hydrophilic properties. In one example, the polymer may be used as a surfactant to stabilize latex emulsion polymers. The polymer is comprised of (a) at least one monomer residue of an aromatic dicarboxylic acid, wherein a side chain is attached from the aromatic ring and is described by the formula:
Q
I
-c=o (i)
wherein Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof; (b) at least one monomer residue of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or mixtures thereof; and (c) at least one monomer residue of an aliphatic alcohol, an aromatic alcohol, or mixtures thereof.
The monomer residues of (a), (b), and (c) are arranged to form the backbone of the polymer, and wherein the side chain of formula (I) is a pendant group extending from the polymer backbone. The polymer is capable of displaying surface activity.
The polymer preferably has a number average molecular weight ranging from about 900 to about 10,000.
In the above formula, Q may represent various substituents that are capable of imparting hydrophobic and/or hydrophilic properties to the polymer. The selection of these groups are known to one skilled in the art. Preferably, Q is represented by the formula:
_4- R
I z
I Y
wherein:
R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof;
Y is selected from the group consisting of-O-, and -NH-;
Z may be selected from the group consisting of-(CH2)n-; -(CH2CH2O)n-, and
CH-CH2O-
I
R51
wherein R51 is H or alkyl, preferably CH3; and n is an integer ranging from 1 to 50. Q may also be described by the following formulas:
CH3
CH3 CH3 CH2 O C6H4
CH2 CH2 I O
"θ~ I CH2 I CH2
»"1
O C=O I CH2 C=O O I C=O
wherein m is an integer ranging from 1 to 50; p is an integer ranging from
1 to 50; n is an integer ranging from 1 to 30; and p' is an integer ranging from 1 to 50. In a preferred embodiment, the polymer may be described by the formula
II:
O
II R21— C-O— R12-
Figure imgf000008_0001
SO3 'Na
O O
II II -C ( ID
C-0-R13-
Figure imgf000008_0002
X
In this structure of formula (II), Rπ. R12, R2„ and Ru are each independently selected from the group consisting of a saturated hydrocarbon group and an unsaturated hydrocarbon group. X may be selected from H or halogen. Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof.
Rπ, R,2, R21, and R13 may be the same or different and can be selected from various saturated or unsaturated hydrocarbon groups such as, for example, aliphatic-containing groups, as well as aromatic-containing groups such as benzene and various derivatives thereof. These groups may be substituted with various substituents and functional groups if so desired. Examples of functional groups include, but are not limited to, hydroxyl, carboxyl, halogen, and amino. These groups may also be branched. Specific examples of these groups include, but are not limited to, polyols such as ethylene glycol; propylene glycol; 1.3-propanediol; 2,4-dimethyl-2ethyl-hexane-l ,3-diol; 2,2-dimethyl-l ,3-propanediol; 2-ethyl-2- butyl-l,3-propanediol; 2-ethyl-2-isobutyl-l,3-propanediol; 1,3-butanediol; 1,4- butanediol; 1,5-pentanediol; 1,6-hexanediol; 2,2,4-trimethyl-l,3-pentanediol; thiodiethanol; 1,2-cyclohexanedimethanol; 2,2,4,4,-tetramethy 1-1,3 - cyclobutanediol; and p-xylylenediol. Polyethylene glycols may also be used such as, but not limited to, diethylene glycol, triethylene glycol, tetraethylene glycol; pentaethylene, hexaethylene, heptaethylene, octaethylene, nonaethylene, and decaethylene glycol. Additionally, bis-(2-hydroxyethoxy)-phenol A; trimethylolpropane; trimethylolethane; glycerol, 2,2-bis(hydroxymethyl)-l,3- propanediol, 1,2,3,4,5,6-hexahydroxy hexane, and the like may be employed. Mixtures of any of the above may be used.
Other components which may be used include, but are not limited to, ethoxylated amines; and polyalcohols derived from ethylene oxide and propylene oxide. Poly(ethylene/butylene) diol such as Kraton Liquid™ L-2203 polymer , hydroxy functional polybutadienes, aromatic and cycloaliphatic epoxies, and the like can also be employed. Additionally, it should be emphasized that amines having structures similar to the polyols mentioned above can be used.
Other examples of groups that may represent R,„ R12, R21, and R13 include substituents that are derived from various acids and anhydrides. The use of these acids or anhydrides in making polymers is known to one skilled in the art. These acids or anhydrides include, but are not limited to, anhydrides and acids such as isophathahc, phthalic, terepthalic, acetylated hydroxy aromatic acids (e.g., acetoxy benzoic acid); diphenic, 4,4-oxydibenzoic, 4,4'-sulfonyldibenzoic, 4,4'-biphenyl- dicarboxylic and naphthalenedicarboxylic acids. Linear or branched-chain saturated aliphatic diacids including oxalic, malonic, dimethylmalonic, succinic, glutaric, adipic, trimethyladipic, pimelic, 2,2-dimethylglutaric, azelaic and sebacic acids may be used. Unsaturated aliphatic diacids including fumaric acid, maleic acid and itaconic acid can be employed. Unsaturated aromatic acids can also be used such as, but not limited to, phenylene diacrylic acid and bis-cinnamic acids. Cycloaliphatic diacids which may be used include 1 ,2-cyclohexane dicarboxylic acid and anhydride thereof; 1 ,3-cyclohexane dicarboxylic acid; 1 ,4-cyclohexane
-7- diacarboxylic acid; and 1,3-cyclopentane dicarboxylic acid. Mixtures of the above may also be used.
In formula (II), Q may be represented by the formula:
R
Z
I
Y
wherein R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof; Y is selected from the group consisting of-O-, and -NH-; and Z may be selected from the group consisting of-(CH2)„-, -(CH2CH2O)„-, and
-CH-CH2O-
I
R51
wherein R51 is H or CH3. The alkyl substituent may be substituted or unsubstituted. An example of a substituted alkyl that may be employed for R is CH2C1. The variable "n" is independently selected for each of the various substituents and encompasses integers ranging from 1 to 50.
Substituents which may be employed for R described above include, for example, alkyl groups such as CH3, and (CH2)n wherein n ranges from 0 to 18,
-(-CH— CH2O^- s I n
R
wherein R' can be, for example, -H, CH3, -CH2C1, and the like, and n ranges from 1 to 50.
-8- Various aromatic-containing substituents may be employed for R. Examples of these substituents which may also be used are branched and include:
Figure imgf000011_0001
R"
Figure imgf000011_0002
Examples of R' and R" include, but are not limited to, hydrogen and straight or branched alkyl chains having 6 to 12 carbon atoms.
The variables x, y, and z described in formula (II) preferably are integers ranging from 0 to 20, and more preferably 0 to 15. It is especially preferred that the x, y, and z be chosen such that the sum x+y+z ranges from 1 to 40. More preferably, the sum ranges from 5 to 25.
The above polymer described in formula (II) may be end-capped by use of a number of different components such as, for example, mono-functional alcohols, amines, or acids. Preferred alcohols include those in the Igepal® CO and CA series, fatty alcohols, ethoxylated fatty alcohols, as well as others which are structurally similar. Components having isocyanate functionality may be employed if desired. Mixtures of the above may also be used. A preferred acid includes, for example, benzoic acid. The variable X contained in the polymer of formula II may be selected from a number of substituents such as, but not limited to, hydrogen, chlorine, fluorine, bromine, and the like.
In addition to the more general description set forth hereinabove, the side chains which include Z and R on the polymers represented by the formula II may be either hydrophobic, hydrophilic, or a combination of the two. These side chains may contain various substituents and functional groups known in the art. An example of hydrophilic side chains may be represented by the formulae:
CH3 - O R I CH2 Z
CH2 Y I
I C=O C=O
In this embodiment, R is CH3, Y is -O-, and Z is -(CH2CH2O)m- wherein m is an integer ranging from 1 to 50.
An example of a hydrophobic side chain may be represented by the formula:
CH3
CH2
"-A O P
C=O
wherein R is CH3, Z is -(CH2)p-, Y is -O-, and p is an integer ranging from 1 to 50. Another example of a side chain which may be used is represented by the formula:
-10-
Figure imgf000013_0001
CH2 CH2 O n
C=O
wherein R is CH3(CH2)pC6H4, Z is -(CH2CH2O)n-, Y is -O-, n is an integer ranging from 1 to 30, and p' is an integer ranging from 1 to 50.
Specific side chain substituents for Z and R may be selected from:
— O(CH2CH2O)i4CH3 ,
-O(CH2CH2O) ( f ) ) (CH2)9CH3
wherein r may be an integer ranging from 1 to 50. Groups which may also be used for Y include -O-, -NH-, and the like. Substituents which can be also used for Z include -(CH2CH2O)n,-;
R'"
- -CH-CH2O^- 'n wherein n and n' may be the same or different and range from 0 to 50; and R' ' ' may be, for example, -H, -CH3, -CH2C1, and the like.
Examples of polymers that are preferably used as surfactants and encompassed by the invention are:
-11- I
,C r=0 o 1
II C ZO )- -c-
"C— O — (CH2CH20)
Figure imgf000014_0001
O
wherein s is an integer ranging from 1 to 50, t is an integer ranging from 1 to 50, and Z and R are defined herein;
O C— o- i Λ^
Figure imgf000014_0002
S03 Na+
wherein u is an integer ranging from 1 to 50, v is an integer ranging from 1 to 50, and R is defined herein; and
z
I o
O c=o
II o O CH3 O O
O— C CH3 0 ( «
Figure imgf000014_0003
II I N II II
C-0-CH2CCH2— θ -C-^ ^~ C— O— CH2CCH2-0^ C— CH==CH— C- - CH3 CH3 f
-12- wherein e is an integer ranging from 5 to 40; f is an integer ranging from 0 to 15, and Z is defined herein.
The polymers of the invention are made according to known and accepted techniques. Examples of techniques that may be followed in making these materials are provided in U.S. Patent Nos. 3,787,526; 4,588,668; 4,933,252;
4,393,059; 4,960,664; and 5,241,019, the disclosures of which are incorporated herein by reference in their entirety. Typically, the polymers are formed from the reaction between a polyfunctional organic acid or anhydride and a polyhydric alcohol under specified conditions. The polyfunctional organic acid or anhydride which may be employed are numerous. Suitable polyfunctional acids or anhydrides thereof include, but are not limited to, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexane dicarboxylic acid, succinic anhydride, adipic acid, sebacic acid, azealic acid, malonic acid, alkenyl succinic acids such as n-dodecenylsuccinic acid, docecylsuccinic acid, octadecenylsuccinic acid, and anhydrides thereof. Lower alkyl esters of any of the above may also be employed. Mixtures of any of the above are suitable.
Suitable polyhydric alcohols which may be used in forming the polymers include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1 ,4-butanediol, 1,3 hexanediol, neopentyl glycol, 2-methyl-l,3-propanediol, 1,3-butylene glycol, 1 ,6-hexanediol, hydrogeneated bisphenol "A", cyclohexane dimethanol, 1,4-cyclohexanol, ethylene oxide adducts of bisphenols, propylene oxide adducts of bisphenols, sorbitol, 1,4- sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4- butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-propanetriol, 2 -methyl- 1,2,4- butanetriol, trimethylol ethane, trimethylol propane, and 1,3,5-trihydroxyethyl benzene. Mixtures of the above alcohols may be used. These ingredients may be added in amounts known to the skilled artisan.
In another aspect, the invention relates to a latex emulsion composition. The composition comprises a polymer typically in the form of a surfactant described hereinabove and a latex emulsion polymer. Advantageously, the
-13- polymer acts as a surfactant and interacts with the latex emulsion polymer so as to stabilize the latex emulsion polymer. The polymers can be used to stabilize various latex emulsion polymers without employing conventional surfactants. For the purposes of the invention the term, "latex emulsion polymers" is to be construed broadly to include all of those which are typically stabilized by conventional cationic, anionic, and nonionic surfactants. Examples of emulsion polymers include those made from a number of monomers including, but not limited to, aliphatic conjugated diene monomers, non-aromatic unsaturated ester monomers, aromatic unsaturated monomers, monomers based on the half ester of an unsaturated dicarboxylic acid monomer, unsaturated mono- or dicarboxylic acid monomers, unsaturated nitrogen containing monomers, monoethylenically unsaturated aliphatic hydrocarbons, and vinyl ester monomers. Emulsion polymers which are formed from the above monomers are made in accordance with known and suitable techniques. The polymers of the invention may also be used in conjunction with conventional surfactants if so desired. Examples of these surfactants are typically those of the anionic, cationic, or nonionic type. Examples of surfactants are set forth in U.S. Patent Application Serial No. 08/856,789 filed 15 May 1997 and U.S. Patent No. 5,296,627 to Tang et al., the disclosures of which are incorporated herein by reference in their entirety. The selection of these surfactants is known to one skilled in the art.
Although Applicants do not wish to be bound by any one theory, it is believed that the polymer interacts with the latex emulsion polymer by either being grafted or adsorbed onto the latex emulsion polymer to stabilize the latex emulsion polymer. The process for making these latices can be either batch or semicontinuous.
Typically, the levels of polymers that may be employed in the latex emulsion composition may range from about 0.1 to about 10 percent based on 100 parts of monomer, and more preferably between about 1 and 7 percent based on 100 parts of monomer. The polymers can also be used to make hybrid emulsions where the level of usage of the polymers may range from 10 to 80 percent based on
-14- 100 parts of monomer. A typical procedure for making these polymers and the emulsions are set forth herein.
The following examples are intended to illustrate the invention, and are not meant as a limitation thereon.
Example 1 Polymer Synthesis 150 g (0.2 mol) of poly(ethylene glycol) mono-methyl ether with an average molecular weight of 750 (MPEG 750) was charged with 39.62 g (0.2 mol) of trimellitic anhydride in a 1000 mL four-neck round bottomed flash. The flask was purged with nitrogen and maintained at 80°C for 30 min. Thereafter, 49.92 g of neopentyl glycol, 17.94 g of phthallic anhydride, 7.92 g of maleic anhydride, and 0.5 g of Fascat 2001 were added. The esterification reaction proceeded at 232°C and was monitored by acid value titration. The polymer thus synthesized possessed an acid value of 2.5 (PS-3412-67),
Example 2 Polymer Synthesis
245.45 g of poly(ethylene glycol) mono-methyl ether with an average molecular weight of 2000 (MPEG 2000) was charged with 146.05 g of Brij 98, and 48.89 g of trimellitic anhydride in a 1000 mL four-neck round bottomed flash.
The flask was purged with nitrogen and maintained at 80°C for 30 min.
Thereafter, 76.34 g of poly(ethylene glycol) (average molecular weight 200), 37.69 g of 5-sulfoisophthalic acid sodium salt, and 0.5 g of Fascat 2001 were added. The esterification reaction proceeded at 232°C and was monitored by acid value titration. The polymer thus synthesized possessed an acid value of 10.49 (PS-
3414-24),
-15- Example 3 Preparation of Emulsions
A 1000 ml reactor was charged with a pre-charge composition having the following recipe:
Ingredient parts
PS-3412-67 (50%) 8
PS-3414-24 (50%) 7.5
Water 150 NH4OH 3.1
The mixture was agitated and then exposed to a inert nitrogen atmosphere. The mixture was heated to 70°C, and then 5 ml of initiator solution including lpart of APS and 50 parts of water was added. The resulting mixture was held for 10 minutes. A seeding composition was subsequently added to the above mixture.
The seeding composition was as follows:
Ingredient parts
Pre-Emulsion 27 MAA 4
The pre-emulsion had the following composition:
Ingredient parts Styrene 20
MMA 60
BA 120
PS-3412-67 (50%) 16
S-120 0.4 Water 130
The seeding took place for 45 minutes. After seeding, the temperature was raised to 75°C and a remaining amount of pre-emulsion was fed to the mixture at a rate of 0.5 g/min. Initiator solution was fed to this mixture at a rate of 4 ml/hr. Subsequently, the polymerization continued for about 1 hour. The solids content of the resulting latex was 37.7 percent. The latex particle size was 143 πm.
-16- Examples 4-23
Molecular Weight Determination
Examples 4-23 listed in Tables 2-6 represent molecular weight data of polymers described herein. The polymers in each of the tables correspond in structure to the figure referred to by each table. As can be seen, a wide variety of polymers can be made.
Table 2 - Figure 1 Structure
POLYMER SIDE CHAIN MAIN CHAIN Mn Mw/Mn AN
Example 4 MPEG 750 Jeffamine J-230 940 1.9 10.54
Example 5 MPEG 750 PEG 200 2220 2.3 17.68
Example 6 MPEG 750 PEG 600 1830 2.5 20.53
Figure imgf000019_0001
Table 3 - Figure 2 Structure
POLYME SIDE CHAIN SIDE MAIN Mn M„./Mn AN R CHAIN CHAIN
Example 7 Lgepal CO- MPEG 750 Neopentyl 2370 2.1 17.5 210 glycol
Example 8 Lgepal CO- MPEG 750 PEG 200 2720 2.3 14.2 210
Example 9 Lgepal CO- MPEG 750 PEG 400 2280 2.8 14.8 210
Example 10 Lgepal CO- MPEG 750 PEG 600 2330 2.1 17.7 210
Figure imgf000019_0002
Table 4 - Figure 3 Structure
POLYMER SIDE CHAIN MAIN CHAIN Mn M M, AN
Example 11 Lgepal CO-210 PEG 200 1500 3.5 22
Example 12 Lgepal CO-210 PEG 600 1240 2.6 18.99
Example 13 Lgepal CO-210 PEG 1000 1270 2.6 16.7
Example 14 Lgepal CO-210 PEG 1450 1900 2.8 16
Figure imgf000019_0003
-17- Table 5 - Figure 4 Structure
POLYMER SIDE CHAIN MAIN CHAIN Mn Mw/Mn AN
Example 15 Lgepal CO-210 PEG 200 900 2.4 19.62
Example 16 Lgepal CO-210 PEG 600 670 2.2 25.04
Example 17 Lgepal CO-210 PEG 1000 1560 2.6 16.78
Example 18 Lgepal CO-210 PEG 1450 1560 2.5 14
Figure imgf000020_0001
Table 6 - Figure 5 Structure
POLYMER SIDE CHAIN y Mn Mw/Mn AN
Example 19 MPEG 750 1 2800 1.9 0.6
Example 20 MPEG 750 2 2640 2 2.5
Example 21 MPEG 750 3 2650 2.5 1.2
Example 22 MPEG 750 5 3490 2.1 0.68
Example 23 MPEG 750 7 2150 2.9 3.8
Figure imgf000020_0002
The latex emulsion polymers which contain the polymers of the invention are useful in a number of applications. For example, the latex emulsion polymers may be used in printing inks, slasher dyeing, toner applications, sizing applications for use with glass or other fibers to improve strength, pigment encapsulation for imaging applications, coatings, and the like.
The applications for which the polymers can be used are many in number. The polymers themselves can be used as aids in dispersion or suspension polymerization, low profile additives, sizing and coating applications, hot melt adhesives, powder coatings, emulsifiers/dispersants for pigment dispersions and hydrophobic polymers (e.g., alkyds), and in general applications where low molecular weight surfactants have traditionally been used. It should be noted that the polymers can be used in non-aqueous (i.e., organic) solutions if so desired by the end user.
-18- Disclosed herein are typical preferred embodiments of the invention and, although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation of the scope of the invention.
-19-

Claims

THAT WHICH IS CLAIMED:
1. A polymer having designed hydrophobicity and hydrophilicity properties, said polymer being comprised of:
(a) at least one monomer residue of an aromatic dicarboxylic acid, wherein a side chain is attached from the aromatic ring and is described by the formula:
Q
I (I)
ΓÇö C=O
wherein Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof;
(b) at least one monomer residue of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or mixtures thereof; and (c) at least one monomer residue of an aliphatic alcohol, an aromatic alcohol, or mixtures thereof; wherein said monomer residues of (a), (b), and (c) are arranged to form the backbone of said polymer, and wherein the side chain of formula (I) is a pendant group extending from the polymer backbone.
2. The polymer according to Claim 1 , wherein Q is by the formula:
R
I z
I Y
I wherein: R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof;
-20- Y is selected from the group consisting of-O-, and -NH-; Z may be selected from the group consisting of-(CH2)n-; -(CH2CH2O)n- and
-CH-CH2O- I R51
wherein R51 is H or CH3; and n is an integer ranging from 1 to 50.
3. The polymer according to Claim 1 , wherein Q is selected from the group consisting of:
CH3
CH3 CH3 CH2
O ^ C6H4
CH2 CH2
O
1
A2Ϊ2 1 CH2
Tr^ C=O 1
O
1 CH2
Figure imgf000023_0001
C=O "cTn
C=O
wherein m is an integer ranging from 1 to 50; p is an integer ranging from 1 to 50; n is an integer ranging from 1 to 30; and p' is an integer ranging from 1 to 50.
-21-
4. A polymer according to Claim 1 , said polymer being represented by the formula:
Q
I
,c=o
Figure imgf000024_0001
O O
II II o-C C-OΓÇö R╬╣ -CΓÇö R2rΓÇö C-OΓÇö R12-
II II O o
SO3 "Na
O O
II II
-c C-O-R13-
Figure imgf000024_0002
wherein:
Ru. R12, R21, and R13 are each independently selected from the group consisting of a saturated hydrocarbon group and an unsaturated hydrocarbon group;
X may be selected from H or halogen;
Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof; and wherein x, y, and z are independently selected and are integers ranging from 0 to 20.
-22-
5. The polymer according to Claim 4, wherein Q is represented by the formula:
R
I z
I Y
wherein:
R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof;
Y is selected from the group consisting of-O-, and -NH-; Z may be selected from the group consisting of -(CH2)n-; -(CH,CH2O)n-, and
-CH-CH2O-
I R51
wherein R5I is H or CH3; .and n is an integer ranging from 1 to 50.
-23-
6. The polymer according to Claim 4, wherein Q is selected from the group consisting of:
CH3 CH3 O
CH2
CH2 1 CH2 1
Figure imgf000026_0001
"
Figure imgf000026_0002
' Υx
O C=O
CH2
C=O O " I C=0
wherein m is an integer ranging from 1 to 50; p is an integer ranging from 1 to 50; n is an integer ranging from 1 to 30; and p' is an integer ranging from 1 to 50.
7. The polymer according to Claim 4, wherein x=l ; y=0; z=l; R,,is represented by the formula -(OCH2CH2)u- wherein u is an integer ranging from 1 to 50; X is -H; and R13 is represented by the formula -(OCH2CH2)v- wherein v is an integer ranging from 1 to 50.
-24-
8. The polymer according to Claim 1 , wherein said polymeric surfactant is represented by the formula:
z
I o
C=0
O O CH3 CΓÇö
Figure imgf000027_0001
|| I / ■ϊ O IIΑ> 0 CH3 O O
ΓÇóO- \ / II I x II II
CΓÇö 0-CH2CCH2ΓÇö O -C-^ ^C-0-CH2CCH2-O - ΓÇö CΓÇö CH=CH-C
CH3 CH3 f
Figure imgf000027_0002
-Y ,
wherein e is an integer ranging from 5 to 40; and f is an integer ranging from 0 to 15.
9. The polymer according to Claim 1, wherein said polymer displays surface active properties and is a polymeric surfactant.
10. A latex emulsion composition comprising: a latex emulsion polymer; and a polymer used for stabilizing the latex emulsion polymer, said polymer being comprised of:
(a) at least one monomer residue of an aromatic dicarboxylic acid, wherein a side chain is attached from the aromatic ring and is described by the formula:
Q I (i) -C=O
wherein Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof;
-25- (b) at least one monomer residue of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or mixtures thereof; and
(c) at least one monomer residue of an aliphatic alcohol, an aromatic alcohol, or mixtures thereof; wherein said monomer residues of (a), (b), and (c) are
> arranged to form the backbone of said polymer, and wherein the side chain of formula (I) is a pendant group extending from the polymer backbone, and wherein said polymer displays surface activity; wherein said polymer interacts with said latex emulsion polymer to stabilize said latex emulsion polymer. Q
11. The composition according to Claim 10, wherein Q is by the formula:
R
I z
I Y
5 wherein:
R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof;
Y is selected from the group consisting of-O-, and -NH-;
Z may be selected from the group consisting of-(CH2)n-, -(CH2CH2O)n-, 0 and
-CH-CH2O-
I R╬┤1
5 wherein R51 is H or CH3; and n is an integer ranging from 1 to 50.
-26-
12. The composition according to Claim 10, wherein Q is selected from the group consisting of:
CH3 CH3 O
I y"r CH2 CH2 -I — n Υ
CH2 O I C=O
I C=O
Figure imgf000029_0001
C=O
wherein m is an integer ranging from 1 to 50; p is an integer ranging from 1 to 50; n is an integer ranging from 1 to 30; and p' is an integer ranging from 1 to 50.
-27-
13. The composition according to Claim 10, wherein said polymer is represented by the formula:
O O
II II
CΓÇö R2╬╣ΓÇö C-OΓÇö R12-
Figure imgf000030_0001
SO3 " Na
O O
II II
-c- C-O-R13-
Figure imgf000030_0002
wherein:
Rπ. R12, R2„ and R13 are each independently selected from the group consisting of a saturated hydrocarbon group and an unsaturated hydrocarbon group;
X may be selected from H or halogen;
Q is a substituent having a hydrophilic group, a hydrophobic group, or mixtures thereof; and wherein x, y, and z are independently selected and are integers ranging from 0 to 20.
-28-
14. The composition according to Claim 13, wherein Q is represented by the formula:
R
I z
I Y
wherein:
R is a substituent containing an alkyl group, an aromatic group, or mixtures thereof;
Y is selected from the group consisting of-O-, -NH-; Z may be selected from the group consisting of -(CH2)n-; -(CH2CH2O)n-, and
-CH-CH2O-
I
R51
wherein R51 is H or CH3; and n is an integer ranging from 1 to 50.
-29-
15. The composition according to Claim 13, wherein Q is selected from the group consisting of:
CH3
CH3 CH3 CH2. fΛ
O C6H4
CH2 f ╬│ H2 I CH2
O t^ C=O I
CH2 c=o ~ς y
' I
C=O
wherein m is an integer ranging from 1 to 50; p is an integer ranging from 1 to 50; n is an integer ranging from 1 to 30; and p' is an integer ranging from 1 to 50.
16. The composition according to Claim 13, wherein y is 0; x is 1; z is 1; R,, is represented by the formula:
ΓÇö (OCH2CH2)ΓÇö
wherein u is an integer ranging from 1 to 50; X is hydrogen; and R13 is represented by the formula:
-(OCH2CH2)ΓÇö v
wherein v is an integer ranging from 1 to 50.
-30-
17. The composition according to Claim 10, wherein said polymer is represented by the formula:
z
I o
O c I=o
II O CH3 O U )) 0 CH3 O O OΓÇö C
Figure imgf000033_0001
II I / • ° iIiI< AπS-AV>° n II I N II II
CΓÇö 0-CH2CCH2ΓÇö ╬╕f-C-^ ^-C-0-CH2CCH2-0^- ΓÇö CΓÇö CH= CH-C CH3 CH3 f
wherein e is an integer ranging from 5 to 40; and f is an integer ranging from 0 to 15.
18. The composition according to Claim 10, wherein said latex emulsion polymer is formed from at least one monomer selected from the group consisting of an aliphatic conjugated diene monomer, a non-aromatic unsaturated ester monomer, an aromatic unsaturated monomer, a monomer based on the half ester of an unsaturated dicarboxylic acid monomer, an unsaturated mono- or dicarboxylic acid monomer, an unsaturated nitrogen-containing monomer, a monoethylenically unsaturated aliphatic hydrocarbon, a vinyl ester monomer, and mixtures thereof.
-31-
PCT/US1999/005594 1998-03-16 1999-03-15 Surface active polyesters WO1999047578A1 (en)

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US6699931B2 (en) 2001-04-09 2004-03-02 Eastman Chemical Company Modified alkyd compositions comprising diol latex compositions and processes of making the same
US6844390B2 (en) 2001-04-09 2005-01-18 Eastman Chemical Company Modified alkyd compositions comprising polyol latex compositions and processes of making them
US9067821B2 (en) 2008-10-07 2015-06-30 Ross Technology Corporation Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
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US9914849B2 (en) 2010-03-15 2018-03-13 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
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US9532649B2 (en) 2008-06-27 2017-01-03 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US11786036B2 (en) 2008-06-27 2023-10-17 Ssw Advanced Technologies, Llc Spill containing refrigerator shelf assembly
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US9179773B2 (en) 2008-06-27 2015-11-10 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US9207012B2 (en) 2008-06-27 2015-12-08 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
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US9279073B2 (en) 2008-10-07 2016-03-08 Ross Technology Corporation Methods of making highly durable superhydrophobic, oleophobic and anti-icing coatings
US9926478B2 (en) 2008-10-07 2018-03-27 Ross Technology Corporation Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
US9243175B2 (en) 2008-10-07 2016-01-26 Ross Technology Corporation Spill resistant surfaces having hydrophobic and oleophobic borders
US9067821B2 (en) 2008-10-07 2015-06-30 Ross Technology Corporation Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
US9074778B2 (en) 2009-11-04 2015-07-07 Ssw Holding Company, Inc. Cooking appliance surfaces having spill containment pattern
US9914849B2 (en) 2010-03-15 2018-03-13 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
US9546299B2 (en) 2011-02-21 2017-01-17 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
US10240049B2 (en) 2011-02-21 2019-03-26 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
US10317129B2 (en) 2011-10-28 2019-06-11 Schott Ag Refrigerator shelf with overflow protection system including hydrophobic layer
US9528022B2 (en) 2011-12-15 2016-12-27 Ross Technology Corporation Composition and coating for hydrophobic performance
US9139744B2 (en) 2011-12-15 2015-09-22 Ross Technology Corporation Composition and coating for hydrophobic performance
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