Sulfonated copoly(norbornene)s bearing sultone pendant groups and application as proton exchange membranes candidates

Novel copolynorbornenes bearing pendant sultone groups (designated as P(BN/SulNBOH) and P(BN/SulNBOMe)) have been successfully synthesized via copolymerization of functionalized norbornenes bearing sultones (designated as SulNBOH and SulNBOMe) with 2-butoxymethylene norbornene (BN). The catalyst system showed high catalyst activity (10⁴ g_polymer/mol_Ni·h) and the obtained copolymers have high molecular weight and a narrow molecular weight distribution. Furthermore, the achieved copolymers P(BN/SulNBOH) and P(BN/SulNBOMe) were converted into sulfonated copolymers sP(BN/NBOH) and sP(BN/NBOMe). Both sP(BN/NBOH) and sP(BN/NBOMe) membranes displayed low water uptake, high thermal properties, good mechanical properties, and better proton exchange membranes properties. The proton conductivities measured in the hydrated state at 80?°C ranged from 10^?5 to 7.19?×?10^?3?S·cm^?1.

Preparation and properties of bisphenol A‐based sulfonated poly(arylene ether sulfone) proton exchange membranes for direct methanol fuel cell

Novel bisphenol A‐based sulfonated poly(arylene ether sulfone) (bi A‐SPAES) copolymers were successfully synthesized via direct copolymerization of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone, 4,4′‐dichlorodiphenylsulfone, and bisphenol A. The copolymer structure was confirmed by Fourier transform infrared spectra and ¹H NMR analysis. The series of sulfonated copolymers based membranes were prepared and evaluated for proton exchange membranes (PEM). The membranes showed good thermal stability and mechanical property. Transmission electron microscopy was used to obtain the microstructures of the synthesized polymers. The membranes exhibit increased water uptake from 8% to 66%, ion exchange capacities from 0.41 to 2.18 meq/g and proton conductivities (25°C) from 0.012 to 0.102 S/cm with the degree of sulfonation increasing. The proton conductivities of bi A‐SPAES‐6 membrane (0.10–0.15 S/cm) with high‐sulfonated degree are higher than that of Nafion 117 membrane (0.095–0.117 S/cm) at all temperatures (20–100°C). Especially, the methanol diffusion coefficients of membranes (1.7 × 10^?8 cm²/s–8.5 × 10^?7 cm²/s) are much lower than that of Nafion 117 membrane (2.1 × 10^?6 cm²/s). The new synthesized copolymer was therefore proposed as a candidate of material for PEM in direct methanol fuel cell. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Syntheses and Properties of Novel Copolymers of Polylactide and Aliphatic Polycarbonate Based on Ketal-Protected Dihydroxyacetone

The novel random copolymers of L-LA and 2, 2-ethylenedioxy-1, 3-propanediol carbonate (EOPDC) were synthesized in bulk using Sn(Oct)₂ as a catalyst. The poly(EOPDC -co- L-LA)s obtained were characterized by FT IR, ¹H NMR, ¹³C NMR, GPC and DSC. The copolymers were obtained with yield of 87.9–95.6%. The number average molecular weight of the copolymer is 1.85–6.18 × 10⁴ with a polydispersity of 1.41–1.73. The properties of the copolymer including the enzymatic degradation by proteinase K and drug-controlled release property were also investigated. The results show that the degradation rate of the copolymers increases with increasing LA content in the copolymers.     

Syntheses and properties of novel copolymers of polycaprolactone and aliphatic polycarbonate based on ketal-protected dihydroxyacetone

The random copolymers of ε-caprolactone (CL) and 2,2-ethylenedioxy propane-1,3-diol carbonate (EOPDC) were synthesized in bulk at 120 °C using Sn(Oct)₂ as a catalyst. The poly(EOPDC-co–CL)s obtained were characterized by FT IR, ¹H NMR, ¹³C NMR, GPC and DSC. The copolymers were obtained with yield of 84.2–97.8 %. The number-average molecular weight of the copolymer is 2.75–7.76 × 10⁴ with a polydispersity of 1.52–1.68. The properties of the copolymer including the enzymatic degradation by Pseudomonas Cepacia lipase and drug-controlled release property were also investigated. The results showed that the copolymers are degradable at physiological conditions, and their degradation rate and release of Tegafur in the copolymers increase with increasing CL content in the copolymers.     

Water soluble copolymers. 54: N-isopropylacrylamide-co-acrylamide copolymers in drag reduction: Synthesis,characterization, and dilute solution behavior

Copolymers of N-isopropylacrylamide (IPAM) and acrylamide (AM) have been synthesized by free radical polymerization in deionized water using potassium persulfate as the initiator. Copolymer compositions were obtained by elemental analysis and ¹³C NMR. An r₁r₂ value of 0.99 indicates ideal copolymerization with random incorporation of the comonomers in the copolymers. Weight average molecular weights, second virial coefficients, diffusion coefficients, and average diameters were obtained via classical and quasielastic low angle laser light scattering. The molecular weights for all the copolymers and the homopolymers of IPAM and AM ranged from 2.2 × 10⁶ to 5.2 × 10⁶ g/mol. The second virial coefficients in deionized water increased with increasing acrylamide content in the copolymers. The dilute solution properties of the copolymers were studied by turbidimetry, microcalorimetry and viscometry. All the copolymers, with the exception of IPAM-40 (the copolymer synthesized with 40 mole% IPAM in the feed), showed lower critical solution temperatures below 100°C. The solution studies were performed in deionized water, 0.514 M NaCl, and 1 M urea. The properties of the IPAM copolymers were influenced by both hydrophobic associations and hydrogen bonding. In 0.2% (～7mM) sodium dodecyl sulfate, the alkyl chain of the surfactant molecules associates with the IPAM moieties on the copolymer backbone, leading to high intrinsic viscosities and the elevation of the LCST above 100°C.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Copolymerization of styrene and methyl methacrylate mediated by iron wire/N,N,N′,N′-tetramethyl-1,2-ethanediamine as catalyst in the presence of air

Random copolymers of P(MMA-co-styrene) were synthesized via single electron transfer-living radical polymerization (SET LRP) at 25 °C in N,N-dimethylformamide (DMF) and benzene using CCl₄ as initiator and Fe(0) wire/N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)/hydrazine (NH₂NH₂) complexes as catalyst in the presence of air. Fe(0) wire-mediated single electron transfer-living radical copolymerization of MMA and styrene represented a robust and versatile technique to synthesize the well-defined copolymers. The copolymerization rate was faster in DMF than in benzene, as determined by the apparent rate constants. The results showed that the copolymerization followed first-order kinetics model in the presence of polar DMF and non-polar benzene. The molecular weights increased linearly with the increase of monomer conversion with a narrow polydispersity index when the conversion was beyond 25 %. The polarity and the quantity of solvent had significant effects on the polymerization, and the apparent rate constants were 1.28 × 10^?4, 1.21 × 10^?4, and 9.23 × 10^?5 s^?1 in the order of DMF amount, 5, 10, and 15 mL. The conversion increased from 29.3 to 48.5 % and the polydispersity index (PDI) changed from 1.24 to 1.21 with [CCl₄]₀/[TMEDA]₀ molar ratio changing from 1:0.5 to 1:5. The chain extension experiment demonstrated that the copolymerization exhibited a living characteristic.     

UV light copolymerization of dimethyl vinylphosphonate with bisphenol A ethoxylate dimethacrylate

Dimethyl vinylphosphonate (DMVP), a very promising monomer, was copolymerized with acrylic monomer bisphenol A ethoxylate dimethacrylate (BEMA), in different molar ratios, by radical photoinitiated polymerization in the presence of photoinitiator Darocur 4265 (3 wt%) and in the absence of solvent. The UV light polymerization was an efficient method to obtain polymers in a green procedure. The molar ratio between DMVP and acrylic monomer BEMA varied between 1:1 and 5:1. The copolymers were characterized by FTIR, thermal analysis, water uptake and conductivity. From the ATR-FTIR spectra of DMVP-BEMA copolymers at the molar ratios of 1:1–5:1, it was observed that the intensity of P-O-C aliphatic band increased with increases in DMVP content. The synthesized copolymers showed good thermal stability in the range of 335–390 °C. DMVP:BEMA copolymer at 1:1 molar ratio displayed the highest stability, with decomposition temperature above 390 °C, the highest temperature in the series. The water uptake decreased with increases in DMVP content and this behavior was correlated with the ionic conductivity. Based on the Bode diagrams, the ionic conductivity of DMVP:BEMA of 1:1 molar ratio was 6.15 × 10^?8 S cm^?1 and that of DMVP:BEMA of 2:1 molar ratio was 3.69 × 10^?8 S cm^?1 which were considered promising as valuable conducting materials.     

Chitosan-<Emphasis Type="Italic">g</Emphasis>-poly(4-acrylamidobenzenesulfonamide) copolymers: synthesis,characterization, and bioactivity

The monomer, 4-acrylamidobenzenesulfonamide (ABS), was synthesized via reaction of acryloyl chloride with 4-aminobenzenesulfonamide in acetone at 0 °C. This monomer was then grafted onto chitosan using solution containing 2% acetic acid and mixture of K₂S₂O₈ and Na₂SO₃ as the redox promoter. An optimal G% of 150% was obtained when the process is conducted at 60 °C for 3 h employing 3.0 × 10^?3 M K₂S₂O₈ and 1.5 × 10^?3 M Na₂SO₃. The graft copolymers, chitosan-g-poly(4-acrylamidobenzenesulfonamide), were characterized by using FTIR, XRD, and SEM. The results were shown that the crystallinity of chitosan is enhanced by increasing the monomer content through the grafting process. Potential Antimicrobial activities of the permethyl ammonium salt forms of chitosan and its grafted copolymers against selected microorganisms were evaluated. The results show that the graft copolymers display better inhibitory effects on the growth of bacteria and some fungi than does chitosan.     

Novel Thermosets from the Cationic Copolymerization of Modified Linseed Oils and Dicyclopentadiene

A series of soft to tough copolymers have been prepared by the cationic copolymerization of the modified linseed oils Dilulin or ML189 with DCPD. Soxhlet extraction and solid‐state ¹³C NMR spectra indicate that the bulk copolymers consist of a cross‐linked oil/DCPD network interpenetrated with certain amounts of soluble components. The T_gs of the resulting Dil/DCPD and ML189/DCPD copolymers are in the range 15–83 and 8–77 °C, respectively, and increase linearly with the increase of the DCPD amount. The room‐temperature storage moduli range from 4.43 × 10⁶ to 1.52 × 10⁹ Pa for the Dil/DCPD copolymers and from 3.72 × 10⁶ to 1.44 × 10⁹ Pa for the ML189/DCPD copolymers.

     

Synthesis and polymerization of methacrylate bearing a phosphorylcholine, analogous moiety

Summary A new type of methacrylate bearing a phosphorylcholine analogous moiety, 2-[2'-(trimethylammonium)-1-methylethyl-phosphoryl]ethyl methacrylate (TMPM) was synthesized. TMPM was radically homopolymerized and copolymerized with BMA to obtain the polymers. The critical micelle concentration (CMC) of TMPM was 4.9 × 10⁻² mol/l according to the fluorescent probe method. Received: 11 June 2001/Revised version: 30 July 2001/Accepted: 31 July 2001     

Synthesis and characterization of homo‐ and copolymers of 3‐(2‐cyano ethoxy)methyl‐ and 3‐[methoxy(triethylenoxy)]methyl‐3′‐methyl‐oxetane

Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF₃· Et₂O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and¹H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (T_g), the DSC data imply that the resulting copolymers have a lower T_g than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10^?5 S cm^?1 at room temperature and 2.79 × 10^?4 S cm^?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry     

Synthesis and properties of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups for proton‐exchange membrane materials

A series of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups were synthesized via a nucleophilic aromatic substitution reaction from phenolphthalein, hydroquinone sulfonic acid potassium salt, and 2,6‐difluorobenzonitrile in N‐methyl pyrrolidone (NMP) with K₂CO₃ as a catalyst. The synthesized copolymers had good solubility in common polar organic solvents and could be easily processed into membranes from solutions of dimethyl sulfoxide, NMP, N,N′‐dimethyl acetylamide, and dimethylformamide. Typical membranes in acid form were gained, and the chemical structures of these membranes were characterized by Fourier transform infrared analysis. The thermal properties, fluorescence properties, water uptake, ion‐exchange capacity, and proton conductivities of these copolymers were also investigated. The results indicate that they had high glass‐transition temperatures in the range 151–187°C and good thermal stability, with the 10 wt% loss temperatures ranging from 330 to 351°C under nitrogen. The copolymers showed characteristic unimodal ultraviolet–visible (UV–vis) absorption and fluorescence emission, and the UV–vis absorption, fluorescence excitation, and emission peaks of the copolymers were obvious. Moreover, the copolymer membranes showed good water uptake and proton conductivities at room temperature and 55% relative humidity because of the introduction of both sulfonic acid groups and carboxyl groups into the copolymers, whose contents were in ranges 18.45–67.86 and 3.4 × 10^?4 to 3.0 × 10^?3 s/cm, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40213.     

Characterization of block copolymers based on poly[3,3-bis(ethoxymethyl)oxetane] and other novel polyethers

Diblock, triblock, and alternating block copolymers based on poly[3,3-bis(ethoxymethyl) oxetane] [poly(BEMO)] and a random copolymer center block poly(BMMO-co-THF) composed of poly[3,3-bis(methoxymethyl)oxetane] [poly(BMMO)], and poly(tetrahydrofuran) [poly(THF)] were synthesized and characterized with respect to molecular weight. Glass transition temperatures T_g and melting temperatures T_m were characterized via DSC, modulus–temperature, and dynamic mechanical spectroscopy (DMS). These polyethers had T_m between 70°C and 90°C, and T_g between ?55°C and ?30°C. The degree of crystallinity of poly(BEMO) was found to be 65% by X-ray powder diffraction. Tensile properties of the triblock copolymer, poly(BEMO-block-BMMO-co-THF-block-BEMO) were also studied. A yield point was found at 4.1 × 10⁷ dyn/cm² and 10% elongation and failure at 3.8 × 10⁷ dyn/cm² and 760 % elongation. Morphological features were examined by reflected light microscopy and the kinetics of crystallization were studied. Poly(BEMO) and its block copolymers were found to form spherulites of 2–10 μm in diameter. Crystallization was complete after 2–5 min.     

Synthesis,characterization, and properties of two‐component amphiphilic polyoxyethylene–containing multiblock copolymers

Amphiphilic (oxyethylene–oxypropylene) and (oxyethylene–styrene) multiblock copolymers, both with high molecular weights, were synthesized by coupling poly(ethylene glycol) (PEG) with poly(propylene glycol) (PPG) or with telechelic dihydroxy polystyrene using 2,4‐toluene diisocyanate as a coupling agent, respectively. The polymerization conditions were investigated. The products were purified and characterized by IR, ¹H‐NMR spectroscopy, and membrane osmometry and identified as multiblock copolymers. Crystallinity of the two kinds of multiblock copolymers was determined by DSC. They showed good emulsifying properties. Their complexes with LiClO₄ showed high room‐temperature conductivities from 3 × 10⁻⁵ to 4 × 10⁻⁴ S/cm at 30°C. High molecular weight (oxyethylene–oxypropylene) multiblock copolymers, at a weight ratio of PEG/PPG = 6/4, behave like thermoplastic elastomers. The (oxyethylene–styrene) copolymer functions as a good compatibilizer for the blend of chlorohydrin rubber and polystyrene. An amount of only 3 wt %, based on the blend, is needed to increase the tensile strength of the blend almost sixfold. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1295–1301, 2005     

Emulsion polymerization of methyl methacrylate using poly(methyl methacrylate-co-2-hydroxypropyl methacrylate)-graft-polyoxyethylene as the stabilizer

This study involved the use of an amphipathic graft copolymer, poly(methyl methacrylate-co-2-hydroxypropyl methacrylate)–graft–polyoxyethylene, as a stabilizer in the emulsion polymerization of methyl methacrylate. The stabilizing effectiveness of this graft copolymer was studied as a function of its chemical structure. It was found that the stabilizing effectiveness of the graft copolymer was independent of the molecular weight of the backbone within the investigated range of 4 × 10³ g/mol to 2 × 10⁴ g/mol. In all cases, stable emulsion polymerizations of methyl methacrylate were observed. Effective stabilization also occurred when the graft moieties possessed a molecular weight of either 2 × 10³ g/mol or 5 × 10³ g/mol. However, the stabilizing effectiveness was found to be dependent on the amount of polyoxyethylene (POE) contained in the graft copolymer. In this case, graft copolymers possessing 67% by weight POE were poor stabilizers, but ones with 85% POE were very good stabilizers. Moreover, the graft copolymers were found to be superior stabilizers as compared to POE homopolymers.     

Effect of Molecular Weight on Performance Properties of Pressure-Sensitive Adhesive of Poly (2-ethylhexyl acrylate) Synthesized by RAFT-Mediated Miniemulsion Polymerization

Reversible addition-fragmentation chain transfer (RAFT) polymerization has been applied in the synthesis of controlled molecular weights and dispersity of poly (2-ethylhexyl acrylate) (PEHA) by the miniemulsion technique. The RAFT agent (2-cyanoethyl morpholine-4-carbodithioate) was synthesized and used for 2-ethylhexyl acrylate (2-EHA) polymerization at molecular weights of 2 × 10⁵, 7 × 10, 14 × 10⁵, and 20 × 10⁵ Da and polymerization reaction kinetics were studied. The RAFT agent was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H-nuclear magnetic resonance (¹H-NMR) spectroscopy, and mass spectroscopy. The synthesized emulsions were characterized by gel permeation chromatography, particle-size analysis, x-ray diffraction (XRD) analysis, and rheological characterization. The PEHAs were used as adhesives for coated and uncoated laminates with low and high surface energies and materials, and their properties such as tack, lap shear strength, peel strength, and shear holding strength were assessed.     

Investigation of charge transport properties in conducting copolymers of aniline with 3‐aminobenzenesulfonic acid for their applications as antistatic encapsulation materials blended with low‐density polyethylene

The electrostatic charge dissipative (ESD) properties of conducting self‐doped and PTSA-doped copolymers of aniline (AA), o‐methoxyaniline (methoxy AA) and o‐ethoxyaniline (ethoxy AA) with 3‐aminobenzenesulfonic acid (3‐ABSA) blended with low‐density polyethylene (LDPE) were investigated in the presence of external dopant p‐toluenesulfonic acid (PTSA). Blending of copolymers with LDPE was carried out in a twin‐screw extruder by melt blending by loading 1.0 and 2.0 wt% of conducting copolymer in the LDPE matrix. The conductivity of the blown polymers blended with LDPE was in the range 10^?12–10^?6 S cm^?1, showing their potential use as antistatic materials for the encapsulation of electronic equipment. The DC conductivity of all self‐doped homopolymers and PTSA‐doped copolymers was measured in the range 100–373 K. The room temperature conductivity (S cm^?1) of self‐doped copolymers was: poly(3‐ABSA‐co‐AA), 7.73 × 10^?4; poly(3‐ABSA‐co‐methoxy AA), 3.06 × 10^?6; poly(3‐ABSA‐co‐ethoxy AA), 2.99 × 10^?7; and of PTSA‐doped copolymers was: poly(3‐ABSA‐co‐AA), 4.34 × 10^?2; poly(3‐ABSA‐co‐methoxy AA), 9.90 × 10^?5; poly(3‐ABSA‐co‐ethoxy AA), 1.10 × 10^?5. The observed conduction mechanism for all the samples could be explained in terms of Mott's variable range hopping model; however, ESD properties are dependent upon the electrical conductivity. The antistatic decay time is least for the PTSA‐doped poly(3‐ABSA‐co‐AA), which has maximum conductivity among all the samples. © 2013 Society of Chemical Industry     

Synthesis,characterization, and aqueous solution behavior of copolymers of acrylamide and sodium 10-acryloyloxydecanoate

A new water-soluble monomer of sodium 10-Acryloyloxydecanoate (NaAD), which possesses a hydrophobic group and an ionizable group, was synthesized from acryloyl chloride and 10-hydroxydecanoic acid, and the series of copolymers of NaAD with acrylamide (AM) were prepared by the free radical polymerization in aqueous solution using ammonium persulfate as the initiator. The feed ratio of NaAD:AM was varied from 5:95 to 70:30 mol%, with the total monomer concentration held constant at 0.5 M. The copolymer compositions were determined from elemental analysis. The molecular weights of the copolymers were determined by gel permeation chromatography ranged from 0.76 × 10⁶ to 1.37 × 10⁶ g/mol. All copolymers were soluble in deionized water and salt solutions at pH > 5. The dilute and semidilute solution behavior of the copolymers was studied as a function of composition, pH, and added electrolytes, and the results indicated that NaAD30 exhibited much higher viscosity values. At moderate pH values, the copolymers coils become slightly more expanded and intermolecular association interactions occur, which was indicated by fluorescence and apparent viscosity measurements. Upon the addition of NaCl and in low pH, viscosities tended to decrease because of the disruption of the intermolecular associations.     

Studies of methyl methacrylate-methyl α-chloroacrylate,copolymers and poly(methyl α-chloroactylate) as electron sensitive positive resists

Poly(methyl α-chloroacrylate) (PMCA) and the copolymers of methyl methacrylate and methyl α-chloroacrylate (poly(MMA-co-MCA)) have been reported recently to be more susceptible to radiation degradation than poly(methyl methacrylate) (PMMA). In this paper we report our studies of PMCA and poly(MMA-co-MCA) as electron-sensitive positive resists. It has been found that both PMCA and the copolymers are more sensitive than PMMA. Using mixtures of dimethylformamide and 2-propanol as developers, the sensitivities of PMCA and poly(MMA-co-MCA) (38 mole percent MCA) have been found to be 1 × 10^?5 and 6 × 10^?6 coulomb/cm², respectively. It has also been found that crosslinking predominates in PMCA when the electron dose exceeds 6 × 10^?4 coulomb/cm².