Surface-initiated Ring-opening Metathesis Polymerization Research Articles

Grafting photochromic spiropyran polymer brushes on natural rubber surface via surface-initiated ring-opening metathesis polymerization

The modification of stereoregulated functionalized polymers on the surface of natural rubber (NR) is a challenging task. This work provided a practicable grafting method to design photochromic polymer brushes on the NR surfaces using surface-initiated ring-opening metathesis polymerization (SI-ROMP). The designed photochromic polymer brushes were based on norbornenes with spiropyrin (SP) pendents, and grew from the surface of NR films in the presence of Grubbs 2nd catalyst. The results showed that the grafting rate of polymer brushes with photoisomerization structure reached up to 44.91 %. The modified natural rubber (NR-SP) films exhibited rapid coloring/decolorization property under UV irradiation and visible light. This photochromic property initiated by the light-induced isomerisation of the spiropyran structure and the increased surface energy under light stimuli. NR-SP films exhibited stable photochromic characteristics and outstanding anti-fatigue properties after exposing to over six cycles of consecutive UV/Vis irradiation. A simple and practical strategy for the preparation of highly sensitive photochromic natural rubber materials is proposed and provides a potential application in the fields of information storage and anti-counterfeiting.

Grafting photochromic spiropyran polymer brushes on graphene oxide surfaces via surface-initiated ring-opening metathesis polymerization.

A practical "grafting-from" strategy is described to grow photochromic polymer brushes bearing spiropyran (SP) functional groups on graphene oxide (GO) surfaces via surface-initiated ring-opening metathesis polymerization (SI-ROMP). The Grubbs II catalyst was fixed on the GO surface, and the norbornene derivatives functionalized using spiropyran were synthesized from this active site via the ROMP method. The results indicated that the spiropyran-modified polymer brushes were obtained on the GO surface in the form of thin films. The solubility of GO modified by spiropyran polymers (GO-SPs) in organic solvents was significantly improved. The GO-SPs exhibited excellent photochromic properties, including fast coloration/decoloration. The modified GO with an isomeric structure was colored in 90 s under ultraviolet irradiation and decolored in 360 s under white light. The fading kinetic rate in the dark was slow and the kinetic attenuation curve followed bi-exponential decay. The GO-SP composite materials took more than 2 h to return to thermodynamically stable forms. The reversible change in the water contact angle reached 8° after continuous cycling with ultraviolet and visible light. GO-SP maintained its photochromic performance and possessed excellent fatigue resistance after more than six successive UV/light cycles. This work describes a practical strategy for the preparation of photochromic polymer brush modified GO composite materials and extends the applications of GO in photochromic materials.

Nanocomposites of polyethylene with Fe3O4 nanoparticles via surface-initiated ROMP: Thermomechanical, shape memory and photothermal properties

The nanocomposites of polyethylene with Fe3O4 nanoparticles (NPs) were synthesized via surface-initiated ring-opening metathesis polymerization (SI-ROMP). First, the surfaces of pristine Fe3O4 NPs were functionalized with (5-nicyclo[2.2.1]hept-2-enyl)ethyl]triethoxylsilane. The as-obtained Fe3O4 NPs functionalized with norbornene were used to mediate the ROMP of cyclooctene (COE). By controlling the mass ratios of COE to the surface-functionalized Fe3O4 NPs, the polycyclooctene-grafted Fe3O4 NPs (denoted PCOE-g-Fe3O4 NPs) were obtained with variable contents of Fe3O4 NPs. Finally, these PCOE-g-Fe3O4 NPs were hydrogenated into the corresponding polyethylene-grafted Fe3O4 NPs (PE-g-Fe3O4 NPs). The nanocomposites of PE with Fe3O4 NPs were successfully synthesized as evidenced by the morphologies that the Fe3O4 NPs were well dispersed in PE matrix at the scale of nanometer. The nanocomposites displayed the mechanical properties superior to plain PE. More importantly, the nanocomposites were capable of displaying superparamagnetic, thermally-induced shape memory and photothermal properties. Furthermore, the photothermal behavior can be utilized to trigger the shape memory properties in a non-contact fashion.

Surface Chain-Transfer Ring-Opening Metathesis Polymerization.

Ring-opening metathesis polymerization (ROMP) is a powerful method to graft various types of polymer chains to a given surface. While surface-initiated ROMP (SI-ROMP) serves as an efficient tool for surface modification and is therefore widely reported, the method requires grafting (1) the olefin substrate and (2) the metathesis catalyst to the surface prior to the polymerization with multiple synthetic and work up steps. To overcome this difficulty, we proposed the use of the chain-transfer reaction as an alternative method for surface modification. Terminal olefins are grafted to the surface without the need to graft the metathesis catalysts, and polymers with olefin backbones are polymerized and grafted simultaneously via both ROMP and chain transfer (cross-metathesis between olefins from backbones and surfaces). Compared to SI-ROMP, this surface-chain transfer ROMP (SC-ROMP) method avoids grafting the catalyst and growing polymer chains from the surface and could be achieved in a single step. Various types of surfaces like carbon nanotubes, carbon fibers, graphene nanosheets, and silica microspheres are used for demonstration. We envision that this work could bring a convenient and effective solution to surface modification via ROMP.

Grafting-To and From for Multiplexed Chemical-Warfare-Agent Responsive Polymer Brushes

Surface-tethered polymers have important applications in functional polymer coatings, particularly for the development of chemically responsive surfaces. Here, we combined the traditional grafting-to and grafting-from methods to create a new surface grafting strategy, termed grafting-to and from, using surface-initiated ring-opening metathesis polymerization (SI-ROMP). In this method, poly(pentafluorophenyl methacrylate) is grafted to an amine terminated surface. Surplus reactive esters after reaction with surface amines render this polymer a connecting or tie layer that can be further reacted to provide dense ROMP initiation sites. This amplification of grafting sites results in thick and environmentally stable polymer brushes upon SI-ROMP. With the goal of developing polymer-grafted breathable membranes that autonomously react to multiple chemical warfare agents (CWAs), we demonstrate the benefit of this method by employing amine reactive monomers in the grafting-from step. This enables diverse postsynthetic functionalization for the facile screening of chemical motifs to enhance response capabilities to mustard blister agents. Surface-tethered triarylmethanol-containing polymers with four distinct functional groups are prepared and challenged with the vapor of 2-chloroethyl ethyl sulfide (CEES), a simulant of mustard agent, in humid air. Importantly, hydroxyl groups effectively improve CWA response and the resulting polymer brushes show chain collapse after both CEES and diethylchlorophosphate (DCP) treatment. Our results illustrate that the grafting-to and from method can be used to grow functional and robust polymer coatings for various applications.

Hydrophobic and antifouling modification of graphene oxide with functionalized polynorbornene by surface-initiated ring-opening metathesis polymerization

Surface-initiated ring-opening metathesis polymerization (SI-ROMP), based on the design of hydrophobic and antifouling monomers, was employed for the synthesis of grafting-modified graphene oxide (GO).

Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP): History, General Features, and Applications in Surface Engineering with Polymer Brushes

Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP) has attracted great attention in the past two decades because of its high efficiency in decorating material surfaces with functional polymer brushes. To fill the vacancy of review articles in SI-ROMP, this article is aimed at giving an overview of the history, the general features and procedures, and applications of SI-ROMP, guiding future researchers in this field. In general, SI-ROMP consists of three main steps: surface functionalization with olefin anchors, attachment of catalyst to the surface, and polymerization from the surface. Several metal-based catalysts for ROMP in solution have been developed, but most SI-ROMP reactions use the ruthenium-based Grubbs catalysts. SI-ROMP enables the rapid growth of polymer films on a large variety of substrates such as silica, gold, graphene oxides, carbon nanotubes, metal oxide nanowires, and composite polymer membranes. There are many methods to characterize these polymer brushes. In addition, some novel techniques have been developed to precisely control the surface polymer growth and lead to polymer films with unique structures and functions. Up to this day, SI-ROMP can be applied to the surface engineering of many novel materials, including ultrahydrophobic surfaces, microfluidic channels, electric devices, ion exchange media, and responsive surfaces.

Synthesis of hyaluronated poly(exo-7-oxabicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride) brushes via a combination of surface-initiated ring-opening metathesis polymerization and thiol-ene click reaction

Well-defined hyaluronated poly(exo-7-oxabicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride) [poly(EHDA)-HA] brushes on the hydroxyl-terminated silicon (Si–OH) surface were prepared through the combination of surface-initiated ring-opening metathesis polymerization (ROMP) and thiol-ene click reaction. This process was realized in four successive steps: (i) formation of self-assembled monolayer of (3-aminopropyl) triethoxysilane on the Si–OH surface (Si-APTES), (ii) bonding of EHDA monomer to the Si-APTES surface, (iii) synthesis of poly(EHDA) brushes via surface-initiated ROMP and (iv) coupling of thiolated hyaluronic acid (Th-HA) to poly(EHDA) chains via thiol-ene click reaction. Surface wettability, surface morphology and chemical compositions of poly(EHDA)-HA brushes were characterized by contact angle measurements, atomic force, microscopy and X-ray photoelectron spectroscopy, respectively. Grafting density (σ, chains nm−2) and average distance between grafting points (D, nm) of the poly(EHDA) brushes were measured to be 0.50 chains nm−2 and 1.65 nm, independent of the [catalyst]/[monomer] ratios, which indicated that high grafting was created on the silicon substrate. However, low amounts of HA molecules were bonded to poly(EHDA) chains due to the high volume of Th-HA chains creating some steric hindrances. Biocompatible property of the poly(EHDA)-HA brushes are useful candidate for making advanced biological devices to control the behavior of biomolecules on surfaces.

Surface-Initiated Ring-Opening Metathesis Polymerization: A Method for Synthesizing Polymer-Functionalized Nanoparticles Exhibiting Semicrystalline Properties and Diverse Macromolecular Architectures

Polymer-grafted nanoparticles are effective for designing hybrid materials with optimal component dispersion and enhanced material properties. The olefin chemistry accessible through ring-opening m...

Synthesis of Well-Defined Polyolefin Grafted SiO2 Nanoparticles with Molecular Weight and Graft Density Control.

Recent advances in surface-initiated polymerization have given rise to a range of brush nanocomposites and hybrid functional materials. However, the synthesis of pure polyolefin-grafted nanocomposites by surface-initiated ring-opening metathesis polymerization (SI-ROMP) is a significant challenge due to the particle aggregation and irreversible particle coupling. This study presents a synthetic approach toward well-defined poly(cyclooctene)- and polyethylene-grafted nanoparticles by tethering Grubbs third generation catalyst on the particle surface and initiating the polymerization in a rapid manner. This work also serves as a template to prepare other hairy nanoparticles and functions as a basis toward understanding their thermomechanical behaviors.

Utilizing exfoliated clay–poly(norbornene) nanocomposite prepared by metal-mediated surface-initiated polymerization as model end-tethered polymers on an organoclay substrate

Current interest in dispersion strategies for nanoparticle fillers is driving research into covalently attached polymer brushes. The primary need for these “hairy nanoparticles” is for testing and developing new technologies based on polymer nanocomposites. To that end, we have prepared polymer nanocomposites with covalently tethered chains on a naturally occurring montmorillonite clay template via a metal-mediated surface-initiated ring opening metathesis polymerization approach. The nanocomposites were characterized in terms of polymer:clay composition and of various chain architecture parameters such as molecular weight, polydispersity index, and grafting density.

PH-Responsive Copolymer Films Prepared by Surface-Initiated Polymerization and Simple Modification.

We report the preparation of pH-responsive, ester/carboxylic acid random copolymer films via simple modification of poly(norbornene diacyl chloride) (pNBDAC), prepared via surface-initiated ring-opening metathesis polymerization, with mixtures of water and ethanol to form carboxylic acid and ethyl ester side groups. The pNBDAC film serves as a compositionally versatile platform to controllably obtain copolymers with multiple functionalities. In modifying the pNBDAC to form the copolymer film, ethanol exhibits a significantly higher reactivity with acyl chloride groups within the film than does water. The magnitude and range of the pH-responsive performance are highly dependent on the carboxylic acid content in the copolymer films, which demonstrates the effect of film hydrophilicity on the pH-responsive switching of ionic barrier properties. The resistance of the film against ion transfer can be decreased by a factor of 104 through pH change, demonstrating pH-induced switching from hydrophobic and insulating to swollen and ion-permeable films. The interactions of the copolymer films with water at different pH values were also explored. When the copolymer contains 34% carboxylic acids, a 4× greater film thickness is obtained in high pH solution than in low pH solution due to ionically driven water swelling. The reversibility of the pH-responsive performance of these copolymer films is high based on measurements using quartz crystal microbalance with dissipation (QCM-D).

Metal Chelating Polymer Thin Films by Surface-Initiated ROMP and Modification

We report the surface-initiated ring-opening metathesis polymerization (SiROMP) of hydroxamic acid-containing, metal-chelating polymer thin films. SiROMP of trans-5-norbornene-2,3-dicarbonyl chloride (NBDAC) is introduced as a versatile platform to achieve many functional polymer films via simple exposure of pNBDAC films to reagents. This modification strategy owes its success to the fast and high-yield reaction of acyl chlorides with alcohols, amines, water, and other molecules. The polymerization of NBDAC is performed with monomer in the vapor phase and exhibits rapid kinetics, producing ∼400 nm thick films within 5 min. Because of the high reactivity of the acyl chloride groups in the film, the pNBDAC films are easily modified to produce side chains of carboxylic acids, esters, and amides via the reaction of the acyl group with water, alcohols, and amines, respectively. Exposure of the pNBDAC film to hydroxylamine results in a film with hydroxamic acid functionality that is capable of chelating various metal ions. The chelation process effectively cross-links the polymer chains to greatly improve the thermal and pH stability of the film in solution, elevate resistance against water and ion transfer, and alter the mechanical properties to a more solid-like film.

Co-Poly(ionic liquid) Films via Anion Exchange for the Continuous Tunability of Ion Transport and Wettability.

This manuscript details a novel and simple approach to achieve surface-tethered co-poly(ionic liquid) (coPIL) films through the exchange of the resident anion of a poly(ionic liquid) (PIL) film with two or more anions. Initially, surface-tethered PIL films were prepared by the surface-initiated ring-opening metathesis polymerization of the ionic liquid monomer 3-[(bicyclo[2.2.1]hept-5-en-2-yl)methyl]-1,2-dimethylimidazol-3-ium hexafluorophosphate ([N1-dMIm][PF6]) whose PF6– anion was easily interchanged with aqueous solutions containing a binary mixture of the PF6− anion, along with perchlorate (ClO4−) or bis(fluorosulfonyl)imide (FSI−) anions. The binary mole fraction of each anion in the film was determined from the infrared spectra of the coPIL films. The thermodynamically driven anion selectivity for exchange from the liquid phase into the coPIL films was determined to follow the order ClO4– < PF6– < FSI–. The aqueous wettability of p[N1-dMIm] coPIL films containing both the PF6– and ClO4– anions (p[N1-dMIm][PF6][ClO4]) was quantified by contact angle goniometry with the observation that the surface showed an enrichment in the ClO4– anion compared to the average binary anion mole fraction of ClO4– in the film (yClO4–). The rate of ion transport through the p[N1-dMIm][PF6][ClO4] coPIL films, quantified by electrochemical impedance spectroscopy, linearly depends on the binary anion mole fraction of ClO4– in solution (xClO4–), enabling continuous tunability by over three orders of magnitude for ion conductivity in the coPIL films.

Surface-Initiated Ring-Opening Metathesis Polymerization of Dicyclopentadiene from the Vapor Phase.

Surface-attached polydicyclopentadiene (pDCPD) films were prepared on gold and silicon substrates via surface-initiated ring-opening metathesis polymerization (SI-ROMP) of dicyclopentadiene (DCPD). The films were grown utilizing monomer in both the vapor phase and the solution phase with the former process exhibiting rapid kinetics, producing ∼400-nm-thick pDCPD films in less than 1 min of polymerization. No significant differences in thickness were observed for films grown from monomer in the vapor phase with the different isomers (exo and endo) of DCPD. Decane was used as an inert additive to control the concentration of DCPD monomer in the vapor phase enabling the preparation of pDCPD films with thickness ranging from tens of nanometers to hundreds of nanometers. The thickness of pDCPD films polymerized using monomer in the vapor phase was enhanced by the presence of a rinse solvent on the surface of the ROMP-active gold substrates. The choice of ROMP catalyst was found to be an important consideration when SI-ROMP was conducted on different substrates. Electrochemical impedance spectroscopy was used to reveal that the films provide effective barriers to the diffusion of aqueous ions in excess of 1 × 106 Ω·cm2. The mechanical properties of the surface-tethered pDCPD films were quantified with AFM PeakForce quantitative nanomechanical mapping (QNM) with a measured reduced Young's modulus (Er) of 15 GPa. The measured Er was greater than that of a non-cross-linked surface-tethered polymer, pNB, indicating that the pDCPD films are stiffer.

In situ crosslinking of surface-initiated ring opening metathesis polymerization of polynorbornene for improved stability

HypothesisIn situ crosslinking is expected to increase the solvent stability of coatings formed by surface-initiated ring opening metathesis polymerization (SI ROMP). Solvent-associated degradation limits the utility of SI ROMP coatings. SI ROMP coatings have a unique capacity for post-functionalization through reaction of the unsaturated site on the polymer backbone. Any post-reaction scheme which requires a liquid solvent has the potential to degrade the coating and lower the thickness of the resulting film. ExperimentsWe designed a macromolecular crosslinking group based on PEG dinorbornene. The PEG length is tailored to the expected mean chain to chain distance during surface-initiated polymerization. This crosslinking macromer is randomly copolymerized with norbornene through SI ROMP on a gold coated substrate. The solvent stability of polynorbornene coatings with and without PEG dinorbornene is quantitatively determined, and the mechanism of degradation is further supported through XPS and AFM analyses. FindingsThe addition of the 0.25mol% PEG dinorbornene significantly increases the solvent stability of the SI ROMP coatings. The crosslinker presence in the more stable films is supported with observable PEG absorbances by FTIR and an increase in contact angle hysteresis when compared to non-crosslinked coatings. The oxidation of the SI ROMP coatings is supported by the observation of carbonyl oxygen in the polynorbornene coatings. The rapid loss of the non-crosslinked SI ROMP coating corresponds to nanoscale pitting across the surface and micron-scale regions of widespread film loss. The crosslinked coatings have uniform nanoscale pitting, but the crosslinked films show no evidence of micron-scale film damage. In all, the incorporation of minimal crosslinking content is a simple strategy for improving the solvent stability of SI ROMP coatings.

Dynamic Anion-Adaptive Poly(ionic liquid) Films via Surface-Initiated Ring-Opening Metathesis Polymerization

We report the surface-initiated ring-opening metathesis polymerization (SI-ROMP) of ionic liquid-tethered monomers to grow poly(ionic liquid) (PIL) films on gold and silicon substrates. The kinetics of film growth are rapid, with profilometric thicknesses approaching 600 nm within 15 min of polymerization in a 0.1 M monomer solution and substantial film growth observed at monomer concentrations as low as 0.02 M. The ionic liquid (IL) monomer consists of the cation 3-[(bicyclo[2.2.1]hept-5-en-2-yl)methyl]-1,2-dimethylimidazol-3-ium (N1-dMIm+) with the hexafluorophosphate (PF6–) anion. SI-ROMP of the IL monomer results in a surface-tethered poly(3-[(bicyclo[2.2.1]hept-5-en-2-yl)methyl]-1,2-dimethylimidazol-3-ium hexafluorophosphate) (p[N1-dMIm][PF6]) film whose PF6– anion can be easily interchanged to tune the film properties. The p[N1-dMIm][PF6] films were shown to be adaptive to their anionic environment with the extent of anion exchange characterized by reflectance-absorption infrared spectroscopy and utlraviolet-visible spectroscopy. Anionic dyes incorporated into the p[N1-dMIm] films via anion exchange resulted in a reversible color change in the films. The surface and bulk interaction of the p[N1-dMIm] films with water was analyzed by contact angle goniometry and quartz crystal microbalance with dissipation (QCM-D). The p[N1-dMIm] film with the perchlorate (ClO4–) ion exhibited the lowest advancing contact angle with water of 35 ± 3° compared to the p[N1-dMIm] film with the bistriflate (−NTf2) ion which exhibited the highest water contact advancing angle of 65 ± 3°. The p[N1-dMIm][ClO4] film demonstrated an 8% increase in bulk water content, as determined by QCM-D, compared to the p[N1-dMIm][PF6] film. The rate of ion transfer through the film was highly dependent on the anion as characterized by electrochemical impedance spectroscopy (EIS) in different electrolytes. In particular, resistances to ion transfer ranged from 7.90 ± 0.11 KΩ·cm2 for films containing the PF6– anion to ≤ (4.34 ± 0.04) × 10–3 KΩ·cm2 for films containing the perchlorate ClO4– anion.

Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots.

Core-shell CdSe/ZnS quantum dots (QDs) are useful as tunable photostable fluorophores for multiple applications in industry, biology, and medicine. However, to achieve the optimum optical properties, the surface of the QDs must be passivated to remove charged sites that might bind extraneous substances and allow aggregation. Here we describe a method of growing an organic polymer corona onto the QD surface using the bottom-up approach of surface-initiated ring-opening metathesis polymerization (SI-ROMP) with Grubbs catalyst. CdSe/ZnS QDs were first coated with mercaptopropionic acid by displacing the original trioctylphosphine oxide layer, and then reacted with 7-octenyl dimethyl chlorosilane. The resulting octenyl double bonds allowed the attachment of ruthenium alkylidene groups as a catalyst. A subsequent metathesis reaction with strained bicyclic monomers (norbornene-dicarbonyl chloride (NDC), and a mixture of NDC and norbornenylethylisobutyl-polyhedral oligomeric silsesquioxane (norbornoPOSS)) allowed the construction of tethered organic homo-polymer or co-polymer layers onto the QD. Compounds were characterized by FT-IR, 1H-NMR, X-ray photoelectron spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Atomic force microscopy showed that the coated QDs were separate and non-aggregated with a range of diameter of 48-53 nm.

An exfoliated clay-poly(norbornene) nanocomposite prepared by metal-mediated surface-initiated polymerization

An exfoliated clay−polymer nanocomposite was prepared by surface-initiated ring opening metathesis polymerization (SI-ROMP) of norbornene on a montmorillonite (MMT) clay with a modified surface. Utilizing the hydrothermal-silylation reaction between a norbornenyl-bearing chlorosilane agent and silanol groups of the MMT clay, we were able to bind a metal alkylidene catalyst to the surface in order to grow poly(norbornene) chains directly from the surface using ROMP. Our approach produced nanocomposites having poly(norbornene) chains that are covalently attached to the inorganic substrate, as opposed to most conventional polymer-clay composites that have ionically tethered chains (via the ammonium-based modifiers of the organoclay) or physically adsorbed polymers. POLYM. ENG. SCI., 55:2349–2354, 2015. © 2015 Society of Plastics Engineers

Reproducing superhydrophobic leaves as coatings by micromolding surface-initiated polymerization.

Micromolding surface-initiated polymerization enables the fabrication of polymer coatings that reproduce the microscale surface topography of superhydrophobic leaves onto solid supports. Here, the surfaces of superhydrophobic leaves from Trifolium repens and Aristolochia esperanzae are molded and reproduced as the topography of a partially fluorinated polymer coating through the surface-initiated ring-opening metathesis polymerization of 5-(perfluorooctyl)norbornene (NBF8). The polymer coatings have thicknesses exceeding 100 μm, which can be tailored by the amount of monomer added to the mold. These coatings are robustly bound to the substrate, contain compositions not found in nature, and achieve superhydrophobicity that is comparable to the actual leaf.