Synthesis,modification, and porous properties of new glycidyl methacrylate copolymers

Synthesis, copolymerization, and physicochemical properties of new, of different degrees of crosslinker tetrafunctional bis[4(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide and glycidyl methacrylate copolymers are presented. The monomers were used for the synthesis of porous microspheres in the presence of pore‐forming diluents, decan‐1‐ol, and toluene. Influence of diluents composition on their porous structures was studied. Porous structure of the obtained microspheres in dry (from nitrogen adsorption–desorption measurements) states was studied. Their chemical structures were studied by the use of Fourier transform infrared. The number of epoxy groups of the obtained copolymers, their thermal properties (thermogravimetric analysis), and swelling characteristics in 10 solvents of different chemical nature were examined. Selected copolymers were modified by amines in the epoxide ring‐opening reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies on synthesis and physicochemical properties of new bis[4‐(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide terpolymers

Synthesis and physicochemical properties of the new glycidyl methacrylate, styrene, and bis[4(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide terpolymers of different crosslinking degrees are presented. The terpolymers were obtained in the form of regular microspheres by suspension polymerization. The epoxy group content, thermal properties (DSC, thermogravimetric analysis), and swelling characteristic of the functional microspheres were examined. In addition, a selected terpolymer was modified in the epoxide ring opening reaction with diethylenetriamine. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of a new tetrafunctional monomer, 1,4‐di(2‐hydroxy‐3‐methacryloyloxypropoxy)phenol,and its copolymerization

The new aromatic tetrafunctional methacrylate monomer, 1,4‐di(2‐hydroxy‐3‐methacryloyloxypropoxy) phenol, and its application for the synthesis of porous microspheres have been presented. It was copolymerized with trimethylolpropane trimethacrylate in the presence of pore‐forming diluents mixture (chlorobenzene and 1‐decanol). The results indicate that composition of diluents mixture influence porous structure of copolymers. The porous structure of the copolymer obtained in the presence of 50% chlorobenzene was studied in detail. The results show that pore volume and the most probable pore size diameters determined for the copolymer in the dry and in the wetted states are different. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Micropatterning of polymethacrylates by single‐ or two‐photon irradiation using π‐conjugated o‐nitrobenzyl ester phototrigger as side chains

A new single‐/two‐photon sensitive monomer, (E)‐5‐(4‐ethoxystyryl)?2‐nitrobenzyl methacrylate (ENbMA), was synthesized and copolymerized with methyl methacrylate (MMA) to form a series of photosensitive copolymers P(ENbMA–MMA)s that were well characterized by ¹H NMR and GPC. The photochemical and photophysical properties of both photosensitive monomer and copolymers upon visible light irradiation were studied by UV–Vis, FTIR, and HPLC spectra, which confirmed that 5‐(4‐ethoxystyryl)‐2‐nitrobenzyl ester can be photolyzed effectively with generation of the corresponding 5‐(4‐ethoxystyryl)‐2‐nitrosobenzaldehyde and carboxylic acid groups. The successful photocleavage endowed the optimized copolymers with excellent micropatterning property due to the effective generation of alkaline‐soluble carboxylic acid groups. Moreover, the high two‐photon absorption cross‐sections (over 20 GM at 800 nm) and the comparable photolysis upon two‐photon NIR light irradiation of the chromophores provided the copolymers with significant application in two‐photon microfabrication. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4099–4106, 2013     

4‐chloro‐3‐methylphenyl methacrylate copolymers with 2,4‐dichlorophenyl methacrylate: Synthesis,characterization, and antimicrobial activity

4‐Chloro‐3‐methylphenyl methacrylate (CMPM) and 2,4‐dichlorophenyl methacrylate (2,4‐DMA) were synthesized by reacting methacryloyl chloride with 4‐chloro‐3‐methylphenol (CMP) and 2,4‐dichlorophenol (2,4‐DP), respectively. Homo and copolymers of CMPM and 2,4‐DMA were obtained from different monomer feed ratios, using 2,2′‐azobisisobutyronitrile as initiator in toluene at 70°C. IR‐spectroscopy was employed to characterize the resulting homo and copolymers. Copolymer compositions were determined by ultraviolet (UV) spectroscopy. Fineman–Ross method was used to calculate the reactivity ratios of the monomers. Average molecular weight and polydispersity index were obtained by gel permeation chromatography (GPC). Thermogravimetric analyses (TGA) and differential thermal analysis (DTA) of copolymers were carried out under a nitrogen atmosphere. Antimicrobial effects of the homo and copolymers were also investigated for various microorganisms such as bacteria, fungi, and yeast. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:439–448, 2006     

Synthesis,characterization and conformational transitions in copolymers of 2‐(o‐chlorophenyl)‐4‐methylene‐1,3‐dioxolane with vinyl monomers

Copolymers of 2‐(o‐chlorophenyl)‐4‐methylene‐1,3‐dioxolane with methyl methacrylate and styrene were synthesized in benzene at 85 °C in the presence of 2,2′‐azobisisobutyronitrile as initiator. The structure of the resulting copolymers was investigated and a polymerization mechanism was proposed. The intrinsic viscosity of the copolymers in dilute solutions of carbon tetrachloride was determined as a function of temperature and conformational transitions were investigated. Copyright © 2004 Society of Chemical Industry     

Vesicular and micellar self‐assembly of stimuli‐responsive poly(N‐isopropyl acrylamide‐b‐9‐anthracene methyl methacrylate) amphiphilic diblock copolymers

Dually responsive amphiphilic diblock copolymers consisting of hydrophilic poly(N‐isopropyl acrylamide) [poly(NIPAAm)] and hydrophobic poly(9‐anthracene methyl methacrylate) were synthesized by reversible addition fragmentation chain‐transfer (RAFT) polymerization with 3‐(benzyl sulfanyl thiocarbonyl sulfanyl) propionic acid as a chain‐transfer agent. In the first step, the poly(NIPAAm) chain was grown to make a macro‐RAFT agent, and in the second step, the chain was extended by hydrophobic 9‐anthryl methyl methacrylate to yield amphiphilic poly(N‐isopropyl acrylamide‐b‐9‐anthracene methyl methacrylate) block copolymers. The formation of copolymers with three different hydrophobic block lengths and a fixed hydrophilic block was confirmed from their molecular weights. The self‐assembly of these copolymers was studied through the determination of the lower critical solution temperature and critical micelle concentration of the copolymers in aqueous solution. The self‐assembled block copolymers displayed vesicular morphology in the case of the small hydrophobic chain, but the morphology gradually turned into a micellar type when the hydrophobic chain length was increased. The variations in the length and chemical composition of the blocks allowed the tuning of the block copolymer responsiveness toward both the pH and temperature. The resulting self‐assembled structures underwent thermally induced and pH‐induced morphological transitions from vesicles to micelles and vice versa in aqueous solution. These dually responsive amphiphilic diblock copolymers have potential applications in the encapsulation of both hydrophobic and hydrophilic drug molecules, as evidenced from the dye encapsulation studies. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46474.     

Microphase separation behavior on the surfaces of poly(dimethylsiloxane)‐block‐poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) diblock copolymer coatings

Microphase separation behavior on the surfaces of poly(dimethylsiloxane)‐block‐poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) (PDMS‐b‐PHFBMA) diblock copolymer coatings was investigated. The PDMS‐b‐PHFBMA diblock copolymers were successfully synthesized via atom transfer radical polymerization (ATRP). The chemical structure of the copolymers was characterized by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Surface composition was studied by X‐ray photoelectron spectroscopy. Copolymer microstructure was investigated by atomic force microscopy. The microstructure observations show that well‐organized phase‐separated surfaces consist of hydrophobic domain from PDMS segments and more hydrophobic domain from PHFBMA segments in the copolymers. The increase in the PHFBMA content can strengthen the microphase separation behavior in the PDMS‐b‐PHFBMA diblock copolymers. And the increase in the annealing temperature can also strengthen the microphase separation behavior in the PDMS‐b‐PHFBMA diblock copolymers. Moreover, Flory‐Huggins thermodynamic theory was preliminarily used to explain the microphase separation behavior in the PDMS‐b‐PHFBMA diblock copolymers.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of composition on morphology structure and cell affinity of poly(caprolactone‐co‐glycolide)‐co‐poly(ethylene glycol) microspheres

Poly(caprolactone‐co‐glycolide)‐co‐poly(ethylene gylcol) copolymers (PCEG) with various composition were synthesized by copolymerization of GA, CL, and PEG. PCEG microspheres were fabricated by oil‐in‐water (o/w) emulsion and solvent‐evaporation technique. Effect of chemical composition on hydrophilicity, crystallinity, and degradation of the PCEG was investigated. It was demonstrated that morphology structure of the microspheres was greatly influenced by chemical composition and hydrophilicity of the PCEG polymer. PCEG microspheres could change from a smooth structure to a regular porous structure and an irregular structure. Moreover, the pore size of them increased with increment of PEG content and length. Cell attachment and growth on the PCEG microspheres were evaluated by using mouse NIH 3T3 fibroblasts as model cells in vitro. The result showed that the PCEG microspheres with large porous structure were more favorable for cell attachment and growth. Thus the PCEG microspheres with rapid degradation rate and large porous structure possess potential use as injectable scaffolds in tissue engineering. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42861.     

Self‐assembled nanostructures: preparation,characterization, thermal,optical and morphological characteristics of amphiphilic diblock copolymers based on poly(2‐hydroxyethyl methacrylate‐block‐N‐phenylmaleimide)

A series of well‐defined amphiphilic poly[(2‐hydroxyethyl methacrylate)‐block‐(N‐phenylmaleimide)] diblock copolymers containing hydrophilic and hydrophobic blocks of different lengths were synthesized by atom transfer radical polymerization. The properties of the diblock copolymers and their ability to form large compound spherical micelles are described. Their optical, morphological and thermal properties and self‐assembled structure were also investigated. The chemical structure and composition of these copolymers have been characterized by elemental analysis, Fourier transform infrared, ¹H NMR, UV–visible and fluorescence spectroscopy, and size exclusion chromatography. Furthermore, the self‐assembly behavior of these copolymers was investigated by transmission electron microscopy and dynamic light scattering, which indicated that the amphiphilic diblock copolymer can self‐assemble into micelles, depending on the length of both blocks in the copolymers. These diblock copolymers gave rise to a variety of microstructures, from spherical micelles, hexagonal cylinders to lamellar phases. © 2013 Society of Chemical Industry     

Synthesis of graft copolymers. II. Synthesis of polystyrene‐g‐poly(methyl methacrylate)

The thermolysis of labile 1,2‐bis(trimethylsilyloxy)tetraphenylethane groups pendant along polystyrene chains in the presence of various vinyl monomers leads to the direct synthesis of graft copolymers. Depending on the monomer chosen, the polymerization temperature, and the number of active sites by the macroinitiator molecule, crosslinked or total soluble graft copolymers can be prepared. Several conditions were studied in order to attain soluble polystyrene‐g‐poly(methyl methacrylate) copolymers under a controlled polymerization mechanism. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 12–18, 2002     

Binary copolymerization of 4‐methyl‐1,3‐pentadiene with styrene,butadiene and isoprene catalysed by a titanium [OSSO]‐type catalyst

Binary copolymerization of 4‐methyl‐1,3‐pentadiene (4MPD) with styrene, butadiene and isoprene promoted by the titanium complex dichloro{1,4‐dithiabutanediyl‐2,2′‐bis[4,6‐bis(2‐phenyl‐2‐propyl)phenoxy]}titanium activated by methylaluminoxane is reported. All the copolymers are obtained in a wide range of composition and the molecular weight distributions obtained from gel permeation chromatographic analysis of the copolymers are coherent with the materials being copolymeric in nature. The copolymer microstructure was fully elucidated by means of ¹H NMR and ¹³C NMR spectroscopy. Differential scanning calorimetry shows an increase of glass transition temperature (T_g) with the amount of 4MPD in the copolymers with butadiene and isoprene, while in the copolymers with styrene T_g is increased on increasing the amount of styrene. © 2016 Society of Chemical Industry     

Synthesis and characterization of ABA‐type triblock copolymers derived from polyimide and poly(2‐methyl‐2‐adamantyl methacrylate)

ABA‐type triblock copolymers derived from 4,4‐(hexafluoroisopropylidene)diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine and 2‐methyl‐2‐adamantyl methacrylate (2‐MAdMA) were synthesized via atom transfer radical polymerization. The component ratios of polyimide (PI) and poly(2‐MAdMA) (PMAdMA) were about 8/2, 6/4 and 3/7, as determined using ¹H NMR spectroscopy and thermogravimetric analysis (TGA). The film structure of the triblock copolymers was dependent on the PI structure. Hydrophobicity increased as the component ratio of PMAdMA increased. Based on TGA, three‐step decomposition behaviors of all triblock copolymers derived from PI and PMAdMA in nitrogen and air atmosphere were observed. The gas permeability of the triblock copolymers was lower than that of PI. This finding can be attributed to the decrease in fractional free volume by the adamantane component and the decrease in permeability of the triblock copolymers compared with PI. The dielectric constant of the triblock copolymers was lower than that of PI. The dielectric constant was dependent on molar volume and molar porlarizability, and the dielectric constant derived from the symmetric structure of adamantane was reduced. The ABA‐type triblock copolymers derived from PI and PMAdMA can be considered as new polymer materials with high hydrophobicity, high H₂/CO₂ selectivity and low dielectric constant. © 2013 Society of Chemical Industry     

Preparation and characterization of copolymers containing (+)‐bornyl methacrylate and their racemate for positive‐tone photoresist

This study investigated the chemical behavior of polymers bearing cycloaliphatic bornyl units along with the steric difference of the chiral (+)‐bornyl methacrylate [(+)‐BMA] and racemic (±)‐BMA, expressed in the physical properties of the copolymers and the resist characteristics. To do this, a series of copolymers containing (+)‐bornyl methacrylate [(+)‐BMA] and (±)‐BMA] units was synthesized. Comonomers of tert‐butyl methacrylate (TBMA), methyl methacrylate (MMA), and maleic anhydride (MA) were used. The thermogravimetric curves, glass‐transition temperature (T_g), and molecular weight (MW) of the copolymers were evaluated. Exposure characteristics of chemical‐amplified positive photoresists comprising various copolymers were investigated. It was found that copolymers bearing (±)‐BMA have higher T_g and better thermostability than those of copolymers containing (+)‐BMA units. The copolymers with (±)‐BMA units, however, revealed an inert photochemical behavior on the positive‐tone photoresist. The patterning properties of the positive photoresist, composed of copolymers bearing (+)‐BMA and (±)‐BMA, and the photoacid generator (PAG) were also investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3538–3544, 2001     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006     

Characterization of macroporous 1‐vinyl‐2‐pyrrolidone copolymers obtained by suspension polymerization

Radical suspension copolymerization of 1‐vinyl‐2‐pyrrolidone (VP) with three different cross‐linkers: divinylbenzene (DVB), trimethylolpropane trimethacrylate (TRIM), and di(methacryloxymethyl) naphthalene (DMN) was used to prepare macroporous microspheres. During the copolymerization, the mixture of toluene and n‐dodecane as a pore‐forming diluent was used. All samples were characterized in terms of particle size and distribution, nitrogen content, specific surface area total pore volume, and pore size distribution. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and the type of cross‐linker and achieves value from 27 to 845 m²/g. To determine the influence of chemical structure of cross‐linkers on the selectivity and polarity of the copolymers, inverse gas chromatography was applied. In addition, VP–DVB and VP–DMN copolymers were modified by sulfonation into cation‐exchangers with cation exchange capacity equal 1.98 and 2.31 mmol/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Reaction of phenol‐ and thiophenol‐terminated compounds with bisoxazolines

Bulk reactions of phenolic compounds (bisphenol‐A and α,ω‐diphenol oligosulfone) or thiols (thiophenol and bis(4‐mercaptophenyl)sulfide) with bisoxazoline coupling agents, namely 2,2'‐(1,3‐phenylene)bis(2‐oxazoline) ( mbox ), 2,2'‐(1,4‐phenylene)bis(2‐oxazoline) ( pbox ), and 2,2'‐(2,6‐pyridylene)bis(2‐oxazoline) ( pybox ), were carried out in the bulk at 140–240°C. The reactions were followed by viscosimetry, size exclusion chromatography, and ¹H‐ and ¹³C‐NMR spectroscopy. The phenol/bisoxazoline bulk reactions at 240°C required the presence of sodium methoxide catalyst. Bisoxazoline pybox gave the best results in this case. Thiol and dithiol/bisoxazoline reactions were faster and did not require any catalyst. High‐molar‐mass polymers were obtained within 5 min at 200°C while using bis(4‐mercaptophenyl)sulfide (BMPS) and any of the bisoxazolines. The NMR spectra of model compounds and polymers were fully assigned, showing that the oxazoline/phenol and oxazoline/thiophenol (tph) polyaddition reactions proceed in the expected way, without any noticeable side reaction. All polymers were amorphous and displayed good thermal stability. Bisoxazolines were also used as coupling agents for the preparation of copolymers of BMPS and α,ω‐dicarboxy polyamide‐12 and for the preparation of polysulfone‐polyamide‐12 block copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and surface properties of polydimethylsiloxane‐based block copolymers: poly[dimethylsiloxane‐block‐ (ethyl methacrylate)] and poly[dimethylsiloxane‐block‐(hydroxyethyl methacrylate)]

A polydimethylsiloxane (PDMS) macroazoinitiator was synthesized from bis(hydroxyalkyl)‐terminated PDMS and 4,4′‐azobis‐4‐cyanopentanoic acid by a condensation reaction. The bifunctional macroinitiator was used for the block copolymerization of ethyl methacrylate (EMA) and 2‐(trimethylsilyloxy)ethyl methacrylate (TMSHEMA) monomers. The poly(DMS‐block‐EMA) and poly(DMS‐block‐TMSHEMA) copolymers thus obtained were characterized using Fourier transform infrared and ¹H NMR spectroscopy and differential scanning calorimetry. After the deprotection of trimethylsilyl groups, poly(DMS‐block‐HEMA) and poly(DMS‐block‐EMA) copolymer film surfaces were analysed using scanning electron microscopy and X‐ray photoelectron spectroscopy. The effects of the PDMS concentration in the copolymers on both air and glass sides of films were examined. The PDMS segments oriented and moved to the glass side in poly(DMS‐block‐EMA) copolymer film while orientation to the air side became evident with increasing DMS content in poly(DMS‐block‐HEMA) copolymer film. The block copolymerization technique described here is a versatile and economic method and is also applicable to a wide range of monomers. The copolymers obtained have phase‐separated morphologies and the effects of DMS segments on copolymer film surfaces are different at the glass and air sides. Copyright © 2010 Society of Chemical Industry     

Degradation and initiation polymerization mechanism of α‐methylstyrene‐containing macroinitiators

Copolymers obtained from radical copolymerization of α‐methylstyrene (AMS) and glycidyl methacrylate (GMA) behave as macroinitiators, when heated in the presence of a second monomer, giving rise to block copolymers. The relevant degradation and initiation polymerization mechanism of the macroinitiators were studied. Thermal depropagation of the macroinitiators generated monomers, identified by ¹H‐NMR, photoionization mass spectroscopy and FT‐IR. According to the results of structure analysis by GPC, ESR and NMR spectroscopy, the AMS‐GMA (head‐head) and AMS‐AMS (head‐head) bonds in the macroinitiators are easily scissored providing free radicals when the temperature is above 80°C. The radicals lead to subsequent polymerization of the second monomer, and thereby block copolymers are formed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of PMMA‐PTHF‐PMMA and PMMA‐PTHF‐PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly‐THF)‐polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF₆ and bis(4,4′ bromo‐methyl benzoyl) peroxide (BBP) or bis (3,5,3′,5′ dibromomethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly‐THF initiators with M_w varying from 7,500 to 59,000 Da. Poly‐THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF‐b‐MMA) block copolymers containing the peroxide group in the middle. Poly(MMA‐b‐THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA‐b‐PTHF‐b‐PMMA and PMMA‐b‐PTHF‐b‐PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT‐IR, DSC, TGA, ¹H‐NMR, and ¹³C‐NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 219–226, 2004