Elsevier

Polymer

Volume 42, Issue 13, June 2001, Pages 5599-5606
Polymer

Reactions of some anhydride-containing copolymers with γ-aminopropyltriethoxysilane

https://doi.org/10.1016/S0032-3861(00)00924-1Get rights and content

Abstract

This work describes the synthesis and macromolecular reactions of maleic anhydride (MA)–methyl methacrylate (MMA) binary and MA–trans-stilbene (Stb)–n-butyl methacrylate (BMA) ternary reactive copolymers with γ-aminopropyltriethoxysilane (APTS) as a polyfunctional crosslinker. Copolymers with given compositions of MA–MMA (77.7 mol%) and MA (22.7 mol%)–Stb–BMA (54.2 mol%) are synthesised by radical binary and ternary copolymerisations with benzoyl peroxide as an initiator in toluene at 70°C and initial monomer ratios 1:4 and 1:1:1, respectively. It is shown that the network structure is formed in MA–MMA/APTS and MA–Stb–BMA/APTS in methyl ethyl ketone (MEK) solutions by intermolecular reactions between the anhydride unit and the amine group, as well as between the ethoxysilyl fragment and the free carboxyl group formed after the amidisation of the anhydride unit. Swelling parameters, such as the beginning time of xerogel-formation, initial rate of swelling and equilibrium swelling, are determined for the copolymer/APTS/MEK system with various polymer/crosslinker ratios. Formation of a hyperbranched network structure through the fragmentation of side-chain reactive groups in the studied systems is confirmed by FTIR, TGA and DSC methods.

Introduction

Design and synthesis of novel macromolecular architectures based on hyperbranched polymers and new type of composites including crosslinked networks, hydrogels and solvent–gel systems are important fields of polymer science and macromolecular engineering [1], [2], [3], [4]. From this position, highly reactive anhydride-containing macromolecules including alternating and random copolymers and terpolymers, cyclocopolymers, block and graft copolymers of maleic anhydride and its isostructural analogies can serve as starting materials for the realisation of the above-mentioned synthesis. Synthesis and macromolecular reactions of anhydride-containing polymers and copolymers with various amines, epoxides, alcohols, polyols, etc. were described and discussed [5], [6].

Non-linear optical polymers with high glass transition temperature (178–228°C) were prepared by the polymer analogous reaction of maleic anhydride copolymers with aminoalkyl-functionalised azo- and stilbene chromophores [7]. A series of all solvent–gel organic–inorganic non-linear optical materials based on the melamines and an alkoxysilane dye was also investigated [8].

Silane-based coupling agents, most frequently γ-aminopropyltriethoxysilane (APTS), were used to improve the surface adhesion in various polymer composites [9], to surface modify polypropylene[10] and polyethylene films [11], and for the preparation of silica hybrid materials by situ solvent (THF)–gel process using maleic anhydride (12 mol%)–styrene random copolymer/tetraethoxysilane/APTS system [12]. The interactions of MA–styrene or MA–α-olefins alternating copolymers with APTS were studied by means of FTIR-ART spectroscopy [13]. Reaction of plasma-activated polyolefin films with maleic anhydride–vinyltriethoxysilane oligomer led to an increase in the hydophobicity of polypropylene surfaces as well as to a reduction in the swelling degree of films in cyclohexanone [10]. It was shown that the reaction of plasma-activated polypropylene with maleic anhydride–vinyltriethoxysilane oligomer proceeded through intermolecular esterification, intramolecular reaction of free carboxyl group with ethoxysilyl fragments and polycondensation of ethoxysilyl groups with the formation of crosslinked poly (organosiloxane) structures on the polymer surface [10]. Polyimide–silica hybrids were obtained using the non-aqueous solvent–gel process by polycondensation of phenyltriethoxysilane in a polyamic acid solution [14]. Self-catalysed hydrolysis of phenyl-substituted aloxysilane and modification on the polyimide structure were applied and resulted in highly compatible polyimide–silica hybrids. The prepared hybrid films with high silica content (45%) had high thermostability.

Recently we have reported that some anhydride-containing copolymers easily undergo crosslinking with APTS in non-aqueous solutions [15]. In the present work, the experimental results on the macromolecular reactions of maleic anhydride (MA unit of 22 mol%)–methyl methacrylate (MMA) random copolymer and MA (24.3 mol%)–trans-stilbene (Stb)–n-butyl methacrylate (BMA unit of 45.3 mol%) terpolymer with APTS as a polyfunctional crosslinker and the swelling process in the MA–MMA/APTS/MEK (solvent) and MA–Stb–BMA/APTS/MEK systems are described and discussed.

Section snippets

Materials

Initial monomers such as methyl methacrylate (MMA) and n-butyl methacrylate (BMA) supplied by Fluka, were distilled before use. They had the following characteristics: MMA, b.p. 99.5°C, d420=0.943 and nD20=1.414; BMA, b.p. 162.5°C, d420=0.892 and nD20=1.420. Maleic anhydride (MA, Fluka product) was purified before use by recrystallisation from anhydrous benzene and by sublimation in vacuo, m.p. 52.8°C and sublimation temperature 199°C. Commercial trans-stilbene (Stb) was purified before use by

Macromolecular reactions of binary and ternary copolymers with γ-aminopropyltriethoxysilane

For the studies of crosslinking and swelling process, anhydride containing MA–MMA random copolymer with 22.5 mol% of MA-units and MA–Stb–BMA terpolymer with a monomer unit composition of m1:m2:m3=22.97:23.15:53.94 are used as crosslinkable polymers. APTS containing amine and triethoxysilyl reactive groups is used as a polyfunctional crosslinker.

From the structural peculiarities of these polymers/crosslinker systems and classical principle of macromolecular reactions it can be assumed that the

Acknowledgements

This study was carried out in accordance with Polymer Science Program of Department of Chemistry, Hacettepe University and was supported by TÜBİTAK (Turkish National Scientific and Technical Research Council) through Project MISAG-146 which is acknowledged.

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