CN107629538B

CN107629538B - Novel nonionic polyamide rheology modifiers for aqueous coatings

Info

Publication number: CN107629538B
Application number: CN201610557145.0A
Authority: CN
Inventors: 黃伟仁; 颜俊宏; 黃彩绫; 林美青; 林宏益
Original assignee: Elementis Specialties Inc
Current assignee: Elementis Specialties Inc
Priority date: 2016-07-15
Filing date: 2016-07-15
Publication date: 2022-01-14
Anticipated expiration: 2036-07-15
Also published as: CN107629538A; WO2018010615A1

Abstract

Nonionic rheology modifiers are prepared for use in aqueous coatings, comprising a polyamide prepared from an acid-terminated polymer, which is terminated with a polymer comprising a nonionic hydrophilic segment and subsequently dispersed in water, and provide excellent pigment suspension and rheology properties to water-based coatings.

Description

Novel nonionic polyamide rheology modifiers for aqueous coatings

Technical Field

A non-ionic rheology modifier composition for aqueous coatings which prevents settling of pigments and solid particles in the coating.

Background

To prevent settling of the pigment or other finely dispersed solid particles in the coating during storage, a pigment suspending or anti-settling agent is added to the composition. The anti-settling agent provides excellent pigment suspension and rheology properties to the aqueous coating composition. The use of pigment suspending agents or anti-settling agents overcomes the settling problems that occur in coatings. Without such anti-settling agents, pigments and other undissolved materials, once settled, may be difficult to redisperse in a coating system. Thus, additives (anti-settling agents) are known in the art to control the rheological properties and pigment suspension properties of aqueous fluid systems comprising finely dispersed solid particles and to make them easy to use.

Because the particle size of the pigment is large and the specific gravity is also large, an aluminum pigment or a pearl pigment, such as mica or a corrosion resistant pigment used in a metallic paint and a corrosion resistant paint, will cause easy sedimentation in the paint. In solvent-based coatings, anti-settling agents of the amide wax type or polyethylene oxide wax type are used to prevent settling, but many of these additives are not suitable for use in waterborne coatings.

Materials used as anti-settling agents or pigment suspending agents for organic (or non-aqueous) coating compositions are emulsifiable polyethylene waxes dispersed in organic solvents. This is disclosed in us patent nos. 3,123,488 and 3,184,233. Us patent No. 3,985,568 describes a creamy paste comprising finely dispersed particles of an emulsifiable polyethylene wax suspended in a sulfated/sulfonated castor oil solution for modifying the rheological and suspending properties of a non-aqueous fluid system comprising finely dispersed solid particles.

Us patent No. 3,937,678 discloses that the rheological and suspension properties of non-aqueous fluid systems containing finely dispersed solid particles can be improved by applying a mixture of amide waxes obtained by reacting hydrogenated castor oil fatty acid or an organic mixture containing hydrogenated castor oil fatty acid with an amine in a non-aqueous fluid system.

Thickeners such as fumed silica or clays such as montmorillonite, hectorite or attapulgite have been used in aqueous coating systems to adjust for pigment settling problems. However, these materials have the disadvantage of reducing the gloss associated with cured coating systems and are difficult to use as a post-addition conditioner at the completion of the coating preparation. During the manufacture of coatings, these materials are difficult to disperse and require high shear mixing equipment to achieve adequate dispersion.

4,381,376 discloses a method of forming ionic copolymer salts of low molecular weight copolymer acids formed from ethylene and an α, β -ethylenically unsaturated carboxylic acid having at least one carboxylic acid group with a cation having a valence of 1 to 3. These materials may be dispersing aids to disperse finely dispersed inert materials such as pigments in a variety of non-aqueous polymer compositions comprising polypropylene and polyethylene.

5,374,687 discloses a substance obtained by neutralizing an emulsified copolymer obtained from an α -olefin and an α, β -ethylenically unsaturated carboxylic acid with a neutralizing agent. The composition acts as an aqueous anti-settling agent. This additive is liquid and therefore has operational advantages, but it is not effective enough as an anti-settling agent for aluminum pigments or pearlescent pigments such as mica in aqueous metallic coatings.

U.S. patent No. 5,994,494 discloses anti-settling agents for aqueous coatings. The composition is obtained by the following method: polyamides obtained by reacting a primary diamine having 2 to 12 carbon atoms with an amount of dimer dicarboxylic acid in excess of diamine, wherein the dimer dicarboxylic acid is obtained by polymerizing an unsaturated fatty acid (common name: dimer acid) or a mixture of dimer acids with another dicarboxylic acid having 3 to 21 carbon atoms and/or a monocarboxylic acid having 2 to 22 carbon atoms. The polyamide is neutralized with a neutralizing base and the neutralized polyamide is subsequently dispersed in a medium consisting essentially of water.

In recent years, tests have been actively proposed for aqueous coatings due to environmental problems and ease of use problems. Therefore, anti-settling agents for aqueous systems are naturally sought. Although, as described above, various anti-settling agents have hitherto been proposed as aqueous anti-settling agents, they have problems, for example, they are insufficient in effect to prevent settling of pigments having a large particle diameter and a large specific gravity, for example, aluminum pigments used in aqueous metallic paints and pearl pigments such as mica, corrosion-resistant pigments used in aqueous corrosion-resistant paints. In addition, gloss and water resistance are reduced.

The anti-settling agents containing polyamide compositions previously disclosed include aromatic solvents to improve dewatering, which will result in residual aromatic solvent remaining in the coating even if a solvent removal process is applied (U.S. patent No. 5,994,494). Furthermore, many of the early anti-settling agents for aqueous coatings required the use of amine neutralizers. As a result, the coating properties become pH sensitive. In some cases, the neutralizing agent will also cause volatility problems.

The present invention overcomes the problems and deficiencies of the prior art by providing excellent pigment suspension and rheology properties to aqueous coating compositions without the amine neutralizers and the consequent pH sensitivity.

Summary of The Invention

In one embodiment, the present invention provides a nonionic rheology modifier composition for waterborne coatings obtained by a process having the steps of: reacting a polyacid-terminated polyamide with a mono-epoxy-terminated polymer having a non-ionic hydrophilic segment to thereby form a polymer; and dispersing the polymer in water containing a co-solvent to obtain a rheology modifier dispersion.

In another embodiment, the present invention provides a nonionic rheology modifier composition for waterborne coatings obtained by a process comprising: reacting a polyacid-terminated polyamide with a hydrocarbyl glycidyl ether to form an intermediate; reacting the intermediate with a monoisocyanate terminated polymer having a non-ionic hydrophilic segment to thereby form a polymer; and dispersing the polymer in water containing a co-solvent to obtain a rheology modifier dispersion.

In yet another embodiment, the present invention provides a nonionic polyamide rheology modifier of formula (1)

In the formula (1), X is polyacid terminated polyamide, n is 2-6, and Y in the formula (1) is one or more of the following end groups:

wherein R1 in formula (1) is an aliphatic, alicyclic or aromatic end group containing 1 to 22 carbon atoms. In one embodiment, R2 in formula (1) is the residue moiety of a diisocyanate compound selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4 ' -diisocyanate, dicyclohexylmethane-4, 4 ' -diisocyanate, 1, 4-bis (2-isocyanato-2-yl) benzene, trimethylhexamethylene diisocyanate, and X ' is poly (C)_2-4Alkylene oxide).

PREFERRED EMBODIMENTS FOR CARRYING OUT THE INVENTION

It is an object of the present invention to provide anti-settling agents or pigment suspending agents by non-aromatic and non-volatile methods, which are more environmentally friendly when compared to existing materials used for anti-settling and pigment suspension in aqueous coating systems. The anti-settling agent is easy to handle and easy to incorporate into the aqueous composition. In addition, by using raw materials containing the designed composition instead of the mixture, the process and composition ratio can be controlled, and the physical properties and application properties can be controlled in manufacturing the material for anti-settling of the present invention. Embodiments of rheological additives to achieve this are described herein.

One embodiment of the present disclosure provides a nonionic polyamide rheology modifier obtainable by a process comprising: reacting a polyacid terminated polyamide with a monoepoxy terminated polymer having a nonionic hydrophilic segment. Subsequently, the polyamide was dispersed in water containing a co-solvent to obtain a rheology modifier of 25% solids content.

In some embodiments, the polyacid-terminated polyamide is made by reacting at least one dicarboxylic and/or tricarboxylic acid having 3 to 54 carbon atoms with at least one diamine. In such embodiments, the dicarboxylic acid is selected from: malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid and dimerized fatty acids. In another embodiment, the tricarboxylic acid is selected from the group consisting of: citric acid, propane-1, 2, 3-tricarboxylic acid, 1,2, 4-butanetricarboxylic acid, benzene-1, 3, 5-tricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, biphenyl-3, 4', 5-tricarboxylic acid, and trimerized fatty acid. In various of the foregoing embodiments, the diamine is selected from: ethylenediamine, 1, 4-diaminobutane, hexamethylenediamine, 1, 10-decamethylenediamine, 1, 11-undecamethylenediamine, 1, 12-dodecamethylenediamine, xylylenediamine, and 4, 4' -diaminodiphenylmethane.

In some embodiments, the monoepoxy-terminated polymer having a nonionic hydrophilic segment is made by reacting epichlorohydrin with a monohydroxy nonionic hydrophilic compound, or by reacting a mono-hydrocarbyl acid with a diglycidyl-terminated nonionic hydrophilic compound. In such embodiments, the monohydroxy nonionic hydrophilic compound has a molecular weight of from 500 g/mole to 3000 g/mole andpoly (C) comprising aliphatic, cycloaliphatic or aromatic end groups having 1 to 22 carbon atoms_2-4Alkylene oxide).

In some embodiments, where a mono-hydrocarbyl acid is reacted with a diglycidyl-capped nonionic hydrophilic compound, the mono-hydrocarbyl acid is selected from: acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 1, 2-hydroxystearic acid and oleic acid. In such embodiments, the non-ionic hydrophilic segment of the diglycidyl-capped compound has a molecular weight of 500 to 3000 and includes a poly (C) containing 10% -100% ethylene oxide groups_2-4Alkylene oxide) segments.

The various foregoing embodiments of the polyacid-terminated polyamide and the monoepoxy-terminated polymer may be combined into different embodiments of the nonionic polyamide rheology modifier.

Another embodiment of the present disclosure provides a nonionic polyamide rheology modifier obtainable by a process comprising: reacting a polyacid-terminated polyamide with a hydrocarbyl glycidyl ether to form an intermediate and subsequently reacting the intermediate with a monoisocyanate-terminated polymer having a nonionic hydrophilic segment.

In one embodiment, the polyacid-terminated polyamide is made by reacting at least one dicarboxylic and/or tricarboxylic acid having 3 to 54 carbon atoms with at least one diamine. In such embodiments, the dicarboxylic acid is selected from: malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid and dimerized fatty acids. In another embodiment, the tricarboxylic acid is selected from: citric acid, propane-1, 2, 3-tricarboxylic acid, 1,2, 4-butanetricarboxylic acid, benzene-1, 3, 5-tricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, biphenyl-3, 4', 5-tricarboxylic acid, and trimerized fatty acid. In each of the foregoing embodiments, the diamine is selected from: ethylenediamine, 1, 4-diaminobutane, hexamethylenediamine, 1, 10-decamethylenediamine, 1, 11-undecamethylenediamine, 1, 12-dodecamethylenediamine, xylylenediamine, and 4, 4' -diaminodiphenylmethane.

In one embodiment, the hydrocarbyl glycidyl ether is selected from: hydrocarbyl glycidyl ethers having a C2 to C16 hydrocarbyl group such as: ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl (tetradedyl) glycidyl ether and hexadecyl glycidyl ether.

In another embodiment, monoisocyanate terminated polymers having nonionic hydrophilic segments are made by reacting diisocyanates with monohydroxy nonionic hydrophilic compounds. In such embodiments, the diisocyanate is selected from: toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, 1, 4-bis (2-isocyanato-2-yl) benzene, trimethylhexamethylene diisocyanate, or mixtures of such diisocyanates. In such embodiments, the monohydroxy nonionic hydrophilic compound has a molecular weight M of from 500 g/mole to 3000 g/mole and comprises a poly (C) having an aliphatic, cycloaliphatic, or aromatic end group having from 1 to 22 carbon atoms_2-4Alkylene oxide).

Each of the foregoing embodiments of the polyacid-terminated polyamide, the hydrocarbyl glycidyl ether, and the monoisocyanate-terminated polymer may be combined into a different embodiment of the nonionic polyamide rheology modifier.

For each of the foregoing embodiments of the nonionic polyamide rheology modifier, the co-solvent is selected from the group consisting of: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, butyl cellosolve solvent, N-methyl-2-pyrrolidone, 3-methoxy-3-methyl-1-butanol acetate, methyl-5- (dimethylamino) -2-methyl-5-oxopentanoate, N-formylmorpholine.

In another embodiment of the present disclosure, a nonionic polyamide rheology modifier of formula (1) is provided

Wherein X is a polyacid-terminated polyamide and n is 2-6. Y in the formula (1) is one or more selected from the following end groups:

in some embodiments, R1 is an aliphatic, cycloaliphatic, or aromatic end group containing from 1 to 22 carbon atoms. In some other embodiments, R2 is the residue moiety of a diisocyanate compound selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, 1, 4-bis (2-isocyanato-2-yl) benzene, trimethylhexamethylene diisocyanate,

and X' is poly (C)_2-4Alkylene oxide).

Examples

Example A-1: synthesis of polyacid-terminated polyamides

0.49 mol of dimer acid and 0.11 mol of adipic acid were charged in a 1L four-necked flask equipped with a stirring device, a temperature regulator, a flow guide device and a nitrogen introduction tube, followed by stirring and heating to 50 ℃. 0.4 mole of ethylenediamine was gradually added and the exotherm was observed, and the mixture was stirred and gradually heated to 175 ℃ to effect dehydration. After a reaction time of two (2) hours, a brown polyacid-terminated polyamide A-1 was obtained, having an acid value of 74mg KOH/g.

Examples A-2 to A-8: synthesis example of polyacid-terminated polyamide

Further examples of the synthesis of the polyacid-terminated polyamides were carried out according to the synthesis method of example 1, with the compositions shown in Table 1, to obtain polyacid-terminated polyamides A-2 to A-8.

TABLE 1 composition of synthetic examples of polyacid-terminated polyamides

Examples B1-B2: synthesis of Monoepoxy terminated polymers with non-ionic hydrophilic segments

MPEG1000 was charged to a four-necked round bottom flask equipped with a stirring device, a cold water condenser, a temperature regulator and a nitrogen inlet tube. To the flask was added dropwise an equivalent amount of epichlorohydrin, the reaction was allowed to proceed at 60 ℃ for (3) hours and further extracted with a 5% aqueous NaOH solution through a separatory funnel to obtain a monoepoxy-terminated polymer B-1 having a nonionic hydrophilic segment.

Diglycidyl PEG1000 and triethylamine as a catalyst were charged into a four-necked round-bottomed flask equipped with a stirring device, a cold water condenser, a temperature regulator and a nitrogen introduction tube. Half an equivalent of lauric acid was pre-melted at 70 ℃ and gradually added to the flask, and the reaction was allowed to proceed at 85 ℃ for six (6) hours to obtain a monoepoxy-terminated polymer B-2 having a nonionic hydrophilic segment.

Table 2 synthetic examples of monoepoxy-terminated polymers with nonionic hydrophilic segments

Examples C1-C2: synthesis of monoisocyanate terminated polymers with non-ionic hydrophilic segments

One (1) mole of MPEG550 was charged into a 1L four-necked flask equipped with a stirring device, a temperature regulator and a nitrogen introduction tube, heated to 70 ℃, to which one (1) mole of IPDI was gradually added while the MPEG compound was melted, followed by cooling to 50 ℃, and 0.15 wt% of triethylamine was added. Synthesis example C-1 of a monoisocyanate terminated polymer was obtained in which the% NCO had changed from 10.8% to 5.4%.

Synthesis of a monoisocyanate terminated polymer, example C-2, was carried out according to the synthesis procedure of example C-1 and the target intermediate was obtained with a% NCO change from 6.9% to 3.45%.

Table 3 synthesis examples of monoisocyanate terminated polymers with non-ionic hydrophilic segments

Example 1: synthesis of nonionic Polyamide rheology modifier

One (1) mole of polyacid-terminated polyamide A-1 and 2 moles of monoepoxy-terminated polymer B-1 were charged to a four-necked round-bottomed flask equipped with a stirring device, a cold water condenser, a temperature regulator and a nitrogen inlet tube. To the flask was added 0.15 wt% triethylamine as a catalyst and the reaction was allowed to proceed at 120 ℃ for six (6) hours to obtain the non-ionic rheology modifier example 1.

Examples 2 to 4: synthesis examples of nonionic Polyamide rheology modifiers

Other synthetic examples of nonionic polyamide rheology modifiers were made according to the synthetic method of example 1, with the compositions shown in table 4 to obtain nonionic polyamide rheology modifiers examples 2 to 4.

Example 5: synthesis of nonionic Polyamide rheology modifier

One (1) mole of polyacid-terminated polyamide a-3 was charged into a four-necked round-bottomed flask equipped with stirring means, a cold water condenser, a temperature regulator and a nitrogen introduction tube, heated to 120 ℃ to melt, 2 moles of BGE, 0.15% by weight of triethylamine as a catalyst, was added to the flask, followed by six (6) hours at 120 ℃ to obtain a hydroxypolyamide intermediate having an acid value <1mg KOH/g, followed by cooling to 70 ℃, two (2) moles of monoisocyanate-terminated polymer C-1 was added to the flask and allowed to react with the hydroxypolyamide intermediate for five (5) hours while the NCO% was below 0.1% to obtain a nonionic polyamide rheology modifier.

Examples 6 to 12: synthesis examples of nonionic Polyamide rheology modifiers

Synthesis examples of other nonionic polyamide rheology modifiers were carried out according to the synthesis method of example 5 with the compositions shown in table 4 to obtain examples 6-12 of nonionic polyamide rheology modifiers.

Table 4 synthetic examples of nonionic polyamide rheology modifiers

Test examples

The performance tests of the nonionic polyamide rheology modifier for aqueous coatings were performed on aqueous styrene acrylic resin coatings of the composition of table 5 below.

TABLE 5 composition of aqueous styrene acrylic resin coating

The preparation method of the water-based paint comprises the following steps:

DI water, Levelol W-469, DAPRO DF677, AS2610 and Deuadd MA-95 (10%) were mixed with stirring to give the base paint AS part A. Using BG and DI water as co-solvents, NUOSPESE FN265 and AWA40596 (50%) were mixed with stirring to obtain an aluminum paste as part B. To part a, part B was added, followed by the rheology modifier and thickener Rheolate 150, with stirring, to give a waterborne coating.

Evaluation of KU viscosity and Brookfield viscosity of aqueous coating:

the KU viscosity of the initial and overnight waterborne coatings was measured by a KU viscometer at 25 ℃.

Brookfield viscosities (cPs) of the waterborne coatings were measured at 25 ℃ using a DV-II viscometer with spindle LV3 at 10rpm to 100rpm and the ratio (viscosity at 10 rpm/viscosity at 100 rpm) was calculated.

And (3) anti-sedimentation test:

the dope was diluted with deionized water so that the viscosity measured with an NK2 viscosity cup could be 12 to 15 seconds (25 ℃), the diluted dope was transferred to a 50-mL glass test tube, and the volume of AWA40596 that settled was measured as a percentage of the volume of the whole dope.

TABLE 6 Performance testing of the examples (2% use level)

(tables above) table 6 Performance testing of the examples (2% dose)

The results of the performance testing of the nonionic polyamide rheology modifier for aqueous coatings are shown in table 6. The results show that the rheology modifiers of the present invention show good results in thixotropic properties, preventing settling of the metallic pigment, and help to improve the pigment orientation of the metallic pigment when used in aqueous coating systems.

Claims

1. A non-ionic rheology modifier composition for aqueous coatings obtained by a process comprising:

(1) reacting a polyacid-terminated polyamide with a mono-epoxy-terminated polymer having a non-ionic hydrophilic segment to thereby form a polymer; and

(2) dispersing the polymer in water containing a co-solvent to obtain a rheology modifier dispersion,

wherein the polyacid-terminated polyamide is obtained by reacting at least one dicarboxylic and/or tricarboxylic acid having from 3 to 54 carbon atoms with at least one diamine.

2. The non-ionic rheology modifier composition of claim 1, wherein said dicarboxylic acid is selected from malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, and dimer fatty acid.

3. The non-ionic rheology modifier composition of claim 1, wherein said tricarboxylic acid is selected from the group consisting of citric acid, propane-1, 2, 3-tricarboxylic acid, 1,2, 4-butanetricarboxylic acid, benzene-1, 3, 5-tricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, biphenyl-3, 4', 5-tricarboxylic acid, and trimerized fatty acid.

4. The non-ionic rheology modifier composition of claim 1, wherein said diamine is selected from the group consisting of ethylenediamine, 1, 4-diaminobutane, hexamethylenediamine, 1, 10-decamethylenediamine, 1, 11-undecamethylene diamine, 1, 12-dodecamethylenediamine, xylylenediamine, and 4, 4' -diaminodiphenylmethane.

5. The nonionic rheology modifier composition of claim 1, wherein the mono-epoxy terminated polymer with nonionic hydrophilic segment is obtained by:

(1) by reacting epichlorohydrin with monohydroxy non-ionic hydrophilic compounds, or

(2) Reacting a mono-hydrocarbyl acid with a diglycidyl-capped nonionic hydrophilic compound.

6. The nonionic rheology modifier composition of claim 5, wherein the monohydroxy nonionic hydrophilic compound comprises a poly (C) having an aliphatic, cycloaliphatic, or aromatic end group of 1 to 22 carbon atoms_2-4Alkylene oxide) and wherein the monohydroxy non-ionic hydrophilic compound has a molecular weight of from 500 g/mole to 3000 g/mole.

7. The non-ionic rheology modifier composition of claim 5, wherein said mono-hydrocarbyl acid is selected from acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 1, 2-hydroxystearic acid, and oleic acid.

8. The nonionic rheology modifier composition of claim 5 wherein the nonionic hydrophilic segment of the diglycidyl capped nonionic hydrophilic compound has a molecular weight of 500 to 3000 and comprises poly (C) containing 10% -100% ethylene oxide groups_2-4Alkylene oxide) segments.

9. A non-ionic rheology modifier composition for aqueous coatings obtained by a process comprising:

(1) reacting a polyacid-terminated polyamide with a hydrocarbyl glycidyl ether to form an intermediate;

(2) reacting the intermediate with a monoisocyanate terminated polymer having a non-ionic hydrophilic segment to thereby form a polymer; and

(3) the polymer is dispersed in water containing a co-solvent to obtain a rheology modifier dispersion.

10. The non-ionic rheology modifier composition of claim 9, wherein said polyacid-terminated polyamide is obtained by reacting at least one dicarboxylic and/or tricarboxylic acid having 3 to 54 carbon atoms with at least one diamine.

11. The non-ionic rheology modifier composition of claim 10, wherein said dicarboxylic acid is selected from malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, and dimer fatty acid.

12. The non-ionic rheology modifier composition of claim 10, wherein said tricarboxylic acid is selected from the group consisting of citric acid, propane-1, 2, 3-tricarboxylic acid, 1,2, 4-butanetricarboxylic acid, benzene-1, 3, 5-tricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, biphenyl-3, 4', 5-tricarboxylic acid, and trimerized fatty acid.

13. The non-ionic rheology modifier composition of claim 10, wherein said diamine is selected from the group consisting of ethylenediamine, 1, 4-diaminobutane, hexamethylenediamine, 1, 10-decamethylenediamine, 1, 11-undecamethylene diamine, 1, 12-dodecamethylenediamine, xylylenediamine, and 4, 4' -diaminodiphenylmethane.

14. The nonionic rheology modifier composition of claim 9 wherein the hydrocarbyl glycidyl ether is selected from hydrocarbyl glycidyl ethers in which the hydrocarbyl group has two to sixteen carbon atoms.

15. The nonionic rheology modifier composition of claim 9 wherein the hydrocarbyl glycidyl ether is selected from ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, and hexadecyl glycidyl ether.

16. The nonionic rheology modifier composition of claim 9 wherein the monoisocyanate terminated polymer is made by reacting a diisocyanate with a monohydroxy nonionic hydrophilic compound.

17. The non-ionic rheology modifier composition of claim 16 wherein the diisocyanate is selected from toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, dicyclohexylmethane-4, 4' -di-isocyanate, 1, 4-bis (2-isocyanato-2-yl) benzene, trimethylhexamethylene diisocyanate, or mixtures of the foregoing diisocyanates.

18. The nonionic rheology modifier composition of claim 16, wherein the monohydroxy nonionic hydrophilic compound comprises poly (C)_2-4Alkylene oxide)_nAnd an aliphatic terminal having 1 to 22 carbon atomsA cycloaliphatic end group or an aromatic end group, and wherein the monohydroxy nonionic hydrophilic compound has a molecular weight of from 500 g/mole to 3000 g/mole.

19. The non-ionic rheology modifier composition according to claim 1 or 9, wherein said co-solvent is selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, butyl cellosolve solvent, N-methyl-2-pyrrolidone, 3-methoxy-3-methyl-1-butanol acetate, methyl-5- (dimethylamino) -2-methyl-5-oxopentanoate, N-formylmorpholine.

20. A nonionic polyamide rheology modifier represented by formula (1),

wherein X is a polyacid-terminated polyamide,

n is 2-6, and Y in the formula (1) is one or more selected from the following end groups:

wherein R1 is an aliphatic, cycloaliphatic or aromatic end group having from 1 to 22 carbon atoms,

r2 is the residue moiety of a diisocyanate compound selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, 1, 4-bis (2-isocyanato-2-yl) benzene, trimethylhexamethylene diisocyanate,

and X' is poly (C)_2-4Alkylene oxide).

21. The nonionic polyamide rheology modifier of claim 20 wherein Y is:

22. the nonionic polyamide rheology modifier of claim 20 wherein Y is:

23. the nonionic polyamide rheology modifier of claim 20 wherein Y is: