Radiation degradation behavior of chlorine-containing vinyl copolymers. Search for improved electron-beam resists

Vinyl copolymers with high radiation degradation sensitivity have been synthesized by copolymerizing vinylidene chloride (VDC), CH₂ = CCl₂, with methyl methacrylate (MMA), methacrylonitrile, methyl α-chloroacrylate, and dimethyl itaconate using emulsion techniques. In addition, copolymers of methyl α-chloroacrylate with methyl methacrylate and poly(α-chloroaerylonitrile) were studied. Introduction of vinylidene chloride into methyl methacrylate polymers caused a sharp increase in G_s even at relatively low VDC incorporation. Upon 29 percent VDC incorporation, the G_s value increased from 1.3 (homopolymer of MMA) to 3.4. G_s was found to be a linear function of copolymer content for several systems, but G_x was not. At higher VDC levels, the increase in G_s was countered by increases in G_x. At lower VDC levels, G_x was suppressed below the values predicted by a linear G_x dependence on composition for such systems as VDC/MMA, MCA/MMA, and α-chloroacrylonitrile/MMA. The VDC/MMA co-polymer(29 percent VDC) gavea sensitivity of 4.0 × 10^?5C/cm² to electron beam exposure using the 0 percent unexposed resist thickness loss criterion and is 2–3 times more sensitive than PMMA. Poly(α-chloroacrylonitrile) is a negative resist with a sensitivity of 5 × 10^?5 C/cm² using one-micron line images for testing.     

Thermal Stability of Lubricating Oil Additives Based on Styrene and n-Alkyl Methacrylate Terpolymers

In this work the thermal stability of polymeric additives for the improvement of rheological behavior of mineral lubricating oils was investigated. The systems studied comprised methyl methacrylate (MMA)/dodecyl methacrylate (DDMA)/octadecyl methacrylate (ODMA) and styrene (Sty)/DDMA/ODMA terpolymers. The composition of the terpolymers was determined by the ¹H nuclear magnetic resonance spectroscopy and molar mass distribution by the size exclusion chromatography. The thermal degradation of terpolymers was studied by the thermogravimetric analysis. Sty/DDMA/ODMA terpolymers exhibited an improved thermal stability in comparison with MMA/DDMA/ODMA terpolymers of the corresponding compositions. Thus, the temperatures of 50% weight loss were found to be 313°C and 363°C for MMA terpolymer and Sty terpolymer, respectively, where x (MMA) = x (Sty) = 30 mol%.     

The synthesis and evaluation of cyclic olefin sulfone copolymers and terpolymers as electron beam resists

Poly(cyclopentene sulfone) (PCPS) and poly(bicycloheptene sulfone) (PBCHS) copolymers have been evaluated as potential positive electron beam resists which have good thermal properties and which show high sensitivity to ionizing radiation. It was found that thin copolymer films could be processed as resists but that films greater than 3000 Å thick cracked in the solvents used to dissolve the radiation-exposed regions. Incorporation of plasticizing additives did not improve the film properties. Films from low molecular weight polymer fractions cracked less in solvents, but higher radiation doses were required to offset the reduced sensitivity. This resulted in the formation of intractable residues in the exposed regions which appear to be crosslinked polymer. Bicycloheptene monomers with specific functional groups did not improve the properties of the copolymer films. Terpolymerization with α-olefins such as butene-1 and cis-2-butene plasticized these films and reduced their tendency to crack in solvents. Poly(cyclopentene sulfone–co–butene-1 sulfone) films were found to have the best properties, and 1.25-μ resist images could be etched in SiO₂ layers at an exposure dose of 4 × 10^?6 C/cm² at 25KV. However, one important limitation of this terpolymer was the low dissolution rate ratio between the exposed and unexposed regions. Since straight-walled relief images are essential to the formation of high-resolution patterns, the usefulness of this terpolymer as an electron beam resist appears to be hindered by the limited choice of good solvents to maximize the dissolution rate ratio. PBCHS block terpolymers containing methyl methacrylate (MMA) or methacrylic acid (MAA) were synthesized to improve the solubility in solvents and to incorporate the properties of methacrylates. PBCHS–MMA films cracked in solvents after irradiation; PBCHS–MAA polymers were too insoluble to form resist films.     

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.     

Electron-sensitive resists. II. Positive resists derived from high polymers of methyl methacrylate,methyl α-chloroacrylate,and hexyl methacrylate

This paper reports the synthesis, characterization, and evaluation of copolymers of methyl methacrylate (MMA) and hexyl methacrylate (HMA) and of HMA and methyl α-chloroacrylate (MCA) and of terpolymers of MMA, MCA, and HMA as electron-sensitive positive resists. The sensitivities of the resists were found to be strongly dependent on the composition. Two of the terpolymers were found to be significantly more sensitive than poly(methyl methacrylate) (PMMA).     

Microstructure determination of the acrylonitrile–styrene–methyl methacrylate terpolymers by NMR spectroscopy

Acrylonitrile–styrene–methyl methacrylate (A–S–M) terpolymers were prepared by photopolymerization using uranyl nitrate ions as photo initiators, which were analyzed by NMR spectroscopy. The terpolymer compositions were determined by Goldfinger's equation using comonomer reactivity ratios: r_as = 0.04; r_sa = 0.31; r_am = 0.17, r_ma = 1.45; r_sm = 0.52; r_ms = 0.47. The terpolymer compositions were also determined from the quantitative ¹³C(¹H)‐NMR spectroscopy. The sequence distribution of the acrylonitrile‐, styrene‐, and methyl methacrylate–centered triads were determined from the ¹³C(¹H)‐NMR spectra of the terpolymers and are in good agreement with triad concentrations calculated from the statistical model. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3026–3032, 1999     

Synthesis of methacrylate copolymers and their effects as pour point depressants for lubricant oil

In this study, polymethacrylate polymers were synthesized by free‐radical polymerization for use as pour point depressants in lubricant oil, and their low‐temperature properties were investigated. Four methacrylate monomers were synthesized by the esterification of methyl methacrylate (MMA) with four kinds of fatty alcohols. The purification step was performed to prepare the pure monomers. Two polymerization experiments were carried out with four kinds of methacrylate monomers obtained previously and MMA. Copolymers, which were made from one kind of monomer and MMA, and terpolymers, which were made from two kinds of monomers and MMA, were prepared. The molecular structures of the synthesized methacrylate monomers and polymethacrylate polymers were verified by ¹H‐NMR, and the molecular weight data were obtained by gel permeation chromatography. The pour points of the base oils containing 0.1 wt % polymethacrylate polymers were measured according to ASTM D 97‐93. The pour points of most base oils containing each polymer decreased compared to that of the pure base oil. Particularly, poly(dodecyl methacrylate‐co‐hexadecyl methacrylate‐co‐methyl methacrylate), made of dodecyl methacrylate, hexadecyl methacrylate, and MMA at a molar ratio of 3.5 : 3.5 : 3, showed the best low‐temperature properties. This terpolymer dropped the pour point of the base oil by as much as 23°C, and its yield was 93.5%. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Miniemulsion copolymerizations of styrene and methyl methacrylate in the presence of reactive costabilizer

Miniemulsion stability of three‐component disperse phase systems comprising styrene [ST (1)], methyl methacrylate [MMA (2)], and stearyl methacrylate [SMA (3)] was investigated. The Ostwald ripening rate (ω) increases with increasing MMA content in the monomer mixture. The empirical equation 1 /ω = k(φ₁/ω₁ + φ₂/ω₂) + φ₃/ω₃ was proposed to adequately predict the miniemulsion stability data. The empirical parameter k was determined to be 555.77, and the Ostwald ripening rate (ω₃) and water solubility of SMA were estimated to be 8.77 × 10^?21 cm³/s and 1.90 × 10^?9 mL/mL, respectively. A water‐insoluble dye was used as a molecular probe to study particle nucleation mechanisms in the miniemulsion copolymerizations. In addition to the primary monomer droplet nucleation, homogeneous nucleation also plays an important role in the formation of particle nuclei, and this mechanism becomes more important for the polymerization systems with higher MMA contents as a result of the enhanced aqueous phase polymer reactions. The polymer composition data suggest that, during the early stage of polymerization, MMA is consumed more rapidly by free radical polymerization compared with ST. The final latex particle surface potential data also support this conclusion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Terpolymer films having semipolar structure: Preparation,wettability, and mechanical properties

A terpolymer, obtained by the free‐radical terpolymerization of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMMA), methyl methacrylate(MMA), and isobutyl methacrylate (IBMA), was allowed to react with hydrogen peroxide, chloroacetic acid, and diethyl sulfate to form the corresponding modified terpolymers: (1) N,N‐dimethyl‐N‐(2‐methacryloyloxyethyl)amine N‐oxide, MMA and IBMA (DMANO series); (2) N‐(carboxymethyl)‐N,N‐dimethyl‐ N‐(2‐methacryloyloxyethyl)ethyl ammonium, MMA and IBMA (CDME series); and (3) N‐(ethyl)‐N,N‐dimethyl‐N‐(2‐methacryloyloxyethyl)ethyl ammonium ethylsulfonate, MMA and IBMA (EDMEES series), respectively. The terpolymer compositions were determined using ¹³C NMR spectrometry. Surface free energies of the terpolymers were estimated by measuring the contact angles of water and methylene iodide on the three series films (DMANO, CDME, and EDMEES), and the effect of the N‐oxide group on wettability was discussed. It was found that the upper surface of the films for the DMANO and CDME series are more hydrophobic than that for the EDMEES series. Notably, elongation to break for the DMANO series was relatively larger than that for the CDME series because of the water bound to the N‐oxide functional group. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1235–1243, 2005     

Miniemulsion copolymerizations of methyl methacrylate and butyl acrylate in the presence of reactive costabilizer

The storage stability and free radical polymerizations of miniemulsions comprising methyl methacrylate (MMA), butyl acrylate (BA), and a reactive costabilizer stearyl methacrylate (SMA) were investigated. The Ostwald ripening rate increases with increasing MMA content in the monomer mixture. Both the pseudo‐two‐component model and empirical equation with one adjustable parameter k adequately predicted the Ostwald ripening rate data. For the empirical model, the least‐squares best fit technique gave a value of k equal to 677.5 and values of Ostwald ripening rate and water solubility equal to (8.8 ± 0.2) × 10^?21 cm³/s and 1.8 × 10^?9 cm³/cm³ for SMA, respectively. These two models were combined to impart some physical insight to the parameter k. The kinetic studies showed that the polymerization rate increased with increasing MMA content. This is closely related to the nature of the constituent monomers MMA and BA and the particle nucleation mechanisms. The reactive costabilizer SMA is not hydrophobic enough to completely eliminate the Ostwald ripening effect, thereby increasing the probability of polymer reactions in the continuous aqueous phase. Thus, in addition to monomer droplet nucleation, particle nuclei can be generated in the aqueous phase via homogeneous nucleation. The extent of homogeneous nucleation increased with increasing MMA content and, as a result, the number of reaction loci available for the major polymerization to take place followed the same trend. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of a terpolymer of limonene,styrene, and methyl methacrylate via a free‐radical route

The free‐radical terpolymerization of a monocyclic terpene, namely, limonene (Lim), with styrene (Sty) and methyl methacrylate (MMA) in xylene at 80 ± 0.1°C for 2 h, with benzoyl peroxide (BPO) as an initiator under an inert atmosphere of nitrogen was extensively studied. The kinetic expression was R_pα[BPO]^0.5[Sty]^1.0[MMA]^1.0[Lim]^?1.0, where R_p is the rate of polymerization. The overall energy of activation was calculated as 26 kJ/mol. R_p decreased as [Lim] increased. This was due to a penultimate unit effect. The Fourier transform infrared spectra of the terpolymer showed bands at 3025–3082, 1728, and 2851–2984 cm^?1 due to C? H stretching of phenyl (? C₆H₅) protons of Sty, ? OCH₃ of MMA, and trisubstituted olefinic protons of Lim, respectively. The ¹H‐NMR spectra showed peaks at 7.3–8.1, 3.9–4.4, and 5.0–5.5 δ due to the phenyl, methoxy, and trisubstituted olefinic protons of Sty, MMA and Lim, respectively. The values of the reactivity ratios r₁ (MMA; 0.33) and r₂ (Sty + Lim; 0.06) were calculated with the Kelen–T?udos method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2343–2347, 2004     

Studies of reactions with polymers. III. Syntheses and properties of poly(vinyl alcohol) graft terpolymers

A condensation-coupling reaction through esterification is performed between the hydroxy groups of poly(vinyl alcohol) (PVA) and the anhydride groups of methyl methacrylate (MMA)-co-maleic anhydride (MA) copolymer to produce the PVA-g-MMA/MA graft terpolymer. The MMA-co-MA copolymer was obtained by copolymerization of MA and MMA in dimethyl sulfoxide by using azobisisobutyronitrile as initiator. The structure of reaction products was confirmed by infrared analysis, and the dependence of composition, viscosity, and yield of the graft terpolymer on the MA content in MMA-co-MA as well as the concentration of the reactants fed were investigated. Mechanical properties, water content, and gel content of the membranes of terpolymers were measured over a wide range of compositions. PVA-g-MMA/N-ethylol maleimide was also synthesized by reacting the residual anhydride groups on PVA-g-MMA/MA with ethanol amine, this reaction proceeds through the PVA-g-MMA/N-ethylol maleamic acid intermediate.     

Determination of diffusion coefficient of oxygen into polymers by using electron spin resonance spectroscopy. I. Poly(methyl methacrylate)

A simple technique has been proposed for the measurement of the diffusion coefficient of oxygen into polymeric spheres. The technique is based on the scavenging of radicals produced by high energy radiation by oxygen. The diffusion coefficient of oxygen determined for poly(methyl methacrylate) has shown an inverse dependency on the dose received. Diffusion coefficient determined for low doses (D = 3.4 × 10^?8 cm²/s) as well as that determined after extrapolation to zero dose (D₀ = 3.7 × 10^?8 cm²/s) are in excellent agreement with the values reported in the literature.     

Fast transient fluorescence technique (FTRT) for studying dissolution of polymer glasses

The fast transient fluorescence technique (FTRT) was used for studying the swelling and dissolution of a glassy polymer formed by free‐radical polymerization of methyl methacrylate (MMA). Anthracene (An) was introduced during polymerization as a fluorescence probe to monitor swelling and dissolution. Swelling and dissolution processes of disc‐shaped poly(methyl methacrylate) (PMMA) glasses in a chloroform–heptane mixture were monitored by measuring the fluorescence lifetimes of An from its decay traces. A method is developed for low quenching efficiencies for measuring lifetimes, τ, of An, and it was observed that τ values decreased as the dissolution process proceeded. Desorption, D, and mutual diffusion, D_m, coefficients of An molecules were measured during dissolution of PMMA and found to be around 5.4 × 10⁻⁶ (cm²/s) and 2.2 × 10⁻⁵ (cm²/s), respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 948–957, 1999     

Effect of primary polymer chain rigidity on intramolecular cyclization and intramolecular crosslinking in free‐radical crosslinking monomethacrylate/dimethacrylate copolymerizations

d‐Bornyl methacrylate (BoMA) was chosen as a typical example of bulky monomethacrylate monomers, the polymerization of which led to the formation of a rigid polymer chain. To discuss the effect of primary polymer chain rigidity on intramolecular cyclization, we compared the solution copolymerization results of BoMA with 1 mol % ethylene dimethacrylate (EDMA; n = 1) and poly(ethylene glycol dimethacrylate) [CH₂?C(CH₃)CO(OCH₂CH₂)_nOCOC(CH₃)?CH₂, n = 9 (PEGDMA‐9)] with those of methyl methacrylate (MMA) with 1 mol % EDMA and PEGDMA‐9; the dependence of the weight‐average degree of polymerization on conversion for the former BoMA copolymerization systems was completely opposed to that for the latter MMA systems, and this was a reflection of a reduced occurrence of intramolecular cyclization caused by the rigidity of the primary polymer chain. The effect of primary polymer chain rigidity on intramolecular crosslinking was discussed through a comparison of both BoMA/EDMA and MMA/EDMA copolymerizations. The correlations of the intrinsic viscosity, root‐mean‐square (rms) radius of gyration, and second virial coefficient with the molecular weight were examined for both BoMA/EDMA (90/10) and MMA/EDMA (90/10) copolymerizations in a dilute solution because microgelation was observed in solution MMA/EDMA (90/10) copolymerization as a reflection of a locally extensive occurrence of intramolecular crosslinking. The logarithmic plots of both the intrinsic viscosity and rms radius of gyration versus the molecular weight for MMA/EDMA copolymerization were compared with those for the corresponding BoMA/EDMA copolymerizations. The second virial coefficients were greater than 10^?5 mol cm³ g^?2 for BoMA/EDMA copolymers, even when the conversion was very close to the gel point, whereas they were quite low, that is, less than 10^?5 mol cm³ g^?2, for an MMA/EDMA copolymer obtained at more than 15% conversion. These were ascribed to a suppressed occurrence of intramolecular crosslinking, a reflection of the lessened flexibility of the polymer main chain and a steric effect due to the bulky d‐bornyl groups. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1086–1093, 2004     

Terpolymerization kinetics of N,N‐dimethylaminoethyl methacrylate/alkyl methacrylate/styrene systems

Low conversion kinetics of terpolymerization of N,N‐dimethylaminoethyl methacrylate (DMAEM) and dodecyl methacrylate (DDMA) with methyl methacrylate (MMA) or styrene (ST) was investigated. Reactions were performed at 70°C, in toluene solutions, using peroxide initiator. The interdependence between terpolymer and monomer feed composition was successfully described by Alfrey‐Goldfinger equation and the unitary, binary, and ternary azeotropes were calculated. In MMA‐containing system, the wide pseudoazeotropic region with existence of true azeotropic point was observed and experimentally confirmed at the DMAEM:MMA:DDMA molar ratio of 56:41:3. In the ST‐containing system compositional heterogeneity was significant, more than 10 mol%. Required copolymerization reactivity ratios were determined by linear and nonlinear methods. The glass transition temperatures of synthesized terpolymers are found to be between those of the corresponding homopolymers and relative to their content. Increase in the MMA or ST contents and decrease in the DDMA content in terpolymers results in an increase in their glass transition temperatures. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Grafting of methyl methacrylate to nitrocellulose by ceric ions

Studies were carried out on grafting of various vinyl monomers to nitrocellulose by ceric ions. It was observed that graft copolymerization occurred only with methyl methacrylate (MMA) and methyl acrylate monomer. The variables such as initiator concentration, monomer concentration, time of grafting, and nitrocellulose content on grafting of MMA are discussed. By hydrolyzing away the nitrocellulose backbone, the grafted poly(methyl methacrylate) branches were isolated and the >c?o peak at 1740 cm^?1 in the infrared spectra of these isolated branches gave definite evidence of grafting. The molecular weight of isolated branches has been determined by viscometry. The probable mechanism of grafting may be at the α-carbon atom of primary alcohol or at a C₂-C₃ glycol group of the anhydro glucose unit or at the hemiacetal group of the end unit of nitrocellulose, as nitrocellulose is formed by the partial nitration of cotton cellulose.     

Oxygen transport in crosslinked,silicon-containing copolymers of methyl methacrylate

Copolymers of methyl methacrylate and 1,3-bis(methacryloxy methyl)-1,1,3,3-tetramethyl disiloxane were prepared by chemically induced copolymerization/crosslinking at 60°C and 49 mm Hg. Crosslinked, glassy copolymers were obtained with copolymer mole fraction of the silicon-containing monomer varying from 0.09 to 0.55. Oxygen transport studies were performed with thin films as prepared and after sub-T_g annealing. The results of this study indicated that an enhancement of both the steady state oxygen permeation rate and the oxygen diffusion coefficient was achieved through copolymerization. The oxygen diffusion coefficients through the copolymers were found, within experimental error, to be independent of silicon content and ranged from 0.80 × 10^?7 to 1.90 × 10^?7 cm²/s vs. oxygen diffusion coefficient for pure poly(methyl methacrylate) of 1.5 × 10^?8 cm²/s. Sub-T_g annealing effected a reduction of approximately equal magnitude in both the oxygen diffusion coefficient and the steady state oxygen flux for the copolymers. In addition, the normalized oxygen flux data were predicted with Fick's law, assuming constant boundry conditions and diffusion coefficient. These results were explained in terms of the free volume theory and the combined effects of increased crosslinking density, chain mobility, and oxygen solubility with increased copolymer silicon content.     

Kinetics of ylide-initiated radical copolymerization of 4-vinylpyridine and methyl methacrylate

The ylide-initiated radical copolymerization of 4-vinylpyridine (4-VP) with methyl methacrylate (MMA) at 60°C using carbon tetrachloride as inert solvent yields non-alternating copolymers. The kinetic parameters, average rate of polymerization (R_p) and orders of reaction with respect to monomers and initiator, have been evaluated and the kinetic equation is found to be R_pα[ylide]^0.94 [MMA]^1.0 [4-VP]^1.5. The values of the energy of activation and k_p²/k_t are 48 kJ mol^?1 and 6.6 × 10^?5 litre mol^?1s^?1, respectively. The copolymers have been characterized by IR and NMR spectroscopy.