阅读说明：本技术 用芳基醚烷氧基化物嵌段共聚物封端的环氧烷聚合物 (Alkylene oxide polymers capped with aryl ether alkoxylate block copolymers ) 是由 J·J·拉巴斯克 D·A·扫克丽 A·K·凡戴克 于 2020-02-03 设计创作，主要内容包括：本发明涉及一种化合物,其包含具有由结构I表示的疏水性片段的疏水改性聚(氧化烯-氨基甲酸酯)：<Image he="379" wi="700" file="DDA0002379610280000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中Ar<Sup>1</Sup>、Ar<Sup>2</Sup>；R<Sup>1</Sup>、m和n定义于本文中。本发明化合物提供含有疏水改性聚(氧化烯-氨基甲酸酯)流变改性剂,更确切地说HEUR流变改性剂的油漆在着色后的粘度稳定性。(The present invention relates to a compound comprising a hydrophobically modified poly (oxyalkylene-urethane) having a hydrophobic segment represented by structure I: wherein Ar is 1 、Ar 2 ；R 1 M and n are defined herein. The compounds of the present invention provide viscosity stability after tinting for paints containing hydrophobically modified poly (oxyalkylene-urethane) rheology modifiers, more specifically HEUR rheology modifiers.)

1. A compound comprising a hydrophobically modified alkylene oxide polymer having a hydrophobic segment represented by structure I:

wherein the dashed line represents the point of attachment of the segment to the hydrophobically modified alkylene oxide polymer; ar (Ar)¹Is unsubstituted phenyl, naphthyl, phenyl-O-CH₂-, phenyl-CH₂-O-CH₂-or naphthyl-O-CH₂-; or by 1 to 3C₁-C₆Alkyl-or alkoxy-substituted phenyl, naphthyl, phenyl-O-CH₂-, phenyl-CH₂-O-CH₂-or naphthyl-O-CH₂-; and Ar²Is phenyl, phenyl-OCH₂CH₂-, phenyl- (OCH)₂CH₂)_y-, benzyl, naphthyl-CH₂-, naphthyl-OCH₂CH₂-or naphthyl- (OCH)₂CH₂)_y-, wherein Ar²The phenyl or naphthyl moiety of (A) being unsubstituted or substituted by 1 to 3C₁-C₆Alkyl substitution; wherein y is 2 to 10; each R¹Independently is H or C₁-C₆An alkyl group; x is O or NR²Wherein R is²Is H, C₁-C₆Alkyl, phenyl or benzyl; m is 1 to 20; and n is 0 to 100.

2. The compound of claim 1, wherein Ar¹Is phenyl-O-CH₂-or O-methylphenyl-O-CH₂-；Ar²Is phenyl, benzyl, phenyl-OCH₂CH₂-or o-methylphenyl; each R¹Independently is H or CH₃(ii) a m is 1 to 10; and n is 0 to 40; wherein the hydrophobically modified alkylene oxide polymer is a hydrophobically modified alkylene oxide urethane polymer.

3. The compound of claim 2, wherein the hydrophobic segment has a number average molecular weight (M)_n) In the range of 500 to 10,000 g/mol; and X is O or N-CH₃N-phenyl or N-benzyl; wherein the hydrophobically modified alkylene oxide polymer is a hydrophobically modified ethylene oxide urethane polymer.

4. The compound of claim 3, wherein M of the hydrophobic segment_nIn the range of 500 to 2500g/mol and selected from the group consisting of:

wherein R is¹' is H or CH₃(ii) a And R is²' is CH₃Or a benzyl group.

5. A composition comprising an aqueous dispersion having: a) from 10 to 60 weight percent, based on the weight of the composition, of polymeric particles; and b) from 0.05 to 2 weight percent, based on the weight of the composition, of the compound of claim 1.

6. The composition of claim 1 comprising less than 10PVC of TiO₂Or BsSO₄And (3) granules.

7. The composition of claim 5, further comprising one or more materials selected from the group consisting of: binders, dispersants, pigments, defoamers, surfactants, solvents, extenders, coalescents, biocides, and opacifying polymers.

Background

The present invention relates to alkylene oxide polymers capped with aryl ether alkoxylate block copolymers that are useful for improving the viscosity retention of pigmented coating formulations.

Hydrophobically modified alkylene oxide polymers, more specifically hydrophobically modified ethylene oxide urethane polymers (HEUR), are preferred rheology modifiers for paints because they provide a combination of good flow and sag resistance. However, a long-standing disadvantage of standard HEUR is that the viscosity of HEUR-thickened paints typically decreases significantly when colorants are added. This undesirable effect is particularly troublesome for medium and deep pigmented paints. The viscosity loss makes the paint too "thin" and, in particular, sag resistance becomes unacceptably low, causing it to run and drip on the wall surface, and/or very poor roller stippling patterns. Therefore, it would be an advance in the art of pigmented paints to find a HEUR-containing paint formulation with improved viscosity retention after addition of a colorant.

Disclosure of Invention

The present invention addresses a need in the art by providing a compound comprising a hydrophobically modified alkylene oxide polymer having a hydrophobic segment represented by structure I:

wherein the dashed line represents the point of attachment of the segment to the hydrophobically modified alkylene oxide polymer; ar (Ar)¹Is unsubstituted phenyl, naphthyl, phenyl-O-CH₂-, phenyl-CH₂-O-CH₂-or naphthyl-O-CH₂-; or by 1 to 3C₁-C₆Alkyl-or alkoxy-substituted phenyl, naphthyl, phenyl-O-CH₂-, phenyl-CH₂-O-CH₂-or naphthyl-O-CH₂-; and Ar²Is phenyl, phenyl-OCH₂CH₂-, phenyl- (OCH)₂CH₂)_y-, benzyl, naphthyl-CH₂-, naphthyl-OCH₂CH₂-or naphthyl- (OCH)₂CH₂)_y-, wherein Ar²The phenyl or naphthyl moiety of (A) being unsubstituted or substituted by 1 to 3C₁-C₆Alkyl substitution; wherein y is 2 to 10; each R¹Independently is H or C1-C6 alkyl; x is O or NR²Wherein R is²Is H, C1-C6 alkyl, phenyl or benzyl; m is 1 to 20; and n is 0 to 100. The compounds of the invention are prepared by providing a composition containing a hydrophobeThe viscosity stability of paints modified with alkylene oxide rheology modifiers after tinting addresses a need in the art.

Detailed Description

The present invention is a compound comprising a hydrophobically modified alkylene oxide polymer having a hydrophobic segment represented by structure I:

wherein the dashed line represents the point of attachment of the segment to the hydrophobically modified alkylene oxide polymer; ar (Ar)¹Is unsubstituted phenyl, naphthyl, phenyl-O-CH₂-, phenyl-CH₂-O-CH₂-or naphthyl-O-CH₂-; or by 1 to 3C₁-C₆Alkyl-or alkoxy-substituted phenyl, naphthyl, phenyl-O-CH₂-, phenyl-CH₂-O-CH₂-or naphthyl-O-CH₂-; and Ar²Is phenyl, phenyl-OCH₂CH₂-, phenyl- (OCH)₂CH₂)_y-, benzyl, naphthyl-CH₂-, naphthyl-OCH₂CH₂-or naphthyl- (OCH)₂CH₂)_y-, wherein Ar²The phenyl or naphthyl moiety of (A) being unsubstituted or substituted by 1 to 3C₁-C₆Alkyl substitution; wherein y is 2 to 10; each R¹Independently is H or C1-C6 alkyl; x is O or NR²Wherein R is²Is H, C1-C6 alkyl, phenyl or benzyl; m is 1 to 20; and n is 0 to 100.

As used herein, the term "alkylene oxide polymer" refers to water-soluble polyethylene oxide polymers, as well as water-soluble polyethylene oxide/polypropylene oxide and polyethylene oxide/polybutylene oxide copolymers. Preferably, the alkylene oxide polymer is an alkylene oxide urethane polymer, more preferably an ethylene oxide urethane polymer.

As used herein, hydrophobically modified alkylene oxide urethane polymer refers to polyethylene, polypropylene or polybutylene oxide urethane polymer, preferably a polyethylene oxide urethane polymer (HEUR) modified with a hydrophobic moiety having structure I.

The segment having structure I is produced from an end-capping agent that is conveniently prepared by contacting together under reactive conditions: a) a diisocyanate; b) a water-soluble polyalkylene glycol; and c) an endcapping agent that is a compound represented by structure II:

examples of suitable diisocyanates include 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-decamethylene diisocyanate, 4' -methylenebis (isocyanatocyclohexane) (H₁₂-MDI), 2,4 '-methylenebis (isocyanatocyclohexane), 1, 4-cyclohexylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (IPDI), m-and p-phenylene diisocyanates, 2, 6-and 2, 4-Toluene Diisocyanate (TDI), xylene diisocyanate, 4-chloro-1, 3-phenylene diisocyanate, 4' -Methylenediphenyl Diisocyanate (MDI), 1, 5-naphthylene diisocyanate and 1, 5-tetrahydronaphthylene diisocyanate. Examples of commercially available diisocyanates are Desmodur W cycloaliphatic diisocyanate (DesW) and Desmodur H (HDI).

Water-soluble polyalkylene glycols are water-soluble polyethylene oxides, water-soluble polyethylene oxide/polypropylene oxide copolymers and water-soluble polyethylene oxide/polybutylene oxide copolymers. Preferred water-soluble polyalkylene oxides are polyethylene glycols, especially polyethylene glycols having a weight average molecular weight in the range of 600 to 12,000 daltons (Dalton). An example of a suitable polyethylene glycol is carbopax^TM8000 PEG8000 (PEG-8000, a trademark of dow affiliated Company of The dow chemical Company ("dow") or Midland (Midland, MI), michigan) available from polyethylene glycol.

Under the reaction condition, diisocyanate, polyalkylene glycol and the organic compound with the structureAnd II, contacting the end-capping reagent to form the hydrophobically modified alkylene oxide urethane polymer. Preferably, the hydrophobically modified alkylene oxide urethane polymer has a weight average molecular weight (M) as determined by Size Exclusion Chromatography (SEC) as described herein_w) In the range of 2000, more preferably 4000 dalton to preferably 50,000, more preferably 25,000 dalton. Examples of preferred subclasses of fragments of the present invention are represented by the following structures:

wherein R is¹' is H or CH₃(ii) a And R is²' is CH₃Or a benzyl group.

Preferably, Ar¹Is phenyl-OCH₂-or o-methylphenyl-OCH₂-; preferably, when X ═ O, Ar²Is phenyl, benzyl, phenyl-OCH₂CH₂-or o-methylphenyl; preferably, when X ═ NR²When is, Ar²Is benzyl or phenyl; and R is²Is benzyl, methyl or ethyl. Preferably, m is in the range of 1, more preferably 2 to 10, more preferably 6; and n is in the range of 0 to 40. Preferably, each R¹Independently H, methyl or ethyl; more preferably H or methyl; most preferably, each R¹Is H. Preferably, X is O, N-CH₃N-phenyl or N-benzyl.

Preferably, the number average molecular weight (M.sub.M.) of the fragments having structure I (and compounds having structure II) is determined by matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS), as described in the examples section below_n) In the range of 500g/mol, more preferably 750g/mol to 10,000, more preferably to 2500g/mol, and most preferably to 1500 g/mol.

The compounds of formula II can be conveniently prepared by the following steps: first, an aryl alcohol or amine is contacted with an aryl epoxide or aryl glycidyl ether in the presence of a catalytic amount of a suitable base (e.g., KOH) under conditions sufficient to prepare an aryl alkoxy ether oligomer intermediate, and then, preferably, the intermediate is contacted with an alkylene oxide (e.g., ethylene oxide) under conditions sufficient to form the desired compound of formula II. Preferably, the aryl alcohol is phenol, cresol or phenoxyethanol or a combination thereof; the arylamine is preferably N-methylbenzylamine or dibenzylamine or a combination thereof; and the arylalkoxy ether is preferably phenyl glycidyl ether or cresyl glycidyl ether or a combination thereof.

The compounds of the present invention are advantageously dissolved in water together with various other additives to prepare aqueous thickener compositions. The aqueous thickener composition comprises 1 wt%, and more preferably from 5 wt% to 60 wt%, and more preferably to 40 wt% thickener solids, based on the total weight of the aqueous thickener composition. Other additives may be included in the aqueous thickener composition to inhibit the viscosity of the aqueous thickener composition. Such other additives include water-miscible solvents such as propylene glycol and diethylene glycol butyl ether. Examples of other additives include cyclodextrins and various nonionic and anionic surfactants. Examples of preferred nonionic surfactants include

C₆-C₁₈Alcohol ethoxylates, lauryl alcohol ethoxylates, guerbet alcohol ethoxylates and castor oil ethoxylates. In TERGITOL^TMSurfactants under the trademark dow chemical company or its subsidiary companies are also suitable. Examples of suitable anionic surfactants include C₆-C₁₈Alcohol sulfates, sulfonates, sulfosuccinates, phosphates, and ethoxylates thereof, including sodium lauryl sulfate, sodium 2-ethylhexyl sulfate, sodium dodecylbenzene sulfonate, and sodium dioctyl sulfosuccinate.

For where X ═ NR²Preferably sufficient acid is added to the corresponding aqueous thickener composition to adjust its pH to a range of 2.1 to 6.0. Any acid compound that can lower the pH to this range is suitable. Examples of preferred acids include gluconic acidPhosphoric acid, hydrochloric acid, sulfuric acid, lactic acid, and poly (acrylic acid).

The compounds of the present invention are useful as rheology modifiers in pigmented coating formulations. In another embodiment, the invention is a composition comprising an aqueous dispersion having the following: a) from 10 to 60% by weight of the composition of polymer particles; b) and from 0.05 wt% to 2 wt%, by weight of the composition, of a hydrophobically modified alkylene oxide urethane polymer having a hydrophobic segment, the hydrophobic segment having structure I.

The aqueous dispersion of polymer particles (i.e., latex) is preferably a dispersion of polymer particles comprising structural units of an acrylate or methacrylate monomer or a vinyl ester monomer or a combination thereof.

The term "structural unit" referring to a monomer refers to the residue of the monomer after polymerization. For example, the structural units of methyl methacrylate are shown:

wherein the dashed lines represent the points of attachment of the building blocks to the polymer backbone.

Preferably, the polymeric particles comprise at least 30 wt%, more preferably at least 50 wt% structural units of acrylate and methacrylate monomers, or preferably at least 30 wt%, more preferably at least 50 wt% structural units of vinyl ester monomers. Examples of suitable acrylate and methacrylate monomers include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ureido methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-propylheptyl acrylate. A preferred combination of acrylate and methacrylate monomers includes methyl methacrylate and one or more monomers selected from the group consisting of ethyl acrylate, butyl acrylate, ureido methacrylate, 2-propylheptyl acrylate, and 2-ethylhexyl acrylate. More preferred combinations of acrylic monomers include methyl methacrylate and butyl acrylate; methyl methacrylate and 2-ethylhexyl acrylate; and methyl methacrylate, butyl acrylate and ethyl acrylate, with the combination of methyl methacrylate and butyl acrylate being most preferred. Examples of vinyl ester-based monomers include vinyl acetate and vinyl versatate. An example of a vinyl ester-based copolymer is vinyl acetate-ethylene (VAE).

The polymer particles may also include structural units of other monomers, such as styrene, acetoacetoxyethyl methacrylate, acrylonitrile, acrylamide, and 2-acrylamido-2-methylpropanesulfonic acid. In addition, the polymer particles preferably comprise 0.2 wt%, more preferably 0.5 wt%, most preferably 1 wt% to preferably 5 wt%, more preferably to 3 wt% of structural units of an ethylenically unsaturated carboxylic acid monomer (such as acrylic acid, methacrylic acid or itaconic acid).

The composition of the second aspect of the invention may be contacted with the colorant in sufficient concentration to impart the desired color. As used herein, "colorant" refers to a liquid dispersion of colored pigments. The concentration of the colorant is typically 5 to 20 volume percent of the total volume of paint and colorant. Examples of colored pigments include phthalocyanine blue, phthalocyanine green, monoaryl yellow, diaryl yellow, benzimidazolone yellow, heterocyclic yellow, DAN orange, quinacridone magenta, quinacridone violet, organic reds (including metallized azo reds and non-metallized azo reds), carbon black, lamp black, iron oxide yellow, iron oxide brown, and iron oxide red.

In another aspect, the composition comprises less than 15PVC of TiO₂Or BaSO₄Particles; in yet another aspect, the composition comprises less than 10PVC of TiO₂And BaSO₄And (3) granules. For dark base formulations, TiO₂And BaSO₄Granulated PVC<1. The PVC is defined by the following formula:

where binder solids refer to the polymeric contribution of the aqueous dispersion of polymer particles to bind the pigment and extender particles together.

The composition may further comprise any or all of the following materials: binders, dispersants, pigments, defoamers, surfactants, solvents, extenders, coalescents, biocides, and opacifying polymers.

Examples of the invention

Molecular weight measurement

_nMALDI-MS M method for measuring molecular weight of intermediate examples

MALDI mass spectra were obtained on a Bruker Daltonics ultra flex MALDI-TOF mass spectrometer equipped with a nitrogen laser (λ ═ 337 nm). In MALDI experiments, 20mg of 2, 5-dihydroxybenzoic acid was dissolved in 1mL of THF as MALDI matrix. The sample solution in MeOH was premixed with the matrix solution in a ratio of 1: 20. To facilitate ionization of species in the sample mixture, NaI is added to the sample/matrix mixture. Then, 0.3. mu.l of the mixture sample was placed on a sample plate and air-dried for MALDI-MS analysis. The reflector (reflexon) mode was chosen in the analysis to improve the resolution of the mass spectrum.

_wSEC method for measuring M of HEUR

Samples were prepared by dissolving 1-2mg polymer/g 100mM ammonium acetate in methanol. The sample was placed in solution by shaking overnight on a mechanical shaker at room temperature. The sample solution was filtered using a 0.45 μm PTFE filter.

The separation was performed on a Waters Acquity APC system consisting of an isocratic pump, degasser, sample injector, column oven, and UV and RI detectors operating at 40 ℃. System control, data acquisition, and data processing were performed using Empower software version 3 (Waters, Milford, MA). Two BEH diol particles (pore size labeled BEH) from Watt (Milford, Mass.) were usedAnd BEHParticle size 1.7 and 2.5 μm) water APC column (150 × 4.6.6 mM ID), SEC separation was performed at a rate of 0.5mL/min in 100mM ammonium acetate containing methanol (Optima grade from Fisher.) injection of 20 μ L of sample for APC separation.

A twelve point calibration curve of order 3 was obtained from a narrower polyethylene oxide (PEO) standard.

Intermediate example 1 preparation of phenyl glycidyl Ether Polymer

Phenol (102.44 g, 1.09 mol), toluene (337.83 g) and KOH chips (8.12g, 90% pure) were charged to a 2L round bottom flask equipped with a temperature controlled heating mantle, addition funnel, reflux/distillation head and overhead stirrer. The solution is placed in N₂Then heated to distill off a portion of toluene (110 g). Phenyl glycidyl ether (490.78g, 3.27 moles) was then added to the resulting concentrated solution over a period of 4 hours at 110 ℃ to 120 ℃. The mixture was stirred for an additional 2 hours and the flask was allowed to cool. The product was treated with acetic acid and the solvent was removed in vacuo to form M as measured by MALDI-MS_nAn intermediate distribution of 780g/mol, and the intermediate comprises a compound having the structure:

intermediate example 2 preparation of phenyl glycidyl ether ethoxylate Block copolymer

Phenol (62.94g, 0.67 mole), toluene (341.34g) and KOH flakes (4.75g, 90% pure) were charged to a 2L round bottom flask equipped with a temperature controlled heating mantle, addition funnel, reflux/distillation head and overhead stirrer. The solution is placed in N₂Then heated to distill off a portion of the toluene (82.81 g). Phenyl glycidyl ether (502.18g, 3.34 moles) was then added to the resulting concentrated solution at 110 ℃ to 120 ℃ over 4 hours, and the mixture was stirred for an additional 2 hours. A portion of the resulting solution (374.9g) was charged to a 2L Parr reactor (Parr reactor) with a conical bottom. Sealing the reactor, checking the pressure, using N₂Purged and then heated to 120 ℃. Ethylene oxide (289.3g) was added at a rate of 1 to 2 g/min. Maintaining the mixture at 120 deg.C1 hour, then cooled to 60 ℃ before pouring off the product (650.6 g). The reaction product was treated with acetic acid (1.07g) and the solvent was removed in vacuo to form M as measured by MALDI-MS_nAn intermediate distribution of 1840g/mol, and the intermediate comprises a compound having the structure:

intermediate example 3 preparation of phenyl glycidyl ether ethoxylate Block copolymer

Will DOWANOL^TMEPh (trademark of Dow chemical company or its subsidiary, 179.95g) and 90% potassium hydroxide (3.36g) were charged into a 2L Parr reactor with a conical bottom and the reactor was sealed, pressure checked, purged with nitrogen, and then heated to 100 ℃. Phenyl glycidyl ether (587g) was then added to the reactor using a Gilson HPLC pump at a rate of 4 mL/min. The reaction is evident by the heat generated during this addition. After the addition of phenyl glycidyl ether was complete, the mixture was kept at 100 ℃ overnight. The reaction mixture temperature was increased to 120 ℃ and ethylene oxide (286.9g) was then added to the reactor at a rate of 1.5 g/min. After the ethylene oxide addition was complete, the reaction mixture was kept at 120 ℃ overnight. After cooling the reaction mixture to 80 ℃, the reactor headspace was purged. The reaction mixture was treated with acetic acid (3.18g) and then poured out of the reactor to form M as measured by MALDI-MS_nAn intermediate distribution of 968g/mol, and the intermediate includes a compound having the structure:

intermediate example 4 preparation of aminophenyl glycidyl ether ethoxylate Block copolymer

N-methylbenzylamine (157.8g) and 90% potassium hydroxide (3.36g) were charged to a 2L Parr reactor having a conical bottom. The reactor was sealed, pressure checked, and purged with nitrogen, then heated to 100 ℃. Then use GilsonPhenyl glycidyl ether (587g) was added to the reactor at a rate of 4mL/min by an HPLC pump. After the addition of phenyl glycidyl ether was complete, the mixture was kept at 100 ℃ overnight. The reaction mixture temperature was increased to 120 ℃ at which time ethylene oxide (286.9g) was added to the reactor at a rate of 1.5 g/min. After the ethylene oxide addition was complete, the reaction mixture was kept at 120 ℃ overnight. After cooling the reaction mixture to 80 ℃, the reactor headspace was purged. The reaction mixture was treated with acetic acid (3.18g) and then poured from the reactor to form M as measured by MALDI-MS_n(ii) an intermediate distribution of 878g/mol, and the intermediate includes a compound having the structure:

intermediate example 5 preparation of aminophenyl glycidyl ether ethoxylate Block copolymer

Dibenzylamine (256.9g) and 90% potassium hydroxide (3.36g) were charged to a 2L Parr reactor with a conical bottom. The reactor was sealed, the pressure checked and purged with nitrogen and then heated to 100 ℃. Phenyl glycidyl ether (587g) was then added to the reactor using a Gilson HPLC pump at a rate of 4 mL/min. After the addition of phenyl glycidyl ether was complete, the mixture was kept at 100 ℃ overnight. The reaction mixture temperature was increased to 120 ℃ at which time ethylene oxide (286.9g) was added to the reactor at a rate of 1.5 g/min. After the ethylene oxide addition was complete, the reaction mixture was kept at 120 ℃ overnight. After cooling the reaction mixture to 80 ℃, the reactor headspace was purged. The reaction mixture was treated with acetic acid (3.18g) and then poured out of the reactor to form M as measured by MALDI-MS_nAn intermediate distribution of 1009g/mol and including compounds having the following structure:

example 1: preparation of polyaryl alkoxylated HEUR

A mixture of PEG8000(75.0g) in toluene (150g) was heated to reflux and dried by azeotropic distillation for 2 hours. The reactor was then cooled to 90 ℃ and Desmodur W cycloaliphatic diisocyanate (Des W, 6.64g) was added to the reactor and stirred for 5 minutes. Dibutyltin dilaurate (0.21g) was then added, and the reaction mixture was stirred at 90 ℃ for 1 hour. The reaction mixture was cooled to 80 ℃ and the polyarylalkoxide prepared in intermediate example 1(30.56g) was added to the reactor and the resulting mixture was stirred at 80 ℃ for 1 hour. The solvent was removed in vacuo to yield the product as a white solid. M was found by SEC measurements as described above_wIs 17,298. An aqueous solution containing 20 wt.% HEUR polymer and 16 wt.% butyl carbitol was prepared prior to addition to the coating formulation.

Example 2: preparation of polyaryl alkoxylated HEUR

A mixture of PEG8000 (50.0g) in toluene (150g) was heated to reflux and dried by azeotropic distillation for 2 hours. The reactor was then cooled to 90 ℃ and Des W (4.43g) was added to the reactor and stirred for 5 minutes. Dibutyltin dilaurate (0.21g) was then added, and the reaction mixture was stirred at 90 ℃ for 1 hour. The reaction mixture was then cooled to 80 ℃ and the polyarylalkoxide prepared in intermediate example 2(47.19g) was added to the reactor and the resulting mixture was stirred at 80 ℃ for 1 hour. The solvent was removed in vacuo to yield the product as a white solid. M was found by SEC measurements as described above_wIs 17,903. An aqueous solution containing 20 wt.% HEUR polymer and 16 wt.% butyl carbitol was prepared prior to addition to the coating formulation.

Example 3 preparation of polyarylalkylated HEUR

Mixing CARBOWAX^TMA mixture of PEG8000(75.0g) in toluene (150g) was heated to reflux and dried by azeotropic distillation for 2 hours. The reactor was then cooled to 90 ℃ and Des W (7.18g) was added to the reactor and stirred for 5 minutes. Dibutyltin dilaurate (0.21g) was then added, and the reaction mixture was stirred at 90 ℃ for 1 hour. The reaction mixture was then cooled to 80 ℃ and intermediate example 3(38.59g) was addedThe prepared polyarylalkoxide was added to the reactor, and the resulting mixture was stirred at 80 ℃ for 1 hour. The solvent was removed in vacuo to yield the product as a white solid. M was found by SEC measurements as described above_wIs 17,609. An aqueous solution containing 20 wt% polymer and 16 wt% butyl carbitol had a Brookfield viscocity of 1420cP (spindle 3, 6 rpm). The polymer can also be dissolved in the absence of an organic solvent by replacing the butyl carbitol with a surfactant. For example, 20 wt.% polymer and 20 wt.% TERGITOL^TMAn aqueous solution of 15-S-9 surfactant (15-S-9) had a Brookfield viscosity of 2800cP (rotor # 3, 6 rpm).

Example 4 preparation of amino polyaryl alkoxylated HEUR

CARBOWAX is introduced into a batch melt reactor under vacuum^TM8000 polyethylene glycol (PEG; 1200g) was heated to 110 ℃ for 2 hours. Butylated hydroxytoluene (BHT, 0.132g) and Desmodur W (114.9g) were then added to the reactor and the reaction mixture was stirred for 5 minutes. Bismuth octoate (28% Bi, 3.0g) was then added to the reactor and the resulting mixture was stirred at 110 ℃ for 10 minutes. Intermediate example 4(500.09g) was then added to the reactor and the resulting mixture was stirred at 110 ℃ for 10 minutes. The resulting molten polymer was removed from the reactor and cooled. The aqueous thickener composition is prepared by dissolving the polymer in gluconic acid-containing water containing 20 wt.% polymer solids, 2 wt.% gluconic acid, and 78 wt.% water.

Table 1 shows the advantage of using a small amount of acid (such as gluconic acid) in the aqueous preparation of HEURs with hydrophobic fragments having structure I (where X ═ NR)²). The viscosity was measured using a brookfield viscometer, spindle 3 and 6 rmp.

TABLE 1 aqueous solution viscosity of HEUR of EXAMPLE 4 with and without gluconic acid

Example 4 Polymer (wt%)	Water (% by weight)	Gluconic acid (% by weight)	Viscosity of aqueous solution (cP)	pH
					20％	80％	0	Gel	About 7.9
20％	78％	2％	3309	3.62

TERGITOL, TAMOL and RHOPLEX are trademarks of the Dow chemical company or its subsidiary.

Example 5 preparation of polyarylalkoxides and amino HEUR

CARBOWAX is introduced into a batch melt reactor under vacuum^TM8000 polyethylene glycol (PEG; 1350g) was heated to 110 ℃ for 2 hours. Butylated hydroxytoluene (BHT, 0.145g) and Desmodur W (100.53g) were then added to the reactor and the reaction mixture was stirred for 5 minutes. Bismuth octoate (28% Bi, 3.38g) was then added to the reactor and the resulting mixture was stirred at 110 ℃ for 10 minutes. Intermediate example 3(401.86g) and 2- [ bis (2-ethylhexyl) amino]Ethanol (19.92g) was added to the reactor and the resulting mixture was stirred at 110 ℃ for 10 minutes. Melt-polymerizing the obtained polymerThe compound was removed from the reactor and cooled. M was found by SEC measurements as described above_wIs 23,518. An aqueous thickener composition was prepared by dissolving the polymer in water containing 20 wt% polymer solids, 20 wt% 15-S-9, and 60 wt% water.

Example 6 preparation of amino polyaryl alkoxylated HEUR

CARBOWAX is introduced into a batch melt reactor under vacuum^TM8000 polyethylene glycol (PEG; 1200g) was heated to 110 ℃ for 2 hours. Butylated hydroxytoluene (BHT, 0.132g) and Desmodur W (114.9g) were then added to the reactor and the reaction mixture was stirred for 5 minutes. Bismuth octoate (28% Bi, 3.0g) was then added to the reactor and the resulting mixture was stirred at 110 ℃ for 10 minutes. Intermediate example 5(554.95g) was then added to the reactor and the resulting mixture was stirred at 110 ℃ for 10 minutes. The resulting molten polymer was removed from the reactor and cooled. The aqueous thickener composition is prepared by dissolving the polymer in water with gluconic acid. Table 2 is a formulation of an unthickened pigmented base paint formulation, i.e. a paint without colorants and HEUR rheology modifiers.

TABLE 2 non-thickened pigmented base paint formulations

RHOPLEX and ACRYSOL are trademarks of the Dow chemical company or its subsidiary companies.

Paint coloring data

Tables 3a and 3b illustrate the KU viscosity of dark base paint formulations prepared as described in Table 2 and separately prepared with the commercially available HEUR (ACRYSOL)^TMRM 995 rheology modifier (RM-995), a trademark of the Dow chemical company or its affiliates, or the HEUR of the present invention, and then colored with 12 ounces of Colortrend 808 carbon black. All paints were formulated with ICI thickener, ACRYSOL^TMRM-3030 rheology modifier (RM-3030) co-thickens. The amounts of experimental HEUR and RM-3030 are in units of pounds effective per 100 gallons (lbs/100 gal). Use of sufficient RM + in all paints3030 to adjust the consistency of the paint to an ICI viscosity in the range of 1.1 to 1.3 poise. The KU viscosity of the paint was measured at room temperature using a Brookfield KU-1+ viscometer or an equivalent KU viscometer.

TABLE 3a KU viscosity data for HG-706 formulations pigmented with carbon Black

TABLE 3b KU viscosity data for HG-706 formulations pigmented with carbon Black

Δ KU refers to the change in KU viscosity of the paint after coloring with carbon black obtained by subtracting the viscosity of the colored KU from the original KU viscosity of the paint before coloring.

The HEUR used in the paint formulations of examples 1-6 exhibited a significant improvement in the KU viscosity stability of the paint upon addition of the colorant. After adding 12 ounces of carbon black colorant to 116 ounces of paint base, the paint thickened with RM-995 drops by up to 27 KU units. In contrast, the paint thickened with HEUR example 2 decreased only 8 KU units when pigmented, the paint thickened with HEUR example 4 decreased only 4 KU units when pigmented, and the paint thickened with example 3HEUR exhibited a fairly constant KU viscosity when pigmented, as KU actually increased slightly by 1.2 KU units.