Tin effect in formation and photocross-linking reactions of tri-n-butylstannyl methacrylate-allyl chloroacetate copolymer

Radical-initiated copolymerization of tri-n-butylstannyl methacrylate (TBSM) with allyl chloroacetate (ACA) was carried out in the presence of benzoyl peroxide as initiator in benzene at 70 degrees C in nitrogen atmosphere. Monomer reactivity ratios of the TBSM (M-1)-ACA (M-2) monomer pair were determined by the Kelen-Tudos method: r(1) = 1.25 +/- 0.02 and r(2) = 0.13 +/- 0.005. From copolymerization kinetic data the Values of effective energy of activation (E-a) and orders with respect to initiator (n) and to monomers (m), E-a = 79.0 kJ/mol, n = 0.51, and m = 1.2, were determined. Photochemical reactions of the copolymer were studied by using monochromatic W-irradiation at 405 nm and FTIR spectroscopy. For the copolymer synthesized the quantum efficiency (phi(crl) = 0.62 mol/Einstein and photosensitivity S = 25.5 cm(2)/J (in the presence of 1,9-dibromoanthracene as a sensitizer) were found. It was shown that the effects observed of the tin atom and Cl substituent via pentacoordinated complex (-R3Sn...O=C-) and sigma(Cl-CH2)-pi(C=O)-pi(allyl) conjugation, respectively, are the main factors for reducing degradative chain transfer and for increasing the tendency of monomers to alternate as well as for the photocrosslinking of copolymer macromolecules. (C) 1998 John Wiley & Sons, Inc

Complex-radical terpolymerization of glycidyl(methyl) methacrylates, styrene, and maleic anhydride

The ternary copolymerizations of glycidlyl(methyl) methacrylates (GMA and MMA), styrene (St), and maleic anhydride (MA), considered as acceptor(A(1))donor-acceptor(A(2)) systems, were carried out in methyl ethyl ketone in the presence of benzoyl peroxide as initiator at 50-80 degrees C. Constants of copolymerization, complex formation, and some kinetic parameters for the monomer systems studied were determined by the methods of Hanna-Ashbaugh, Kelen-Tudos, and Seiner-Litt, as well as by dilatometry, respectively. The results show that terpolymerizations were carried out through primary "complex" mechanisms at near-binary copolymerization of GMA (or MMA) with the St MA complex. The terpolymers synthesized which comprised free anhydride and epoxide reactive groups easily underwent crosslinking by thermotreatment and by UV irradiation, which was confirmed by DTA, TMA, and FTIR analyses. (C) 1999 John Wiley & Sons, Inc

ALTERNATING CYCLOPOLYMERIZATION OF ALLYL TRANS-CINNAMATE AND MALEIC-ANHYDRIDE

Some features of the radical copolymerization of allyl cinnamate bifunctional monomers, containing donor (allyl)-acceptor (beta-phenylacryl) double bonds in the molecule, with maleic anhydride have been revealed. The kinetic parameters of the reactions, including their complex-formation, cyclization and copolymerization constants, as well as the ratios of chain growth rates for the participation of monomeric charge-transfer complexes and free monomers, are all determined. It has been established that an alternative cyclocopolymerization reaction is realized, which is carried out via a complex mechanism with the formation of macromolecules with unsaturated cycle-linear structures. The synthesized copolymers show high sensitivity to ultraviolet irradiation, electron beams and X-rays, but their negative resists differed, with high lithographic parameters and plasma stability

Complex-radical cyclocopolymerization of allyl a-(N-maleimido)acetate with styrene and maleic anhydride

Radical copolymerizations of allyl alpha-(N-maleimido)acetate (AMI) with styrene (D, electron-donor) or maleic anhydride (A, electron-acceptor) were carried out in benzene and/or methyl ethyl ketone (MEK) at 50-70 degrees C in the presence of 2,2'-azoisobutyronitrile (AIBN) as initiator. The structure and properties of copolymers synthesized were derived from IR, chemical, DTA and TGA analyses. Side-chain unsaturation of macromolecules was also proved by the crosslinking effect observed. Kinetic parameters of copolymerization such as complex-formation (K-c), cyclization (k(cyc)), and copolymerization constants and ratios of chain growth rates for the participation of monomer charge transfer complexes (CTC) and free monomers for both systems were obtained: K-c = 0,20 +/- 0,01 and 0,05 +/- 0,005 L/mol in CH3COOH-d(4) at 35 +/- 0,1 degrees C (H-1 NMR method) for D...AMI and AMI... A complexes, respectively; k(cyc) . 10(5) = 1.71 and 0,66 L/(mol . s), r(1) = 0,13 +/- 0,01 and 0,037 +/- 0,002, r(2) = 0,048 +/- 0.002 and 0,052 +/- 0,002 (by Kelen-Tudos method), k(12)/ k(21) = 0,20 and 0,62, k(1c)/k(12) = 0,6 and 29,8, k(2c)/k(21) = 4,8 and 9,1 for the D-AMI and AMI- A systems, respectively. The results show that alternating cyclocopolymerization reactions are realized which are carried out via a ''mixed'' mechanism in the D-AMI system and via a ''complex'' mechanism in the AMI-A system, with formation of cyclolinear macromolecules containing side-chain unsaturated fragments of ''allyl'' (D-AMI copolymer) and ''imide' (AMI-A copolymer) types. The synthesized copolymers easily undergo crosslinking by thermotreatment (105 degrees C, 30 min) and/or by UV-irradiation (25 degrees C, 15 min), which was confirmed by DTA and TGA analyses

Plasma surface modification of polyethylene with organosilicon and orcanotin monomers

Plasmochemical modification of a polyethylene (PE) film surface by several selected silicon and tin containing monomers, such as vinyltriethoxysilane (VTES), hexamethyldisiloxane (HMDS), 3-aminopropyltriethoxysilane (APTS), tetraethylstannane (TES) and hexabutyldistannoxane (HBDS) were all examined. The structure and properties of plasma polymers obtained and plasma modified PE film surfaces were studied by FTIR, photoacoustic FTIR spectroscopies and by using surface energy and swelling measurements. It is shown that the structure of plasma polymers formed either on the inorganic non-active or on the organic active (PE films) surfaces do not differ much from each other. In the structure of the organosilicon surface plasma polymers, mainly polysiloxane type fragments emerge; while for the organotin analogs primarily carboxylate fragments predominate, The plasma of organosilicon and organotin compounds were used to modify PE film surfaces to produce thin hydrophobic, biologically active and inactive surfaces. The results of surface energy studies as followed by the interaction with methylene iodide (non-polar) and ethylene glycol (polar components), and degree of swelling studies for both unmodified as well as plasma modified PE films, in xylene showed decrease in the latter and an increase of hydrophobic components as expected

Effect of inorganic salts on the main parameters of the dilute aqueous poly(vinylpyrrolidone) solutions

The effect of inorganic salts (cosolute) on the main parameters of dilute aqueous poly(vinylpyrrolidone) (PVP) solutions, such as cloud points, phase diagram, theta temperature and viscosity was studied experimentally using various concentrations of salts and said polymer at varying temperatures. It is shown that, thermodynamic incompatibility of aqueous PVP-salts solutions strongly depends on the character of effect of salts (water-structure breakers or water-structure makers). Inclusion of salts into aqueous PVP solution leads to decreasing of the theta temperature and intrinsic viscosity which is caused by effect of the cosolute ions in enhancing the segment-segment interactions. (C) 1996 Elsevier Science Ltd

COMPLEX-RADICAL COPOLYMERIZATION OF ALLYL CINNAMATE WITH STYRENE

Some peculiarities in the radical copolymerization of trans-allyl cinnamate, a bifunctional monomer containing donor (allyl) and acceptor (cinnamic) double bonds in the molecule, with styrene in methyl ethyl ketone, at 60 degrees C, using 2,2'-azobis(isobutyronitile) as the initiator have been revealed. Kinetic parameters of copolymerization such as complex formation, cyclization, and copolymerization constants and ratios of chain growth rates for the participation of monomeric charge transfer complexes (CTC) and free monomers are all determined. The results show that an alternative copolymerization reaction is realized which is carried out via a ''mixed'' mechanism with formation of macromolecules of unsaturated cyclolinear structures. It has been established that the chain growth proceeds predominantly through the reaction of cinnamic macroradicals with CTC and free styrene monomer. It has been proved that obtained copolymer is highly sensitive to UV-irradiation, E-beams, and X-rays, providing high lithographic parameters and plasmastability for its negative resists

Side-chain functionalization of polystyrene with maleic anhydride in the presence of Lewis acids

Polystyrenes with different molecular weights were chemically modified with maleic anhydride by use of certain cationic catalysts of Lewis acid type (BF3 . OEt(2), AlCl3, TiCl4, ZnCl2, FeCl3, and SnCl4) in chloroform. The effects of molecular weight of polystyrene, as well as type of Lewis acid used, on properties and structure of products were investigated. The interrelation between the molecular weight of polystyrene and content of carboxyl groups in the products was made. A direct relationship between the activity of catalyst used and the number of carboxyl groups was found. For characterization of side-chain functionalized polystyrene, fractional precipitation was applied which yielded carboxyl groups in all fractions. The carboxyl group concentrations were found to be the highest in the case of BF3 . OEt(2). Modified polystyrene samples containing - CO - CH = CH - COOH fragments in side chains are easily crosslinked at 140-150 degrees C and by UV irradiation as proved by IR, DTA, and TGA analyses. Functionalized polymers obtained are characterized by their high thermostability, adhesion, and photosensitivity. (C) 1996 John Wiley & Sons, Inc