Preparation and photolysis of poly-4′-acetylacrylophenone and its copolymers with styrene and methyl methacrylate

Poly-4′-acetylacrylophenone (P4AcAP) and its copolymers with styrene (4AcAP/S) and methyl methacrylate (4AcAP/MMA) were prepared. Ultraviolet (UV) spectra of these polymers show an absorption band at 29,500 cm^?1 (? = 270) of n-π* character. The low temperature emission spectra of films of copolymers studied exhibit a less resolved vibrational structure and are bathochromically shifted with respect to those of polyacrylophenone and its styrene and methyl methacrylate copolymers. The emission decay is slightly nonexponential and has a lifetime of about 0.02 sec. Quantum yields of main chain scission in solution with 366-nm radiation are of the same order as those of the unsubstituted polyacrylophenone. Substitution by a strong electron-accepting group, in comparison with polyacrylophenone, influences the value of the quantum yield only a little but prolongs the lifetime of the lowest triplet state. This is also evident in an increase in the Stern–Volmer constant in passing from polyacrylophenone–naphthalene in benzene (68 mole^?1) to P4AcAP–naphthalene in dioxane (380 mole^?1). With biphenyl as a triplet quencher, the Stern–Volmer constants are low because of back transfer:     

Preparation and photolysis of poly-p-methoxyacrylophenone and its copolymers with styrene and methyl methacrylate

Poly-p-methoxyacrylophenone (PPMeOAP) and its copolymers with styrene (PMe-OAP–S) and with methyl methacrylate (PMeOAP–MMA) were prepared. The photolysis in solution with 313 and 366 nm radiation was followed viscometrically. In solvents such as chlorobenzene and ethyl benzoate, random main-chain scission from n–π^* excited triplet state occurs. The lowest excited triplet state in formic acid and in ethylene chlorhydrin is of the character π–π^*, from which no main-chain scission occurs. In solvents in which destruction occurs, the main-chain scission is retarded by triplet quenchers, such as naphthalene, 2,5-dimethyl-2,4-hexadiene, and biphenyl. Quenching experiments indicate that the lifetime for the excited triplet state of PPMeOAP is 25 times that for polyacrylophenone. In PMeOAP–MMA copolymers, quantum yields of main-chain scissions were lower and lifetimes of excited triplets were longer than in PPMeOAP, due to hindered intramolecular photoreaction.     

Photolysis and emission spectra of substituted polyacrylophenones

Poly-[3′,4′-dimethoxyacrylophenone], poly-4′-phenylacrylophenone, poly-2′-acrylonaphthone and copolymers of acrylophenone monomers with styrene and methyl methacrylate were prepared. Quantum yields of main chain scission in chlorobenzene by 313 nm radiation were 10³ times lower for all homopolymers and copolymers studied than for polyacrylophenone. The emission spectra of the polymers, copolymers and model compounds were taken for films at 77 K. The 3′,4′-dimethoxyacrylophenone, 4′-phenylacrylophenone and 2′-acrylonaphthone structural units exhibited poorly resolved emission spectra in homopolymer, copolymer and model compound. No difference in the emission spectra of films and dispersed homopolymer or copolymer in a poly(methyl methacrylate) matrix was observed. The decay of the emission of all homopolymers and copolymers under study was exponential, the life-time exceeding 0.20 sec.     

Homopolymerization and copolymerization of isocyanatoethyl methacrylate

This article describes the homopolymerization of isocyanatoethyl methacrylate (IEM) and its copolymerization with methyl methacrylate (MMA) in acetonitrile in the presence of 2,2′‐azobisisobutyronitrile. The constant characteristic of IEM polymerizability (k_p²/k_te = 128 × 10^?3 L mol^?1 s^?1, where k_p is the propagation constant and k_te is the termination constant) was determined. The study of IEM reactivity toward MMA gave ratios of 0.88 and 1.20 for IEM and MMA, respectively. The physicochemical properties of the IEM homopolymer and IEM/MMA copolymers were also studied. The glass‐transition temperature of poly(isocyanatoethyl methacrylate) was found to be 47 °C. From the thermogravimetric analysis of the weight‐loss percentage corresponding to the first wave of the thermogram, it was shown that the degradation mechanism of the IEM/MMA copolymers started from the isocyanate group. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4762–4768, 2006     

ATRP of methyl methacrylate initiated with a bifunctional initiator bearing bromomethyl functional groups: Synthesis of the block and graft copolymers

This article reports the synthesis of the block and graft copolymers using peroxygen‐containing poly(methyl methacrylate) (poly‐MMA) as a macroinitiator that was prepared from the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in the presence of bis(4,4′‐bromomethyl benzoyl peroxide) (BBP). The effects of reaction temperatures on the ATRP system were studied in detail. Kinetic studies were carried out to investigate controlled ATRP for BBP/CuBr/bpy initiating system with MMA at 40 °C and free radical polymerization of styrene (S) at 80 °C. The plots of ln ([M_o]/[M_t]) versus reaction time are linear, corresponding to first‐order kinetics. Poly‐MMA initiators were used in the bulk polymerization of S to obtain poly (MMA‐b‐S) block copolymers. Poly‐MMA initiators containing undecomposed peroygen groups were used for the graft copolymerization of polybutadiene (PBd) and natural rubber (RSS‐3) to obtain crosslinked poly (MMA‐g‐PBd) and poly(MMA‐g‐RSS‐3) graft copolymers. Swelling ratio values (q_v) of the graft copolymers in CHCl₃ were calculated. The characterizations of the polymers were achieved by Fourier‐transform infrared spectroscopy (FTIR), ¹H‐nuclear magnetic resonance (¹H NMR), gel‐permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and the fractional precipitation (γ) techniques. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1364–1373, 2010     

Characterization of organometallic polymers by 13C- and 119Sn-NMR: Configurational/compositional triads in poly(tri-n-butyltin methacrylate/methyl methacrylate)

The 1:1 and 2:1 formulations of the free radical initiated copolymers of methyl methacrylate (MMA) and tri-n-butyltin methacrylate (TBTM), and the homopolymer, poly(TBTM), are characterized by ¹³C- and ¹¹⁹C-NMR structural analyses were performed on the tributyltin-free hydrolyzate, a copolymer of MMA and methacrcylic acid (MAA). Configurational sequencing at the triad level is performed using the α-methyl region of the ¹³C-NMR spectrum. The probability of isotactic (meso) dyad placement at 80°C in the homopolymer (0.19) is determined to be significantly less than the probabilities observed for the copolymers (0.23–0.24). Random compositional sequencing is established for the copolymers through a comparison of the carbonyl regions of the ¹³C-NMR spectra of the hydrolyzates with the carbonyl regions in published spectra of structurally characterized copolymers of MMA and MAA. The ¹¹⁹Sn chemical shift and the tin-carbon J coupling for the polymers are dependent on the solvent employed. This dependence is attributed to electron donor or acceptor interactions between the solvent and the strong Sn? O dipole. The tin-containing copolymers exhibit multiple ¹¹⁹Sn resonances, which appear related to compositional sequencing.     

Dielectric study of side-group rotation of methyl methacrylate in copolymers

The dielectric absorption due to the side-group rotation of the methyl methacrylate (MMA) unit in MMA-styrene and MMA-p-chlorostyrene (pCS) copolymers was measured. The relaxation time for MMA-pCS copolymers with low MMA contents could be interpreted quantitatively in terms of the Kramers rate-constant theory at the low-friction limit. On the other hand, the frictional effect on the relaxation time could not be ignored for any copolymers except for the MMA-pCS copolymers with low MMA contents. The relaxation time for pure poly(methyl methacrylate) could be interpreted by the Kramers theory at the high-friction limit.     

Photolysis of unsubstituted and p-methoxycarbonyl substituted 2-methyl-1-phenylprop-2-en-1-one copolymers in solution

A new monomer, methyl 4-(2-methyl-1-oxoprop-2-en-1-yl)benzoate (p-(methoxycarbonyl)phenyl isopropenyl ketone, MeOCO-PIPK), was synthesized and copolymerized with styrene and methyl methacrylate (MMA). The copolymers of MeOCO-PIPK and 2-methyl-1-phenylprop-2-en-1-one (phenyl isopropenyl ketone, PIPK) with styrene and MMA were photolyzed by deep-, mid- and near-UV light in dilute solution; and the quantum yields of scission, ϕ_g, and the UV absorption spectra were measured. The p-methoxycarbonyl substitution increased the molar extinction coefficients of the ketone monomer units extensively, but slightly lowered the ϕ_g values in styrene and MMA copolymers. This is expected to increase the net sensitivity of solid films of the polymers. The ϕ_g was found independent of the wavelength, despite the concurrent absorption by styrene units in the styrene copolymers. Larger ϕ_g values were obtained for the MMA copolymers than the corresponding styrene copolymers. Solvents with larger dielectric constants gave larger ϕ_g for the copolymer of MMA with PIPK; but when the dielectric constants were similar, lower ϕ_g values were observed in the solvents with more easily abstractable hydrogens. A large bleaching effect was seen in MMA copolymers, which should make possible the formation of resist patterns with steep profiles when used in photolithography. © 1996 John Wiley & Sons, Inc.     

Synthesis and properties of new photosensitive triazene polyacrylates

1‐(Phenyl)‐3‐(2‐acryloyloxyethyl)‐3‐methyl triazene‐1 (M1) and 1‐(p‐nitrophenyl)‐3‐(2‐acryloyloxyethyl)‐3‐methyl triazene‐1 (M2) were synthesized to study the substituent effect of the triazene unit on the copolymerization with methyl methacrylate (MMA). From the ¹H NMR spectra of the resulting copolymers, their compositions were determined to be 1:3.18 M1/MMA and 1:2.45 M2/MMA, respectively. The polymers were examined with respect to their structure, thermal properties, and surface morphology. The influence of the triazene structure on the photosensitive properties of the copolymers exposed to ultraviolet/laser irradiation was also investigated and compared with that of the parent derivatives. The copolymer containing the phenyl triazene chromophore as the photochemically most active group exhibited a low threshold of ablation and a high etching rate for fluences under 400 mJ cm^?2. Scanning electron microscopy images confirm the formation of ablated craters more clearly in the copolymer made with M1, for which the thermal effects of the ablation mechanism were visible only with 2500× magnification. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5271–5282, 2006     

Copolymerization of n‐butylacrylate with methylmethacrylate by a novel photoinitiator, 1‐(bromoacetyl)pyrene

The photopolymerization efficiency of pyrene (Py), 1‐acetylpyrene (AP), and 1‐(bromoacetyl)pyrene (BP) for copolymerization of n‐butylacrylate (BA) with methylmethacrylate (MMA) was compared. A kinetic study of solution copolymerization in DMSO at 30 ± 0.2°C showed that the Py could not initiate copolymerization even after 20 h, whereas with AP as initiator, less than 1% conversion was observed. However, introduction of a Br in α‐methyl group of AP significantly enhanced the percent conversion. The kinetics and mechanism of copolymerization of BA with MMA using BP as photoinitiator have been studied in detail. The system follows nonideal kinetics (R_p α [BP]^0.67[BA]¹[MMA]^0.98), and degradative solvent transfer reasonably explains these kinetic nonidealities. The monomer reactivity ratios (MRRs) of MMA and BA have been estimated by the Finemann–Ross and Kelen–Tudos methods, by analyzing copolymer compositions determined by ¹H‐NMR spectra. The values of r₁ (MMA) and r₂ (BA) were found to be 2.17 and 0.44, respectively, which suggested the high concentration of alternating sequences in the random copolymers obtained. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 261–267, 2007     

Studies of methyl methacrylate–glycidyl methacrylate copolymers: Copolymerization to low molecular weights and modification by ring-opening reaction of epoxy side groups

The copolymerization of methyl methacrylate (MMA) with glycidyl methacrylate (GMA) at 60°C with 2,2′-azobisisobutyronitrile (AIBN) as radical initiator and in the presence of thiophenol (TP) as chain-transfer agent has been investigated. Monomer reactivity ratios for MMA and GMA are found to be r₁ (MMA) = 0.80 ± 0.015 and r₂ (GMA) = 0.70 ± 0.015, from which Q and e values are calculated to be 0.68 and ?0.36 for GMA. The initial rate of copolymerization R_p at 60°C with AIBN (0.02 mole/l.) and TP (0.1, 0.01 mole/l.) were found to increase nonlinearly with increasing GMA concentration in the monomer feed. Homopolymerizations of MMA and GMA monomers were studied in the presence and in the absence of thiophenol. The values of δ (= k_t^1/2/k_p) for MMA and GMA were determined to be 10.25 and 3.00 (mole-sec/l.)^1/2, respectively. Using the values r₁ (MMA), r₂ (GMA), δ₁ (MMA), δ₂ (GMA), and R_p, the cross-termination constants ? for MMA–GMA monomers were determined (average value ? = 0.42). The increase in R_p values with increasing GMA content has been attributed to the cross-termination of MMA–GMA radicals. The transfer constant of TP has also been determined for GMA and found to be 1.00. A MMA–GMA copolymer of low molecular weight, containing 2.01% of oxirane oxygen, was modified by opening of the oxirane ring of GMA by reaction with diethanolamine (DEA). The reaction was carried out at 70 ± 1°C, the copolymer content of epoxy groups and the amine being assumed to be in the molar ratio of 1:4. Addition of a hydrogen-bond acceptor like nitrobenzene decreases, while addition of a hydrogen-bond donor like phenol increases the rate of epoxy ring opening with DEA. This indicates that a hydrogen-bonded intermediate is involved in this reaction and that it weakens the epoxy ring and enhances the rate of its opening with DEA. From the studies of the conversion rates, existence of a “nonspecific” side reaction has been shown which involves the reaction of the terminal epoxy groups of the copolymer and the hydroxyl groups of DEA or formed in the reaction with DEA (involves a chain coupling). DEA can be trifunctional in this reaction. This has been further confirmed from the increase of number-average molecular weights M?_n of the copolymers resulting from this coupling and the nitrogen content in the copolymers after modification with DEA.     

Preparation and characterization of copolymers of chloroprene and methyl methacrylate

The preparation of chloroprene–methyl methacrylate copolymers in the presence of Lewis acids (Et_1.5AlCl_1.5) in hydrocarbon solvent and the effect of Lewis acids concentration on copolymer composition are described. ¹³C NMR spectra were obtained on these copolymers. In samples of high MMA content, tactic placements of MMA were observed as well as several different kinds of sequences for chloroprene and MMA. In samples of low MMA content, no tactic placements of MMA were found but several different kinds of chloroprene sequences were observed. From the analysis of the ¹³C NMR spectra of the different copolymers examined, it is apparent that all the various kinds of chloroprene sequences in these copolymers can be determined.     

Synthesis of poly(β‐pinene)‐g‐poly(meth)acrylate by the combination of living cationic polymerization and atom transfer radical polymerization

New graft copolymers of β‐pinene with methyl methacrylate (MMA) or butyl acrylate (BA) were synthesized by the combination of living cationic polymerization and atom transfer radical polymerization (ATRP). β‐Pinene polymers with predetermined molecular weights and narrow molecular weight distributions (MWDs) were prepared by living cationic polymerization with the 1‐phenylethyl chloride/TiCl₄/Ti(OiPr)₄/nBu₄NCl initiating system, and the resultant polymers were brominated quantitatively by N‐bromosuccinamide in the presence of azobisisobutyronitrile, yielding poly(β‐pinene) macroinitiators with different bromine contents (Br/β‐pinene unit molar ratio = 1.0 and 0.5 for macroinitiators a and b , respectively). The macroinitiators, in conjunction with CuBr and 2,2′‐bipyridine, were used to initiate ATRP of BA or MMA. With macroinitiator a or b , the bulk polymerization of BA induced a linear first‐order kinetic plot and gave graft copolymers with controlled molecular weights and MWDs; this indicated the living nature of these polymerizations. The bulk polymerization of MMA initiated with macroinitiator a was completed instantaneously and induced insoluble gel products. However, the controlled polymerization of MMA was achieved with macroinitiator b in toluene and resulted in the desired graft copolymers with controlled molecular weights and MWDs. The structures of the obtained graft copolymers of β‐pinene with (methyl)methacrylate were confirmed by ¹H NMR spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1237–1242, 2003     

Laser‐induced decomposition of 2,2‐dimethoxy‐2‐phenylacetophenone and benzoin in methyl methacrylate homopolymerization studied via matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry

Pulsed laser polymerization (PLP) experiments were performed on the bulk polymerization of methyl methacrylate (MMA) at ?34 °C. The aim of this study was to investigate the polymer end groups formed during the photoinitiation process of MMA monomer using 2,2‐dimethoxy‐2‐phenylacetophenone (DMPA) and benzoin as initiators via matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectrometry. Analysis of the MALDI‐TOF spectra indicated that the two radical fragments generated upon pulsed laser irradiation show markedly different reactivity toward MMA: whereas the benzoyl fragment—common to both DMPA and benzoin—clearly participates in the initiation process, the acetal and benzyl alcohol fragments cannot be identified as end groups in the polymer. The complexity of the MALDI‐TOF spectrum strongly increased with increasing laser intensity, this effect being more pronounced in the case of benzoin. This indicates that a cleaner initiation process is at work when DMPA is used as the photoinitiator. In addition, the MALDI‐TOF spectra were analyzed to extract the propagation‐rate coefficient, k_p, of MMA at ?34 °C. The obtained value of k_p = 43.8 L mol^?1 s^?1 agrees well with corresponding numbers obtained via size exclusion chromatography (k_p = 40.5 L mol^?1 s^?1). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 675–681, 2002; DOI 10.1002/pola.10150     

Polymerization behavior of 1,2,2,6,6-pentamethyl-4-piperidinyl m-isopropenyl-α,α-dimethylbenzyl carbamate

Copolymers of 1,2,2,6,6-pentamethyl-4-piperidinyl m-isopropenyl-α,α-dimethylbenzyl carbamate (CB) with styrene (S) and with methyl methacrylate (MMA) were synthesized using AIBN as initiator. S–CB copolymers made from feed ranging from 0.45–0.94 mole fractions S and MMA-CB copolymers made from feed of 0.34–0.88 mole fractions MMA were used to determine the monomer reactivity ratios r₁ and r₂. The structure of S–CB copolymers was inferred to be mainly of a random nature and in the MMA–CB copolymerization system there is a stronger tendency to form alternating copolymers. © 1993 John Wiley & Sons, Inc.     

Syntheses and characterizations of aniline/butylthioaniline copolymers: Comparisons of copolymers prepared by the new concurrent reduction and substitution route and the conventional oxidative copolymerization method

New highly solution‐processable aniline/butylthioaniline copolymers were prepared via oxidative copolymerization (OCP) and by concurrent reduction and substitution (CRS). Butylthio‐substituted polyaniline obtained via the CRS route (Pan‐SBu), being in line with the expected property changes after the addition of an electron‐donating substituent to an aromatic ring, displayed a lowered redox potential (E⁰) and a redshifted maximum wavelength (λ_max; ultraviolet–visible) in comparison with its parent unsubstituted polyaniline (Pan). However, copolymers CP1–CP4 (obtained via the OCP method) displayed opposite behaviors, showing higher E⁰ values and blueshifts in λ_max than the unsubstituted Pan. The results suggested that CP1–CP4 had shorter conjugation lengths than the unsubstituted Pan, possibly because of their chain conjugation defects (e.g., 1,3‐ring linkage structures), as evidenced by IR studies. The results of ¹H NMR studies also indicated that Pan‐SBu had much higher structural homogeneity than copolymer CP4. Because the CRS synthetic route involved no backbone alternations, the resultant copolymer (Pan‐SBu) should have maintained the same backbone structure and hence the high conductivity of the parent unsubstituted Pan. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1767–1777, 2005     

Preparation and photochemical study of soluble optically active block copolymethacrylates and azo-containing random copolymethacrylates

A series of soluble optically active block copolymers of trityl methacrylate (TrMA) and cyclohexyldiphenylmethyl methacrylate (CHDPMA) with methyl methacrylate (MMA) and n-butyl methacrylate (n-BuMA) were synthesized using the complex of 9-fluorenyllithium and (S,S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane as an initiator in toluene at −78°C. Soluble optically active random copolymers derived from TrMA and azo methacrylates, 6-(4-phenylazophenoxy)hexyl methacrylate (PAHM) and 2-(4-phenylazophenoxy)ethyl methacrylate (PAEM), were obtained under similar anionic polymerization conditions. Optical activities of the copolymers largely depended on the weight percentage of TrMA or CHDPMA component in the polymer chains. Solubility and film formability were significantly improved for the copolymers. Irradiation of optically active TrMA–MMA and CHDPMA–MMA block copolymer films containing photoacid, diphenyl-p-tolylsulfonium triflate, causes the partial hydrolysis of bulky esters and results in the conformational randomization of helical chains, which in turn leads to a significant change in optical rotation of the films. Photoisomerization studies of azo-containing random copolymers indicate that the trans to cis isomerization induces the helical conformation racemization in solution. © 1997 John Wiley & Sons, Inc.     

Behavior of nitroxyl radical in the polymerization process forming copolymers bearing diarylnitrone pendants and photocontrol of refractive indices for these copolymers

To establish the reaction condition under which the radical copolymerization of methyl methacrylate (MMA) with α‐(2‐hydroxy‐4‐methacryloyloxyphenyl)‐N‐(2,6‐dimethylphenyl)nitrone (HMDN) proceeds smoothly to give photoreactive copolymers, the effects of the nitrone chromophore on the extent to which the radical polymerization of MMA is inhibited were investigated. It was found that the reversible addition of initiating radical to the CH?N⁺(? O^?) moiety in the nitrone chromophore readily occurs to give the nitroxyl radical. It was also found that the latter radical undergoes an efficient coupling reaction with propagating radical to inhibit the radical copolymerization of MMA with HMDN. However, on raising the reaction temperature and the radical concentration, the copolymerization was successfully carried out. This polymerization condition allowed us to prepare the HMDN/MMA, HMDN/styrene, and HMDN/cyclohexyl acrylate copolymers in good yields. The photoirradiation of the copolymer film prepared on a silicon wafer lowered its refractive index by 0.003–0.023, depending on the relative composition of the diarylnitrone chromophore in these copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 88–97, 2006     

SYNTHESIS OF ABA TYPE TRIBLOCK COPOLYMERS BY RADICAL POLYMERIZATION WITH 1,4-BIS(p-TERTBUTYLPHENYLSELENOMETHYL) BENZENE AS A PHOTOINIFERTER

1,4-Bis(p-tert-butylphenylselenomethyl)benzene was used as a bifunctional photoiniferter for the polymerization of methyl methacrylate (MMA). Both the polymer yields and the number average of molecular weights ([Mbar]_n) of polymers increased with the polymerization time and the [Mbar]_n linearly increased with polymer yield. The addition of MMA to the poly(MMA) with irradiation increased the [Mbar]_n of the polymer. Photoirradiation of telechelic polystyrene having phenylseleno groups at both ends as polymeric photoiniferter in the presence of MMA or p-chloromethylstyrene afforded effectively corresponding to the ABA type triblock copolymers. On the other hand, photopolymerization of p-methylstyrene with ABA type triblock copolymer of styrene and p-chloromethylstyrene as polymeric photoiniferter afforded to multiblock copolymer of styrene and p-substituted styrenes.     

Metal-Ylide Complex-Initiated Radical Copolymerization of Methylmethacrylate and Styrene

Abstract

Phenacyl dimethylsulfonium ylide complex of mercuric chloride (PDSY-HgCl₂)-initiated radical copolymerization of styrene with methylmethacrylate (MMA) at 85 ± 0.1°C using dioxane as an inert solvent yields random copolymers as evidenced by NMR spectroscopy. The kinetic equation for the present system was R_p α [PDSY-HgCl₂]^0.5 [Sty]^1.0 [MMA]^1.0. The values of energy of activation (ΔE) and k² _p/k₁ were 48.0 kJ mol^?1 and 8.6 × 10^?4 L mol^?1 s^?1, respectively. The mechanism of the reaction has also been proposed for the present system. The properties of copolymer were studied in the form of film. The film was highly absorptive for nitric acid but less absorptive for acetic acid. The film was water impermeable.