Associative thickeners for waterborne paints: Structure, characterization, rheology, and modeling

Larson, Ronald G.; Dyk, Antony K. Van; Chatterjee, Tirtha; Ginzburg, Valeriy V.

doi:10.1016/j.progpolymsci.2022.101546

Cited by 29 publications

(46 citation statements)

References 167 publications

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“…They are water-soluble associative polymers consisting of a hydrophilic backbone and hydrophobic terminal groups. 3 − 5 Typical HEURs are oligomeric molecules with a hydrophilic core based on poly(ethylene glycol) (PEG) with a molar mass in a range of 6,000–35,000 g·mol –1 and short hydrophobic terminal chains. 3 , 6 Hydrophobes most often contain C8–C18 alkyl groups, 2 , 7 , 8 alkyl phenyl groups, 9 − 12 or fluorocarbons.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the fluent and reversible shear thinning enables easy application of paint, limits the spattering behavior, and simplifies its levelling. 3 − 5 …”

Section: Introductionmentioning

confidence: 99%

“…Hydrophobically modified ethoxylated polyurethanes (HEURs) are a representative class of polyurethane (PU) rheological thickeners. They are water-soluble associative polymers consisting of a hydrophilic backbone and hydrophobic terminal groups. − Typical HEURs are oligomeric molecules with a hydrophilic core based on poly(ethylene glycol) (PEG) with a molar mass in a range of 6,000–35,000 g·mol –1 and short hydrophobic terminal chains. , Hydrophobes most often contain C8–C18 alkyl groups, ,, alkyl phenyl groups, − or fluorocarbons. , The hydrophilic segment of HEURs is typically obtained via polyaddition of PEG ,, and diisocyanate (e.g., isophorone diisocyanate ,,,,− or 4,4′-methylenedicyclohexyl diisocyanate ,, ), used in molar excess and yielding a telechelic prepolymer, terminated by isocyanate groups. In a subsequent step, the prepolymer is end-capped with hydrophobic alcohol or amine to obtain the amphiphilic HEURs.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the thickening effect of the physically cross-linked HEURs in waterborne paints determines their shelf-life and prevents sedimentation of additives. Furthermore, the fluent and reversible shear thinning enables easy application of paint, limits the spattering behavior, and simplifies its levelling. − …”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Reactive Extrusion Synthesis of Biobased Isocyanate-Free Hydrophobically Modified Ethoxylated Urethanes with Pendant Hydrophobic Groups

Wołosz

Fage

Parzuchowski

et al. 2022

ACS Sustainable Chem. Eng.

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Development of hydrophobically modified ethoxylated urethane (HEUR) rheology modifiers enabled the widespread application of waterborne paints and coatings, replacing their environmentally burdening solvent-based predecessors. However, the diisocyanates, required for the conventional synthesis of HEURs, pose severe eco-sustainability threats. In this paper, we demonstrate an innovative approach to avoiding toxic components in the preparation of rheology modifiers by obtaining a new class of water-soluble isocyanate-free hydrophobically modified ethoxylated poly(hydroxy-urethane)s (IFHEURs). The first step in the synthetic pathway was the preparation of CO 2 -based five-membered poly(ethylene glycol) bis(cyclic carbonate) and its subsequent aminolysis using 4,7,10-trioxa-1,13-tridecanediamine, yielding poly(hydroxy-urethane) (PHU) prepolymers terminated with cyclic carbonate groups. The PHU prepolymers were further extended in a reactive extrusion (REX) synthesis using biobased hydrophobic diamine PRIAMINE 1075. The REX technique made it possible to overcome the typical limitations of the aminolysis reaction and to reach the desired conversion within a moderate reaction time. IFHEURs have been structurally elucidated using FT-IR and NMR spectroscopy techniques, MALDI-ToF mass spectrometry, and SEC analysis and applied as rheology modifiers. The study of their associative behavior in aqueous solutions confirmed that the architectural flexibility of the obtained IFHEURs, containing terminal and pendant hydrophobic groups, opens a perspective for tuneable thickening performance.

show abstract

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the fluent and reversible shear thinning enables easy application of paint, limits the spattering behavior, and simplifies its levelling. 3 − 5 …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reactive Extrusion Synthesis of Biobased Isocyanate-Free Hydrophobically Modified Ethoxylated Urethanes with Pendant Hydrophobic Groups

Wołosz

Fage

Parzuchowski

et al. 2022

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…Lately, Ginzburg et al discussed the structure, the rheology and the models of HEUR aqueous solutions and model paints containing HEURs. 13 Our team has also recently published a perspective article focusing on the structure/rheological properties relationship of HEURs, highlighting the influence of the different structural parameters and the new trends of architectures and innovative HEURs. 14 We also put our interest to the synthesis pathways reported in the literature to obtain HEURs and mentioned the possibility to develop less toxic and more ecofriendly routes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of hydrophobically modified ethoxylated non-isocyanate urethanes (HENIURs) and their use as rheology additives

Quienne

Pinaud

Caillol

2022

European Polymer Journal

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Experimental and modeling studies of IPDI‐based polyurea elastomers – The role of hard segment fraction

Tzelepis

Suzuki

et al. 2023

J of Applied Polymer Sci

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Segmented polyureas (PUa) are industrially important class of polymers widely used in coatings, sealant, and adhesive applications. Here, we report synthesis, characterization, and modeling of Isophorone Diisocyanate-Diethyl-Toluene-Diamine-Polyether amine (IPDI-DETDA-PO PUa) with varied hard segment contents of 20, 30, and 40 weight percent. For each of the three materials, we study its structure and phase behavior using FTIR, DSC, and TEM, and clearly show the presence of microphase separation between the hard and soft nanodomains. We then measure the linear viscoelastic response of the PUa-s using DMA (frequency sweeps at multiple temperatures). The DMA data are shown to obey the time-temperature superposition. Finally, we develop a new micromechanical model describing the DMA results; the model describes a phaseseparated PUa as two "Fractional-order Maxwell gels" branches, connected in parallel, with the first FMG branch representing the "percolated hard phase" and the second one modeling the "filled soft phase". In agreement with the earlier thermodynamic theories, the volume-fraction of the percolated hard phase is related to the hard segment weight-fraction (HSWF), defined as the combined mass of IPDI and DETDA normalized to the total mass of the polymer. The data and model are found to be in a good qualitative and quantitative agreement.adhesive, dynamic mechanical analysis, fractional calculus, hard domains, polyurea, time temperature superposition | INTRODUCTIONPolyurethanes (PU), polyureas (PUa), and poly (urethaneureas) (PUU) represent a fascinating family of polymers. [1][2][3][4] Their applications include coatings, 5 adhesives and sealants, 6,7 elastomers, 8 as well as rigid foams for thermal insulation 9 and flexible foams for furnishings

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Associative thickeners for waterborne paints: Structure, characterization, rheology, and modeling

Cited by 29 publications

References 167 publications

Reactive Extrusion Synthesis of Biobased Isocyanate-Free Hydrophobically Modified Ethoxylated Urethanes with Pendant Hydrophobic Groups

Reactive Extrusion Synthesis of Biobased Isocyanate-Free Hydrophobically Modified Ethoxylated Urethanes with Pendant Hydrophobic Groups

Synthesis of hydrophobically modified ethoxylated non-isocyanate urethanes (HENIURs) and their use as rheology additives

Experimental and modeling studies of IPDI‐based polyurea elastomers – The role of hard segment fraction

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