Synthesis of Poly(Vinyl Alcohol) / Silica Gel Polymer Hybrids by In-Situ Hydrolysis Method
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APPLIED ORGANOMETALLIC CHEMISTRY Appl. Organometal. Chem. 12, 755–762 (1998) Synthesis of Poly(vinyl alcohol) / Silica Gel Polymer Hybrids by In-Situ Hydrolysis Method Ryo Tamaki and Yoshiki Chujo* Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan Homogeneous poly(vinyl alcohol) (PVA)–silica biosensors6 or thermally stable nonlinear optical gel polymer hybrids were prepared by in-situ materials.7–10 The homogeneous combination of hydrolysis of poly(vinyl acetate) (PVAc) in a sol– two materials also produces an enhancement of the gel reaction mixture with tetramethoxysilane mechanical strength of organic polymers such as (TMOS). The degree of hydrolysis was evaluated poly(dimethylsiloxane) with silica particles11–15 or by FTIR and 13C CP/MAS NMR; it increased a modification of the mechanical properties of silica with an increase in the acid catalyst and reached by introduction of organic polymers into the silica 85% with 1.6 ml of 0.1 M HCl. The homogeneity phase.16 The hybrid materials are also potential of the polymer hybrids obtained was maintained candidates for catalysts17–19 and gas separation when the reaction was performed at 60 °C. membranes.20–24 However, the polymer hybrid became turbid The sol–gel technique applied to metal alkoxides with an increase of the amount of catalyst is one of the most efficient methods for the present when the reaction was conducted at preparation of composite materials. The method room temperature. The homogeneity of the comprises initial hydrolysis of those metal alk- polymer hybrids obtained was evaluated by oxides and subsequent condensation and removal of nitrogen sorption porosimetry of a porous silica the solvents, resulting in metal oxides (Scheme 1 that was obtained by charring the PVA hybrid. top).25–30 The advantage of the sol–gel technique The results confirmed the molecular-level dis- for preparing composite materials is the low persion of the PVA in the hybrid. # 1998 John reaction temperature, e.g. room temperature, at Wiley & Sons, Ltd. which the reactions are conducted, while the conventional melt fusion technique of silica glasses Keywords: poly(vinyl alcohol) (PVA); sol–gel; needs a high temperature. Thus, it enables the polymer hybrid incorporation of organic elements into inorganic Received 24 September 1997; accepted 23 December 1997 materials without deterioration of their function- ality. It is also noteworthy that silica gels obtained by the sol–gel reaction contain a large number of residual hydroxyl groups. We have succeeded in preparing homogeneous INTRODUCTION organic–inorganic polymer hybrids by incorporat- ing organic polymers such as poly(2-methyl-2- In recent years, organic–inorganic polymer hybrids oxazoline), poly(vinylpyrrolidone) or poly(N,N- dimethylacrylamide) into the sol–gel reaction with a large variety of functionality have been 31–41 studied intensively. The combination of the two mixture of alkoxysilanes. The residual silanol components at a molecular level would provide groups in the silica gel and amide groups in the novel properties that are hardly obtained from polymers would develop hydrogen-bonding inter- conventional organic or inorganic materials. It actions which would help uniform dispersion of results, for instance, in waveguides,1–5 optical each segment. As a precondition for the formation of homogeneous polymer hybrids, polymers should be * Correspondence to: Yoshiki Chujo, Department of Polymer dispersed uniformly in the sol–gel reaction solution. Chemistry, Graduate School of Engineering, Kyoto University, Organic polymers with highly polar functional Yoshida, Sakyo-ku, Kyoto 606-8501, Japan. groups, however, aggregate as the sol–gel reaction Contract/grant sponsor: Ministry of Education, Science, Sports and Culture, Japan. proceeds, to form a silica matrix due to the strong Contract/grant sponsor: Grant-in-Aid for Scientific Research on interaction between the polymers themselves. Priority Areas; Contract/grant number: 08231242. In our group, a method has been utilized to # 1998 John Wiley & Sons, Ltd. CCC 0268–2605/98/100755–08 $17.50 756 R. TAMAKI AND Y. CHUJO Scheme 1 Top: reductions involved in the conventional sol–gel technique for preparing composite materials. Bottom: PVAc hydrolysis. suppress the aggregation, namely the modification after distillation under nitrogen. Methanol (Wako of these functional groups by adequate substitutes. Pure Chemical Industries Ltd) was used after For example, hydroxyl and amino groups of distillation with sodium under nitrogen. PVAc chitosan were converted into urethane and phtha- (Aldrich Chemical Co. Inc., average Mw ca limide groups, respectively. These functional 167 000) and 0.1 M HCl (Wako Pure Chemical groups act not only as hydrogen-bonding accepting Industries Ltd) were used as supplied. groups but as the hindering groups for the aggregation by diminishing the polarity.42 These methods, however, altered the structure of Preparation of poly(vinyl alcohol) the organic polymers and affected their properties. and silica gel hybrids In some cases their high polarities play an PVAc (0.4 g or 1.0 g) was dissolved in 20 ml of important role in manifestation of unique properties methanol. TMOS (2.0 g) and 0.1 M HCl were added 43 such as gas-barrier or metal-chelating activities. to the solution with continuous mixing at ambient Thus, another synthetic technique is desired to temperature. The reaction mixture was stirred at the incorporate the polymers without such a modifica- same temperature for 5 h and subsequently heated tion. at 60 °C for one week (or left at room temperature Here we introduce a novel synthetic method in for two weeks) with an aluminum foil cover having which precursor polymers were employed instead a few pinholes. After the heating period, a hard of targeted organic polymers. The method com- glass-like material was obtained. These reactions prises the initial incorporation of the precursors of were carried out in air. desired polymers into a sol–gel reaction solution of alkoxysilanes and the following simultaneous hydrolysis of the functional groups of the precursor Measurement polymers and alkoxysilanes. PVAc was used as a The dried gel obtained was crushed into powder and precursor for the synthesis of PVA and silica gel kept in a desiccator until the analyses were polymer hybrids. conducted. Thermal gravimetric analysis (TGA) was performed on a Shimadzu TG-30, TGC-30 1 system with a heating rate of 10 °C min in air. Fourier transform infrared (FTIR) spectra were EXPERIMENTAL obtained from KBr powder-pressed pellets on a Perkin-Elmer 1600 Series FT-IR instrument. Solid- 13 Chemicals state C CP/MAS NMR spectra were measured on a JNM-GSX FT-NMR spectrometer. The data were TMOS (Tokyo Kasei Kogyo Co. Ltd) was used obtained in the mode of total suppression of # 1998 John Wiley & Sons, Ltd. Appl. Organometal. Chem. 12, 755–762 (1998) POLY(VINYL ALCOHOL)/SILICA GEL POLYMER HYBRIDS 757 Scheme 2 Preparation of polymer hybrids. spinning sidebands (TOSS) at a frequency of the polymer and the residual silanol groups in silica 100.15 MHz at ambient temperature. Nitrogen gels. It was also reported that the functional groups absorption porosimetry of a porous silica obtained of PVAc provide hydroxyl groups effectively via by charring the polymer hybrid at 600 °C under the hydrolysis reactions with either acid or base ambient atmosphere was conducted with a BEL catalysts, particularly in alcohol solvents by ester Japan Inc. instrument. The porous silica was dried exchange ( Scheme 1, bottom). Therefore, it was at 200 °C for 2 h at reduced pressure under a expected that PVAc would produce homogeneous nitrogen atmosphere before the measurement. A PVA polymer hybrids by hydrolysis of the func- surface area, a pore volume and a pore size were tional groups, if sufficient acid catalyst was calculated with the MP equation program supplied employed. The relation between the rate of with the apparatus.44 hydrolysis of PVAc and that of silica gel formation might be critical for the homogeneity of PVA polymer hybrids. To control these factors, the acid catalyst and the reaction temperature were varied. RESULTS AND DISCUSSION The polymer hybrids were prepared according to Scheme 2. PVAc was added to a methanol solution PVA has high crystallinity due to the hydroxyl of TMOS and the volume of 0.1 M HCl aq was groups in its side-chain. The groups cause the phase altered from 0.02 to 0.60 ml. The weight ratio of separation when the polymer is used as a starting organic polymer to TMOS was 0.2. The mixture material for the synthesis of hybrids with silica gel. was then heated at 60 °C for seven days to yield PVAc, on the other hand, has acetyl groups as homogeneous and transparent glassy materials, repeating units and its polarity is not as strong as though the samples with high acid-catalyst content that of PVA. The polymer hybrid containing PVAc became dark. was prepared by Landry et al.45–47 by utilizing the The degree of hydrolysis was evaluated with hydrogen-bonding interaction of acetyl groups in FTIR. As illustrated in Fig. 1 the intensity of the # 1998 John Wiley & Sons, Ltd. Appl. Organometal. Chem. 12, 755–762 (1998) 758 R. TAMAKI AND Y. CHUJO Figure 1 IR spectra for hydrolysis of poly(vinyl alcohol) hybrids. carbonyl stretching vibration peak decreased with action between silanol groups in the silica gel with an increase of the amount of catalyst and it almost an increase of the acid content as reported disappeared when the acid content was 1.6 ml. It previously.45 The degree of hydrolysis was calcu- was also observed that the peak shifted to lower lated by comparing the relative intensity due to the wavenumbers due to the hydrogen-bonding inter- carbonyl groups with that of the Si–O–Si stretching Table 1 Preparation of poly(vinyl alcohol) hybridsa PVAc/TMOS Reaction Vol.