Amphiphilic Statistical Copolymers from Catalytic Chain Transfer as Reactive Surfactants in Emulsion Polymerization

Schreur-Piet, Ingeborg; Heuts, Johan P. A.

doi:10.1021/acsapm.1c00715

Cited by 6 publications

(10 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is one of the main reasons that this technique is highly scalable and useful for industrial applications. Recently, oligomers from CCTP have been used as reactive surfactants and emulsion stabilizers, − in pigment dispersants, and as oil viscosity modifiers; however, this is the first time they have been applied as additives to a rubber cure package.…”

Section: Resultsmentioning

confidence: 99%

Oligomeric Curing Activators Enable Conventional Sulfur-Vulcanized Rubbers to Self-Heal

Wemyss

Marathianos

Heeley

et al. 2022

ACS Appl. Polym. Mater.

View full text Add to dashboard Cite

When introducing self-healing properties to elastomers, it is often difficult to balance their ability to recover properties after damage with a good mechanical strength prior to damage. We demonstrate that by replacing the activator system used in conventional accelerated vulcanization (CV) chemistry, from the traditional zinc oxide (ZnO) and stearic acid to a complex formed between ω-propenyl functional oligomers of poly(zinc methacrylate) (pZnMA/ZnO), the self-healing properties of vulcanized natural rubbers are enhanced while maintaining good tensile strengths. The pZnMA oligomers, as synthesized by catalytic chain transfer polymerization (CCTP), act as an activator for the sulfur curing system, while also forming an ionic network in the rubber. The addition of 20 phr of pZnMA/ZnO to a CV system resulted in a cured natural rubber with a tensile strength of 7.47 ± 0.64 MPa, which recovered 86.7% after self-healing at 80 °C for 2 h. Further addition of 40 phr of carbon black N234 unexpectedly enhanced the self-healing efficiency of these vulcanized rubbers to 92.2% under the same conditions and also improved the self-healing at room temperature. Finally, dynamic mechanical thermal analysis indicated that the natural rubber formulations containing pZnMA/ZnO showed improved wet traction but with higher rolling resistance to a standard formulation. These results point to an interesting direction for further research into the performance of self-healing composites in vehicle tire applications.

show abstract

Section: Resultsmentioning

confidence: 99%

Oligomeric Curing Activators Enable Conventional Sulfur-Vulcanized Rubbers to Self-Heal

Wemyss

Marathianos

Heeley

et al. 2022

ACS Appl. Polym. Mater.

View full text Add to dashboard Cite

show abstract

“…To avoid the negative effects of small molecule emulsifiers, reactive surfactants, or amphiphilic methacrylic oligomers with ω-end unsaturated groups have been taken advantage of SF-RAFT emulsion polymerization for the preparation of polymer colloid particles. Heuts et al − reported that the amphiphilic statistic copolymers were synthesized via cobalt (II)-CCTP and further utilized as reactive surfactants in the emulsion polymerization of MMA. However, in the presence of pigment particles, those amphipathic statistical macro-RAFT agents with a ω-end unsaturated group may be an issue for the controlled synthesis and stability of hybrid latex-encapsulating pigment.…”

Section: Resultsmentioning

confidence: 99%

“…To address these issues, the Haddleton group proposed first that sequence-controlled methacrylic acid multiblock copolymers through a sulfur-free RAFT (SF-RAFT) emulsion polymerization strategy. − The combination of catalytic chain-transfer polymerization (CCTP) and SF-RAFT strategies paved the way for construction of sequence-controlled methacrylic acid multiblock copolymers and maintained fast polymerization rates, quantitative conversions, and low dispersion value. Heuts et al. − compounded poly(methacrylic acid) macromonomers by CCTP, used the macromonomers for batch and semibatch emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA), and obtained steady polymer latex. Bon et al − carried out polymerization-induced self-assembly (PISA) in the absence of monomers using macromonomers as seed emulsions.…”

Section: Introductionmentioning

confidence: 99%

Sulfur-free and Surfactant-free RAFT-Mediated Hybrid Emulsion Polymerization: A Model System for Understanding the Controlled Synthesis of Hybrid Latex-Encapsulating Pigment

Zhang

et al. 2022

ACS Appl. Polym. Mater.

View full text Add to dashboard Cite

Reversible addition−fragmentation chain-transfer (RAFT)-mediated hybrid emulsion polymerization is an in situ growth method of increasing interest for preparation of colloidal polymers/inorganic hybrid latex with precise structures and properties. However, the challenges of the conventional organic sulfur-based RAFT agents causing color and undesired odor problems still attract attention. In response to this problem, herein, a cationic amphipathic statistic sulfur-free (SF) macro-RAFT agent with a vinyl end group is proposed to disperse organic pigment particles (C.I. Pigment Red 170), where the vinyl group is the living point to regulate the sulfur-free and surfactant-free RAFT hybrid emulsion polymerization of methyl methacrylate (MMA) or MMA with butyl acrylate (BA). Benefitting from this SF macro-RAFT agent acting as both coupling agent and stabilizer, the "living" chain growth of the polymers onto the C.I. Pigment Red 170 surface causes the formation of encapsulating pigment hybrid particles as proven by size-exclusion chromatography and transmission electron microscopy analyses. As a proof-of-concept experiment, the film-forming P(MMA-co-BA)/pigment hybrid latex particles are applied to textile colorants to pad dyeing cotton fabric. Owing to the unique structure of hybrid particles with high pigment content (81.3%), the dyed cotton fibers exhibit high color strength, dryand wet-rubbing fastness, good air permeability, and softness in comparison with the traditional mixture system. This study will not only broaden the area of RAFT-mediated hybrid emulsion polymerization for preparing hybrid particles but also provide a facile application for clear production.

show abstract

“…were purchased from Merck and used as received. Macromonomers were synthesized and characterized as part of previously published work, − and their main characteristics are summarized in Table .…”

Section: Methodsmentioning

confidence: 99%

The Effect of Macromonomer Surfactant Microstructure on Aqueous Polymer Dispersion and Derived Polymer Film Properties

Schreur-Piet,

Heuts

2024

Biomacromolecules

Self Cite

View full text Add to dashboard Cite

Water-borne coatings were prepared from poly(methyl methacrylate-co-butyl acrylate) latexes using different methacrylic acid containing macromonomers as stabilizers, and their physical properties were determined. The amphiphilic methacrylic acid macromonomers containing methyl, butyl, or lauryl methacrylate as hydrophobic comonomers were synthesized via catalytic chain transfer polymerization to give stabilizers with varying architecture, composition, and molar mass. A range of latexes of virtually the same composition was prepared by keeping the content of methacrylic acid groups during the emulsion polymerization constant and by only varying the microstructure of the macromonomers. These latexes displayed a range of rheological behaviors: from highly viscous and shear thinning to low viscous and Newtonian. The contact angles of the resulting coatings ranged from very hydrophilic (<10°) to almost hydrophobic (88°), and differences in hardness, roughness, and water vapor sorption and permeability were found.

show abstract

Amphiphilic Statistical Copolymers from Catalytic Chain Transfer as Reactive Surfactants in Emulsion Polymerization

Cited by 6 publications

References 50 publications

Oligomeric Curing Activators Enable Conventional Sulfur-Vulcanized Rubbers to Self-Heal

Oligomeric Curing Activators Enable Conventional Sulfur-Vulcanized Rubbers to Self-Heal

Sulfur-free and Surfactant-free RAFT-Mediated Hybrid Emulsion Polymerization: A Model System for Understanding the Controlled Synthesis of Hybrid Latex-Encapsulating Pigment

The Effect of Macromonomer Surfactant Microstructure on Aqueous Polymer Dispersion and Derived Polymer Film Properties

Contact Info

Product

Resources

About