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

Quienne, Baptiste; Pinaud, Julien; Caillol, Sylvain

doi:10.1016/j.eurpolymj.2022.111384

Cited by 6 publications

(10 citation statements)

References 44 publications

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“…Detailed procedures for the macroRAFT agent and PISA are provided elsewhere. 28,29 HEUR10kC12 was synthesized as per earlier work, 25 except that the molar mass of poly(ethylene glycol) was 10000 g mol −1 and dodecyl isocyanate was used to create HEUR10kC12. Here, 7.5 g (1 equiv) of poly(ethylene glycol) (10000 g mol −1 ) and 0.016 g of DBTDL (0.2 wt % of the total mass) were solubilized in 15 mL of dried toluene.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

One Step Closer to Coatings Applications Utilizing Self-Stratification: Effect of Rheology Modifiers

Murdoch,

Quienne,

Argaiz

et al. 2023

ACS Appl. Polym. Mater.

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Self-stratification of model blends of colloidal spheres has recently been demonstrated as a method to form multifunctional coatings in a single pass. However, practical coating formulations are complex fluids with upward of 15 components. Here, we investigate the influence of three different rheology modifiers (RMs) on the stratification of a 10 wt % 7:3 w:w blend of 270 and 96 nm anionic latex particles that do not stratify without RM. However, addition of a high molar mass polysaccharide thickener, xanthan gum, raises the viscosity and corresponding Péclet number enough to achieve small-on-top stratification as demonstrated by atomic force microscopy (AFM) measurements. Importantly, this was possible due to minimal particle–rheology modifier interactions, as demonstrated by the bulk rheology. In contrast, Carbopol 940, a microgel-based RM, was unable to achieve small-on-top stratification despite a comparable increase in viscosity. Instead, pH-dependent interactions with latex particles lead to either laterally segregated structures at pH 3 or a surface enrichment of large particles at pH 8. Strong RM–particle interactions are also observed when the triblock associative RM HEUR10kC12 is used. Here, small-on-top, large-enhanced, and randomly mixed structures were observed at respectively 0.01, 0.1, and 1 wt % HEUR10kC12. Combining rheology, dynamic light scattering, and AFM results allows the mechanisms behind the nonmonotonic stratification in the presence of associative RMs to be elucidated. Our results highlight that stratification can be predicted and controlled for RMs with weak particle interactions, while a strong RM–particle interaction may afford a wider range of stratified structures. This takes a step toward successfully harnessing stratification in coatings formulations.

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Section: ■ Materials and Methodsmentioning

confidence: 99%

One Step Closer to Coatings Applications Utilizing Self-Stratification: Effect of Rheology Modifiers

Murdoch,

Quienne,

Argaiz

et al. 2023

ACS Appl. Polym. Mater.

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“…19,20 The network structure can provide a certain shear resistance. 10,21 Meanwhile, hydrophobic associative polymers also have good rheology, 20,22 thickening ability, 10,23 drag reduction ability 24,25 and certain temperature resistance. 10,21 For example, Quienne et al 22 synthesized three polyhydroxyurethanes (PHUs) with amphiphilic properties and low toxicity using polyethylene glycol bicyclic carbonate with hydrophobic amines of 14 $ 18 carbon chain lengths.…”

Section: Introductionmentioning

confidence: 99%

“…10,21 Meanwhile, hydrophobic associative polymers also have good rheology, 20,22 thickening ability, 10,23 drag reduction ability 24,25 and certain temperature resistance. 10,21 For example, Quienne et al 22 synthesized three polyhydroxyurethanes (PHUs) with amphiphilic properties and low toxicity using polyethylene glycol bicyclic carbonate with hydrophobic amines of 14 $ 18 carbon chain lengths. Meanwhile, the effects of temperature, concentration, and hydrophobic chain length on the transient network relaxation time of the polymers were analyzed.…”

Section: Introductionmentioning

confidence: 99%

Preparation and properties research of a bifunctional hydrophobic associative polymer drag reduction agent for slick water

Sun

Zhou

et al. 2023

J of Applied Polymer Sci

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In this study, the bifunctional hydrophobic associative polymer of Acrylamide/2‐Acrylamido‐2‐Methylpropane Sulfonic Acid/Lauryl Methacrylate/N,N‐dodecyl Acrylamide (AALD12) with better salt resistance and shear resistance was synthesized by free‐radical micelle polymerization for use as a drag reduction in shale slip water fracturing. In deionized water, the critical associative concentration (CAC) of AALD12 was 0.23%. AALD12 was determined to be theoretically usable for a shale reservoir within 240°C based on its TG study. Microstructure, viscoelasticity, and shear recovery tests show that the polymer has good drag reduction potential and shear resistance. The reduction rates of the polymer AALD12 and the drag reduction agent RSH‐1 in clear water were 77% and 73% (RSH‐1 is a commonly used emulsion‐type drag reduction agent in the market). At the same salt concentration (K+ and Ca2+, 50,000 ppm) and flow rate (40 L/min), AALD12 can maintain a maximum reduction rate of about 63%. The drag reduction rate of RSH‐1 in K+ and Ca2+ solutions can only be maintained at about 52% and 28%, respectively. In the shear resistance test, AALD12 and RSH‐1 were each subjected to three times of cyclic shear in the test pipe. The drag reduction rate of the polymer AALD12 solution can still reach more than 72%. The drag reduction rate of the RSH‐1 solution is about 56%. The drag reduction agent has good salt resistance and anti‐shear bifunction.

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“…26−29 Among the various synthetic routes to non-isocyanate polyurethanes (NIPUS), the polyaddition of cyclic carbonates with amines has emerged as a promising method to produce polyhydroxyurethanes (PHUs). 26,27 Despite the potential benefits of this technology, including the elimination of isocyanate-related hazards, there are challenges that hinder its broad adoption and industrial scaling-up. The limitations include low reactivity of the cyclic carbonate/amine reaction and limited degree of polymerization at room temperature, resulting in low molar mass PHUs.…”

Section: Introductionmentioning

confidence: 99%

“…However, the use of isocyanates in this process poses significant health and environmental risks, and alternative approaches have been sought. − Among the various synthetic routes to non-isocyanate polyurethanes (NIPUS), the polyaddition of cyclic carbonates with amines has emerged as a promising method to produce polyhydroxyurethanes (PHUs). , Despite the potential benefits of this technology, including the elimination of isocyanate-related hazards, there are challenges that hinder its broad adoption and industrial scaling-up. The limitations include low reactivity of the cyclic carbonate/amine reaction and limited degree of polymerization at room temperature, resulting in low molar mass PHUs. , Efforts have also been made to explore the use of the reactive extrusion (REX) technique to overcome the kinetic limitations associated with the aminolysis of cyclic carbonates. , While this method shows promise to increase the reactivity and molar mass of PHUs, further studies are needed to optimize this method and make it a viable alternative for large-scale PHU production. Despite the promising future of PHUs and NIPUs, HEURs, made with diisocyanates, are still necessary in various applications .…”

Section: Introductionmentioning

confidence: 99%

One-Step versus Two-Step Synthesis of Hydrophobically Modified Ethoxylated Urethanes: Benefits and Limitations

Tzortzi,

Xiouras,

Choustoulaki

et al. 2023

Ind. Eng. Chem. Res.

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Associative thickeners, such as hydrophobically modified ethoxylated urethanes (HEURs), are an important class of rheological modifiers allowing precise control and optimization of the rheology of waterborne coatings. In this work, we present a novel, comprehensive investigation of one-step and two-step HEUR synthesis processes, highlighting their impact on the final HEUR properties. In the conventional one-step process (current industrial practice), there are inherent limitations in producing high molecular weight polymers due to the complex competition between end-capping and polymerization. We show that the two-step method allows for much higher molecular weight polymers than the one-step method while using less amounts of toxic diisocyanates. Additionally, using the two-step method, the polymerization can be simply and efficiently controlled by the addition timepoint of the end-capping agent, which can be tailored to provide HEURs with a wide range of molecular weight and polydispersity index. However, the efficient end-capping of high molecular weight polymers remains a challenge when using conventional mixing equipment in batch reactors due to mass transfer and mixing limitations associated with the significant increase in the bulk viscosity of the reaction mixture. To overcome these limitations, alternative and more efficient mixing technologies, such as reactive extruders, should be considered for the efficient end-capping of high molecular weight polymers.

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

Cited by 6 publications

References 44 publications

One Step Closer to Coatings Applications Utilizing Self-Stratification: Effect of Rheology Modifiers

One Step Closer to Coatings Applications Utilizing Self-Stratification: Effect of Rheology Modifiers

Preparation and properties research of a bifunctional hydrophobic associative polymer drag reduction agent for slick water

One-Step versus Two-Step Synthesis of Hydrophobically Modified Ethoxylated Urethanes: Benefits and Limitations

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