Synthesis and Modification of Functional Polycarbonates with Pendant Allyl Groups

Functional aliphatic polycarbonates with pendant allyl groups were synthesised by copolymerization of carbon dioxide and allyl glycidyl ether (AGE) in the presence of a catalyst system based on ZnEt₂ and pyrogallol at a molar ratio 2 : 1. The functionality of some polycarbonates was reduced by replacing a part of allyl ether with saturated glycidyl ether, i.e., butyl glycidyl ether (BGE) or isopropyl glycidyl ether (IGE). Polycarbonates obtained by the copolymerization of AGE and CO₂ or by the terpolymerization of AGE, IGE and CO₂ were oxidized with m‐chloroperbenzoic acid to their respective poly(epoxycarbonate)s. The influence of the AGE/ΣGE ratio in the polycarbonates, the polymer concentration in the reaction solution and the duration of the reaction on the conversion of allyl groups into glycidyl ones was examined. A tendency to gelation of the initial and oxidized polycarbonates during storage was observed. The initial polycarbonates and their oxidized forms were degraded in aqueous buffer of pH = 7.4 at 37°C. The course of hydrolytic degradation was monitored by the determination of mass loss.     

Synthesis of amphiphilic particles in the presence of inert solvents and their application to lipase immobilization

To develop monodisperse amphiphilic polymer particles on which a large amount of lipase could be immobilized, we performed seed polymerizations of glycidyl methacrylate and allyl methacrylate in the presence of nonpolar inert and polar inert solvents. The amphiphilic porous polymer particles, which had both hydrophilic guanidino groups and hydrophobic stearoyl groups, were synthesized in the presence of n‐decane and had a large amount of macropores with diameters of 50–1000 nm. The amount of lipase immobilized on the amphiphilic particles synthesized in the presence of n‐decane was 3.85 times that of the lipase immobilized on the amphiphilic particles synthesized in the absence of a solvent. The immobilized lipase prepared with the amphiphilic particles synthesized in the presence of n‐decane exhibited a high transesterification activity in n‐hexane and could be used repeatedly without a considerable activity loss. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 874–884, 2002; DOI 10.1002/pola.10178     

Transparent Films from CO2‐Based Polyunsaturated Poly(ether carbonate)s: A Novel Synthesis Strategy and Fast Curing

Transparent films were prepared by cross‐linking polyunsaturated poly(ether carbonate)s obtained by the multicomponent polymerization of CO₂, propylene oxide, maleic anhydride, and allyl glycidyl ether. Poly(ether carbonate)s with ABXBA multiblock structures were obtained by sequential addition of mixtures of propylene oxide/maleic anhydride and propylene oxide/allyl glycidyl ether during the polymerization. The simultaneous addition of both monomer mixtures provided poly(ether carbonate)s with AXA triblock structures. Both types of polyunsaturated poly(ether carbonate)s are characterized by diverse functional groups, that is, terminal hydroxy groups, maleate moieties along the polymer backbone, and pendant allyl groups that allow for versatile polymer chemistry. The combination of double bonds substituted with electron‐acceptor and electron‐donor groups enables particularly facile UV‐ or redox‐initiated free‐radical curing. The resulting materials are transparent and highly interesting for coating applications.     

Synthesis of allyl end‐block functionalized poly(ε‐caprolactone)s and their facile post‐functionalization via thiol–ene reaction

A simple and facile strategy for the functionalization of commercial poly(ε‐caprolactone) diols (PCLs) with pendant functionalities at the polymer chain termini is described. Well‐defined allyl‐functionalized PCLs with varying numbers of allyl end‐block side‐groups were synthesized by cationic ring‐opening polymerization of allyl glycidyl ether using PCL diols as macroinitiators. Further functionalization of the allyl‐functionalized PCLs was realized via the UV‐initiated radical addition of a furan‐functionalized thiol to the pendant allyl functional groups, showing the suitability for post‐modification of the PCL materials. Changes in polymer structure as a result of varying the number of pendant functional units at the PCL chain termini were demonstrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 928–939     

Synthesis and thermal crosslinking reaction of polymers containing pendant carboxyl and epoxy groups

Polymers containing both pendant carboxyl and epoxy groups were synthesized by the radical copolymerization of p-vinylbenzyl glycidyl ether (VBGE) and itaconic acid monomethyl ester (IAME). The copolymerization proceeded smoothly under various conditions, and polymer soluble in 1,4-dioxane with no gel fraction was obtained. However, the carboxyl-epoxy addition reaction between VBGE and IAME was observed, when DMSO or DMF were used as polymerization solvents. The IR and ¹H-NMR spectrum of copolymers of VBGE and IAME showed the corresponding structure. The thermal crosslinking reaction of the resulting copolymers was examined under various conditions. Tetrabutylammonium bromide (TBAB) showed catalytic activity for the reaction. However, a 100% gel fraction of polymer was achieved after only 15 min without any catalyst, when the crosslinking reaction was performed at 150°C. © 1996 John Wiley & Sons, Inc.     

Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate‐free polyurethane networks

Poly(allyl glycidyl ether) and poly(allyl glycidyl ether‐co‐epichlorohydrin) were prepared by monomer‐activated anionic polymerization. Quantitative and controlled polymerization of allyl glycidyl ether (AGE) giving high molar mass polyether was achieved in a few hours at room temperature in toluene using tetraoctylammonium salt as initiator in presence of an excess of triisobutylaluminum ([i‐Bu₃Al]/[NOct₄Br] = 2?4). Following the same polymerization route, the copolymerization of AGE and epichlorohydrin yields in a living‐like manner gradient‐type copolymers with controlled molar masses. Chemical modification of the pendant allyl group into cyclic carbonate was then investigated and the corresponding polymers were used as precursors for the isocyanate‐free synthesis of polyurethane networks in presence of a diamine. Formation of crosslinked materials was followed and characterized by infrared and differential scanning calorimetry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of Novel Glycidol Copolymers with Pendant Alkene and Hydroxyl Groups

A series of linear poly glycidol copolymers, tethering with both alkene and hydroxyl groups, were prepared by a combination of anionic ring-opening polymerization （ROP） using specific reactions of ethoxy ethyl glycidyl ether （EEGE） and allyl glycidyl ether （AGE） firstly, and subsequently removal of the protection group of glycidol in EEGE to achieve the linear copolymer pendant with both hydroxyl groups and double bonds. The EEGE/AGE monomer reactivity ratio is measured to be 3.30/1.13. The chemical compositions of the as-synthesized polymers were characterized by tH NMR and GPC, and the glass transition temperatures （Tg） of as-synthesized polymers were determined by DSC. The final copolymers have abundant double bonds and hydroxyl as side groups. Furthermore, the ratio of the double bonds to hydroxyl groups can be controlled by the ratio of the starting materials in a wide range.     

Photochemical addition reaction of a polymer-bearing pendant vinyl ether with various thiol compounds

Photochemical addition reaction of the pendant vinyl ether group in the polymer ( P-1 ), which was synthesized by the alternate ring-opening copolymerization of glycidyl vinyl ether with phthalic anhydride, with various thiol compounds such as benzenethiol, phenylmethanethiol, 2-mercaptoacetic acid, ethyl 2-mercaptoacetate, N-acetyl-L -cysteine (AcCys), and 1,4-phenylenedi(methylthiol) was carried out using benzophenone (BP) as the photosensitizer in the THF solution. Each reaction proceeded very smoothly to give the corresponding polymers with high conversion, although the degree of reaction of the pendant vinyl ether group in P-1 was affected by the molar ratio between the thiol compounds and the vinyl ether group, and the amounts of photosensitizer BP added. Furthermore, it was also found that optically active polymer containing pendant N-acetyl-L -cysteine residue was synthesized by the photochemical addition reaction of P-1 with AcCys. The reactions of P-1 with dithiol or bisazide compounds occurred effectively to give gel products in the film state, and it was found that the polymer film containing P-1 and those compounds can be applied as negative-type photoresists with high practical photosensitivity. © 1993 John Wiley & Sons, Inc.     

Anionic alternating copolymerization of 3,4‐dihydrocoumarin and glycidyl ethers: A new approach to polyester synthesis

Anionic copolymerizations of 3,4‐dihydrocoumarin (DHCM) and a series of glycidyl ethers (n‐butyl glycidyl ether, tert‐butyl glycidyl ether, and allyl glycidyl ether) with 2‐ethyl‐4‐methylimidazole as an initiator proceeded in a 1:1 alternating manner to give the corresponding polyesters, whose structures were confirmed by spectroscopic analyses and reductive scission of the ester bonds in the main chain with lithium aluminum hydride, followed by detailed analyses of the resulting fragments. The polyester obtained by the copolymerization of DHCM and allyl glycidyl ether inherited the allyl groups in the side chain, whose applicability to chemical modifications of the polyester was successfully demonstrated by a platinum‐catalyzed hydrosilylation reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4092–4102, 2008     

Synthesis and photopolymerization of 1-propenyl glycidyl ether

The ambifunctional monomer, 1-propenyl glycidyl ether, was prepared from allyl glycidyl ether, by a ruthenium-catalyzed isomerization reaction in high yield. 1-Propenyl glycidyl ether undergoes facile photoinduced cationic polymerization to yield a crosslinked polymer. The structure of this polymer was studied using ¹H- and, ¹³C-NMR spectroscopies and employing well-characterized related polymers as models. The model polymers were prepared by the cationic polymerization of allyl glycidyl ether with BF₃OEt₂ followed by isomerization of the pendant allyl groups by a ruthenium catalyst. Subsequently, the resulting polyether-bearing pendant 1-propenyl ether groups was subjected to a diaryliodonium salt-photoinitiated polymerization. A comparison of the spectra of the polymers indicated the presence of cyclic acetal units in the polymer backbone. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of epoxy-functional polystyrene particles

Colloidal polystyrene particles with surface epoxy groups have been synthesized through surfactant-free emulsion copolymerization of styrene with glycidyl methacrylate; and through copolymerization of glycidyl methacrylate (GMA) and methyl methacrylate as shells around existing polystyrene seed particles. We developed two titration methods to quantify the number of epoxy groups that survived the polymerization processes. The styrene-GMA copolymer particles were judged to be unsatisfactory as model colloidal materials due to their size polydispersity and unknown internal distribution of epoxy groups. The core-shell particles had high epoxy surface densities with at least 60% of the initial epoxy groups surviving the synthesis process. Transmission electron microscopy shows that the thickness of the epoxy-rich shell is less than expected based on the volume of monomers added, suggesting that some of the monomer forms water-soluble oligomers. Photon correlation spectroscopy measurements imply that the shell is swollen with water and consists of polymer configurations which extend out into solution. The morphological details vary consistently with the GMA content, and hence the hydrophilicity, of the shell polymer. © 1995 John Wiley & Sons, Inc.     

Reactive blends of thermoplastics and latex particles

Monodisperse homogeneous and core–shell latex particles of various sized between 200 and 600 nm were synthesized by emulsion copolymerization. Some of the core–shell particles were functionalized with epoxy groups at their peripheries upon introduction of glycidyl methacrylate (GMA) during the synthesis. The core consisted of crosslinked polybutylacrylate and the shell polymethylmethacrylate. Synthesis conditions at high and low temperatures were optimized to obtain coreshell particles with a well-defined morphology. The particles were characterized by quasi-elastic light scattering, scanning electron microscopy and transmission electron microscopy. The latex particles functionalized with GMA were then dispersed into a reactive matrix (styrene and maleic anhydride copolymer) using a batch mixer to obtain blends with well-defined and stabilized morphology. 4 Dimethylaminopyridine was used as a catalyst. The reaction between the epoxy groups at the particle surface and the maleic anhydride or diacid groups of the matrix was evaluated by torque and extraction techniques. A small amount of conversion generates sufficient amounts of grafted species at the matrix and particle interfaces to ensure a good interfacial adhesion.     

Temperature‐sensitive hydrogel microspheres formed by liquid–liquid phase transitions of aqueous solutions of poly(N,N‐dimethylacrylamide‐co‐allyl methacrylate)

Poly(N,N‐dimethylacrylamide‐co‐allyl methacrylate) (DMA‐co‐AMA) copolymers were prepared by the copolymerization of N,N‐dimethylacrylamide with allyl methacrylate (AMA). The methacryloyl group of AMA reacted preferentially, and this resulted in pendant allyl groups along the copolymer chains. Aqueous solutions of these DMA‐co‐AMA copolymers were thermoresponsive and showed liquid–liquid phase transitions at temperatures that depended on the AMA content. Hydrogel microspheres were prepared from these thermally phase‐separated liquid microdroplets by the free‐radical crosslinking of the pendant allyl groups. The morphologies of the resulting thermoresponsive microspheres as a function of the reaction temperature and the amount of the initiator were examined. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1641–1648, 2005     

Novel elastomeric polyurethanes with pendant epoxy groups as highly reactive auxiliary groups for further derivatizations

The introduction of pendant, reactive groups into polyurethane macromolecules is a challenging problem. A variant of the nondegradative modification of polyurethanes with epoxy groups attached to the urethane sites is proposed. Two types of commercial elastomeric segmented polyurethanes, represented by a poly(ether urethane) and a poly(urethane urea), were functionalized by base‐induced N‐glycidylation of the urethane hard segments with an excess of epibromohydrin in dimethylacetamide solutions at low temperatures. This resulted in the modification of polymers with 0.30–0.44 mmol/g of pendant epoxy groups. Lithium or potassium tert‐butoxides were used as bases to initiate the reaction. A nonpolymeric urethane model (ethyl N‐p‐tolylcarbamoate) was used to verify the course of glycidylation. One of the polymers was subjected to epoxy ring opening with 1‐propanethiol, demonstrating the versatility of pendant glycidyl groups as auxiliary groups for further bulk modifications of polyurethanes. These functionalized polyurethanes are useful for the further covalent attachment of suitable moieties (stabilizing or biocompatibility‐enhancing agents). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4378–4385, 2002     

Microwave‐assisted phospha‐michael addition of dialkyl phosphites,a phenyl‐H‐phosphinate,and diphenylphosphine oxide to maleic derivatives

A series of new >P(O)‐substituted succinic derivatives was synthesized by the microwave‐assisted phospha‐Michael addition of dialkyl phosphites, ethyl phenyl‐H‐phosphinate, and diphenylphosphine oxide to N‐phenyl and N‐methyl maleimide, as well as to maleic acid anhydride. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:235–240, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21007     

A new type of functional polymer: Preparation and crosslinking of poly(allenyl glycidyl ether)

The radical polymerization behavior of alkoxyallene containing the epoxy group, allenyl glycidyl ether ( I ), was investigated to obtain the more reactive polymer. The desired polymer was successfully synthesized only by the copolymerization of I with acrylonitrile (AN) at 80°C in DMF, although the homopolymer of I was converted to the crosslinked polymer during its purification. The same number of epoxy and two kinds of methylene groups were simultaneously introduced onto the polymer through propagating allyl radical. The obtained copolymer, therefore, was readily converted to the gelled polymer with methods such as heating and treating with Lewis acids or amines. Further, the copolymer containing two kinds of methylene groups was prepared similarly from methoxyallene ( II ) and AN, and was also converted to the crosslinked polymer with the cationic catalyst. These copolymers of I or II with AN will be expected to be new types of reactive polymers.     

Synthesis,Characterization and Polymerization of a Novel Glycidyl Phosphinate

With the aim to obtain flame‐retardant epoxy resins, a new glycidyl phosphinate, 9‐(9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide)‐2,3‐epoxypropyl (DOPO‐Gly) was synthesized via a two‐step synthesis. The subsequent reaction of DOPO‐Gly with BF₃·Et₂O resulted in a polyether with a pendant bulky phosphorylated group. Likewise, the reaction with phthalic acid anhydride gave the expected dihydroxy ester. However, the reaction with tertiary or primary amines led to isomerization and no polymer was obtained.     

Stereoselective synthesis of trisubstituted alkenes containing (Z)‐allylthio units from the acetates of Baylis–Hillman adducts

A series of trisubstituted alkenes containing (Z)‐allylthio moieties as key structural units, that is, sodium (Z)‐allyl thiosulfates, symmetrical di(Z‐allyl) sulfides, and di(Z‐allyl) disulfides, unsymmetrical diallyl sulfides were prepared in moderate to good yields via chemical transformations from the acetates of Baylis‐‐Hillman adducts. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:188–198, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20394     

Surface characterization of macroporous glycidyl methacrylate based copolymers by inverse gas chromatography

Two samples of macroporous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), PGME, with different porosity parameters were synthesized by suspension copolymerization and modified by ring-opening reaction of the pendant epoxy groups with ethylene diamine, EDA. Inverse gas chromatography at infinite dilution was used for the determination of adsorption properties of PGME, and copolymer modified with ethylene diamine, PGME-en. Thermodynamic parameters of adsorption, dispersive components of the surface free energies, and the acid/base constants for the copolymer samples were calculated. The calculated dispersive surface energy values, , for PGME and PGME-en are comparable with the literature data for nonconductive polymers.     

Synthesis of polyester having sequentially ordered two orthogonal reactive groups by anionic alternating copolymerization of epoxide and bislactone

This article presents a route to a novel polyester having sequentially ordered two orthogonal reactive groups. The polyester was given by the imidazole‐initiated alternating copolymerization of allyl glycidyl ether (AGE) and a bislactone 1 . This copolymerization system is characterized by the following three reaction behaviors: (1) the selective participation of only one of the two lactone moieties of 1 to the copolymerization to give a linear polyester, and the consequent introduction of the second lactone into the side chain of the polyester, (2) the participation of the epoxy moiety in AGE to the copolymerization, and the consequent introduction of the carbon–carbon double bond into the side chain of the polyester, and (3) arrangement of the sequentially ordered two orthogonal reactive groups according to the alternating manner. The introduction of the two reactive groups to the side chain of the alternating copolymer allowed two routes of sequential chemoselective reactions: (A) The ring‐opening reaction of the lactone moiety with n‐propylamine and the following Pt‐catalyzed hydrosilylation of the carbon–carbon double bond with dimethylphenylsilane and (B) the sequential reactions of the reverse order. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009