Multiamine polyester dispersants made via anhydride intermediates

Abstract

The present invention relates to dispersants derived from alcohol-terminated polymers via an anhydride intermediate. The anhydride-functionalized polyester is then reacted with a multiamine species to form amide and salt bonds. The present invention also provides dispersants having the structure of Formula I, where X is RQ or a cyclic amine. When X is RQ, R is a hydrocarbon chain containing 1 to 50 carbon atoms, and Q is O or NR 7 or NH, provided that when n is 0 and b is 0, Q can only be NH, and R 7 is a straight or branched hydrocarbon chain containing 1 to 18 carbon atoms, which may optionally contain ether, ester, or amide functional groups or halide substituents. X may also represent a cyclic secondary amine.

Description

[Technical field]

[0001] The present invention relates to dispersants of the multiamine species (polyamines such as polyethyleneimine) reacted with polyester and / or polyether chains, and to a method of making the dispersants via an anhydride intermediate. [Background technology]

[0002] Polyamine-based dispersants are generally understood to be effective as pigment dispersants. The composition and molecular weight of the sterically stabilized chains of these dispersants are important to effectively disperse solids in both polar and non-polar continuous media. Many formulations, such as inks, paints, mill bases, and plastic materials, require dispersants to uniformly disperse particulate solids in organic media. Therefore, it is desirable for pigment dispersions to be compatible with a variety of ink or coating formulations.

[0003] It has also been found that multi-amine based dispersants with a mixture of salt and amide bonds provide more effective dispersants. However, these dispersants can be difficult to make using alcohol-terminated polymers. It would be desirable to have a dispersant that contains both internal salt and amide bonds, but can be conveniently prepared from alcohol-terminated polyether and / or polyester based polymers. Summary of the Invention [Means for solving the problem]

[0004] The present invention provides a method for preparing a dispersant from an alcohol-terminated polymer having the formula: [ka] A method for preparing a dispersant of formula I includes: (a) providing a compound of formula X—(CHCHR 1 -O) n- [R 5 -N(R 6 )] b- [(C=O)R 2-O] m The method includes the steps of: (a) providing an alcohol-terminated polymer of formula II; (b) reacting the alcohol-terminated polymer with a cyclic anhydride to provide an acid-terminated polymer; (c) reacting the acid-terminated polymer with a non-cyclic anhydride to provide a mixture of anhydrides; and (d) reacting the mixture of anhydrides with a multiamine species, the multiamine species having a number average molecular weight of 300 to 20,000 to form a dispersant molecule, where q and t are each at least 1 such that the dispersant contains both amide and salt bonds. In formula II, X represents either RQ or a cyclic secondary amine. When X is RQ, R is a branched or straight chain, saturated or unsaturated, or cyclic hydrocarbon chain containing 1 to 50 carbon atoms, and Q is O or NR 7 or NH, provided that when n is 0 and b is 0, Q can only be NH; R 7 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 18 carbon atoms, which may optionally contain ether, ester, or amide functional groups or halide substituents. Alternatively, X may also be a cyclic amine structure derived from one or more cyclic secondary amines. In formula II, R 1 is H, methyl, or ethyl; R 5 is a linear or branched hydrocarbon chain containing up to 3 carbon atoms, R 6 is hydrogen, a hydrocarbyl group containing 1 to 22 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide. The variable b is 0 or 1, except that when both n and m are both at least 1, then b can only be 1. R 2 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 15 carbon atoms or -R 8 (C=O)YR 9 where Y is O, NH, or NR 10 and R 8 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 9 is a hydrocarbon chain containing 2 to 10 carbon atoms, and R 10is a hydrocarbon chain containing 1 to 20 carbon atoms. In some embodiments, R 10 R may contain an ester, ether, or amide group. 2 is a hydrocarbon chain containing 1 to 15 carbon atoms, R 2 In one embodiment, R may be a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms, and in another embodiment, R 2 is the formula -N(R 11 )-(C=O)-, and may be a hydrocarbon chain containing 2 to 15 carbon atoms, including an amide functional group, wherein R 11 is H or a hydrocarbon chain containing 1 to 4 carbon atoms. In Formula II, n is any integer from 0 to 65, and m is any integer from 0 to 35, with the proviso that m+n is at least 3.

[0005] The present invention also provides a dispersant having a structure of Formula I, where X is RQ or a cyclic amine. When X is RQ, R is a hydrocarbon chain containing 1 to 50 carbon atoms and Q is O or NR 7 or NH, with the proviso that when n is 0 and b is 0, Q can only be NH; R 7 is a linear or branched hydrocarbon chain containing 1 to 18 carbon atoms, which may optionally contain ether, ester, or amide functional groups or halide substituents. X may also represent a cyclic secondary amine. In formula I, R 1 is H, methyl, or ethyl; R 5 is a linear or branched hydrocarbon chain containing up to 3 carbon atoms, R 6 is hydrogen, a hydrocarbyl group containing 1 to 50 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide; b is 0 or 1, except that when both n and m are both at least 1, then b can only be 1; R 2 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 15 carbon atoms or -R 8 (C=O)YR 9 -, where Y is O, NH or NR 10and R 8 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 9 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 10 R is a hydrocarbon chain containing 1 to 20 carbon atoms, which may contain ester, ether, or amide groups. 2 is a hydrocarbon chain containing 1 to 15 carbon atoms, R 2 In one embodiment, R may be a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms, and in another embodiment, R 2 is the formula -N(R 11 )-(C=O)-, and may be a hydrocarbon chain containing 2 to 15 carbon atoms, including an amide functional group, wherein R 11 is H or a hydrocarbon chain containing 1 to 4 carbon atoms. The variable n is any integer from 0 to 65, and the variable m is any integer from 0 to 35, provided that m+n is at least 3. 3 is a straight or branched, saturated or unsaturated hydrocarbon containing 2 to 80 carbons. The variables q and t are each at least 1, but q+t can be any integer from 2 to 150. MA is a multiamine species having a number average molecular weight of 300 to 20,000 g / mol. The variables p or z can each be 0, or p+z can be 0, or 1, or any integer from 2 to 200, and R 4 is a linear or branched saturated carbon chain containing 1 to 4 carbons, for example 1 to 3 carbons. In one embodiment, in formula I, n is 0. In another embodiment, in formula I, n is any integer from 3 to 65, and m is 0. In yet another embodiment, in formula I, m is 0. In another embodiment, in formula I, m is any integer from 3 to 35, for example 5 to 16, and n is 0. In another embodiment, in formula I, both n and m are positive integers, and n+m is 3 to 65, for example 5 to 30. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] In the detailed description and claims that follow, the term "hydrocarbyl" will refer to a monovalent hydrocarbon group that may optionally contain other heteroatoms (such as O and N) in conventional or specified amounts, such as one oxygen and / or nitrogen for every two or ten carbon atoms in the group, but preferably contains only carbon and hydrogen. As used broadly herein, the term "hydrocarbon chain" will refer to a compound that contains carbon and hydrogen, including variants that are branched, straight-chain, saturated, unsaturated, or cyclic in structure. The hydrocarbon chain may optionally contain other atoms, such as heteroatoms, including oxygen in the form of an ether group, or nitrogen in the form of an amide group.

[0007] The present invention relates to a dispersant having the following structure: [ka] The dispersant molecule may specifically include polyether species, polyester species, or a combination of both polyether and polyester. Additionally, the dispersant molecule may contain both amide and salt linkages.

[0008] In one embodiment, in formula I, X represents an RQ group or a cyclic amine group. When X is RQ, R represents a branched or linear, saturated or unsaturated hydrocarbon chain containing 1 to 50 carbon atoms, for example 1 to 30 carbon atoms. In one embodiment, R may optionally include a halogen, such as Cl or F, or a heteroatom, such as an N or O atom, present as a tertiary amine or ether group, or mixtures thereof. In some embodiments, the hydrocarbon chain may be selected from an alkyl, aryl, aralkyl, or alkylaryl hydrocarbon chain. In one embodiment, R is aryl, including naphthyl, phenyl, or biphenyl. In one embodiment, R is aralkyl, including 2-phenylethyl or benzyl. In one embodiment, R may be alkaryl, including octylphenyl or nonylphenyl. In another embodiment, R is C, such as cyclopropyl or cyclohexyl. 3~8 -cycloalkyl, including cycloalkyl.

[0009] In formula I, Q is O, NR 7 or NH, provided that when n is 0 and b is 0, Q can only be NH. 7 can be a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 18 carbon atoms, which may optionally include ether, ester, or amide functional groups or halide substituents. In some embodiments, R 7 may also be derived from an acrylate, methacrylate, acrylamide or methacrylamide.

[0010] In another embodiment, RQ is derived from an alcohol or an amine or mixtures thereof. Useful alcohols include methanol, ethanol, n-propanol, n-butanol, neopentyl alcohol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, oleyl alcohol, n-octadecanol, isopropanol, isobutanol, tert-butanol, 2-ethylbutanol, 2-ethylhexanol, 3-heptanol, 3,5,5-trimethylhexanol, 3,7-dimethyloctanol, cyclohexanol, cyclopentanol, cyclopentanemethanol, cyclohexylmethanol, 4-cyclohexyl-1-butanol, 4-ethylcyclohexanol, cycloheptanol, phenol, o-cresol, 2-ethylphenol, 2-propylphenol, 4-ethylphenol, octylphenol, nonylphenol, dodecylphenol, di- and tri-styrylphenol. , benzyl alcohol, 2-phenylethanol, 1-naphthol, 2-naphthol, 2-phenylphenol, 4-phenylphenol, polyisobutylenephenol, sec-phenethyl alcohol, 4-ethylbenzyl alcohol, 4-butylbenzyl alcohol, 2-naphthalenemethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, cinnamyl alcohol and 4-propoxyphenol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dibutylaminoethanol, 2-propen-1-ol, allyl alcohol, 4-penten-1-ol, 2-hexen-1-ol, 3-nonen-1-ol, 7-dodecen-1-ol, 2-allyloxyethanol, 2-allylphenol, 2-vinyloxyethanol, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, trade name Unilin (Baker Hughes), and saturated branched alcohols (including mixtures thereof), such as "Guerbet" alcohol, available under the trade name Isofol (available from Sasol GmbH).Specific examples of commercially available Guerbet alcohols are Isofol 12, 14T, 16, 18T, 18E, 20, 24, 28, 32, 32T and 36.Useful amines include primary amines: methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undeylamine, dodecylamine, tridecylamine, 1-tetradecylamine, pentadecylamine, 1-hexadecylamine, octadecylamine, isopropylamine, sec-butylamine, isobutylamine, tert-butylamine, 1-methylbutylamine, 1,3-dimethylbutylamine, 1,4-dimethylbutylamine, 1,5-dimethylbutylamine, 1,6-dimethylbutylamine, 1,7-dimethylbutylamine, 1,8-dimethylbutylamine, 1,9-dimethylbutylamine, 1,10-dimethylbutylamine, 1,11-dimethylbutylamine, 1,20-dimethylbutylamine, 1,21-dimethylbutylamine, 1,32-dimethylbutylamine, 1,33-dimethylbutylamine, 1,41-dimethylbutylamine, 1,42-dimethylbutylamine, 1,52-dimethylbutylamine, 1,53-dimethylbutylamine, 1,62-dimethylbutylamine, 1,73-dimethylbutylamine, 1,82-dimethylbutylamine, 1,93-dimethylbutylamine, 1,12-dimethylbutylamine, 1,13-dimethylbutylamine, 1,14-dimethylbutylamine, 1,15-dimethylbutylamine, 1,16-dimethylbutylamine, 1,17-dimethylbutylamine, 1,18-dimethylbutylamine, 1,19-dimethylbutylamine, 1,22-dimethylbutylamine, 1,23-dimethylbutylamine, 1,24-dimethylbutylamine, 1,25-dimethylbutylamine, 1,36-dimethylbutylamine, 1,37-dimethylbutylamine, 1,38-dimethylbutylamine, 1,39-dimethylbutylamine, 1,41-dimethylbutylamine, 1,42-dimethyl ethylamine, 3,3-dimethylbutylamine, 2-ethylhexylamine, 3-dimethylaminopropylamine, N-methylethylenediamine, N,N'-dimethylethylenediamine, cyclopentylamine, cyclohexylamine, cyclohexanemethylamine, cycloheptylamine, allylamine and oleylamine, aniline, 2-ethylaniline, 4-butylaniline, 4-cyclohexylaniline, 4-aminobiphenyl, 1-aminonaphthalene, 2-aminonaphthalene, benzylamine, phenethylamine, 3 -phenyl-1-propylamine, 3-aminopropylimidazole, 4-phenylbutylamine, m-anisidine and p-phenetidine; and secondary amines: dimethylamine, N-ethylmethylamine, diethylamine, dipropylamine, diisopropylamine, N-methylbutylamine, N-methyl-tert-butylamine, dibutylamine, dihexylamine, di-(2-ethylhexyl)amine, diisobutylamine, di-nonylamine, dipentylamine, di-dodecylamine, dioctylamine, didodecylamine, Amines include, but are not limited to, N-methyloctadecylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine, bis(2-methoxyethyl)amine, N-methylallylamine, diallylamine, N-methylaniline, N-ethylaniline, N-butylaniline, diphenylamine, N-ethyl-1-naphthylamine, N-benzylmethylamine, dibenzylamine, N-ethylbenzylamine, and N-methylphenylamine (including mixtures thereof).

[0011] When X is a cyclic amine, it is derived from a cyclic secondary amine. Useful cyclic secondary amines include, but are not limited to, piperidine, morpholine, 4-methylpiperidine, 4-phenylpiperidine, thiomorpholine, azetidine, 1-methylpiperazine, 2-methylpiperazine, and pyrrolidine, including mixtures thereof.

[0012] In the present invention, the dispersant molecule of formula I may contain polyether chains, polyester chains, polyesteramide chains, or combinations of these various chains, such as polyether-co-polyester, polyether-co-polyesteramide, polyether-co-polyester-co-polyesteramide, or polyester-co-polyesteramide chains. Thus, in one embodiment, the sum of the variables m+n in the present invention is at least 3. For example, m+n may be from 3 to 65, such as from 5 to 50. In one embodiment of the present invention, n may be any integer from 0 to 65. In another embodiment, n may be any integer from 1 to 65, such as at least 2, 3, 4, or even such as from 5 to 50. In yet another embodiment, n is 0. The variable m may be any integer from 0 to 35. In one embodiment, m may be any integer from 1 to 35, such as at least 2, 3, 4, or even such as from 5 to 16. In another embodiment, m is 0.

[0013] In embodiments of Formula I that contain a polyether segment (i.e., n is 1 or greater), R 1can be H, methyl, or ethyl groups. The polyether segments are derived from the ring-opening reaction of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof. In one embodiment of the invention, n can be any integer from 0 to 65. In another embodiment, n is any integer from 1 to 65, such as at least 2, 3, 4, or even such as 5 to 30. In yet another embodiment, n is 0. The polyether segments can be synthesized by any method known to those skilled in the art, including, but not limited to, polymerizing alkylene oxides in the presence of a monoalcohol or a secondary amine to initiate polyether chain extension. The polymerization can be conveniently carried out in the presence of a base catalyst, such as potassium hydroxide or sodium hydroxide, at a temperature of 50° C. to 150° C. or 70° C. to 140° C., preferably under pressure to prevent loss of volatile alkylene oxide. In one embodiment, polyether monoalcohol compounds of formula II, where n is 3 or more and b and m are both 0, are commercially available. Examples include, but are not limited to, polypropylene glycol monobutyl ether, poly(ethylene glycol-lan-propylene glycol) monobutyl ether, or polyethylene glycol monomethyl ethers of various molecular weights from Aldrich, or Synalox from Dow, or Polyglykol from Clariant. Specific examples of Synalox™ are 100-D20, 100-40B, 100-50B, 100-D95, and 100-150B. Specific examples of Polyglykol™ are B01 / 20, B01 / 40, B01 / 80, B01 / 120, and B01 / 240. Polypropylene glycol monoisotridecyl ether ether is available from Clariant under the Polyglykol™ trade name, an example being T01 / 35. Other monosubstituted alk(en)yl ethers, cycloalkyl ethers or aryl ethers of polyethylene oxide are also available from a variety of sources, such as Sigma-Aldrich, Croda, Clariant, BASF, Dow, and Ineos.

[0014] In an embodiment of Formula I, the variable b is 0 or 1, except that b can only be 1 when both n and m are at least 1. In one embodiment, b is 1 and the sum of the variables, m+n, is at least 4. 5 represents a linear or branched hydrocarbon chain containing up to 3 carbon atoms; R 6 represents hydrogen (H), a hydrocarbyl group having 1 to 22 carbon atoms, which may optionally contain ether, ester, tertiary amine, or amide functionality. In one embodiment, R 6 may be an alkyl (meth)acrylate or a (meth)acrylamide. In one embodiment, R 6 comprises the residue of an alkyl (meth)acrylate, or a mixture thereof. In one embodiment, R 6 is an alkyl acrylate, and in another embodiment, R 6 is an alkyl methacrylate. In one embodiment, R 6 is an alkylacrylamide, and in another embodiment, R 6 is an alkyl methacrylamide. In one embodiment, R 6 is H. Examples of suitable alkyl (meth)acrylates or (meth)acrylamides include those (meth)acrylate or (meth)acrylamide compounds, where the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2-dimethylaminoethyl, 3-dimethylaminopropyl, or mixtures thereof. As used herein, the expression (meth)acrylate or (meth)acrylamide includes acrylate or methacrylate, or mixtures thereof, or acrylamide or methacrylamide, or mixtures thereof.

[0015] In some embodiments of formula I that contain both polyether segments (i.e., n is 1 or greater) and polyester or polyesteramide segments or mixtures thereof (i.e., m is 1 or greater) and b is 0, the polyether segments are derived from the ring-opening reaction of alkylene oxides in the presence of monoalcohols or secondary amines to initiate polyether chain extension, or are derived from the commercially available polyether monoalcohols disclosed above.

[0016] In another embodiment of Formula I containing both polyether segments (i.e., n is 1 or greater) and polyester or polyesteramide segments or mixtures thereof (i.e., m is 1 or greater) and b is 1, the polymer may be a residue of Formula II, i.e., X-(CHCHR 1 -O) n- [R 5 -N(R 6 )] bmay include polyetheramines, such as polyalkylene oxide monoalkyl or aryl ether monoamines. The polyetheramines may be synthesized by any method known to those skilled in the art, including but not limited to ring-opening reaction of an alkylene oxide, such as ethylene oxide, propylene oxide, or butylene oxide or mixtures thereof, in the presence of a monoalcohol initiator to form an alcohol-terminated polyether chain, followed by conversion of the alcohol-terminated polyether chain to an amine using known amination reaction conditions, such as ammonia, in the presence of a metal catalyst, as described in US 3,654,370, US 4,618,717, US 4,960942, and US 5,457,147. In one embodiment, the polyetheramines may be obtained by alkoxylation of amino alcohols, as described in US 5,879,445 (particularly the disclosure in column 2, line 50 to column 7, line 50). In another embodiment, polyetheramines can be obtained by base-catalyzed addition of alcohol-terminated polyether chains to acrylonitrile followed by hydrogenation to obtain amine-terminated polyether chains. Polyetheramines are commercially available from Huntsman Corporation under the tradename Jeffamine™ M series or Surfonamine™ B and L series monoamines. Specific examples of Jeffamine™ amines are M-600 (9,1,600), M-1000 (3,19,1000), M-2005 (29,6,2000), M2095 (4,41,2000) and M-2070 (10,31,2000). Specific examples of Surfonamine™ amines are B-60 (9,1,600), L-100 (3,19,1000), B-200 (29,6,2000), B100 (12.5,0,1000), L200 (4,41,2000), L207 (10,31,2000) and L300 (8,58,3000). The numbers in parentheses are the approximate repeat units of propylene oxide, ethylene oxide and number average molecular weight, respectively. Commercially available polyetheramines such as those described herein can be incorporated into the alcohol-terminated polymers of formula II by means understood by those skilled in the art.

[0017] In embodiments of Formula I that contain polyester segments (i.e., m is 1 or greater), R 2 is a branched or linear, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms, for example 2 to 7 carbon atoms, or -R 8 (C=O)YR 9 where Y is oxygen and R 8 is a branched or linear, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms; R 9 is a branched or linear, saturated or unsaturated hydrocarbon chain containing 2-10 carbon atoms, which may also include heteroatoms such as oxygen present as ether groups. The variable m may be any integer from 0 to 35. In one embodiment, m may be any integer from 1 to 35, such as at least 2, 3, 4, or even such as 5 to 16. In another embodiment, m is 0. The polyester segment may be synthesized by any method known to one skilled in the art, including, but not limited to, (i) the polymerization of lactones and / or hydroxycarboxylic acids in the presence of monoalcohols or amines to initiate polyester chain extension, or (ii) the polymerization reaction of diols with diacids or derivatives thereof (e.g., acid chlorides, anhydrides, or dialkyl esters) in the presence of stoichiometric amounts of monoalcohols or amines to control molecular weight and inhibit the formation of dicarboxylic acid polyesters, which may be conveniently carried out at temperatures between 50° C. and 250° C. or between 70° C. and 200° C., optionally in the presence of an esterification catalyst and under an inert atmosphere. The inert atmosphere can be provided by any inert gas of the periodic table, but is preferably nitrogen. The esterification catalyst can be any previously known in the art, including, but not limited to, tetraalkyl titanates, such as tetrabutyl titanate, zinc salts of organic acids, such as zinc acetate, zirconium salts of aliphatic alcohols, such as zirconium isopropoxide or zirconium butoxide, methanesulfonic acid, toluenesulfonic acid, phosphoric acid, diphenyl phosphate, or strong organic acids such as trifluoroacetic acid.

[0018] In another embodiment, the synthesis of the polyester segment can be accomplished by any method known or hereafter developed without departing from the scope of the present invention. For example, the polyester segment can be synthesized by polymerizing hydroxycarboxylic acids and / or lactones in the presence of monoalcohols or amines to initiate polyester chain extension. The raw materials used can also include those now known or hereafter developed. Specific examples of suitable hydroxycarboxylic acids are glycolic acid and lactic acid, including their cyclic dimers, glycolide and lactide, 6-hydroxycaproic acid, 5-hydroxyvaleric acid, 5-hydroxydodecanoic acid, 10-hydroxyundecanoic acid and 4-hydroxydecanoic acid or mixtures thereof. Examples of lactones include C1-4 alkyl substituted ε-caprolactone or optionally substituted C1-4 alkyl δ-valerolactone and β-propiolactone or mixtures thereof. The alkyl substituents in ε-caprolactone and δ-valerolactone can be C1-4-alkyl and can be linear or branched. Examples of suitable lactones are ε-caprolactone and its 7-methyl-, 2-methyl-, 3-methyl-, 5-methyl-, 6-methyl-, 4-methyl-, 5-tert-butyl-, 4,4,6-trimethyl-, and 4,6,6-trimethyl analogs and δ-valerolactone and β-methyl-δ-valerolactone analogs.

[0019] In another embodiment, the polyester segment can be synthesized by the polymerization reaction of a diol with a diacid or its derivative (e.g., acid chloride, anhydride, or dialkyl ester) in the presence of a stoichiometric amount of a monoalcohol or amine to control the molecular weight and suppress the formation of dicarboxylic acid polyesters. 9Specific examples of suitable diols from which the hydrocarbon chain is generated include alkylene glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, cis and trans 1,2- and 1,4-cyclohexanedimethanol, diols having ether bonds such as diethylene glycol, dipropylene glycol, tripropylene glycol and triethylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, mixed block and random copolymers of polyethylene glycol and polypropylene glycol having a number average molecular weight (MW) of less than 1000 (Pluronic™ and reverse Pluronic™, formerly manufactured by BASF), and the like. 8 Specific examples of suitable dibasic acids, diesters, and anhydrides from which the hydrocarbon chains arise include maleic anhydride, succinic anhydride, glutaric acid, fumaric acid, malonic acid, adipic acid, sebacic acid, phthalic anhydride, pimelic acid, dimer fatty acids and their hydrogenated forms, and cyclohexanedicarboxylic anhydride. Specific examples of alcohols and amines used to initiate the polymerization of the polyester segments have been disclosed above.

[0020] In embodiments of Formula I that contain polyesteramide segments (i.e., m is 1 or greater), R 2 is the amide functional group -N(R 11 )-(C=O)-, a hydrocarbon chain containing 2 to 15 carbon atoms, wherein R 11 is H or a hydrocarbon chain containing 1 to 4 carbon atoms, or R 2 -R 8 (C=O)YR 9 -, where Y is nitrogen and R 8 is a branched or linear, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms; R 9is a branched or linear, saturated or unsaturated hydrocarbon chain containing 2-10 carbon atoms, which may also include heteroatoms such as oxygen present as ether groups. The variable m may be any integer from 0 to 35. In one embodiment, m may be any integer from 1 to 35, such as at least 2, 3, 4, or even such as 5 to 16. In another embodiment, m is 0. The polyesteramide segment may be synthesized by any method known to one skilled in the art, including, but not limited to, (i) polymerization of a lactone with an amino carboxylic acid in the presence of a monoalcohol or amine to initiate polyesteramide chain extension, or (ii) polymerization reaction of an amino alcohol with a diacid or a derivative thereof (e.g., acid chloride, anhydride, or dialkyl ester) in the presence of a stoichiometric amount of a monoalcohol or amine to control molecular weight and inhibit the formation of a dicarboxylic acid polyester.

[0021] In another embodiment, the synthesis of the polyesteramide segment can be accomplished by any method known or hereafter developed without departing from the scope of the present invention. For example, the polyesteramide segment can be synthesized by polymerizing a lactone with an amino carboxylic acid in the presence of a monoalcohol or amine to initiate polyesteramide chain extension, which can be conveniently carried out at temperatures between 50°C and 250°C or between 70°C and 200°C, optionally in the presence of an esterification catalyst and in an inert atmosphere. The inert atmosphere and esterification catalysts have been previously known in the art and include, but are not limited to, those previously disclosed. The raw materials used can also include those now known or hereafter developed. Specific examples of suitable amino carboxylic acids (or amino acids) include 11-aminoundecanoic acid, 12-aminododecanoic acid, 6-aminocaproic acid, 4-aminobutyric acid, β-alanine, glycine, and sarcosine. Mixtures of amino carboxylic acids can be used. Specific examples of suitable lactones, alcohols, and amines have been previously disclosed.

[0022] In another embodiment, the synthesis of polyesteramide segments can be achieved by polymerization reaction of an amino alcohol with a diacid or its derivative (e.g., acid chloride, anhydride, or dialkyl ester) in the presence of a stoichiometric amount of a monoalcohol or amine to control the molecular weight and suppress the formation of dicarboxylic acid polyesters. The amino alcohol can be a C2-10 amino alcohol and can also contain heteroatoms such as oxygen present as ether groups. Specific examples of suitable amino alcohols include ethanolamine, 3-amino-1-propanol, 4-aminobutanol, 2-aminobutanol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 5-amino-2-pentanol, 2-amino-3-methyl-1-butanol, 6-amino-1-hexanol, 2-amino-1-hexanol, serinol, 4-aminocyclohexanol, 2-(2-aminoethoxy)ethanol, or mixtures thereof. Specific examples of suitable diacids, diesters and anhydrides, alcohols and amines have been disclosed above.

[0023] In Formula I, R 3 comprises a branched or straight chain, saturated or unsaturated hydrocarbon chain containing from 2 to 80 carbon atoms. 3 is a linear saturated carbon chain containing 20 carbons. In another embodiment, R 3 is derived from a cyclic anhydride.

[0024] In formula I, the variables q and t are each at least 1, so that each dispersant molecule contains a mixture of both salt and amide linkages. In one embodiment, q+t is any integer from 2 to 200, for example, from 2 to 150, where q is greater than or equal to t.

[0025] In formula I, MA represents a multiamine species. In one embodiment, the multiamine species used in the present invention may have a number average molecular weight (MW) of 300 to 20,000 g / mole, e.g., 300 to 10,000 g / mol, as measured by ebulliometric analysis. In another embodiment, the MA comprises at least four amines. In one embodiment, the MA is a polyamine and is selected from polyethyleneimine, modified polyethyleneimine, polyallylamine, modified polyallylamine, polyvinylamine, modified polyvinylamine, or mixtures thereof. In one embodiment, at least 70, 80, 90, or 95 weight percent of the multiamine species is polyethyleneimine.

[0026] MA can be linear or branched. Linear polyethyleneimine can be prepared by hydrolysis of poly(N-acyl)alkylenimine, for example, as described in Takeo Saegusa et al., Macromolecules, 1972, Vol. 5, page 4470. Branched polyethyleneimines of different molecular weights are commercially available from BASF and Nippon Shokubai. Polyallylamines and poly-(N-alkyl)allylamines of different molecular weights are commercially available from Nitto Boseki. Polyvinylamines of different molecular weights are available from Mitsubishi Kasei. Poly(propyleneimine) dendrimers are commercially available from DSM Fine Chemicals, and poly(amidoamine) dendrimers are available as "Starburst" dendrimers from Aldrich Chemical Co. In one embodiment, MA is poly(C2-6-alkylenimine) and / or polyethyleneimine.

[0027] In another embodiment, the MA is modified by reacting a portion of its primary and / or secondary amino groups with an ester such as ethyl acetate or butyl acetate, an isocyanate such as phenyl isocyanate, a lactone such as ε-caprolactone and δ-valerolactone, an anhydride such as succinic acid, maleic acid, phthalic acid, isatoic acid, anhydrides such as 1,2-naphthalic anhydride, 1,8-naphthanoic anhydride or 1,2,4-benzenetricarboxylic anhydride, a cyclic carbonate such as ethylene carbonate, a (meth)acrylate such as ethyl acrylate or 2-hydroxyethyl acrylate, or an epoxide such as phenyl glycidyl ether, while ensuring that the primary and / or secondary amino groups of the modified polyamine are still unmodified and still in the form of an amine.

[0028] In another embodiment, the MA can be a polyethyleneimine. The polyethyleneimine can be modified by replacing one or more protons of the NH units with C2-4 alkyleneoxy units. The polyethyleneimine can be modified by alkoxylation using a C2-4 alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof. Examples of alkoxylated polyethyleneimines are commercially available from BASF and Nippon Shokubai. In this embodiment, the MA so modified still contains the primary and / or secondary amino groups that are unmodified and still in the form of amines to form the dispersant polymers described herein.

[0029] Modification of MA can be carried out under reaction conditions generally understood by those of skill in the art, whether currently existing or later developed. It will be understood that modification of MA prior to addition of chains to form a dispersant can be carried out under reaction conditions (such as higher temperatures) that may not be feasible after the dispersant molecule is formed.

[0030] In formula I, H +represents the proton species created when the anhydride reacts with the multiamine MA to form amide and salt bonds. The H species bonds to one of the nitrogen atoms of the amine group of MA to form an ammonium cation. In one embodiment, H + The number of species is equal to the sum of q+p, so that, taken as a whole, the dispersant molecule of formula I is uncharged.

[0031] In formula I, the variables p and z can be 0, or greater than or equal to 1. In one embodiment, p+z is any integer between 1 and 200. In another embodiment, p+z is any integer between 2 and 200.

[0032] In Formula I, R 4 may be a linear or branched saturated carbon chain containing 1 to 4, such as 1 or 2, carbon atoms. In one embodiment, R4 is derived from an acyclic anhydride.

[0033] The dispersants of the present invention (e.g., Formula I) can be prepared by the following steps: (a) reacting a compound of formula X—(CHCHR 1 -O) n- [R 5 -N(R 6 )] b -[(C=O)R 2 -O] m The dispersants are made using a novel process comprising the steps of: (a) providing an alcohol-terminated polymer of formula II; (b) reacting the alcohol-terminated polymer with a cyclic anhydride to provide an acid-terminated polymer; (c) reacting the acid-terminated polymer with a non-cyclic anhydride to provide a mixture of anhydrides; and (d) reacting the mixture of anhydrides with a multi-amine species, the multi-amine species having a number average molecular weight of 300-20,000 to form a dispersant molecule, where q and t are each at least 1 such that the dispersant contains both amide and salt bonds. In formula II, X represents either RQ or a cyclic secondary amine. When X is RQ, R is a branched or straight chain, saturated or unsaturated, or cyclic hydrocarbon chain containing 1-50 carbon atoms, and Q is O or NR 7or NH, provided that when n is 0 and b is 0, Q can only be NH; R 7 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 18 carbon atoms, which may optionally include ether, ester, or amide functional groups or halide substituents. X may also be a cyclic amine structure derived from one or more cyclic secondary amines. In formula II, R 1 is H, methyl, or ethyl; R 5 is a linear or branched hydrocarbon chain containing up to 3 carbon atoms, R 6 is hydrogen, a hydrocarbyl group containing 1 to 22 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide. The variable b is 0 or 1, except that when both n and m are both at least 1, then b can only be 1. R 2 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 15 carbon atoms, or -R 8 (C=O)YR 9 where Y is O, NH, or NR 10 and R 8 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 9 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 10 R is a hydrocarbon chain containing 1 to 20 carbon atoms, which may include an ester, ether, or amide group. 2 is a hydrocarbon chain containing 1 to 15 carbon atoms, R 2 In one embodiment, R may be a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 10, e.g., 2 to 7, carbon atoms, in another embodiment. 2 is the formula -N(R 11 )-(C=O)-, wherein R 11 is H or a hydrocarbon chain containing 1 to 4 carbon atoms. In Formula II, n is any integer from 0 to 65, and m is any integer from 0 to 35, with the proviso that m+n is at least 3.

[0034] In one embodiment, the alcohol-terminated polymer has a number average molecular weight of 300 to 5000 g / mol, for example, 500 to 3000 g / mol.

[0035] In one embodiment, the alcohol-terminated polymer and the cyclic anhydride are combined in a molar ratio of about 1:1 and reacted at a temperature high enough to solubilize the cyclic anhydride. For example, in one embodiment, a temperature of about 130° C. may be suitable. In one embodiment, the reaction may be carried out for 2 to 48 hours and may be conveniently carried out at a temperature of 50 to 150° C. or 70 to 140° C. in an inert atmosphere, optionally in the presence of a catalyst such as phosphoric acid. Examples of suitable cyclic anhydrides include, for example, glutaric anhydride, 1,2-cyclohexanedicarboxylic anhydride, homophthalic anhydride, succinic anhydride, diglycolic anhydride, polyisobutylene succinic anhydride, 2-phenylsuccinic anhydride, or alkyl(enyl)succinic anhydride.

[0036] The subsequent acid-terminated polymer is then reacted with acyclic anhydride. Suitable acyclic anhydrides include butyric anhydride, isobutyric anhydride, propionic anhydride, and acetic anhydride or mixtures thereof. In one embodiment, the reaction provides a mixture of heteroanhydride and homoanhydride products, where a heteroanhydride is an anhydride where half is from the polymer and the other half is from the acyclic anhydride, and a homoanhydride is either anhydride where both halves are made from the polymer or residual acyclic anhydride. In one embodiment, the acid-terminated polymer and the acyclic anhydride are combined in a molar ratio of 1:0.5 to 1:2.

[0037] The above reaction steps are carried out using settings that allow excess anhydride and acid by-products to be removed from the reaction vessel. In one embodiment, the reaction is carried out for 2-10 hours at a reaction temperature higher than the boiling point of the acid produced but lower than the boiling point of the non-cyclic anhydride. For example, when acetic anhydride is used, a temperature of about 120°C is suitable. The reaction temperature is then increased to a temperature higher than the boiling point of the non-cyclic anhydride (for example, about 150°C when acetic anhydride is used) and the reaction is carried out for an additional 1-72 hours. The reactions described herein can be carried out at atmospheric pressure. It should be understood by those skilled in the art that the reaction can be carried out under reduced pressure, such as under vacuum, thereby reducing both the reaction temperature and reaction time.

[0038] The resulting mixture of anhydrides is then reacted with a multiamine species as described herein. The mixture of anhydride and multiamine components are combined in a weight ratio of 1:1 to 25:1, for example, 3:1 to 18:1. The reaction is carried out at a temperature of less than 100° C., preferably less than 80° C., in an inert atmosphere, for a period of 15 minutes to 6 hours.

[0039] The process for making the dispersant of the present invention comprises: (a) reacting a compound of the formula X-(CHCHR 1 -O) n- [R 5 -N(R 6 )] b- [(C=O)R 2 -O] m (b) reacting the alcohol-terminated polymer with a cyclic anhydride to provide an acid-terminated polymer; (c) reacting the acid-terminated polymer with a non-cyclic anhydride to provide a mixture of anhydrides; and (d) reacting the mixture of anhydrides with a multi-amine species, wherein the multi-amine species has a number average molecular weight of 300 to 20,000 to form a dispersant molecule having formula I. [ka] The process involves making a dispersant having formula I, where X is RQ or a cyclic amine, and when X is RQ, R is a branched or straight chain, saturated or unsaturated, alkyl, aryl, aralkyl, or alkylaryl hydrocarbon chain, optionally substituted with halogens such as Cl and F, or substituted with heteroatoms such as N and O present as tertiary amine or ether groups, and Q is O or NR 7 or NH, with the proviso that when n is 0 and b is 0, Q can only be NH. X can alternatively be a cyclic secondary amine derived from amines such as piperidine, morpholine, 4-methylpiperidine, 4-phenylpiperidine, thiomorpholine, azetidine, 1-methylpiperazine, 2-methylpiperazine, and pyrrolidine, including mixtures thereof. R 1 is H, methyl, or ethyl. 5 R is a linear or branched hydrocarbon chain containing up to 3 carbon atoms. 6 is hydrogen, a hydrocarbyl group containing 1 to 22 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide. b is 0 or 1, except that when both n and m are both at least 1, b can only be 1. R 2 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 15 carbon atoms, or -R 8 (C=O)YR 9 where Y is O, NH, or NR 10 and R 8 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 9 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 10 R is a hydrocarbon chain containing 1 to 20 carbon atoms, which may include an ester, ether, or amide group. 2 is a hydrocarbon chain containing 1 to 15 carbon atoms, R 2 In one embodiment, R may be a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms, and in another embodiment, R 2 is the formula -N(R 11)-(C=O)-, wherein R 11 is H or a hydrocarbon chain containing 1 to 4 carbon atoms. The variable n is any integer from 0 to 65, and the variable m is any integer from 0 to 35, provided that m+n is at least 3. 3 is a linear or branched, saturated or unsaturated hydrocarbon containing 2 to 80 carbons. The variables q and t are each at least 1, but q+t can be any integer between 2 and 150. MA is a multiamine species having a number average molecular weight between 300 and 20,000 g / mol. p+z is 0 or 1 or any integer between 2 and 200, and R 4 is a linear or branched saturated carbon chain containing 1 to 4 carbons, preferably 1 to 3 carbons. In one embodiment, in formula I, n is 0. In another embodiment, in formula I, n is any integer from 3 to 65, and m is 0. In yet another embodiment, in formula I, m is 0. In another embodiment, in formula I, m is any integer from 3 to 35, for example, 5 to 16, and n is 0. In another embodiment, in formula I, both n and m are positive integers, and n+m is 3 to 65, for example, 5 to 30.

[0040] In one embodiment, the process of making a dispersant as disclosed above results in a dispersant of formula I, where n is 0 and m is at least 3. In another embodiment, the process of making a dispersant as disclosed above results in a dispersant of formula I, where m is 0 and n is at least 3. In another embodiment, the process of making a dispersant as disclosed above results in a dispersant of formula I, where either m or n is 0, but m+n is at least 3. In another embodiment, the process of making a dispersant as disclosed above results in a dispersant of formula I, where m+n is any integer from 3 to 65, for example 5 to 30.

[0041] In one embodiment, the dispersants of the present invention can be further functionalized to tailor their properties and application performance to specific requirements. These modification reactions described below can be between various reagents listed below and amines of the polyamine species that have not yet reacted with the polyether and / or polyester and / or polyesteramide groups detailed above. The modification of the remaining amino groups can be carried out in any manner known to those skilled in the art. Such modification is desirable, for example, when reacting the amino groups with binder systems in which pigment dispersions or pastes are incorporated to cause flocculation. Such modification can be carried out under reaction conditions generally understood by those skilled in the art, whether currently existing or hereafter developed. For modifications of amines that are carried out after the multiamine (MA) species is incorporated into the dispersant molecule as described herein, it should be understood that such modification may need to be carried out at a controlled temperature, for example, below 100°C.

[0042] The above mentioned modifications are advantageous embodiments of the present invention and are realized by: a) Reaction of one or more of the remaining free primary and secondary amino groups of the polyamine species with an isocyanate, lactone, anhydride, epoxide, cyclic carbonate, or (meth)acrylate. Specific examples of suitable isocyanates include phenylisocyanate. Specific examples of suitable lactones include caprolactone and valerolactone. Reaction of one or more of the remaining free primary and secondary amino groups of the polyamine species with an anhydride is disclosed in US 6,878,799 and 7,767,750. Specific examples of suitable anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,8-naphthalic anhydride (optionally substituted with nitro or halogen substituents such as Cl and Br), isatoic anhydride, trimellitic anhydride, C 1~20Examples of suitable epoxides include alkenyl and alkyl succinic anhydrides. The reaction of one or more of the remaining free primary and secondary amino groups of the polyamine species with epoxides is disclosed in JP4031471. Examples of suitable epoxides include styrene oxide, propylene oxide and ethylene oxide. Examples of suitable cyclic carbonates include ethylene carbonate and 2,2-dimethyltrimethylene carbonate. Examples of suitable (meth)acrylates include ethyl acrylate and 2-hydroxyethyl acrylate. b) Salification and / or reaction of one or more of the remaining free primary, secondary or tertiary amino groups of the polyamine species with mono- or polycarboxylic acids, mineral acids, phosphorus and polyoxometalate-containing acids or strong acids. Suitable reagents for this purpose include hydrochloric acid, acetic acid, sulfuric acid, alkylsulfonic acids, alkyl hydrogen sulfates or arylsulfonic acids. Salification and / or reaction of one or more of the remaining free amino groups of the amine-based polyamine species with mono- or polycarboxylic acids or phosphorus-containing acids is disclosed in JP9157374, US2010 / 0017973 and US2013 / 0126804. Specific examples of suitable monocarboxylic acids include optionally substituted C1-50 aliphatic monocarboxylic acids such as acetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, arachidic acid, erucic acid, behenic acid, methoxyacetic acid, mixtures of fatty acids derived from oils from natural sources such as sunflower oil, rapeseed oil, castor oil and olive oil, branched alkyl carboxylic acids available under the trade name Isocarb™ (formerly Sasol), Unicid™ acids, which are linear C25-50 synthetic primary acids available from Baker Hughes, and aromatic carboxylic acids such as benzoic acid, salicylic acid, and naphthoic acid. Specific examples of suitable polycarboxylic acids include succinic acid, malonic acid, adipic acid, sebacic acid, malic acid, fumaric acid, citric acid, and tartaric acid. Specific examples of suitable phosphorus-containing acids include phosphoric acid and phosphorous acid.Specific examples of suitable polyoxometallate-containing acids include phosphomolybdic acid, phosphotungstic acid, and silicomolybdic acid. c) Oxidation of one or more of the remaining free primary, secondary or tertiary amino groups of the polyamine species to nitric oxide. d) Quaternization of one or more of the remaining free tertiary amino groups of the polyamine species. This can be accomplished using alkyl sulfates, alkyl or aralkyl halides, halocarboxylic acid esters, alkyl oxalates or epoxides. Suitable reagents for this purpose include dimethyl sulfate, benzyl chloride, methyl halides such as chlorine, bromine and iodine, dimethyl oxalate, ethylene oxide, propylene oxide and styrene oxide in the presence of acid, and propane (or butane) sultone. e) Reaction of one or more of the remaining free primary, secondary, or tertiary amino groups of the polyamine species with one or more monoamino reactive group terminated polymer(s) of MW 150 to 3000. Suitable examples of carboxylic acid terminated polyester, polyesteramide and polyamide polymers are disclosed in US 4,224,212, 4,861,380, 5,700,395, 5,760,257, 6,197,877, 8,202,935, JP 4866255, JP 8010601, JP 9157361, WO 2006 / 113258 and WO 2007 / 039605. Suitable examples of carboxylic acid terminated polyether polymers are disclosed in JP4248207, US7,767,750, 7,671,119, 7,872,070, 8,076,409 and 8,168,713. Suitable examples of phosphate, sulfate and sulfonate terminated polyester polymers are disclosed in US4,861,380 and 6,197,877. Suitable examples of (meth)acrylate terminated polyester, polyesteramide and polyamide polymers are disclosed in EP713894, JP3488001, JP2010-222522 and US8,202,935. Suitable examples of (meth)acrylate terminated polyether polymers are disclosed in US7,923,474 and JP2010-222522. Suitable examples of phosphate, sulfate and sulfonate terminated polyether, polyether / polyester, polyether / polyurethane and polyether / polyester / polyurethane polymers are disclosed in US 5,130,463, 5,151,218, 6,111,054, 6,310,123, 7,595,416 and 8,202,935. Suitable examples of isocyanate terminated polyester and polyether polymers are disclosed in JP 4031471, JP 7149855 and WO 2007 / 039605. Suitable examples of epoxide or acetoacetoxy or cyclocarbonate terminated polyacrylate polymers are disclosed in US 5,100,969.

[0043] One objective of the present invention is to provide compounds that can improve color strength or other coloring properties, increase particulate solids loading, and / or form improved dispersions with improved brightness of the final composition. This is accomplished while producing compositions with reduced viscosity, good dispersion stability, reduced particle size and particle size distribution, reduced haze, improved gloss, and improved jetness (especially when the composition is black). The composition(s) of the present invention can also be stable under ambient storage and elevated storage conditions that also provide reduced discoloration / yellowing of the final coating.

[0044] The inventive polymers herein are useful as dispersants for a variety of small particle dispersions, such as pigments and particulates suspendable in a variety of polar and non-polar media. Various particulate, dispersant, and continuous phase compositions are useful as inks, coatings, paints, and millbases for pigmented inks, coatings, and paints.

[0045] Industrial Applications The particulate solid present in the composition may be any inorganic or organic solid material that is substantially insoluble in the organic medium at the temperature of interest and for which it is desirable to stabilize it in finely divided form therein. The particulate solid may be in the form of a granular material, fiber, platelet, or in the form of a powder, often in the form of a sprayed powder. In one embodiment, the particulate solid is a pigment.

[0046] Particulate solids (usually pigments or fillers) may have an average particle size as measured by light scattering measurements of from 10 nm to 10 μm, or from 10 nm to 1, 2, 3 or 5 μm, or from 20 nm to 1, 2, 3 or 5 μm in diameter.

[0047] Examples of suitable solids are pigments for solvent inks; pigments, extenders, fillers, blowing agents and flame retardants for paints and plastic materials; dyes, especially disperse dyes; optical brighteners and textile auxiliaries for solvent dye baths; pigments for inks, toners and other solvent coated systems; solids for oil-based and inverse emulsion drilling muds; soils and solid particles in dry cleaning fluids; metals; ceramics, piezo-ceramic printing, refractories, abrasives, castings, capacitors, fuel cells, ferrofluids, conductive inks, magnetic recording media, particulate ceramic and magnetic materials for water treatment and hydrocarbon soil remediation; organic and inorganic monodisperse solids; metals, metal oxides and carbon for battery electrodes, fibres such as wood, paper, glass, steel, carbon and boron for composites; and insecticides, pesticides and drugs applied as dispersions in organic media.

[0048] In one embodiment, the solid is an organic pigment, for example, any of the widely recognized classes of pigments described in the chapter entitled "Pigments" in the Third Edition of the Colour Index (1971) and its subsequent revised editions and supplements. Examples of organic pigments are azo, disazo, trisazo, condensed azo, azo lakes, naphthol pigments, anthanthrones, anthrapyrimidines, anthraquinones, benzimidazolones, carbazoles, diketopyrrolopyrroles, flavanthrones, indigoid pigments, indanthrones, isodibenzanthrones, isoindanthrones, isoindolinones, isoindolines, isoviolanthrones, metal complex pigments, oxazines, perylenes, perinones, pyranthrones, pyrazoloquinazolones, quinacridones, quinophthalones, thioindigo, triarylcarbonium pigments, triphendioxazines, xanthenes and phthalocyanine series, especially copper phthalocyanine and its nuclear halogenated derivatives, and also acid, basic and mordant dye lake pigments. Carbon black is strictly an inorganic pigment, but in its dispersing properties it behaves more like an organic pigment. In one embodiment, the organic pigments are phthalocyanines, especially copper phthalocyanines, monoazos, disazos, indanthrones, anthranthrones, quinacridones, diketopyrrolopyrroles, perylenes, and carbon blacks.

[0049] Examples of inorganic pigments include metal oxides such as titanium dioxide, rutile titanium dioxide, and surface-coated titanium dioxide; titanium oxides of different colors such as yellow and black; iron oxides of different colors such as yellow, red, brown, and black; zinc oxide, zirconium oxide, aluminum oxide, bismuth vanadate, cobalt aluminate, cobalt stannate, cobalt zincate, zinc chromate, and oxymetal compounds such as mixed metal oxides of two or more of manganese, nickel, titanium, chromium, antimony, magnesium, praseodymium, cobalt, iron, or aluminum; Prussian blue, vermilion red, ultramarine, zinc phosphate, zinc sulfide, calcium and zinc molybdates, and chromates; metal effect pigments such as aluminum flakes, copper, and copper / zinc alloys; pearlescent flakes such as lead carbonate and bismuth oxychloride.

[0050] Inorganic solids include ground and precipitated calcium carbonate, calcium sulfate, calcium oxide, calcium oxalate, calcium phosphate, calcium phosphonate, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, natural magnesium hydroxide or hydrotalcite, precipitated magnesium hydroxide, magnesium carbonate, dolomite, aluminum trihydroxide, aluminum hydroperoxide or boehmite, calcium and magnesium silicates, aluminosilicate-containing nanoclays, kaolin, bentonite with montmorillonite, hectorite and saponite. Nite, natural, synthetic and expandable with ball clay, mica, muscovite with talc, phlogopite, lepidolite and chlorite, chalk, synthetic and precipitated silica, fumed silica, metal fibers and powders, zinc, aluminum, glass fibers, refractory fibers, single and multi-walled carbon nanotubes with carbon black, reinforced and unreinforced carbon black, graphite, buckminsterfullerene, asphaltenes, graphene, diamond, alumina, quartz, perlite, pegmatite, silica gel, wood flour, soft and hard wood with wood flakes, sawdust, powdered paper / fiber and other extenders and and fillers, kenaf, hemp, sisal, flax, cotton, cotton linters, jute, ramie, rice husk or husk, raffia, cattail, coconut fibre, coir, oil palm fibre, kapok, banana leaves, karo, curawa, henequen leaves, harakeke leaves, abaca, sugarcane bagasse, straw, bamboo chips, wheat flour, MDF and the like, vermiculite, zeolite, hydrotalcite, fly ash from power plants, incinerated sewage sludge ash, pozzolana, blast furnace slag, asbestos, chrysotile, anthophyllite, crocidolite, wollastonite, attapulgite and the like. Particular ceramic materials such as cellulose fibers, alumina, zirconia, titania, ceria, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, mixtures of silicon-aluminum nitride with metal titanates; particulate magnetic materials such as magnetic oxides of transition metals, often iron and chromium, e.g., gamma-Fe2O3, Fe3O4, and cobalt doped iron oxide, ferrites, e.g., barium ferrite; and metal particles such as the metals aluminum, iron, nickel, cobalt, copper, silver, gold, palladium, and platinum and alloys thereof.

[0051] Other useful solid materials include pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate, melamine, melamine cyanurate, flame retardants such as antimony oxide and borates; Kirk-Othmer's Encyclopedia of Chemical Technology, Vol. 13, 1981, 3 rd Examples of suitable antimicrobial agents include biocides or industrial microbiological agents such as those listed in Tables 2, 3, 4, 5, 6, 7, 8 and 9 of the chapter entitled "Industrial Microbial Agents" in the International Publication of the US Pat. No. 6,339,663, and the like, as well as pesticides such as the fungicides flutriafen, carbendazim, chlorothalonil and mancozeb.

[0052] In one embodiment, the organic medium present in the composition of the invention is a plastic material, and in another embodiment, an organic liquid. The organic liquid may be a non-polar or polar organic liquid. By the term "polar" in relation to an organic liquid, it is meant that the organic liquid is capable of forming medium to strong bonds, as described in the article entitled "A Three Dimensional Approach to Solubility" by Crowley et al. (Journal of Paint Technology, Vol. 38, 1966, page 269). Such organic liquids generally have a hydrogen bond number of 5 or more, as defined in the above article.

[0053] Examples of suitable polar organic liquids are amines, ethers, especially lower alkyl ethers, organic acids, esters, ketones, glycols, glycol ethers, glycol esters, alcohols and amides. Numerous specific examples of such suitably strong hydrogen bonding liquids are given in Table 2.14 on pages 39-40 of "Compatibility and Solubility" by Ibert Mellan, published by Noyes Development Corporation in 1968, and all of these liquids are included within the scope of the term polar organic liquid as used herein.

[0054] In one embodiment, the polar organic liquid is a dialkyl ketone, an alkyl ester of an alkane carboxylic acid and an alkanol, particularly such liquids containing and including a total of up to 6 carbon atoms. Examples of polar organic liquids include dialkyl and cycloalkyl ketones such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isoamyl ketone, methyl n-amyl ketone, and cyclohexanone; alkyl esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, methyl propionate, methoxypropyl acetate, and ethyl butyrate; glycols and glycol esters and ethers such as ethylene glycol, 2-ethoxyethanol, 3-methoxypropylpropanol, 3-ethoxypropylpropanol, 2-butoxyethyl acetate, 3-methoxypropyl acetate, 3-ethoxypropyl acetate, and 2-ethoxyethyl acetate; alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol (also known as 2-methylpropanol), terpineol, and dialkyl and cyclic ethers such as diethyl ether and tetrahydrofuran. In one embodiment, the solvent is an alkanol, an alkanecarboxylic acid, or an ester of an alkanecarboxylic acid. In one embodiment, the present invention is suitable for organic liquids that are substantially insoluble in aqueous media. Furthermore, one skilled in the art will appreciate that small amounts of aqueous media (such as glycols, glycol ethers, glycol esters, and alcohols) may be present in the organic liquid, provided that the entire organic liquid is substantially insoluble in the aqueous medium.

[0055] Examples of organic liquids that can be used as polar organic liquids are film-forming resins that are suitable for preparing inks, paints, and chips for use in various applications such as paints and inks. Examples of such resins include polyamides such as Versamid™ and Wolfamid™, and cellulose ethers such as ethyl cellulose and ethylhydroxyethyl cellulose, nitrocellulose, and cellulose acetate butyrate resins, including mixtures thereof. Examples of paint resins include short oil alkyd / melamine formaldehyde, polyester / melamine formaldehyde, thermosetting acrylic / melamine formaldehyde, long oil alkyd, medium oil alkyd, short oil alkyd, polyether polyol, and multi-media resins such as acrylic and urea / aldehyde.

[0056] The organic liquid may be a polyol, i.e., an organic liquid having two or more hydroxyl groups. In one embodiment, the polyol includes an α-ω diol or an α-ω-diol ethoxylate.

[0057] In one embodiment, the non-polar organic liquid is a compound containing an aliphatic group, an aromatic group, or a mixture thereof. Non-polar organic liquids include non-halogenated aromatic hydrocarbons (e.g., toluene and xylene), halogenated aromatic hydrocarbons (e.g., chlorobenzene, dichlorobenzene, chlorotoluene), non-halogenated aliphatic hydrocarbons (e.g., straight-chain and branched-chain aliphatic hydrocarbons containing 6 or more carbon atoms, both fully saturated and partially saturated), halogenated aliphatic hydrocarbons (e.g., dichloromethane, carbon tetrachloride, chloroform, trichloroethane) and natural non-polar organics (e.g., vegetable oils, sunflower oil, rapeseed oil, linseed oil, terpenes and glycerides).

[0058] In one embodiment, the organic liquid comprises at least 0.1 wt. % or 1 wt. % or more of a polar organic liquid based on the total organic liquid, hi one embodiment, the organic liquid is free of water.

[0059] The plastic material may be a thermosetting resin. Thermosetting resins useful in the present invention include resins that undergo a chemical reaction and become relatively insoluble when subjected to heat, catalysis, or ultraviolet, laser light, infrared, cation, electron beam, or microwave radiation. Typical reactions of thermosetting resins include oxidation of unsaturated double bonds, reactions involving epoxy / amine, epoxy / carbonyl, epoxy / hydroxyl, reactions of epoxy with Lewis acids or Lewis bases, polyisocyanate / hydroxy, amino resin / hydroxy moieties, free radical reactions or polyacrylates, cationic polymerization of epoxy resins with vinyl ethers, and condensation of silanols. Examples of unsaturated resins include polyester resins made by the reaction of one or more diacids or anhydrides with one or more diols. Such resins are usually supplied as a mixture with reactive monomers such as styrene or vinyl toluene, and are often referred to as orthophthalic and isophthalic resins. Further examples include resins that use dicyclopentadiene (DCPD) as a co-reactant in the polyester chain. Further examples also include the reaction products of bisphenol A diglycidyl ether with unsaturated carboxylic acids such as methacrylic acid, which are subsequently supplied as solutions in styrene, commonly referred to as vinyl ester resins.

[0060] In one embodiment, the thermoset composite or thermoset plastic may be polyester, polyvinyl acetate, polyester resin in styrene, polystyrene, or mixtures thereof.

[0061] Hydroxy-functional polymers (often polyols) are widely used in thermosetting systems to crosslink with amino resins or polyisocyanates. Polyols include acrylic polyols, alkyd polyols, polyester polyols, polyether polyols, and polyurethane polyols. Typical amino resins include melamine formaldehyde resins, benzoguanamine formaldehyde resins, urea formaldehyde resins, and glycoluril formaldehyde resins. Polyisocyanates are resins with two or more isocyanate groups, including monomeric aliphatic diisocyanates, monomeric aromatic diisocyanates, and their polymers. Typical aliphatic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Typical aromatic isocyanates include toluene diisocyanate and diphenylmethane diisocyanate.

[0062] Optionally, the compositions of the invention may contain other ingredients such as resins (if they do not already constitute the organic medium), binders, cosolvents, crosslinkers, flow agents, wetting agents, anti-settling agents, plasticizers, surfactants, dispersants other than the compounds of the invention, humectants, defoamers, anti-cratering agents, rheology modifiers, heat stabilizers, light stabilizers, UV absorbers, antioxidants, leveling agents, gloss modifiers, biocides and preservatives.

[0063] The compositions typically contain from 1 to 95% by weight of particulate solids, the exact amount depending on the nature of the solid, and the amount depending on the nature of the solid and the relative densities of the solid and the polar organic liquid. For example, a composition in which the solid is an organic material, such as an organic pigment, in one embodiment contains from 15 to 60% by weight solids, based on the total weight of the composition, whereas a composition in which the solid is an inorganic material, such as an inorganic pigment, filler or extender, in one embodiment contains from 40 to 90% by weight solids.

[0064] The composition containing the organic liquid may be prepared by any of the known conventional methods for preparing a dispersion. Thus, the solid, the organic medium, and the dispersant may be mixed in any order, and then the mixture may be subjected to mechanical treatment to reduce the particles of the solid to a suitable particle size, for example, by high speed mixing, ball milling, basket milling, bead milling, gravel milling, sand milling, abrasive grinding, two-roll or three-roll milling, plastic grinding, etc., to form a dispersion. Alternatively, the solid may be treated to reduce its particle size, either independently or in admixture with either the organic medium or the dispersant, and then the other component(s) may be added and the mixture stirred to provide the composition. The composition may also be made by grinding or grinding a dry solid with a dispersant, and then adding a liquid medium, or by mixing the solid with a dispersant in a liquid medium in a pigment flushing process.

[0065] The compositions of the present invention are particularly suitable for liquid dispersions. In one embodiment, such dispersion compositions include a) 0.5 to 80 parts of a finely divided solid; b) 0.1 to 79.6 parts of a polymer / dispersant of formula I; c) 19.9 to 99.4 parts of an organic liquid; All relative parts are by weight and the amount (a)+(b)+(c)=100.

[0066] In one embodiment, component a) comprises 0.5 to 30 parts pigment, such dispersions being useful as (liquid) inks, paints and mill-bases.

[0067] When a composition is to comprise a particulate solid and a dispersant of Formula 1 in dry form, the organic liquid is generally volatile and can be readily removed from the particulate solid by simple separation means such as evaporation. In one embodiment, the composition comprises an organic liquid.

[0068] When the dry composition consists essentially of a dispersant of formula (1) and a particulate solid, it typically contains at least 0.2%, at least 0.5%, or at least 1.0%, based on the weight of the particulate solid, of a dispersant of formula I. In one embodiment, the dry composition contains no more than 100%, no more than 50%, no more than 20%, or no more than 10% by weight of a dispersant of formula 1, based on the weight of the particulate solid.

[0069] As disclosed herein, the compositions of the present invention are suitable for the preparation of mill-bases in which a finely divided solid is ground in an organic liquid in the presence of a compound of Formula 1.

[0070] Thus, according to yet another aspect of the present invention there is provided a mill-base comprising a particulate solid, an organic liquid and a polymer of formula (1).

[0071] Typically, the mill base contains 20-70% by weight of particulate solids, based on the total weight of the mill base. In one embodiment, the particulate solids are 10% or more, or 20% or more, by weight of the mill base. Such mill bases may optionally contain a binder, which is added before or after milling.

[0072] In one embodiment, the binder is a polymeric material capable of binding the composition upon volatilization of the organic liquid.

[0073] Binders are polymeric materials including natural and synthetic materials. In one embodiment, binders include poly(meth)acrylates, polystyrenics, polyesters, polyurethanes, alkyds, cellulose, polysaccharides such as nitrocellulose, and natural proteins such as casein. The binder may be nitrocellulose. In one embodiment, the binder is present in the composition at greater than 100%, greater than 200%, greater than 300%, or greater than 400% based on the amount of particulate solids.

[0074] The amount of optional binder in the mill-base can vary over a wide range, but is usually at least 10% by weight, often at least 20% by weight, of the continuous / liquid phase of the mill-base, hi one embodiment the amount of binder is no more than 50% or no more than 40% by weight of the continuous / liquid phase of the mill-base.

[0075] The amount of dispersant in the mill base depends on the amount of fine particle solids, but is usually 0.5 to 5% by weight of the mill base.

[0076] Dispersions and millbases made from the compositions of the present invention are particularly suitable for use in non-aqueous and solvent-free formulations, or in combinations present in formulations, where energy curable systems (UV, laser light, IR, cationic beam, electron beam, microwave) are used with monomers, oligomers, etc. They are particularly suitable for use in coatings such as paints, varnishes, inks, other coating materials and plastics. Suitable examples include low, medium and high solids coatings, general industrial coatings including bake-on, two-component and metal coating coatings such as coil and can coatings, powder coatings, UV curable coatings, wood varnishes, etc; printing inks for flexography, gravure, offset, lithography, letterpress or relief, screen printing, etc., and packaging printing, non-impact inks such as ink jet including continuous ink jet, thermal, piezo and electrostatic, phase change inks and hot melt wax inks, drop-on-demand ink jet including ink jet printer inks, and printing varnishes such as overprint varnishes; polyol and plastisol dispersions; non-aqueous ceramic processes, especially tape casting, gel casting, and the like. These include applications in molding, doctor blading, extrusion and injection moulding processes, and even in the preparation of dry ceramic powders for isostatic pressing; composites such as sheet moulding and bulk moulding compounds, resin infusion moulding, pultrusion moulding, hand lay-up and spray lay-up processes, matched die moulding; casting resins, cosmetics, personal care such as nail coatings, sunscreens, adhesives, toners such as liquid toners, plastic materials and electronic materials such as coating formulations for colour filter systems in displays including organic light emitting diode (OLED) devices, liquid crystal displays and electrophoretic displays, fibre optic coatings, glass coatings including reflective or anti-reflective coatings, conductive and magnetic inks and coatings, and other construction materials. These aid in surface modification of pigments and fillers to improve the dispersibility of the dry powders used in the above applications.Further examples of coating materials are described in Bodo Muller, Ulrich Poth, Lackformulierung und Lackrezeptur, Lehrbuch fr Ausbildung und Praxis, Vincentz Verlag, Hanover (2003) and PG Garrat, Strahlenhartung, Vincentz Verlag, Hanover (1996). Examples of printing ink formulations are described in EW Flick, Printing Ink and Overprint Varnish Formulations-Recent Developments, Noyes Publications, Park Ridge NJ, (1990) and subsequent editions.

[0077] In one embodiment, the composition of the present invention further comprises one or more additional known dispersants.

[0078] The following examples are provided to illustrate the invention, but are not exhaustive and are not intended to limit the scope of the invention.

[0079] Reagents used 1-Dodecanol, from Sigma Aldrich Isofol(TM)-36, manufactured by Condea Chemie GmbH ε-Caprolactone, Perstorp Diphenyl phosphate, from Sigma Aldrich 1-Butanol, Fisher Scientific mPEG750-Poly(ethylene glycol) methyl ether, from Sigma Aldrich, MW750 Zirconium(IV) butoxide solution, Sigma Aldrich, 80% wt in 1-butanol mPEG 500 Poly(ethylene glycol) methyl ether, Sigma Aldrich, MW 500 δ-Valerolactone, manufactured by BASF BuO PPG 1000 Poly(propylene glycol) butyl ether, Sigma Aldrich, MW 1000 L-lactide-grade Puralact B3, manufactured by Corbion Surfonamine™ B60, manufactured by Huntsman Surfonamine L100, manufactured by Huntsman Succinic anhydride, from Sigma Aldrich Glutaric anhydride, manufactured by TCI Hexadecenyl succinic anhydride, from Vertellus Octadecenyl succinic anhydride, from Vertellus Homophthalic Anhydride, Acros Organics Toluene, Fisher Scientific mPEG1000 - Poly(ethylene glycol) methyl ether, Ineos, MW1000 mPEG350-Poly(ethylene glycol) methyl ether, from Sigma Aldrich, Mw350 Synalox™ 50-30B - Poly(ethylene glycol-ran-propylene glycol) monobutyl ether MW1000, manufactured by Dow Orthophosphoric acid solution, Sigma Aldrich, 85% wt in water C12-C15 alcohols, propoxylated alcohols with 1-24 molar equivalents of propylene oxide initiated with MW1600, manufactured by Lubrizol C12-C15 Alcohols, 1-20 molar equivalents of butoxylated alcohols of butylene oxide initiated with MW1700, manufactured by Lubrizol Acetic anhydride, from Sigma Aldrich Epomin™ SP200 Polyethyleneimine, MW 10000, Nippon Shokubai Epomin™ SP018 Polyethylenimine, MW 1800, Nippon Shokubai Epomin™ SP006 Polyethylenimine, MW 600, Nippon Shokubai Adipic acid, from Sigma Aldrich 1,4-Butanediol, from Sigma Aldrich 6-Aminohexanoic acid, from Sigma Aldrich Orthophosphoric acid, from Sigma Aldrich Dimethyl sulfate, from Sigma Aldrich Polyisobutenyl succinic anhydride 550, Lubrizol, MW550

[0080] Step 1 - Synthesis of alcohol-terminated polymer

[0081] Alcohol Terminated Polymer 1: 1-Dodecanol (100.85 parts) and ε-caprolactone (802.98 parts) were charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, diphenyl phosphate (2.71 parts) was charged. After 4 hours the reaction was stopped to give a white waxy solid. This is Alcohol Terminated Polymer 1.

[0082] Alcohol Terminated Polymer 2: ε-caprolactone (410.01 parts) was charged to a reaction vessel and heated to 110° C. under nitrogen. After 1 hour, the temperature was reduced to 70° C. When at temperature, 1-butanol (88.75 parts) and diphenyl phosphate (1.50 parts) were charged. After 3 hours, the reaction was stopped to give a clear, colorless liquid. This is Alcohol Terminated Polymer 2.

[0083] Alcohol Terminated Polymer 3: mPEG 750 (111.80 parts) and ε-caprolactone (141.23 parts) were charged to a reaction vessel and heated to 120° C. under nitrogen. After 1.5 hours, zirconium butoxide solution (0.95 parts) was charged and the temperature was increased to 180° C. After 20 hours the reaction was stopped to give a yellow paste. This is Alcohol Terminated Polymer 3.

[0084] Alcohol Terminated Polymer 4: mPEG 500 (60.00 parts), ε-caprolactone (46.62 parts), δ-valerolactone (48.10 parts) and L-lactide (51.89 parts) were charged to a reaction vessel and heated to 120° C. under nitrogen. After 1.5 hours, zirconium butoxide solution (0.77 parts) was charged and the temperature was increased to 180° C. After 19 hours, the reaction had stopped to give a clear brown liquid. This is Alcohol Terminated Polymer 4.

[0085] Alcohol Terminated Polymer 5: BuO PPG 1000 (431.04 parts) and L-lactide (310.63 parts) were charged to a reaction vessel and heated to 120° C. under nitrogen. After 1.5 hours, zirconium butoxide solution (2.23 parts) was charged and the temperature was increased to 180° C. After 19 hours, the reaction had stopped to give a brown paste. This is Alcohol Terminated Polymer 5.

[0086] Alcohol Terminated Polymer 6: mPEG 500 (65.02 parts), ε-caprolactone (81.61 parts), and δ-valerolactone (78.10 parts) were charged to a reaction vessel and heated to 70° C. under nitrogen. Orthophosphoric acid solution (0.68 parts) was charged and the temperature was increased to 120° C. After 8 hours the reaction was stopped to give a clear, colorless liquid. This is Alcohol Terminated Polymer 6.

[0087] Alcohol Terminated Polymer 7: 1-dodecanol (25.41 parts), ε-caprolactone (70.00 parts), δ-valerolactone (68.22 parts) and L-lactide (68.75 parts) were charged to a reaction vessel and heated to 120° C. under nitrogen. After 1.5 hours, zirconium butoxide solution (0.87 parts) was charged and the temperature was increased to 180° C. After 8 hours the reaction was stopped to give a cloudy yellow liquid. This is Alcohol Terminated Polymer 7.

[0088] Alcohol-terminated Polymer 8: Isofol™-36 (70.04 parts) and ε-caprolactone (152.81 parts) were charged to a reaction vessel and heated to 70° C. under nitrogen. When the reaction temperature reached 70° C., orthophosphoric acid (0.72 parts) was charged and the temperature was increased to 120° C. After 8 hours the reaction was stopped to give an off-white solid at room temperature. This is Alcohol-terminated Polymer 8.

[0089] Alcohol-terminated Polymer 9: Surfonamine™ B60 (60 parts), ε-caprolactone (99.4 parts) and orthophosphoric acid (0.1 g) were added to a reaction vessel and stirred under nitrogen at 120° C. for several hours. A pale yellow liquid (157 parts) was obtained. This is Alcohol-terminated Polymer 9.

[0090] Alcohol-terminated polymer 10: Surfonamine™ L100 (60 parts) and ε-caprolactone (12.8 parts) were charged to a reaction vessel and heated to 120° C. with stirring under nitrogen. o-Phosphoric acid (0.1 parts) was charged and stirred at 120° C. for 8 hours. The reaction was stopped to give a pale yellow paste. This is alcohol-terminated polymer 10.

[0091] Alcohol-terminated polymer 11: mPEG350 (100 parts), ε-caprolactone (63.6 parts), δ-valerolactone (38.6 parts) and o-phosphoric acid (0.2 parts) were charged to a reaction vessel and heated to 120°C with stirring under nitrogen for 16 hours. The reaction stopped and a colorless liquid was obtained. This is alcohol-terminated polymer 11.

[0092] Alcohol-terminated polymer 12: The procedure of Agent J in US 4518435 was repeated to make a polyether adduct prepared by condensing 2-diethylaminoethanol with 10 moles of ethylene oxide followed by 20 moles of propylene oxide. This is alcohol-terminated polymer 12.

[0093] Alcohol-terminated polymer 13: Adipic acid (81.09 parts), decanol (12.56 parts) and 1,4-butanediol (150.15 parts) were charged to a reaction vessel and heated to 130° C. with stirring under nitrogen. o-Phosphoric acid (0.42 parts) was charged and stirred at 130° C. for 49.5 hours. The reaction was stopped to give a white solid, which is alcohol-terminated polymer 13.

[0094] Alcohol Terminated Polymer 14: Octylamine (11.32 parts) and ε-caprolactone (140 parts) were charged to a reaction vessel and heated to 90° C. with stirring under nitrogen. After 3.5 hours, the temperature was increased to 120° C. and stirred for 30 minutes. Zirconium butoxide (0.46 parts) was charged and the temperature was increased to 180° C. The reaction was stirred at 180° C. for 18 hours. The reaction was stopped to give a white solid. This is Alcohol Terminated Polymer 14.

[0095] Alcohol Terminated Polymer 15: A polyether form from 2-naphthol and 10 moles of ethylene oxide (69.42 parts) and ε-caprolactone (134.75 parts) were charged to a reaction vessel and heated to 70° C. with stirring under nitrogen. o-Phosphoric acid (0.61 parts) was charged and the temperature was increased to 120° C. The reaction was stirred at 120° C. for 18.5 hours. The reaction was stopped to give a cream colored waxy solid. This is Alcohol Terminated Polymer 15.

[0096] Alcohol-terminated polymer 16: 6-aminohexanoic acid (70.13 parts) and ε-caprolactone (127.02 parts) were charged to a reaction vessel and heated to 180°C with stirring under nitrogen for 1.5 hours. After this time the temperature was reduced to 120°C over 0.75 hours. Decanol (20.77 parts) was then added followed 5 minutes later by zirconium butoxide (0.43 parts). The temperature was increased to 180°C and stirred at this temperature for 17.5 hours. The reaction was stopped to give a beige solid which is alcohol-terminated polymer 16.

[0097] Step 2 - Reacting the alcohol-terminated polymer with a cyclic anhydride to produce an acid-terminated polymer

[0098] Acid Terminated Polymer 1: Alcohol Terminated Polymer 1 (843.81 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (50.53 parts) was charged and the temperature increased to 130° C. After 20 hours the reaction was stopped to give a white waxy solid with an acid number of 34 mg KOH / g. This is Acid Terminated Polymer 1.

[0099] Acid Terminated Polymer 2: Alcohol Terminated Polymer 2 (450.00 parts) and toluene (22.37 parts) were charged to a reaction vessel equipped with a condenser and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (108.13 parts) was charged and the temperature increased to 130° C. After 18 hours the reaction was stopped and cooled to 60° C. The toluene was removed using a rotary evaporator to give a slightly hazy pale yellow liquid with an acid number of 116 mg KOH / g. This is Acid Terminated Polymer 2.

[0100] Acid Terminated Polymer 3: Alcohol Terminated Polymer 3 (211.77 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (12.46 parts) was charged and the temperature increased to 130° C. After 7.5 hours the reaction was stopped to give a pale yellow paste with an acid number of 34 mg KOH / g. This is Acid Terminated Polymer 3.

[0101] Acid Terminated Polymer 4: Alcohol Terminated Polymer 4 (180.00 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (10.44 parts) was charged and the temperature increased to 130° C. After 12.5 hours, the reaction was stopped to give a clear brown liquid with an acid number of 44 mg KOH / g. This is Acid Terminated Polymer 4.

[0102] Acid Terminated Polymer 5: Alcohol Terminated Polymer 5 (180.00 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (10.52 parts) was charged and the temperature increased to 130° C. After 31 hours the reaction was stopped to give a viscous amber liquid with an acid number of 34 mg KOH / g. This is Acid Terminated Polymer 5.

[0103] Acid Terminated Polymer 6: mPEG 1000 (300.00 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (30.01 parts) was charged and the temperature increased to 130° C. After 5 hours the reaction was stopped to give a white waxy paste with an acid number of 54 mg KOH / g. This is Acid Terminated Polymer 6.

[0104] Acid Terminated Polymer 7: BuO PPG 1000 (100.00 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (10.04 parts) was charged and the temperature was increased to 130° C. After 18 hours the reaction was stopped to give a clear, colorless liquid with an acid number of 45 mg KOH / g. This is Acid Terminated Polymer 7.

[0105] Acid Terminated Polymer 8: Synalox™ 30-50B (245.03 parts) and orthophosphoric acid solution (0.97 parts) were charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (24.52 parts) was charged and the temperature increased to 130° C. After 9 hours the reaction was stopped to give a clear, colorless liquid with an acid number of 61 mg KOH / g. This is Acid Terminated Polymer 8.

[0106] Acid Terminated Polymer 9: Propoxylated Alcohol 1 (300.00 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (18.76 parts) was charged and the temperature increased to 130° C. After 26 hours the reaction was stopped to give a clear yellow liquid with an acid number of 36 mg KOH / g. This is Acid Terminated Polymer 9.

[0107] Acid Terminated Polymer 10: Alcohol Terminated Polymer 6 (200.00 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (11.57 parts) was charged and the temperature increased to 130° C. After 4.5 hours, the reaction was stopped to give a clear, colorless liquid with an acid number of 42 mg KOH / g. This is Acid Terminated Polymer 10.

[0108] Acid Terminated Polymer 11: Alcohol Terminated Polymer 7 (200.00 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (11.74 parts) was charged and the temperature was increased to 130° C. After 16 hours, the reaction was stopped to give a hazy yellow liquid with an acid number of 41 mg KOH / g. This is Acid Terminated Polymer 11.

[0109] Acid Terminated Polymer 12: Alcohol Terminated Polymer 8 (188.10 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (11.40 parts) was charged and the temperature was increased to 130° C. After 8.5 hours, the reaction was stopped to give an off-white solid with an acid number of 40 mg KOH / g at room temperature. This is Acid Terminated Polymer 12.

[0110] Acid Terminated Polymer 13: Alcohol Terminated Propoxylated Alcohol 1 (140.60 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, glutaric anhydride (9.40 parts) was charged and the temperature increased to 130° C. After 18 hours, the reaction was stopped to give a clear liquid at room temperature with an acid number of 36.10 mg KOH / g. This is Acid Terminated Polymer 13.

[0111] Acid Terminated Polymer 14: Alcohol Terminated Propoxylated Alcohol 1 (150.08 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. When at temperature, an equal weight mixture of hexadecenyl succinic anhydride and octadecenyl succinic anhydride (30.54 parts) was charged and the temperature was increased to 130° C. After 21.5 hours, the reaction was stopped to give a pale yellow clear liquid at room temperature with an acid number of 41.09 mg KOH / g. This is Acid Terminated Polymer 14.

[0112] Acid Terminated Polymer 15: Alcohol Terminated Propoxylated Alcohol 1 (119.98 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, homophthalic anhydride (10.79 parts) was charged and the temperature increased to 130° C. After 23 hours, the reaction was stopped to give a clear liquid at room temperature with an acid number of 39.88 mg KOH / g. This is Acid Terminated Polymer 15.

[0113] Acid Terminated Polymer 16: Alcohol End 9 (150.06 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (9.12 parts) was charged and the temperature was increased to 130° C. After 4.5 hours, the reaction was stopped to give an off-white wax with an acid number of 46.45 mg KOH / g at room temperature. This is Acid Terminated Polymer 16.

[0114] Acid Terminated Polymer 17: Butoxylated Alcohol 1 (283 parts) was charged to a reaction vessel and heated with stirring under nitrogen to 70° C. Once at temperature, succinic anhydride (13.4 parts) was charged and the temperature increased to 120° C. After 20 hours the reaction was stopped to give a colorless liquid with an acid number of 25.3 mg KOH / g. This is Acid Terminated Polymer 17.

[0115] Acid Terminated Polymer 18: Alcohol Terminated Polymer 10 (72.8 parts) was charged to a reaction vessel and heated to 80° C. under nitrogen. Once at temperature, succinic anhydride (5.6 parts) was charged and the temperature was increased to 120° C. After 8 hours the reaction was stopped to give a pale yellow waxy solid with an acid number of 46.1 mg KOH / g. This is Acid Terminated Polymer 18.

[0116] Acid Terminated Polymer 19: Alcohol Terminated Polymer 11 (202.2 parts) was charged to a reaction vessel and heated to 80° C. under nitrogen. Once at temperature, succinic anhydride (28.5 parts) was charged and stirred at 80° C. for 12 hours. The reaction was stopped to give a pale yellow liquid with an acid number of 72.3 mg KOH / g. This is Acid Terminated Polymer 19.

[0117] Acid Terminated Polymer 20: Propoxylated Alcohol 1 (200 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (11.1 parts) was charged and the temperature increased to 120° C. After 20 hours the reaction was stopped to give a colorless liquid with an acid number of 34 mg KOH / g. This is Acid Terminated Polymer 20.

[0118] Acid Terminated Polymer 21: Alcohol Terminated Polymer 12 (153 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (8.7 parts) was charged and the temperature was increased to 120° C. After 10 hours the reaction was stopped to give a pale yellow hazy liquid with an acid number of 31.9 mg KOH / g. This is Acid Terminated Polymer 21.

[0119] Acid Terminated Polymer 22: Propoxylated Alcohol 1 (59.5 parts) and Polyisobutenyl Succinic Anhydride 550 (36.06 parts) were charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, o-phosphoric acid (0.84 parts) was charged and the temperature was increased to 130° C. After 50 hours, the reaction was stopped to give a clear yellow liquid at room temperature with an acid number of 31.25 mg KOH / g. This is Acid Terminated Polymer 22.

[0120] Acid Terminated Polymer 23: Alcohol Terminated Polymer 13 (55.1 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (3.1 parts) was charged and the temperature was increased to 130° C. After 4.5 hours, the reaction was stopped to give a white solid at room temperature with an acid number of 38.38 mg KOH / g. This is Acid Terminated Polymer 23.

[0121] Acid Terminated Polymer 24: Alcohol Terminated Polymer 14 (140.13 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (8.11 parts) was charged and the temperature was increased to 130° C. After 2.5 hours, the reaction was stopped to give a clear liquid at room temperature with an acid number of 32.58 mg KOH / g. This is Acid Terminated Polymer 24.

[0122] Acid Terminated Polymer 25: Alcohol Terminated Polymer 15 (185.04 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (10.80 parts) was charged and the temperature increased to 130° C. After 20 hours the reaction was stopped to give a cream colored solid at room temperature with an acid number of 35.74 mg KOH / g. This is Acid Terminated Polymer 25.

[0123] Acid Terminated Polymer 26: Alcohol Terminated Polymer 16 (115.26 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen. Once at temperature, succinic anhydride (7.04 parts) was charged and the temperature was increased to 130° C. After 3.75 hours, the reaction was stopped to give a cream colored solid with an acid number of 35.15 mg KOH / g at room temperature. This is Acid Terminated Polymer 26.

[0124] Step 3 - Reaction of an acid-terminated polymer with an acyclic anhydride to form a polymeric anhydride

[0125] Polymeric Anhydride 1: Acid terminated Polymer 1 (420.00 parts) and acetic anhydride (30.94 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 4 hours, the reaction stopped to give a white waxy solid, which is Polymeric Anhydride 1.

[0126] Polymeric Anhydride 2: Acid terminated Polymer 2 (120.00 parts) and acetic anhydride (30.30 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 16 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a clear, pale yellow liquid. This is Polymeric Anhydride 2.

[0127] Polymeric Anhydride 3: Acid terminated Polymer 3 (140.00 parts) and acetic anhydride (9.53 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours the temperature was increased to 150° C. After an additional 18 hours the Dean-Stark trap was removed leaving an open port. After an additional hour the reaction had stopped to give a light brown paste. This is Polymeric Anhydride 3.

[0128] Polymeric Anhydride 4: Acid terminated Polymer 4 (99.99 parts) and acetic anhydride (6.73 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours the temperature was increased to 150° C. After an additional 19 hours the Dean-Stark trap was removed leaving an open port. After an additional hour the reaction had stopped to give a clear dark brown liquid. This is Polymeric Anhydride 4.

[0129] Polymeric Anhydride 5: Acid terminated Polymer 5 (99.97 parts) and acetic anhydride (6.73 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 19 hours, the reaction had stopped to give a viscous brown liquid, which is Polymeric Anhydride 5.

[0130] Polymeric Anhydride 6: Acid Terminated Polymer 6 (90.00 parts) and acetic anhydride (10.02 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 17.5 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a dark brown waxy solid. This is Polymeric Anhydride 6.

[0131] Polymeric Anhydride 7: Acid terminated Polymer 7 (40.00 parts) and acetic anhydride (3.94 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 16 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a clear, pale yellow liquid. This is Polymeric Anhydride 7.

[0132] Polymeric Anhydride 8: Acid terminated Polymer 8 (150.00 parts) and acetic anhydride (16.71 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 16 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a dark brown liquid. This is Polymeric Anhydride 8.

[0133] Polymeric Anhydride 9: Acid terminated Polymer 9 (90.00 parts) and acetic anhydride (6.49 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 17.5 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction had stopped to give a clear brown liquid. This is Polymeric Anhydride 9.

[0134] Polymeric Anhydride 10: Acid terminated Polymer 10 (120.00 parts) and acetic anhydride (8.03 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 23 hours, the reaction had stopped to give a clear dark brown liquid, which is Polymeric Anhydride 10.

[0135] Polymeric Anhydride 11: Acid terminated Polymer 11 (120.01 parts) and acetic anhydride (8.15 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 20 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a clear orange liquid. This is Polymeric Anhydride 11.

[0136] Polymeric Anhydride 12: Acid terminated polymer 12 (100.18 parts) and acetic anhydride (6.96 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 9 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a light brown solid at room temperature. This is polymeric anhydride 12.

[0137] Polymeric Anhydride 13: Acid terminated Polymer 13 (69.98 parts) and acetic anhydride (4.73 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours the temperature was increased to 150° C. After an additional 12.75 hours the Dean-Stark trap was removed leaving an open port. After an additional hour the reaction had stopped to give a clear liquid at room temperature. This is Polymeric Anhydride 13.

[0138] Polymeric Anhydride 14: Acid terminated Polymer 14 (86.04 parts) and acetic anhydride (5.19 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 16 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a pale yellow clear liquid at room temperature. This is Polymeric Anhydride 14.

[0139] Polymeric Anhydride 15: Acid terminated Polymer 15 (65.01 parts) and acetic anhydride (4.02 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 16.5 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a clear yellow liquid at room temperature. This is Polymeric Anhydride 15.

[0140] Polymeric Anhydride 16: Acid terminated Polymer 16 (60.00 parts) and acetic anhydride (4.26 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated to 120° C. under nitrogen. After 6 hours, the temperature was increased to 150° C. After an additional 15 hours, the Dean-Stark trap was removed leaving an open port. After an additional hour, the reaction stopped to give a gold colored clear liquid at room temperature. This is Polymeric Anhydride 16.

[0141] Polymeric Anhydride 17: Acid terminated Polymer 17 (102 parts) and acetic anhydride (12 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated with stirring under nitrogen to 120° C. After 10 hours, the temperature was increased to 150° C. After an additional 4 hours, the reaction was stopped to give a pale yellow liquid, which is Polymeric Anhydride 17.

[0142] Polymeric Anhydride 18: Acid terminated Polymer 18 (78 parts) and acetic anhydride (10 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. to remove excess acetic anhydride and residual acetic acid. After an additional 4 hours, the reaction was stopped to give a pale amber waxy solid, which is Polymeric Anhydride 18.

[0143] Polymeric Anhydride 19: Acid terminated polymer 18 (230 parts) and acetic anhydride (35 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. to remove excess acetic anhydride and residual acetic acid. After an additional 4 hours, the reaction was stopped to give a pale yellow liquid, which is polymeric anhydride 19.

[0144] Polymeric Anhydride 20: Acid terminated Polymer 20 (101 parts) and acetic anhydride (10 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 10 hours, the temperature was increased to 150° C. After an additional 10 hours, the reaction had stopped to give a pale yellow liquid, which is Polymeric Anhydride 20.

[0145] Polymeric Anhydride 21: Acid terminated polymer 21 (52 parts) and acetic anhydride (6 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. to remove excess acetic anhydride and residual acetic acid. After an additional 4 hours, the reaction was stopped to give a dark amber liquid, which is polymeric anhydride 21.

[0146] Polymeric Anhydride 22: Acid terminated polymer 22 (85.04 parts) and acetic anhydride (3.87 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 7 hours, the reaction had stopped to give a brown viscous liquid, which is polymeric anhydride 22.

[0147] Polymeric Anhydride 23: Acid terminated polymer 23 (50.03 parts) and acetic anhydride (3.2 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 13.25 hours, the reaction was stopped to give a brown solid, which is polymeric anhydride 23.

[0148] Polymeric Anhydride 24: Acid terminated polymer 24 (130.05 parts) and acetic anhydride (8.72 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 12.75 hours, the reaction stopped to give a pale cream colored solid, which is polymeric anhydride 24.

[0149] Polymeric Anhydride 25: Acid terminated Polymer 25 (60.04 parts) and acetic anhydride (4.04 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 9 hours, the reaction was stopped to give a cream-colored waxy solid, which is Polymeric Anhydride 25.

[0150] Polymeric Anhydride 26: Acid terminated polymer 26 (60.08 parts) and acetic anhydride (4.33 parts) were charged to a reaction vessel fitted with a Dean-Stark trap and heated under nitrogen to 120° C. After 6 hours, the temperature was increased to 150° C. After an additional 26.5 hours, the reaction was stopped to give a brown solid, which is polymeric anhydride 26.

[0151] Step 4 - Reaction of polymeric anhydride with multiamine to form dispersant

[0152] Dispersant 1: Polymeric Anhydride 1 (50.01 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.86 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a pale yellow waxy solid with an acid number of 44 mg KOH / g and a base equivalent of 1060. This is Dispersant 1.

[0153] Dispersant 2: Polymeric Anhydride 1 (45.01 parts) and Polymeric Anhydride 2 (15.03 parts) were charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (4.61 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a brownish yellow waxy solid with an acid number of 56 mg KOH / g and a base equivalent of 1221. This is Dispersant 2.

[0154] Dispersant 3: Polymeric Anhydride 3 (129.75 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (10.00 parts, preheated to 70° C.) was charged. After 1 hour the reaction was stopped to give a brown paste with an acid number of 16 mg KOH / g and a base equivalent of 1053. This is Dispersant 3.

[0155] Dispersant 4: Polymeric Anhydride 4 (40.02 parts) was charged to a reaction vessel and heated to 70° C. followed by Epomin™ SP018 (3.08 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a cloudy dark brown liquid with an acid number of 27 mg KOH / g and a base equivalent of 1246. This is Dispersant 4.

[0156] Dispersant 5: Polymeric Anhydride 5 (40.00 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.09 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a cloudy, viscous, light brown liquid with an acid number of 14 mg KOH / g and a base equivalent of 1228. This is Dispersant 5.

[0157] Dispersant 6: Polymeric Anhydride 6 (50.01 parts) was charged to a reaction vessel and heated to 70° C. followed by Epomin™ SP018 (3.86 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a dark brown waxy solid with an acid number of 26 mg KOH / g and a base equivalent of 993. This is Dispersant 6.

[0158] Dispersant 7: Polymeric Anhydride 7 (34.98 parts) was charged to a reaction vessel and heated to 70° C. followed by Epomin™ SP018 (2.69 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a clear, light yellow liquid with an acid number of 18 mg KOH / g and a base equivalent of 958. This is Dispersant 7.

[0159] Dispersant 8: Polymeric Anhydride 8 (130.01 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (10.01 parts, preheated to 70° C.) was charged. After 1 hour the reaction was stopped to give a dark brown liquid with an acid number of 32 mg KOH / g and a base equivalent of 1008. This is Dispersant 8.

[0160] Dispersant 9: Polymeric Anhydride 9 (50.00 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.85 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a clear brown liquid with an acid number of 16 mg KOH / g and a base equivalent of 1071. This is Dispersant 9.

[0161] Dispersant 10: Polymeric Anhydride 1 (70.04 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.93 parts, preheated to 70° C.) was charged. After 1 hour the reaction was stopped to give a brownish yellow waxy solid with an acid number of 49 mg KOH / g and a base equivalent of 1946. This is Dispersant 10.

[0162] Dispersant 11: Polymeric Anhydride 1 (50.00 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (5.56 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a pale yellow waxy solid with an acid number of 50 mg KOH / g and a base equivalent of 634. This is Dispersant 11.

[0163] Dispersant 12: Polymeric Anhydride 1 (60.00 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP006 (4.61 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a pale yellow solid with an acid number of 43 mg KOH / g and a base equivalent of 1145. This is Dispersant 12.

[0164] Dispersant 13: Polymeric Anhydride 10 (60.00 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (4.62 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a clear, dark brown, viscous liquid with an acid number of 28 mg KOH / g and a base equivalent of 1119. This is Dispersant 13.

[0165] Dispersant 14: Polymeric Anhydride 11 (60.01 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (4.63 parts, preheated to 70° C.) was charged. After 1 hour, the reaction was stopped to give a cloudy, viscous brown liquid with an acid number of 19 mg KOH / g and a base equivalent of 1221. This is Dispersant 14.

[0166] Dispersant 15: Polymeric Anhydride 9 (60.00 parts) was charged to a reaction vessel and heated to 70° C., followed by succinic anhydride (0.94 parts) and Epomin™ SP018 (4.62 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a cloudy brown liquid with an acid number of 24 mg KOH / g and a base equivalent of 1104. This is Dispersant 15.

[0167] Dispersant 16: Polymeric anhydride 12 (70.01 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (5.37 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a dark brown solid at room temperature with an acid number of 32 mg KOH / g and a base equivalent of 910. This is Dispersant 16.

[0168] Dispersant 17: Polymeric anhydride 13 (50.02 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.83 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a cloudy yellow liquid at room temperature with an acid number of 18.25 mg KOH / g and a base equivalent of 1152.11. This is Dispersant 17.

[0169] Dispersant 18: Polymeric anhydride 14 (70.05 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (5.37 parts, preheated to 70° C.) was charged. After 1 hour, the reaction was stopped to give a gold colored liquid at room temperature with an acid number of 28.27 mg KOH / g and a base equivalent of 1013.35. This is Dispersant 18.

[0170] Dispersant 19: Polymeric anhydride 15 (43.98 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.38 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a brown liquid at room temperature with an acid number of 29.89 mg KOH / g and a base equivalent of 1068.52. This is Dispersant 19.

[0171] Dispersant 20: Polymeric anhydride 16 (49.99 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.84 parts, preheated to 70° C.) was charged. After 1 hour, the reaction was stopped to give an orange viscous clear liquid at room temperature with an acid number of 30.64 mg KOH / g and a base equivalent of 1158.4. This is Dispersant 20.

[0172] Dispersant 21: Polymeric anhydride 17 (51 parts) was charged to a reaction vessel and heated to 70° C. with stirring under nitrogen, then Epomin™ SP018 (3 parts, preheated to 70° C.) was charged. After 1 hour the reaction was stopped to give a pale yellow liquid with an acid number of 12.6 mg KOH / g and a base equivalent of 1516. This is Dispersant 21.

[0173] Dispersant 22: Polymeric anhydride 18 (75 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (6.5 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a light brown waxy solid with an acid number of 22.7 mg KOH / g and a base equivalent of 1083. This is Dispersant 22.

[0174] Dispersant 23: Polymeric anhydride 19 (50 parts) was charged to a reaction vessel and heated to 70° C. followed by Epomin SP200 (5 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give an amber liquid with an acid number of 44.5 mg KOH / g and a base equivalent of 930. This is Dispersant 23.

[0175] Dispersant 24: Polymeric anhydride 19 (50 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (5 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give an amber liquid with an acid number of 43.1 mg KOH / g and a base equivalent of 962. This is Dispersant 24.

[0176] Dispersant 25: Polymeric anhydride 20 (51 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP200 (4 parts, preheated to 70° C.) was charged. After 1 hour, the reaction was stopped to give a light amber liquid with an acid number of 19.2 mg KOH / g and a base equivalent of 1203. This is Dispersant 25.

[0177] Dispersant 26: Polymeric anhydride 20 (45 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP200 (5 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a light amber liquid with an acid number of 25 mg KOH / g and a base equivalent of 753. This is Dispersant 26.

[0178] Dispersant 27: Dispersant 18 (39.99 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen then caprolactone (0.81 parts) was charged. After 1 hour the reaction was stopped to give a viscous liquid / paste with an acid number of 27.45 mg KOH / g and a base equivalent of 1257.93. This is Dispersant 27.

[0179] Dispersant 28: Dispersant 16 (40.17 parts) was charged to a reaction vessel and heated to 70°C under nitrogen then orthophosphoric acid (85% w / w, 0.82 parts) and toluene (40.96 parts). After 1 hour the reaction was stopped to give a viscous liquid / paste with an acid number of 24.13 mg KOH / g and a base equivalent of 1174.43. This is Dispersant 28.

[0180] Dispersant 29: Dispersant 19 (30.24 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen then butyl acrylate (0.57 parts) was charged. After 1 hour the reaction was stopped to give a viscous liquid / paste with an acid number of 25.79 mg KOH / g and a base equivalent of 1384.03. This is Dispersant 29.

[0181] Dispersant 30: Dispersant 1 (35.09 parts) was charged to a reaction vessel and heated to 70°C under nitrogen then dimethyl sulfate (0.7 parts) was charged. After 1 hour the reaction was stopped to give a viscous liquid / paste with an acid number of 49.56 mg KOH / g and a base equivalent of 1535.18. This is Dispersant 30.

[0182] Dispersant 31: Dispersant 3 (50.03 parts) was charged to a reaction vessel and heated to 70° C. under nitrogen followed by 1.00 part of Example 198 of US6197877 preheated to 70° C. After 1 hour the reaction was stopped to give a viscous liquid / paste with an acid number of 16.13 mg KOH / g and a base equivalent of 1240.25. This is Dispersant 31.

[0183] Dispersant 32: Polymeric anhydride 21 (52 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.8 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a dark amber liquid with an acid number of 15.9 mg KOH / g and a base equivalent of 679. This is Dispersant 32.

[0184] Dispersant 33: Polymeric anhydride 22 (70.02 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (5.42 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a brown viscous liquid at room temperature with an acid number of 25.23 mg KOH / g and a base equivalent of 1025.32. This is Dispersant 33.

[0185] Dispersant 34: Polymeric anhydride 23 (40.03 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.08 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a brown solid at room temperature having an acid number of 24.95 mg KOH / g and a base equivalent of 990.76. This is Dispersant 34.

[0186] Dispersant 35: Polymeric anhydride 24 (100.14 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (7.66 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a cream colored solid at room temperature with an acid number of 18.85 mg KOH / g and a base equivalent of 1184.82. This is Dispersant 35.

[0187] Dispersant 36: Polymeric anhydride 25 (50.03 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin™ SP018 (3.87 parts, preheated to 70° C.). After 1 hour, the reaction was stopped to give a beige solid at room temperature with an acid number of 22.75 mg KOH / g and a base equivalent of 1123.03. This is Dispersant 36.

[0188] Dispersant 37: Polymeric anhydride 26 (40.01 parts) was charged to a reaction vessel and heated to 70° C., followed by Epomin SP018 (3.11 parts, preheated to 70° C.). After 1 hour the reaction was stopped to give a brown solid at room temperature having an acid number of 22.58 mg KOH / g and a base equivalent of 899.5. This is Dispersant 37.

[0189] Dispersant 38: Polymeric Anhydride 9 (47.09 parts) and Polymeric Anhydride 1 (47 parts) were charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (7.27 parts, preheated to 70° C.) was charged. After 1 hour, the reaction was stopped to give a brown liquid at room temperature with an acid number of 46.21 mg KOH / g and a base equivalent of 1064.50. This is Dispersant 38.

[0190] Comparative Example The following examples are based on literature teachings that acid-terminated polymers can readily react with multifunctional polyamines (especially PEI), and therefore in each comparative example the same acid-terminated polymer was used as the intermediate to create in each case as close a comparative example as possible.

[0191] The reaction conditions used are to stir the acid terminated polymer with the multifunctional polyamine (specifically PEI) at 120° C. for 6 hours, as these are the reaction conditions used in dispersants 1-29 (examples 30-59) of US 6,197,877, where polyester-based PEI dispersants are made, and the same reaction conditions used in dispersants 1-28 of US 7,767,750 (WO 2005 / 010109 A2), where polyether-based PEI dispersants are made.

[0192] Comparative Example 1: Acid Terminated Polymer 1 (30.05 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (2.31 parts, preheated to 70° C.) was charged and the temperature increased to 120° C. After 6 hours, the reaction was stopped to give a brownish orange waxy solid with an acid number of 26 mg KOH / g and a base equivalent of 1392. This is Comparative Example 1.

[0193] Comparative Example 2: Acid Terminated Polymer 3 (60.01 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (4.62 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a brown paste with an acid number of 19 mg KOH / g and a base equivalent of 1505. This is Comparative Example 2.

[0194] Comparative Example 3: Acid Terminated Polymer 4 (60.02 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (4.62 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a cloudy dark brown liquid with an acid number of 31 mg KOH / g and a base equivalent of 1882. This is Comparative Example 3.

[0195] Comparative Example 4: Acid Terminated Polymer 5 (60.01 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (4.64 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a cloudy, viscous, light brown liquid with an acid number of 30 mg KOH / g and a base equivalent of 1791. This is Comparative Example 4.

[0196] Comparative Example 5: Acid Terminated Polymer 6 (50.00 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.87 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a heterogeneous mixture of solids and a cloudy liquid with an acid number of 20 mg KOH / g and a base equivalent of 1745. This is Comparative Example 5.

[0197] Comparative Example 6: Acid Terminated Polymer 7 (50.02 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.85 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a cloudy brown liquid with an acid number of 26 mg KOH / g and a base equivalent of 1369. This is Comparative Example 6.

[0198] Comparative Example 7: Acid Terminated Polymer 8 (80.00 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (6.15 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a milky yellow liquid with an acid number of 35 mg KOH / g and a base equivalent of 1502. This is Comparative Example 7.

[0199] Comparative Example 8: Acid Terminated Polymer 9 (50.01 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.85 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a clear orange liquid with an acid number of 15 mg KOH / g and a base equivalent weight of 1452. This is Comparative Example 8.

[0200] Comparative Example 9: Acid Terminated Polymer 10 (60.01 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (4.62 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a clear orange liquid with an acid number of 25 mg KOH / g and a base equivalent of 1558. This is Comparative Example 9.

[0201] Comparative Example 10: Acid Terminated Polymer 11 (60.00 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (4.64 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a viscous brown liquid with an acid number of 30 mg KOH / g and a base equivalent of 1900. This is Comparative Example 10.

[0202] Comparative Example 11: Acid-terminated Polymer 12 (50.00 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.87 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a yellow solid at room temperature with an acid number of 24 mg KOH / g and a base equivalent of 1409. This is Comparative Example 11.

[0203] Comparative Example 12: Acid Terminated Polymer 13 (50.51 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.98 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a cloudy orange viscous liquid at room temperature with an acid number of 27.01 mg KOH / g and a base equivalent of 1298.10. This is Comparative Example 12.

[0204] Comparative Example 13: Acid terminated polymer 14 (65.98 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (5.06 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a clear brown liquid at room temperature with an acid number of 20.89 mg KOH / g and a base equivalent of 1131.20. This is Comparative Example 13.

[0205] Comparative Example 14: Acid Terminated Polymer 15 (45.13 parts) was charged to a reaction vessel and heated to 70° C., then Epomin™ SP018 (3.59 parts, preheated to 70° C.) was charged and the temperature was increased to 120° C. After 6 hours, the reaction was stopped to give a dull light brown liquid at room temperature with an acid number of 18.71 mg KOH / g and a base equivalent of 2690.50. This is Comparative Example 14.

[0206] Comparative Example 15: Acid Terminated Polymer 17 (51 parts) was charged to a reaction vessel and heated to 70° C. with stirring under nitrogen, then Epomin™ SP018 (3 parts, preheated to 70° C.) was charged. Heat to 120° C. with stirring under nitrogen. After 10 hours the reaction was stopped to give a pale yellow cloudy liquid with an acid number of 9.2 mg KOH / g and a base equivalent of 1998. This is Comparative Example 15.

[0207] Comparative Example 16: Acid Terminated Polymer 20 (39 parts) was charged to a reaction vessel and heated to 70° C. with stirring under nitrogen, then Epomin™ SP200 (3 parts, preheated to 70° C.) was charged. Heat to 120° C. with stirring under nitrogen. After 6 hours, the reaction was stopped to give a dark amber liquid with an acid number of 9.8 mg KOH / g and a base equivalent of 1586. This is Comparative Example 16.

[0208] Comparative Example 17: Acid Terminated Polymer 21 (52 parts) was charged to a reaction vessel and heated to 70° C. with stirring under nitrogen, then Epomin™ SP018 (4 parts, preheated to 70° C.) was charged. Heat to 120° C. with stirring under nitrogen. After 6 hours, the reaction was stopped to give a yellow liquid with an acid number of 12.3 mg KOH / g and a base equivalent of 789. This is Comparative Example 17.

[0209] Application Test Applicable test reagents Dowanol MPA, from Sigma Aldrich Toluene, Fisher Scientific Ethanol, Fisher Scientific Ethyl acetate, Fisher Scientific Exxol D140, manufactured by ExxonMobil Heliogen Blue L7101F, manufactured by BASF Irgalite Rubine D4240, manufactured by BASF Symular Carmine 6B400s, manufactured by Sun Chemicals Bayferrox 130M, manufactured by Lanxess 3mm glass beads, Sigmund Lindner

[0210] Application result

[0211] Each dispersant (0.25 parts) shown in Tables 2-5 below was added to an 8 dram glass bottle and solvent (8.25 parts) was added. The dispersant was then dissolved by shaking and heating as necessary. Once dissolved, 3 mm glass beads (17 parts) were added followed by Heliogen Blue L7101F (1.50 parts). The glass bottle was then sealed and shaken on a horizontal shaker for 16 hours. The resulting dispersions were then evaluated for flowability using a visual characterization scale of A to E (fluid to viscous). A - Free movement of glass beads (fluid) B-Exercise after 1 minute of shaking C-Exercise for 10 seconds after shaking D-Movement during shaking E-No movement (gelation) [Table 1] [Table 2] [Table 3] [Table 4]

[0212] Each dispersant (0.40 parts) shown in Tables 6-9 below was added to an 8 dram glass bottle and solvent (7.60 parts) was added. The dispersant was then dissolved by shaking and heating as necessary. Once dissolved, 3 mm glass beads (17 parts) were added followed by Irgalite Rubine D4240 (2.00 parts). The glass bottle was then sealed and shaken on a horizontal shaker for 16 hours. The resulting dispersions were then evaluated for flowability using a visual characterization scale of A to E (fluid to viscous). A - Free movement of glass beads (fluid) B-Exercise after 1 minute of shaking C-Exercise for 10 seconds after shaking D-Movement during shaking E-No movement (gelation) [Table 5] [Table 6] [Table 7] [Table 8]

[0213] Each dispersant (0.40 parts) shown in Table 10 below was added to an 8 dram glass bottle and solvent (7.60 parts) was added. The dispersant was then dissolved by shaking and heating as necessary. Once dissolved, 3 mm glass beads (17 parts) were added followed by Symuler Carmine 6B400s (2.00 parts). The glass bottle was then sealed and shaken on a horizontal shaker for 16 hours. The resulting dispersions were then evaluated for flowability using a visual characterization scale of A to E (fluid to viscous). A - Free movement of glass beads (fluid) B-Exercise after 1 minute of shaking C-Exercise for 10 seconds after shaking D-Movement during shaking E-No movement (gelation) [Table 9]

[0214] Each dispersant (0.40 parts) shown in Table 11 below was added to an 8 dram glass bottle and solvent (7.60 parts) was added. The dispersant was then dissolved by shaking and heating as necessary. Once dissolved, 3 mm glass beads (17 parts) were added followed by Irgalite Rubine (2.00 parts). The glass bottle was then sealed and shaken on a horizontal shaker for 16 hours. The resulting dispersions were then evaluated for flowability using a visual characterization scale of A to E (fluid to viscous). A - Free movement of glass beads (fluid) B-Exercise after 1 minute of shaking C-Exercise for 10 seconds after shaking D-Movement during shaking E-No movement (gelation) [Table 10]

[0215] Each dispersant (0.10 parts) shown in Table 12 below was added to an 8 dram glass bottle and solvent (4.90 parts) was added. The dispersant was then dissolved by shaking and heating as necessary. Once dissolved, 3 mm glass beads (17 parts) were added, followed by Bayferrox 130M (5.00 parts). The glass bottle was then sealed and shaken on a horizontal shaker for 16 hours. The resulting dispersions were then evaluated for flowability using a visual characterization scale of A to E (fluid to viscous). A - Free movement of glass beads (fluid) B-Exercise after 1 minute of shaking C-Exercise for 10 seconds after shaking D-Movement during shaking E-No movement (gelation) [Table 11]

[0216] Dispersions are prepared by dissolving each of Dispersant Examples 21 and 25 and Comparative Examples 16 and 17 (0.4 parts) in 4:1 ethanol:ethyl acetate (v:v) (7.6 parts), respectively. 3 mm glass beads (17 parts) and Irgalite Rubine D4240 pigment (2.0 parts, Pigment Red 57.1 ex BASF) are then added to each solution and the contents are milled on a horizontal shaker for 16 hours. Viscosity is assessed by determining the freedom of movement of the glass beads throughout the millbase. In all cases except when no reagent is present, the pigment is wetted and a uniform dispersion is formed. The viscosity of the resulting dispersion is assessed using a visual characterization scale of A to E (good to poor). The results are shown below and clearly demonstrate that the dispersants of the present invention produce better and more fluid dispersions. The particle size of each dispersion was obtained by milling the dispersion (0.04 parts), diluting it in 4:1 ethanol:ethyl acetate (v:v) (8 parts) and measuring the particle size with a Nanotrac DLS particle size analyzer. The results obtained are as follows: [Table 12]

[0217] Particle Size Analysis: Selected dispersions from Tables 2-12 above were diluted in an appropriate solvent (approximately 1:50 by volume). Particle size analysis was performed on each of the dispersions shown in Tables 9-10 below. D50 and D90 values ​​were obtained from the intensity-based distribution. [Table 13] [Table 14] [Table 15] [Table 16] [Table 17] [Table 18]

[0218] Viscosity measurements: Viscosity was measured using a rheometer for dispersions selected from Tables 2 to 12 above. -1 and 100s -1 -Two shear rates were selected for data comparison. [Table 19] [Table 20]

[0219] As used herein, the transitional term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each recitation of "comprising" herein, the term is also intended to encompass, as alternative embodiments, the phrases "consisting essentially of" and "consisting of," where "consisting of" excludes any unspecified elements or steps, and "consisting essentially of" allows for the inclusion of additional, unrecited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

[0220] While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is therefore to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims. For example, the present invention provides the following: (Item 1) A dispersant having the following structure: [ka] During the ceremony, X is RQ or a cyclic secondary amine, and when X is RQ, R is a hydrocarbon chain containing 1 to 50 carbon atoms and Q is oxygen or NR 7 or NH, provided that when n is 0 and b is 0, Q can only be NH; R 7 is a hydrocarbon chain containing 1 to 18 carbon atoms, R 1 is H, methyl, or ethyl; R 5 is a hydrocarbon chain containing up to 3 carbon atoms, R6 is hydrogen, a hydrocarbyl group containing 1 to 22 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide; b is 0 or 1, except that when both n and m are both at least 1, b can only be 1; R 2 is a hydrocarbon chain containing 1 to 15 carbon atoms, or -R 8 (C=O)YR 9 -, where Y is O, NH or NR 10 and R 8 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 9 is a hydrocarbon chain containing 2 to 10 carbon atoms, and R 10 is a hydrocarbon chain containing 1 to 20 carbon atoms, n is any integer from 0 to 65, m is any integer from 0 to 35, provided that m+n is at least 3; R 3 is a hydrocarbon containing 2 to 80 carbons, q and t are each at least 1; MA is a multiamine species having a number average molecular weight of 300 to 20,000 g / mol; R 4 is a carbon chain containing 1 to 4 carbons, preferably 1 to 2 carbons, p+z is 0 or any integer from 1 to 200. (Item 2) 2. The dispersant according to item 1, wherein X is RQ and Q is oxygen. (Item 3) X is RQ and Q is NR 7 2. The dispersant according to item 1, wherein (Item 4) 2. The dispersant according to item 1, wherein X is RQ, Q is NH, n is 0, and b is 0. (Item 5) 2. The dispersant according to claim 1, wherein X is a cyclic secondary amine selected from piperidine, morpholine, 4-methylpiperidine, 4-phenylpiperidine, thiomorpholine, azetidine, 1-methylpiperazine, 2-methylpiperazine, and pyrrolidine, and mixtures thereof. (Item 6) 6. The dispersant according to any of items 1 to 5, wherein R is a hydrocarbon chain containing 1 to 30 carbon atoms. (Item 7) 7. The dispersant according to any of items 1 to 6, wherein R is a branched or straight chain, saturated or unsaturated, alkyl, aryl, aralkyl, or alkylaryl hydrocarbon chain. (Item 8) 8. The dispersant according to any one of items 1 to 7, wherein R further contains a halogen group. (Item 9) 8. The dispersant according to any one of items 1 to 7, wherein R contains a heteroatom selected from N or O. (Item 10) R 7 contains a functional group selected from the group consisting of ether, ester, or amide. (Item 11) R 6 is H. (Item 12) R 6 is a hydrocarbon chain containing 1 to 22 carbon atoms. (Item 13) R 6 11. The dispersant according to any one of items 1 to 10, wherein is a residue of an alkyl (meth)acrylate or (meth)acrylamide. (Item 14) R 2 But -R 8 (C=O)YR 9 14. The dispersant according to any one of items 1 to 13, wherein (Item 15) 15. The dispersant according to item 14, wherein Y is NH. (Item 16) Y is NR 10 and R 10 is a hydrocarbon chain containing 1 to 20 carbon atoms. (Item 17) R 10 17. The dispersant according to item 16, wherein comprises an ester, ether, or amide group. (Item 18) R 2 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms. (Item 19) R 2 is a hydrocarbon chain containing 2 to 7 carbon atoms. (Item 20) R 2 is a hydrocarbon chain containing 2 to 15 carbon atoms and has the formula -N(R 11 )-(C=O)-, wherein R 11 is H or a hydrocarbon chain containing 1 to 4 carbon atoms. (Item 21) R 3 is a branched or linear, saturated or unsaturated hydrocarbon chain containing from 2 to 20 carbon atoms. (Item 22) 22. The dispersant according to any one of items 1 to 21, wherein MA has a number average molecular weight of 600 to 10,000 g / mol. (Item 23) 23. The dispersant according to any of the preceding claims, wherein MA has at least four amine groups. (Item 24) 24. The dispersant according to any of the preceding items, wherein the MA comprises polyethyleneimine or modified polyethyleneimine. (Item 25) 25. The dispersant according to item 24, wherein the dispersant is modified by reacting it with (a) a polymeric species having groups which react with isocyanates, lactones, epoxies, anhydrides, cyclic carbonates, (meth)acrylates via Michael addition reaction, and / or primary or secondary amines to form salt or covalent bonds, (b) an oxidizing species capable of converting the amine groups to nitric oxide, (c) a chlorinating agent, or (d) reacting the tertiary amine groups of the multi-amine species, or the dispersant containing the multi-amine species, with a quaternizing agent to form quaternized amine groups. (Item 26) R 4 26. The dispersant according to any of items 1 to 25, wherein (Item 27) 27. The dispersant according to any one of items 1 to 26, wherein q+t is any integer from 2 to 200. (Item 28) 28. The dispersant according to item 27, wherein q+t is any integer from 2 to 150. (Item 29) 29. The dispersant according to any one of items 1 to 28, wherein q is equal to or greater than t. (Item 30) 30. The dispersant according to any one of items 1 to 29, wherein p+z is 0. (Item 31) 30. The dispersant according to any one of items 1 to 29, wherein p+z is any integer from 1 to 200. (Item 32) 32. The dispersant according to any one of items 31, wherein p+z is any integer from 2 to 200. (Item 33) 33. The dispersant according to any one of items 1 to 32, wherein n is any integer from 1 to 65. (Item 34) 33. The dispersant according to any one of items 1 to 32, wherein n is 0. (Item 35) 35. The dispersant according to any one of items 1 to 34, wherein m is an integer of 1 to 35. (Item 36) 34. The dispersant according to any one of items 1 to 33, wherein m is 0. (Item 37) Item 36. The dispersant according to item 35, wherein m is 5 to 16. (Item 38) 38. The dispersant according to any one of items 1 to 37, wherein m+n is 3 to 65. (Item 39) 38. The dispersant according to any one of items 1 to 37, wherein m+n is 5 to 30. (Item 40) 33. The dispersant according to any of the preceding items, wherein b is 1 and m+n is at least 4. (Item 41) 1. A method for preparing a dispersant, the method comprising the steps of: (a) providing an alcohol-terminated polymer of the formula: X-(CH 2 CHR 1 -O) n [R 5 -N(R 6 )] b -[(C=O)R 2 -O] m -H, in the formula, X is RQ or a cyclic amine, R is a hydrocarbon chain containing 1 to 50 carbon atoms, and Q is O, or NR 7 or NH, with the proviso that when n is 0 and b is 0, X can only be NH; R 7 is a hydrocarbon chain containing 1 to 18 carbon atoms, R 1 is H, methyl, or ethyl; R 5 is a hydrocarbon chain containing up to 3 carbon atoms, R 6 is hydrogen, a hydrocarbyl group containing 1 to 22 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide; b is 0 or 1, except that when both n and m are both at least 1, b can only be 1; R 2 is a hydrocarbon chain containing 1 to 15 carbon atoms, or -R 8 (C=O)YR 9 -, where Y is O, NH or NR 10 and R 8 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 9 is a hydrocarbon chain containing 1 to 10 carbon atoms, and R 10 is a hydrocarbon chain containing 1 to 20 carbon atoms, n is any integer from 0 to 65, and m is any integer from 0 to 35, with the proviso that m+n is at least 3. (b) reacting the alcohol-terminated polymer with a cyclic anhydride to provide an acid-terminated polymer; (c) reacting the acid-terminated polymer with a non-cyclic anhydride to provide a mixture of anhydrides; (d) reacting the mixture of anhydrides with a multiamine species having a number average molecular weight of 300 to 20,000 to form a dispersant molecule. (Item 42) 42. The dispersant according to item 41, wherein X is RQ and Q is oxygen. (Item 43) X is RQ and Q is NR 7 Item 42. The dispersant according to item 41, wherein (Item 44) 42. The dispersant according to item 41, wherein X is RQ, Q is NH, n is 0, and b is 0. (Item 45) 42. The dispersant according to item 41, wherein X is a cyclic secondary amine selected from piperidine, morpholine, 4-methylpiperidine, 4-phenylpiperidine, thiomorpholine, azetidine, 1-methylpiperazine, 2-methylpiperazine, and pyrrolidine, and mixtures thereof. (Item 46) 46. ​​The dispersant according to any of items 41 to 45, wherein R is a hydrocarbon chain containing 1 to 30 carbon atoms. (Item 47) 47. The dispersant according to any of items 41 to 46, wherein R is a branched or straight chain, saturated or unsaturated, alkyl, aryl, aralkyl, or alkylaryl hydrocarbon chain. (Item 48) 48. The dispersant according to any one of items 41 to 47, wherein R further contains a halogen group. (Item 49) 48. The dispersant according to any of items 41 to 47, wherein R contains a heteroatom selected from N or O. (Item 50) R 7 contains a functional group selected from the group consisting of ether, ester, or amide. (Item 51) R 6 is H. (Item 52) R 6 is a hydrocarbon chain containing 1 to 22 carbon atoms. (Item 53) R 6 is a residue of an alkyl (meth)acrylate or (meth)acrylamide. (Item 54) R 2 But -R 8 (C=O)YR 9 - 54. The dispersant according to any one of items 41 to 53, wherein (Item 55) 55. The dispersant according to item 54, wherein Y is NH. (Item 56) Y is NR 10 and R 10 is a hydrocarbon chain containing 1 to 20 carbon atoms. (Item 57) R 10 57. A dispersant according to item 56, wherein comprises an ester, ether, or amide group. (Item 58) R 2 is a linear or branched, saturated or unsaturated hydrocarbon chain containing 1 to 10 carbon atoms. (Item 59) R 2 is a hydrocarbon chain containing 2 to 7 carbon atoms. (Item 60) R 2 is a hydrocarbon chain containing 2 to 15 carbon atoms and has the formula -N(R 11 )-(C=O)-, wherein R 11 is H or a hydrocarbon chain containing 1 to 4 carbon atoms. (Item 61) 61. The method according to any one of items 41 to 60, wherein the cyclic anhydride is selected from the group consisting of glutaric anhydride, 1,2-cyclohexanedicarboxylic anhydride, homophthalic anhydride, diglycolic anhydride, succinic anhydride, polyisobutylene succinic anhydride, 2-phenylsuccinic anhydride, alkyl(en)ylsuccinic anhydride, or a mixture thereof. (Item 62) Item 62. The method of item 61, wherein the cyclic anhydride comprises succinic anhydride. (Item 63) 62. The method of claim 61, wherein the cyclic anhydride comprises glutaric anhydride. (Item 64) 64. The method according to any one of items 41 to 63, wherein the acyclic anhydride comprises propionic anhydride. (Item 65) 65. The method according to any one of items 41 to 64, wherein the acyclic anhydride comprises acetic anhydride. (Item 66) 66. The method according to any of items 41 to 65, wherein said mixture of anhydride and multiamine species is reacted in a weight ratio of 1:1 to 25:1. (Item 67) (a) reacting the dispersant molecule with a polymeric species having groups that react with isocyanates, lactones, epoxies, anhydrides, cyclic carbonates, (meth)acrylates via Michael addition reactions, and / or primary or secondary amines to form salt or covalent bonds; (b) an oxidizing species capable of converting the amine groups to nitric oxide; (c) a chlorinating agent; or (d) reacting the tertiary amine groups of the multi-amine species, or the dispersant containing the multi-amine species, with a quaternizing agent to form quaternized amine groups. 67. The method according to any one of items 41 to 66, further comprising:

Claims

1. A dispersant having the following structure: 【Chemistry 1】 During the ceremony, X is R-Q or a cyclic secondary amine, where when X is R-Q, R is a hydrocarbon chain containing 1 to 50 carbon atoms and Q is oxygen, or NR ７ or NH, provided that when n is 0 and b is 0, Q can only be NH; R ７ is a hydrocarbon chain containing 1 to 18 carbon atoms, R １ is H, methyl, or ethyl; R ５ is a hydrocarbon chain containing up to 3 carbon atoms, R ６ is hydrogen, a hydrocarbyl group containing 1 to 22 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide; b is 0 or 1, provided that when both n and m are both at least 1, b can only be 1; R ２ is a hydrocarbon chain containing 1 to 15 carbon atoms, or -R ８ (C=O)YR ９ -, where Y is O or NH or NR １０ and R ８ is a hydrocarbon chain containing 1 to 10 carbon atoms, R ９ is a hydrocarbon chain containing 2 to 10 carbon atoms, R １０ is a hydrocarbon chain containing 1 to 20 carbon atoms, n is any integer from 0 to 65, m is any integer from 0 to 35, provided that m+n is at least 3; R ３ is a hydrocarbon containing 2 to 80 carbons; q and t are each at least 1; MA is a multiamine species having a number average molecular weight of 300 to 20,000 g / mol; R ４ is a carbon chain containing 1 to 4 carbons, A dispersant, wherein p+z is any integer from 1 to 200.

2. R ４ is a carbon chain containing 1 to 2 carbons.

3. 2. The dispersant of claim 1, wherein X is RQ, and Q is oxygen.

4. X is R-Q and Q is NR ７ 2. The dispersant of claim 1 ,

5. 2. The dispersant of claim 1, wherein X is RQ, Q is NH, n is 0, and b is 0.

6. 2. The dispersant of claim 1, wherein X is a cyclic secondary amine selected from piperidine, morpholine, 4-methylpiperidine, 4-phenylpiperidine, thiomorpholine, azetidine, 1-methylpiperazine, 2-methylpiperazine, and pyrrolidine, and mixtures thereof.

7. A dispersant according to any preceding claim, wherein R is a hydrocarbon chain containing from 1 to 30 carbon atoms.

8. A dispersant according to any preceding claim, wherein R is a branched or straight chain, saturated or unsaturated, alkyl, aryl, aralkyl, or alkylaryl hydrocarbon chain.

9. 9. The dispersant of claim 1, wherein R further contains a halogen group.

10. A dispersant according to any preceding claim, wherein R contains a heteroatom selected from N or O.

11. R ７ A dispersant according to any one of claims 1 to 8, wherein contains a functional group selected from the group consisting of ether, ester, or amide.

12. R ６ A dispersant according to any one of claims 1 to 11, wherein is H.

13. R ６ A dispersant according to any preceding claim, wherein is a hydrocarbon chain containing from 1 to 22 carbon atoms.

14. R ６ A dispersant according to any one of claims 1 to 11, wherein is a residue of an alkyl (meth)acrylate or (meth)acrylamide.

15. R ２ But, -R ８ (C=O)YR ９ The dispersant according to any one of claims 1 to 14, wherein

16. 16. The dispersant of claim 15, wherein Y is NH.

17. Y is NR １０ and R １０ A dispersant according to claim 15, wherein is a hydrocarbon chain containing from 1 to 20 carbon atoms.

18. R １０ 20. The dispersant of claim 17, wherein comprises an ester, ether, or amide group.

19. R ２ A dispersant according to any preceding claim, wherein is a linear or branched, saturated or unsaturated hydrocarbon chain containing from 1 to 10 carbon atoms.

20. R ２ A dispersant according to claim 19, wherein is a hydrocarbon chain containing from 2 to 7 carbon atoms.

21. R ２ is a hydrocarbon chain containing 2 to 15 carbon atoms and has the formula -N(R １１ )-(C=O)-, wherein R １１ A dispersant according to any preceding claim, wherein is H or a hydrocarbon chain containing 1 to 4 carbon atoms.

22. R ３ A dispersant according to any preceding claim, wherein is a branched or straight chain, saturated or unsaturated hydrocarbon chain containing from 2 to 20 carbon atoms.

23. 23. A dispersant according to any preceding claim, wherein the MA has a number average molecular weight of 600 to 10,000 g / mol.

24. A dispersant according to any preceding claim, wherein the MA has at least four amine groups.

25. 25. A dispersant according to any preceding claim, wherein the MA comprises polyethyleneimine or modified polyethyleneimine.

26. 26. A dispersant according to claim 25, wherein the dispersant is modified by reacting it with (a) a polymeric species having groups which react with isocyanates, lactones, epoxies, anhydrides, cyclic carbonates, (meth)acrylates via Michael addition reactions, and / or primary or secondary amines to form salt or covalent bonds, (b) an oxidizing species capable of converting the amine groups to nitric oxide, (c) a chlorinating agent, or (d) reacting the tertiary amine groups of the multi-amine species, or the dispersant containing the multi-amine species, with a quaternizing agent to form quaternized amine groups.

27. R ４ A dispersant according to any preceding claim, wherein contains 1 or 2 carbon atoms.

28. 28. A dispersant according to any preceding claim, wherein q+t is any integer from 2 to 200.

29. 29. A dispersant according to claim 28, wherein q+t is any integer from 2 to 150.

30. 30. The dispersant of any one of claims 1 to 29, wherein q is greater than or equal to t.

31. 31. A dispersant according to any of claims 30, wherein p+z is any integer from 2 to 200.

32. A dispersant according to any preceding claim, wherein n is any integer from 1 to 65.

33. A dispersant according to any preceding claim, wherein n is 0.

34. A dispersant according to any preceding claim, wherein m is any integer from 1 to 35.

35. A dispersant according to any preceding claim, wherein m is 0.

36. 35. A dispersant according to claim 34, wherein m is from 5 to 16.

37. A dispersant according to any preceding claim, wherein m+n is from 3 to 65.

38. 37. A dispersant according to any preceding claim, wherein m+n is from 5 to 30.

39. A dispersant according to any preceding claim, wherein b is 1 and m+n is at least 4.

40. 1. A method for preparing a dispersant, the method comprising the steps of: (a) providing an alcohol-terminated polymer of the formula: X-(CH ２ CHR １ -O) ｎ [R ５ -N (R ６ )] ｂ -[(C=O)R ２ -O] ｍ -H, where X is RQ or a cyclic amine, R is a hydrocarbon chain containing 1 to 50 carbon atoms, and Q is O, or NR ７ or NH, with the proviso that when n is 0 and b is 0, X can only be NH, R ７ is a hydrocarbon chain containing 1 to 18 carbon atoms, R １ is H, methyl, or ethyl; R ５ is a hydrocarbon chain containing up to 3 carbon atoms, R ６ is hydrogen, a hydrocarbyl group containing 1 to 22 carbon atoms, or the residue of an alkyl (meth)acrylate or (meth)acrylamide; b is 0 or 1, provided that when both n and m are both at least 1, b can only be 1; R ２ is a hydrocarbon chain containing 1 to 15 carbon atoms, or -R ８ (C=O)YR ９ -, where Y is O or NH or NR １０ and R ８ is a hydrocarbon chain containing 1 to 10 carbon atoms, R ９ is a hydrocarbon chain containing 1 to 10 carbon atoms, R １０ is a hydrocarbon chain containing 1 to 20 carbon atoms, n is any integer from 0 to 65, m is any integer from 0 to 35, and m+n is at least 3. (b) reacting the alcohol-terminated polymer with a cyclic anhydride to provide an acid-terminated polymer; (c) reacting the acid-terminated polymer with a non-cyclic anhydride to provide a mixture of anhydrides; (d) reacting the mixture of anhydrides with a multiamine species having a number average molecular weight of 300 to 20,000 to form a dispersant molecule.

41. 41. The method of claim 40, wherein X is RQ, and Q is oxygen.

42. X is R-Q and Q is NR ７ 41. The method of claim 40, wherein:

43. 41. The method of claim 40, wherein X is RQ, Q is NH, n is 0, and b is 0.

44. 41. The method of claim 40, wherein X is a cyclic secondary amine selected from piperidine, morpholine, 4-methylpiperidine, 4-phenylpiperidine, thiomorpholine, azetidine, 1-methylpiperazine, 2-methylpiperazine, and pyrrolidine, and mixtures thereof.

45. 45. The method of any one of claims 40 to 44, wherein R is a hydrocarbon chain containing from 1 to 30 carbon atoms.

46. 46. ​​The method of any one of claims 40 to 45, wherein R is a branched or straight chain, saturated or unsaturated, alkyl, aryl, aralkyl, or alkylaryl hydrocarbon chain.

47. The method of any one of claims 40 to 46, wherein R further contains a halogen group.

48. The method of any one of claims 40 to 46, wherein R contains a heteroatom selected from N or O.

49. R ７ The method of any of claims 40 to 46, wherein contains a functional group selected from the group consisting of ether, ester, or amide.

50. R ６ The method of any one of claims 40 to 49, wherein is H.

51. R ６ A method according to any one of claims 40 to 49, wherein is a hydrocarbon chain containing from 1 to 22 carbon atoms.

52. R ６ The method of any one of claims 40 to 49, wherein is a residue of an alkyl (meth)acrylate or (meth)acrylamide.

53. R ２ But, -R ８ (C=O)YR ９ The method according to any one of claims 40 to 52, wherein

54. 54. The method of claim 53, wherein Y is NH.

55. Y is NR １０ and R １０ 54. The method of claim 53, wherein is a hydrocarbon chain containing 1 to 20 carbon atoms.

56. R １０ 56. The method of claim 55, wherein comprises an ester, ether, or amide group.

57. R ２ A method according to any one of claims 40 to 52, wherein is a linear or branched, saturated or unsaturated hydrocarbon chain containing from 1 to 10 carbon atoms.

58. R ２ 58. The method of claim 57, wherein is a hydrocarbon chain containing from 2 to 7 carbon atoms.

59. R ２ is a hydrocarbon chain containing 2 to 15 carbon atoms and has the formula -N(R １１ )-(C=O)-, wherein R １１ The method of any of claims 40 to 52, wherein is H or a hydrocarbon chain containing 1 to 4 carbon atoms.

60. 60. The method of any one of claims 40 to 59, wherein the cyclic anhydride is selected from the group consisting of glutaric anhydride, 1,2-cyclohexanedicarboxylic anhydride, homophthalic anhydride, diglycolic anhydride, succinic anhydride, polyisobutylene succinic anhydride, 2-phenylsuccinic anhydride, alk(en)yl succinic anhydride, or mixtures thereof.

61. 61. The method of claim 60, wherein the cyclic anhydride comprises succinic anhydride.

62. 61. The method of claim 60, wherein the cyclic anhydride comprises glutaric anhydride.

63. The method of any one of claims 40 to 62, wherein the acyclic anhydride comprises propionic anhydride.

64. The method of any one of claims 40 to 63, wherein the acyclic anhydride comprises acetic anhydride.

65. 65. The method of any of claims 40 to 64, wherein the mixture of anhydride and multiamine species is reacted in a weight ratio of from 1:1 to 25:

1.

66. (a) reacting the dispersant molecule with a polymeric species having groups that react with isocyanates, lactones, epoxies, anhydrides, cyclic carbonates, (meth)acrylates via Michael addition reaction, and / or primary or secondary amines to form salt or covalent bonds; (b) an oxidizing species capable of converting the amine groups to nitric oxide; (c) a chlorinating agent; or (d) reacting the tertiary amine groups of the multi-amine species, or the dispersant containing the multi-amine species, with a quaternizing agent to form quaternized amine groups. The method of any of claims 40 to 65, further comprising:

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