Graft Polymerization of Methyl Methacrylate- Acrylonitrile onto Poly(ethene-co-1-butene) and Its Toughening Effect on SAN Resin

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN) was prepared by suspension grafting copolymerization of methyl methacrylate (MMA) and acrylonitrile(AN) onto PEB. PEB-g-MAN/SAN resin blends (ABMS) were prepared by blending PEB-g-MAN with styrene-acrylonitrile copolymer (SAN resin). The effects of AN/(MMA+AN) feed ratio (f_AN), PEB/(PEB+MMA+AN) feed ratio (f_PEB) and benzoyl peroxide (BPO) dosage on the monomer conversion ratio (CR), rubber's grafting ratio (GR), grafting efficiency (GE) of the copolymerization and the toughening effect of PEB-g-MAN on the SAN resin were investigated. FTIR quantitative analysis showed that when the weight percent of AN unit in the unextracted product was 21.5 wt% with f_AN of 25 wt%, the toughening effect of unextracted PEB-g-MAN on SAN resin was the highest. Gel permeation chromatography (GPC) analysis showed that when f_AN was 25 wt%, the grafted copolymer had the lowest molecular weight and ABMS had highest toughness. Transmission electron microscopy (TEM) analysis showed that the highest toughness occurred when the phase structure of ABMS was cocontinuous with f_AN of 25 wt%. When f_AN was 25 wt% PEB-g-MAN domains have numerous small SAN domains in them, which was occlusion structure. Scanning electron microscopy (SEM) analysis indicated that the ABMS fracture surfaces had plastic flow visible, which looked like a craze fibers morphology, for the sample with highest impact strength (f_AN = 25 wt%). Dynamic mechanical thermal analysis (DMA) showed that the miscibility of the PEB phase and SAN phase improved after graft copolymerization of MMA and AN onto PEB.     

Progress in Computer Simulation of Bulk,Confined, and Surface‐initiated Polymerizations

In this article we provide a brief summary of computational techniques applied to investigate polymerization reactions in general, with a focus on systems under confinement and initiated from surfaces. We concentrate on two major classes of techniques, i.e., stochastic methods and molecular modeling. We describe the major principles of the two classes of methodologies and point out their strengths and weaknesses. We review a variety of studies from the literature and conclude with an outlook of these two classes of computer simulation approaches as they are applied to “grafting from” polymerizations.

     

Modulation of Foreign Body Reaction against PDMS Implant by Grafting Topographically Different Poly(acrylic acid) Micropatterns

The surface of poly(dimethylsiloxane) (PDMS) is grafted with poly(acrylic acid) (PAA) layers via surface‐initiated photopolymerization to suppress the capsular contracture resulting from a foreign body reaction. Owing to the nature of photo‐induced polymerization, various PAA micropatterns can be fabricated using photolithography. Hole and stripe micropatterns ≈100‐µm wide and 3‐µm thick are grafted onto the PDMS surface without delamination. The incorporation of PAA micropatterns provides not only chemical cues by hydrophilic PAA microdomains but also topographical cues by hole or stripe micropatterns. In vitro studies reveal that a PAA‐grafted PDMS surface has a lower proliferation of both macrophages (Raw 264.7) and fibroblasts (NIH 3T3) regardless of the pattern presence. However, PDMS with PAA micropatterns, especially stripe micropatterns, minimizes the aggregation of fibroblasts and their subsequent differentiation into myofibroblasts. An in vivo study also shows that PDMS samples with stripe micropatterns polarized macrophages into anti‐inflammatory M2 macrophages and most effectively inhibits capsular contracture, which is demonstrated by investigation of inflammation score, transforming‐growth‐factor‐β expression, number of macrophages, and myofibroblasts as well as the collagen density and capsule thickness.     

Systematic Modulation of Thiol Functionalities in Inexpensive Porous Polymers for Effective Mercury Removal

Through accumulation, mercury contamination in aquatic systems still poses serious health risks despite the strict regulations on drinking water and industrial discharge. One effective strategy against this is adsorptive removal, in which a suitably functionalized porous material is added to water treatment protocols. Thiol (SH) group-grafted structures perform commendably; however, insufficient attention is paid to the cost, scalability, and reusability or how the arrangement of sulfur atoms could affect the Hg^II binding strength. We used an inexpensive and scalable porous covalent organic polymer (COP-130) to systematically introduce thiol functional groups with precise chain lengths and sulfur content. Thiol-functionalized COP-130 demonstrates enhanced wettability and excellent Hg^II uptake of up to 936 mg g⁻¹, with fast kinetics and exceptionally high selectivity. These Hg adsorbents are easily regenerated with HCl and can be used at least six times without loss of capacity even after treatment with strong acid, a rare performance in the domain of Hg-removal research.     

Solubilization of silica nanoparticles in alkanes and poly(α-olefin)s by functionalized polyisobutylene oligomers

Covalent and noncovalent chemical methods that use oligomeric lipophilic agents to solubilize silica nanoparticles in heptane and poly(α-olefin) (EPAO) solvents are described. While only modest solubilization efficiencies are seen with an octadecyl group, a variety of terminally functionalized polyisobutylene (PIB) derivatives are more efficient. Both covalent and noncovalent chemistry was found to be effective. Covalent modification solubilized up to 34 wt% of silica nanoparticles (SiNPs) as stable solutions in heptane or PAOs. Noncovalent modification was however more effective, solubilizing up to 70% of SiNPs in heptane or PAOs. The most successful covalent approach used PIB oligomers containing terminal triethoxysilane groups to covalently modify SiNPs. Alternatively, SiNPs that were first functionalized with amine groups could be solubilized in heptane or PAOs with polyisobutylene containing sulfonic acid groups using acid–base chemistry. Studies of these and other solubilization chemistry was also carried out using fluorescent labels, studies that confirmed the gravimetric analyses of the heptane-solubilized SiNPs. Transmission electron microscopy of a PAO solution of these solutions showed that these SiNPs were present as small aggregates dispersed in the PAOs.     

Surface functionalization of multiwalled carbon nanotubes by the photo‐responsive strategy of π‐π stacking and azide‐grafting

In this communication, we report a new, simple, and eco‐friendly method to develop highly dispersible multiwalled carbon nanotubes (MWCNTs) by π‐π stacking and azide‐grafting. MWCNTs were functionalized via standard physisorption, followed by nitrene addition using azido compounds upon ultraviolet activation. The functionalized MWCNTs show excellent dispersibility without raising distinct damage, which can bear comparison with that of MWCNTs oxidized with mixture acids. This method allows for the improvement of the chemical compatibility of MWCNTs with specific polymers for application in nanotube‐based composites and opens a potential pathway for surface protection.     

Improving the interfacial property of carbon fiber/PI resin composite by grafting modification of carbon fiber surface

The poor interfacial adhesion between carbon fibers (CFs) and polyimide (PI) resin has seriously hampered the application of CF/PI composites. In this work, the interfacial adhesion was efficiently enhanced by grafting on the CF surface. Surface morphology and surface composition of modified carbon fibers were characterized, which indicated that acrylamide was grafted successfully on the CF surface and the surface roughness was increased slightly. After grafting, the interface shear strength of modified carbon fibers/PI composites was significantly improved by 86.96%, and the interlaminar shear strength was enhanced by 55.61% due to the covalent bonds in interphase and the toughening effect of sizing agent. Moreover, the mechanical properties of composites with different interfacial adhesion were measured, which further confirmed the effect of the grafting modification.     

Ring Opening Metathesis Polymerization of Bicyclic α,β‐Unsaturated Anhydrides for Ready‐to‐be‐grafted Polymers Having Tailored pH‐Responsive Degradability

Polymers having α,β‐unsaturated anhydrides as repeating units were synthesized by ring opening metathesis polymerization (ROMP). The anhydride moieties were ready‐to‐be‐grafted with amines to form acid‐labile cis‐α,β‐unsaturated acid amide linkages. The pH‐responsive reversible de‐grafting can be controlled by changing the intramolecular accessibility between acid and amide groups. The alendronate‐grafted ROMP polymers showed distinct pH‐dependent cytotoxicity according to the anhydride structures.     

New acrylamide‐based monomer containing metal chelating units: Homopolymer grafted magnetite nanoparticles via ATRP for the magnetic removal of Co(II) ions

In this research, we synthesized and characterized a new acrylamide‐based monomer containing pyridine and 1,3,4‐oxadiazole moieties, N‐(4‐(5‐(pyridin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl)phenyl)acrylamide (POPA). Poly(POPA)‐grafted magnetite nanoparticles were then obtained via surface‐initiated atom transfer radical polymerization. The grafted nanoparticles were characterized by Fourier transform infrared analysis, scanning electron microscopy, wide angle X‐ray diffraction, and vibrating sample magnetometry. The amount of the grafted polymer was 126 mg/g, as calculated from thermo gravimetric analysis experiment. The capability of poly(POPA)‐g‐magnetite nanoparticles (MNPs) to remove Co(II) cations, under optimal time period, pH and adsorbent mass, was shown by atomic absorption. The adsorption kinetics obeyed the pseudo–second‐order kinetic equation, and the adsorption isotherm was best described by the Freundlich model with a maximum adsorption capacity of 59.90 mg/g. In addition, the poly(POPA)‐g‐MNPs were regenerated by simply washing with an aqueous 0.1M HCl solution, and no considerable decrease was observed in the extraction efficiency following the test of up to 7 cycles. These findings suggest that poly(POPA)‐g‐MNPs are stable and reusable adsorbent, and they could be potentially applied to water treatments for an efficient removal of Co(II) cations.     

Improving the hydrophilic and antifouling properties of poly(vinyl chloride) membranes by atom transfer radical polymerization grafting of poly(ionic liquid) brushes

In this study, poly(1‐butyl‐3‐vinylimidazolium bromide) (PBVIm‐Br) was grafted onto the poly(vinyl chloride) (PVC) membrane surface via a 2‐step atom transfer radical polymerization (ATRP) reaction. Poly(2‐hydroxyethylmethacrylate) (PHEMA) was grafted onto the membrane surface by aqueous ATRP reaction; then, BVIm‐Br was introduced onto the surface of the PHEMA‐modified PVC membrane through traditional ATRP reaction. The analysis of surface chemistry confirmed the successful grafting of PHEMA and PBVIm‐Br on PVC membrane surface, and the grafting density (GD) of PBVIm‐Br gradually increased as the grafting time was prolonged. The modified membrane exhibited a positive charge and significantly enhanced surface hydrophilicity. The static water contact angle of the membrane surface decreased from 92.3° to 51.6° as the GD of the PBVIm‐Br brushes increased. Filtration experiments indicated that the water flux of the modified membrane increased with increasing GD, and their recovered fluxes were more than twice than the original. In addition, the total fouling ratio of the membranes decreased from 89% in M0 to 67% in M5, and most of the fouling was reversible as the GD of PBVIm‐Br brushes increased. These results indicated that the positive charged poly(ionic liquid) brushes featuring hydrophilic properties would have potential applications in membrane separation.