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     

Synthesis and photo‐polymerization of bio‐based furanic compounds functionalized by 2‐hydroxypropyl methacrylate group(s)

Bio‐based compounds (FmHPM and FdHPM) with a furan backbone and photo‐polymerizable 2‐hydroxypropyl methacrylate (HPM) group(s) were synthesized from carbohydrate‐derived furanyl alcohols (furan‐2‐methanol and furan‐2,5‐dimethanol) and their photo‐polymerizing behaviors and mechanical properties after photo‐polymerization were investigated. Half time values (t_1/2) of bio‐based FmHPM and FdHPM were 10.4 s and 3.0 s and their shrinkage ratios were 3.0 and 6.1% during photo‐polymerization, respectively. Tensile‐shear strength of glass and polycarbonate joints bonded by bio‐based furanic compounds appeared in range of 0.2–0.6 MPa and pencil hardness of film coated by bio‐based furanic compounds after photo‐polymerization showed 2H–3H. Newly synthesized bio‐based furanic compounds allowed the feasibility to alternate petroleum‐based Bis‐GMA/TEGDMA, photo‐polymerizable composition widely utilized in a variety of applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of poly(methyl methacrylate‐co‐butyl methacrylate) nanoparticles and their reinforcing effect on natural rubber

Poly(methyl methacrylate‐co‐butyl methacrylate) [P(MMA‐co‐BMA)] nanoparticles were synthesized via emulsion polymerization, and incorporated into natural rubber (NR) by latex compounding. Monodispersed, core‐shell P(MMA‐co‐BMA)/casein nanoparticles (abbreviated as PMBMA‐CA) were produced with casein (CA) as surfactant. The chemical structure of P(MMA‐co‐BMA) copolymers were confirmed by ¹H‐NMR and FTIR analyses. Transmission electron microscopy demonstrated the core–shell structure of PMBMA‐CA, and PMBMA‐CA homogenously distributed around NR particles, indicating the interaction between PMBMA‐CA and NR. As a result, the tensile strength and modulus of NR/PMBMA‐CA films were significantly enhanced. The tensile strength was increased by 100% with 10% copolymer addition, when the molar ratio of MMA:BMA was 8:2. In addition, scanning electron microscopy and atomic force microscopy results presented that the NR/PMBMA‐CA films exhibited smooth surfaces with low roughness, and PMBMA‐CA was compatible with NR. FTIR‐ATR analyses also suggested fewer PMBMA‐CA nanoparticles migrated out of NR. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43843.     

Preparation of poly(butyl methacrylate)/γ‐Al2O3 nanocomposites via ultrasonic irradiation

A new technique (ultrasonic irradiation) has been employed to prepare poly(n‐butyl methacrylate) PBMA/γ‐Al₂O₃ nanocomposites, taking advantages of the multiple effects of ultrasonic irradiation, such as dispersion, pulverization and activation. When subjected to ultrasonic irradiation, n‐butyl methacrylate (BMA) is polymerized to form poly(n‐butyl methacrylate) (PBMA) latex without any chemical initiators, and the monomer conversion reaches 72.5% in 25 min. At an appropriate pH, surfactant bilayers are formed through electrostatic interactions between γ‐Al₂O₃ nanoparticles and the anionic surfactant sodium dodecyl sulfate (SDS), which adsorb BMA. After ultrasonic induced polymerization of BMA in the presence of nanoparticles of γ‐Al₂O₃, the γ‐Al₂O₃ nanoparticles are encapsulated by PBMA shells formed. The influence of factors such as pH, surfactant concentration and the nanoparticle content is investigated. The FTIR spectra show that there are still polymers tightly adsorbed by nanoparticles even after extraction by acetone for 72 h. The difference observed in the XPS spectra of nanocomposite residues and the pure γ‐Al₂O₃ nanoparticles may indicate some interactions between γ‐Al₂O₃ nanoparticles and the PBMA matrix. Furthermore, the feasibility of SDS bilayer formation and encapsulating polymerization is proven by XPS characterization. © 2001 Society of Chemical Industry     

Synthesis of Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate copolymers and their application on cotton fabrics

Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate (FOM)/ethyl acrylate (EA)/methyl methacrylate (MMA) copolymer (FOME) latexes, FOM/butyl acrylate (BA)/MMA copolymer (FOMB) latexes, and FOM/octyl acrylate (OA)/MMA copolymer (FOMO) latexes were synthesized by continuous emulsion polymerization. Solution polymerization was also carried out to prepare FOMB. The influences of fluorine content and curing conditions on the surface properties of polymer films were discussed. The water and oil repellency of cotton fabrics treated with the FOM copolymers was better than that of conventional poly(fluoroalkyl acrylate)s containing the same fluorinated chain. The polymer films or the treated fabrics were characterized by Fourier transform infrared, scanning electron microscope, atomic force microscopy, thermogravimetric analysis, x‐ray photoelectron spectrometry, and wide angle x‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

Radical polymerization of n‐butyl methacrylate initiated by stibonium ylide

1,2,3,4‐Tetraphenylcyclopentadiene triphenyl stibonium ylide initiated radical polymerization of n‐butyl methacrylate (n‐BMA) in dioxane at (60 ± 0.2)°C for 90 min under nitrogen atmosphere has been carried out. The system follows nonideal kinetics, i.e., R_p α [ylide]^0.2 [n‐BMA]^1.8. The value of k/k_t and overall energy of activation have been computed as 0.133 × 10^?2 L mol^?1 s^?1, 33 kJ/mol, respectively. The FTIR spectrum shows a band at 1745 cm^?1 due to acrylate group of n‐BMA. The ¹H NMR spectrum shows a peak of two magnetically equivalent protons of methylene group at 2.1 δ ppm. The DSC curve shows glass transition temperature (T_g) as 41°C. The presence of six hyperfine lines in ESR spectrum indicates that the system follows free radical polymerization and the initiation is brought about by phenyl radical. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2457–2463, 2007     

New self‐crosslinkable copolymers based on N‐methyl‐N‐vinylbenzylpyrrolidinium halide and methyl methacrylate

Thermally‐induced self‐crosslinking behaviour has been found in copolymers containing N‐methyl‐N‐vinylbenzylpyrrolidinium chloride (MVBPC) and methyl methacrylate (MMA). NMR, IR and low molecular weight model reactions demonstrate that this crosslinking reaction occurs between the methyl ester groups of the MMA units and the quaternary ammonium salts, with the resulting benzyl esters forming chemical links between the MVBPC and MMA units with the formation of N,N‐dimethylpyrrolidinium chloride. Similar crosslinking behaviour has also been found when the Cl⁻ anion is replaced by Br⁻ and I⁻, but not in the case of BF as counter anion. © 2000 Society of Chemical Industry     

A comprehensive kinetic model for high‐temperature free radical production of styrene/methacrylate/acrylate resins

n‐Butyl methacrylate/styrene/n‐butyl acrylate (BMA/ST/BA) high‐temperature starved‐feed solution semibatch copolymerization and terpolymerization experiments with varying monomer feed composition, final polymer content, monomer feed time, and reaction temperature were carried out. A comprehensive mechanistic terpolymerization model implemented in PREDICI includes methacrylate depropagation, acrylate backbiting, chain scission, and macromonomer propagation, as well as penultimate chain‐growth and termination kinetics. The generality of the model was verified by comparison with terpolymerization data sets from two laboratories that demonstrate the impact of high‐temperature secondary reactions on polymerization rate and polymer molecular weight. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Water‐soluble dual responsive polythiophene‐g‐poly(methoxyethoxy ethyl methacrylate)‐co‐poly(N,N‐diethylamino ethyl methacrylate) for different applications

Polythiophene (PT) based dual responsive water‐soluble graft copolymer (PT‐g‐[poly(methoxyethoxy ethyl methacrylate)‐co‐poly(N,N‐diethylamino ethyl methacrylate)]) (PT‐g‐P(MeO₂MA‐co‐DEAEMA)) (PTDE) has been synthesized by random copolymerization of methoxyethoxy ethyl methacrylate (MeO₂MA) and N,N‐diethylamino ethyl methacrylate (DEAEMA) at 30 °C on the 2,5‐poly(3‐[1‐ethyl‐2‐(2‐ bromoisobutyrate)] thiophene) (PTI) macroinitiator using the Cu based atom transfer radical polymerization technique. The PTDE graft copolymer was characterized by gel permeation chromatography and ¹H NMR techniques and it exhibits thermo‐reversible solubility in water showing a lower critical solution temperature of ca 42 °C in neutral aqueous solution. The PTDE graft copolymer contains a fluorescent PT backbone, and interestingly the system exhibits doubling of fluorescence intensity with rising temperature over the temperature range 41–45 °C at pH 7. The PTDE system therefore acts following the principle of the polymeric AND logic gate and it is also found to be effective in sensing of nitroaromatics, particularly picric acid. The influence of chain hydrophobicity on the logic operation and on the sensing of nitroaromatics is discussed. © 2014 Society of Chemical Industry     

Synthesis,characterization, and swelling behavior of new pH‐sensitive hydrogels derived from copolymers of 2‐hydroxyethyl methacrylate and 2‐(diisopropylamino)ethylmethacrylate

The aim of this work was to synthesize and to characterize new pH‐sensitive hydrogels that can be used in the controlled release of drugs, useful for dermal treatments or ophthalmology's therapies. Copolymers containing 2‐hydroxyethyl methacrylate (HEMA) with different amounts of 2‐(diisopropylamino)ethyl methacrylate (DPA) (10 and 30 wt %) and different amounts of crosslinker agent, ethylene glycol dimethacrylate (EGDMA) (1 and 3 wt %) were prepared by bulk photo‐polymerization. The copolymers were fully characterized by using Fourier‐transform infrared (FTIR) spectra, differential scanning calorimetry, thermogravimetric analysis, UV–visible spectroscopy, and measuring water content and dynamic swelling degree. The results show that modifications in the amount of DPA and/or crosslinker in the hydrogel produce variations in the thermal properties. When adding of DPA, we observed an increase in the thermal stability and decomposition temperature, as well as a change in the mechanism of decomposition. Also a decrease in the glass transition temperature was observed with regard to the value for pure pHEMA, by the addition of DPA. The water content of the hydrogels depends on the DPA content and it is inversely proportional to both the pH value and the crosslinking degree. Pure poly‐HEMA films did not show important changes over the pH range studied in this work. The dynamic swelling curves show the overshooting effect associated with the incorporation of DPA, the pH of the solution, and the crosslinking density. On the other hand, no important variations in the optical properties were observed. The synthesized hydrogels are useful as a drug delivery pH‐sensitive matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 1. Preparation of narrow polydispersity copolymers of methyl methacrylate and 2‐hydroxyethyl methacrylate by atom‐transfer radical polymerization

Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by ¹H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the ¹H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry     

Investigation of microstructure of the N‐vinyl‐2‐pyrrolidone/methyl methacrylate copolymers by NMR spectroscopy

The copolymers containing N‐vinyl‐2‐pyrrolidone (V) and methyl methacrylate (M) units of different compositions were synthesized by free radical bulk polymerization. The copolymer composition of these copolymers was determined by CHN analysis. The distortionless enhancement by polarization transfer (DEPT) technique was used to resolve the methine, methylene, and methyl resonance signals in the V/M copolymer. Comonomer reactivity ratios were determined by the Kelen–Tudos (KT) and nonlinear least‐square error‐in‐variable (EVM) methods. ¹H–¹³C Heteronuclear shift quantum correlation spectroscopy (HSQC) and ¹H–¹H homonuclear total correlation spectroscopy (TOCSY) spectra were used for the resolution of the proton nuclear magnetic resonance (¹H NMR) spectrum of the V/M copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1328–1336, 2002     

Properties of n‐butyl methacrylate copolymer latex films derived from crosslinked latex particles

Films obtained from copolymer latexes of n‐butyl methacrylate (BMA) with a series of crosslinking monomers [i.e., a macromonomer crosslinker (Mac), ethylene glycol dimethacrylate (EGDMA), and aliphatic urethane acrylate] exhibited differences in their tensile properties and swelling behaviors. For P(BMA‐co‐EGDMA) copolymer, a dependence on the initiator type was obtained. It is postulated that the network microstructures for the various copolymers evolved as the result of the copolymerization reactions between the monomer pairs during the synthesis in the miniemulsion free‐radical copolymerization. These network microstructures are, therefore, hypothesized to influence the mechanical properties of the resultant films. Copolymers prepared with Mac were tough in comparison with copolymers made with EGDMA. The presence of longer linear or lightly crosslinked poly(n‐butyl methacrylate) (PBMA) chains and the looseness of the crosslinked network structures in the PBMA‐co‐Mac copolymers appear to be the factors responsible for the differences. All of the copolymer films disintegrated into swollen individual microgels when they were immersed in tetrahydrofuran. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 42–49, 2003     

Studies on atom transfer radical emulsion polymerization of n‐butyl methacrylate

Atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in water‐borne media, catalyzed and initiated by CuCl/4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) and Ethyl 2‐bromopropinate (BrCH₃CHCOOC₂H₅₎ was conducted. The influence of several factors, such as the amount of surfactant, catalyst, initiator and the reaction time, temperature on the stability of the latexes and the control of the polymerization was investigated. The nucleation mechanism of the latexes, thermodynamic data and activation parameters for the ATRP emulsion polymerization of BMA were also reported. POLYM. ENG. SCI. 45:297–302, 2005. © 2005 Society of Plastics Engineers.     

Synthesis,characterization, and thermal degradation of novel poly(2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate)

A novel methacrylate monomer containing benzofuran side group, 2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate (BOEMA), was synthesized from esterification reaction of 2‐bromo‐1‐(5‐bromo benzofuran‐2‐yl) ethanone with sodium methacrylate at 85°C in the presence of 1,4‐dioxane solvent. After characterization with Fourier transform infrared spectrophotometer, nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), its homopolymerization was carried out by free radical polymerization at 60°C in the presence of benzoyl peroxide initiator and 1,4‐dioxane solvent. The glass transition temperature (T_g) of the synthesized novel polymer, poly(2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate) [poly(BOEMA)], was determined to be 137°C with differential scanning calorimetry technique. Thermal degradation kinetics of poly(BOEMA) was investigated by thermogravimetric analysis method at different heating rates with 5°C/min intervals between measurements. From dynamic measurements, the analysis of each process mechanism of Coats–Redfern and Van Krevelen methods showed that the most probable model for the decomposition process of poly(BOEMA) homopolymer agrees with the random nucleation, F₁ mechanism. The apparent decomposition activation energies of poly(BOEMA) by Kissinger's and Flynn–Wall–Ozawa methods in the studied conversion range were 188.47 and 180.13 kJ/mol, respectively. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Synthesis and characterization of polyrotaxanes comprising α‐cyclodextrins and poly(ε‐caprolactone) end‐capped with poly(butyl methacrylate)s

Biodegradable polyrotaxane‐based triblock copolymers were synthesized via the bulk atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) initiated with polypseudo‐rotaxanes (PPRs) built from a distal 2‐bromoisobutyryl end‐capped poly(ε‐caprolactone) (Br‐PCL‐Br) with α‐cyclodextrins (α‐CDs) in the presence of Cu(I)Br/N,N,N′,N″,N″‐pentamethyldiethylenetriamine at 45 ºC. The structure was characterized in detail by means of ¹H NMR, gel permeation chromatography, wide‐angle X‐ray diffraction, DSC and TGA. When the feed molar ratio of BMA to Br‐PCL‐Br was changed from 128 to 300, the degree of polymerization of PBMA blocks attached to two ends of the PPRs was in the range 382 ? 803. Although about a tenth of the added α‐CDs were still threaded onto the PCL chain after the ATRP process, the movable α‐CDs made a marked contribution to the mechanical strength enhancement, blood anticoagulation activity and protein adsorption repellency of the resulting copolymers. Meanwhile, they could also protect the copolymers from the attack of H₂O and Lipase AK Amano molecules, exhibiting a lower mass loss as evidenced in hydrolytic and enzymatic degradation experiments. © 2013 Society of Chemical Industry     

Preparation and characterization of cyhalothrin‐loaded poly(2‐hydroxyethyl methacrylate)‐co‐polylactide (PHEMA‐co‐PLA) ultrafine particles

Poly(2‐hydroxyethyl methacrylate)‐co‐polylactide (PHEMA‐co‐PLA) and its corresponding cyhalothrin‐loaded ultrafine particles were successfully synthesized and prepared, respectively. The chemical structures of the copolymers have been confirmed by Fourier transform infrared spectroscopy (FTIR), ¹H‐nuclear magnetic resonance (¹H‐NMR), ¹³C‐nuclear magnetic resonance (¹³C‐NMR), and thermogravimetric analysis (TGA). Furthermore, the particle size, the cyhalothrin loading content (LC), and the cyhalothrin release behavior were investigated. PHEMA‐co‐PLA proved to be a good material for the preparation of ultrafine particles for lipophilic pesticide delivery. The developed cyhalothrin‐loaded PHEMA‐co‐PLA ultrafine particles showed good dispersity in water and sustained release behavior. In addition, it is easy to be prepared by both nanoprecipitation method and emulsion/solvent evaporation method. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization, and UV‐curing properties of silicon‐containing (Meth)acrylate monomers

Eight different silicon‐containing (meth)acrylate monomers are synthesized by the substitution reaction of chlorosiloxanes with 2‐hydroxyethyl methacrylate or 2‐hydroxyethyl acrylate. Their molecular structures are confirmed by IR, ¹H‐NMR, and ¹³C‐NMR spectroscopic analyses. The effects of silicon content on the UV‐curing behavior, physical, surface, and thermal properties are investigated. The UV‐curing behavior is analyzed by photo differential scanning calorimetry. The surface free energy of the UV‐cured film is calculated from contact angles measured using the Lewis acid‐base three liquids method. The silicon‐containing (meth)acrylate monomers perform much better than traditional (meth)acrylate monomers on UV‐curing. The silicon‐containing monomers have higher final conversions and fast UV‐curing rates in photopolymerization. The surface free energy decreases with increasing silicon content, because silicon in the soft segment is transferred to the surface, producing a UV‐cured film; this is confirmed by X‐ray photoelectron spectroscopy measurements. All these advantageous properties enable these synthetic silicon‐containing monomers to perform better in applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of PMMA‐b‐PBMA block copolymers by atom transfer radical polymerization

The synthesis of diblock copolymers using atom transfer radical polymerization, ATRP, of n‐butyl methacrylate, BMA, and methyl methacrylate, MMA, is reported. These copolymers were prepared from 2‐bromoisobutyryl‐terminated macroinitiators of poly(MMA) and poly(BMA), using copper chloride, CuCl,/N,N,N′,N″,N″‐pentamethyldiethylenetretramine, PMDETA, as the catalyst system, at 100°C in bulk and in benzonitrile solution. The block copolymers were characterized by means of size‐exclusion chromatography, SEC, and ¹H‐NMR spectroscopy. The SEC analysis of the synthesized diblock copolymers confirmed important differences in the molecular weight control depending on the reaction medium (solvent effect) and the chemical structure of the macroinitiator used. In addition, differential scanning calorimetry, (DSC) measurements were performed, showing for all the copolymers a phase separation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2683–2691, 2002     

Synthesis,characterization, and reactivity ratios of copolymers derived from 4‐nitrophenyl acrylate and n‐butyl methacrylate

Free‐radical copolymerization of 4‐nitrophenyl acrylate (NPA) with n‐butyl methacrylate (BMA) was carried out using benzoyl peroxide as an initiator. Seven different mole ratios of NPA and BMA were chosen for this study. The copolymers were characterized by IR, ¹H‐NMR, and ¹³C‐NMR spectral studies. The molecular weights of the copolymers were determined by gel permeation chromatography and the weight‐average (M _w) and the number‐average (M _n) molecular weights of these systems lie in the range of 4.3–5.3 × 10⁴ and 2.6–3.0 × 10⁴, respectively. The reactivity ratios of the monomers in the copolymer were evaluated by Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos methods. The product of r₁, r₂ lies in the range of 0.734–0.800, which suggests a random arrangement of monomers in the copolymer chain. Thermal decomposition of the polymers occurred in two stages in the temperature range of 165–505°C and the glass transition temperature (T_g) of one of the systems was 97.2°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1817–1824, 2003