Nitroxide-mediated photo-controlled/living radical dispersion polymerization of methyl methacrylate

The nitroxide-mediated photo dispersion polymerization of methyl methacrylate (MMA) was performed by irradiation at room temperature using (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator, (4-tert-butylphenyl)-diphenylsulfonium triflate as the photo-acid generator, and polyvinylpyrrolidone (PVP) as the surfactant in a mixed solvent of methanol/water = 3/1 (v/v). The MTEMPO-mediated photo dispersion polymerization produced spherical particles of PMMA, while the uncontrolled photo dispersion polymerization without MTEMPO provided nonspherical particles. The size distribution of the spherical particles decreased as the PVP concentration increased. The spherical particles showed a comparatively narrow molecular weight distribution of ca. 1.6. The livingness of the polymerization was confirmed on the basis of the linear correlations of the first-order time–conversion plots and conversion–molecular weight plots. The simultaneous control of the size distribution and molecular weight was possible as long as the light penetrates into the particles.     

Preparation of micelles with azo dye and UV absorbent at their cores or coronas using non-amphiphilic block copolymers

Micelles with azo dye and UV absorbent at their cores or coronas were prepared from non-amphiphilic random diblock copolymers by α,ω-diamine. Poly[4-(phenylazophenoxymethyl)styrene-ran-4-(2-hydroxybenzophenoxymethyl)styrene-ran-vinylphenol]-block-polystyrene (P(AS-r-HBS-r-VPh)-b-PSt) and poly(vinylphenol)-block-poly[4-(phenylazophenoxymethyl)styrene-ran-4-(2-hydroxybenzophenoxymethyl)styrene-ran-styrene] (PVPh-b-P(AS-r-HBS-r-St)) diblock copolymers were prepared by living radical polymerization mediated by 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. The former copolymer had a molecular weight of Mn[P(AS-r-HBS-r-VPh)-b-PSt] = 10,000-b-250,000 by ¹H NMR and a molar ratio of AS:HBS:VPh = 0.01:0.01:0.98, while the latter had a molecular weight of Mn[PVPh-b-P(AS-r-HBS-r-St)] = 10,000-b-111,000 and a molar ratio of AS:HBS:St = 0.02:0.03:0.95. The copolymers showed no self-assembly in 1,4-dioxane because this solvent was non-selective to the copolymers. Dynamic light scattering demonstrated that the copolymers formed micelles in the solvent in the presence of α,ω-diamine. The hydrodynamic radii of the micelles slightly increased with the copolymer concentration decrease, while the aggregation numbers were almost independent of the copolymer concentration. It was found that P(AS-r-HBS-r-VPh)-b-PSt formed smaller micelles with a lower aggregation number than PVPh-b-P(AS-r-HBS-r-St) because of the steric hindrance of the AS and HBS units present at the micellar coronas.     

Nitroxide-mediated photo-living radical polymerization of methyl methacrylate in the presence of (η6-benzene)(η5-cyclopentadienyl)FeII hexafluorophosphate

The photoradical polymerization of methyl methacrylate (MMA) was performed at room temperature using (2RS,2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator in the presence of (η⁶-benzene)(η⁵-cyclopentadienyl)Fe^II hexafluorophosphate (BzCpFe^II). The bulk polymerization provided narrower molecular weight distributions (Mw/Mn = 1.4 − 1.5) than the solution polymerization in acetonitrile, although BzCpFe^II was insoluble in MMA. The polymerization rate was retarded by an increase in the amount of BzCpFe^II. BzCpFe^II, which had no ability to control the molecular weight by itself, could control it through the interaction with MTEMPO. The interaction of BzCpFe^II and MTEMPO was attributed to the electron transfer involving the MTEMPO–aminoxy anion redox system and the iron redox system. The polymerization was confirmed to occur in accordance with a living mechanism because linear correlations were obtained for both the plots of the first order time–conversion and the conversion–molecular weight.     

Nitroxide-mediated photo-controlled/living radical polymerization of ethyl acrylate

The nitroxide-mediated photo-controlled/living radical polymerization of ethyl acrylate was attained using (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator, and (4-tert-butylphenyl)diphenylsulfonium triflate as the photo-acid generator. The photopolymerization was performed in acetonitrile at room temperature by irradiation with a high-pressure mercury lamp. The molecular weight distribution of the resulting polymer decreased as the monomer concentration decreased. It was confirmed that the polymerization was controlled on the basis of the linear correlations for the first-order time-conversion plots and the plots of the molecular weight vs. the reciprocal of the initial concentration of the initiator, although the conversion–molecular weight plots did not show a completely linear correlation. The block copolymerization with methyl methacrylate accompanied by no deactivation of the growing polymer chain end supported the livingness of the polymerization.     

Photo-controlled/living radical polymerization of tert-butyl methacrylate in the presence of a photo-acid generator using a nitroxide mediator

The photo-controlled/living radical polymerization of tert-butyl methacrylate was performed using a (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) initiator and a 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) mediator in the presence of a (4-tert-butylphenyl)diphenylsulfonium triflate photo-acid generator. The bulk polymerization was carried out at 25 °C by irradiation with a high-pressure mercury lamp. Whereas the polymerization in the absence of MTEMPO produced a broad molecular weight distribution, the MTEMPO-mediated polymerization provided a polymer with a comparatively narrow molecular weight distribution around 1.4 without elimination of the tert-butyl groups. The living nature of the polymerization was confirmed on the basis of the linear correlations for the first-order time–conversion plots and conversion–molecular weight plots in the range below 50% conversion. The block copolymerization with methyl methacrylate also supported the livingness of the polymerization based on no deactivation of the prepolymer.     

Nitroxide-mediated photo-living radical polymerization of methyl methacrylate using (4-tert-butylphenyl)diphenyl-sulfonium triflate as a photo-acid generator

The photo-living radical polymerization of methyl methacrylate (MMA) was performed at room temperature using (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) (r-AMDV) as the initiator, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator, and (4-tert-butylphenyl)diphenylsulfonium triflate ( ^t BuS) as the photo-acid generator. The livingness of the polymerization was confirmed on the basis of linear increases in the ln([MMA]₀/[MMA]_t) vs. time and in the molecular weight vs. the conversion. The molecular weight distributions of the resulting polymers were around 1.45. The polymerization rate was dependent both on the ^t BuS/MTEMPO and MTEMPO/r-AMDV molar ratios. Furthermore, it was found that the polymerization had a photo-latency because the polymerization was retarded by the interruption of the irradiation; however, it was accelerated again by further irradiation without deactivation of the growing polymer chain ends.     

Synthesis of poly(methyl methacrylate)-<Emphasis Type="Italic">block</Emphasis>-poly(tetrahydrofuran) by photo-living radical polymerization using a 2,2,6,6-tetramethylpiperidine-1-oxyl macromediator

The synthesis of a poly(methyl methacrylate)-block-poly(tetrahydrofuran) (PMMA-b-PTHF) diblock copolymer was attained by the photo-living radical polymerization of methyl methacrylate using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) supported on the chain end of poly(tetrahydrofuran) (PTHF) as the macromediator. The polymerization was performed at room temperature by 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) as an initiator in the presence of bis(alkylphenyl)iodonium hexafluorophosphate as a photo-acid generator to produce the diblock copolymer consisting of poly(methyl methacrylate) (PMMA) and PTHF blocks connected through the TEMPO. The polymerization was confirmed to proceed in accordance with a living mechanism based on linear correlations for three different plots of the first order time-conversion, the molecular weight of the copolymer versus the monomer conversion, and the molecular weight versus the reciprocal of the initial concentration of the initiator. The molecular weight distribution of the block copolymer was dependent on the molecular weight of the macromediator based on the miscibility of PMMA and PTHF.     

Photo-living radical polymerization of methyl methacrylate by 2,2,6,6-tetramethylpiperidine-1-oxyl in the presence of a photo-acid generator

The novel photo-living radical polymerization of methyl methacrylate (MMA) was determined using 2,2’-azobis(4-methoxy-2,4-dimethylvaleronitrile) (AMDV) and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) in the presence of bis(alkylphenyl)iodonium hexafluorophosphate (BAI). The polymerization provided a comparatively narrow molecular weight distribution in the range of 1.4–1.7. The resulting PMMA contained no BAI fragments in its structure and had the 1-cyano-1,3-dimethyl-3-methoxybutyl radical and MTEMPO at the 1:1 molar ratio. The experimental molecular weight was in close agreement with the theoretical one when the initiator efficiency was taken into consideration. The plots of ln([MMA]₀/[MMA]) vs. time and the molecular weight of PMMA vs. the conversion and vs. the reciprocal of the initial concentration of AMDV showed linear correlations, indicating that the polymerization proceeded in accordance with a living mechanism. It was found that the polymerization had a photo-switching ability, because the polymerization was interrupted by turning off the irradiation, and then restarted by the irradiation again.     

Stability of growing polymer chain ends for nitroxide-mediated photo-living radical polymerization

The stability of the growing polymer chain ends for the nitroxide-mediated photo-living radical polymerization of methyl methacrylate (MMA) was explored through block copolymerization with isopropyl methacrylate ( ⁱ PMA). The block copolymerization of ⁱ PMA was performed with the PMMA prepolymer prepared by the photopolymerization of MMA using the racemic-(2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) (r-AMDV) as the initiator, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator, and (4-tert-butylphenyl)-diphenylsulfonium triflate ( ^t BuS) as the photo-acid generator. When the polymerization of MMA was carried out for 6.5 h, the resulting block copolymer showed a bimodal GPC due to the deactivation of part of the growing chain ends of the prepolymer. On the other hand, when the MMA polymerization was shortened to 5 h, the unimodal block copolymer was obtained without deactivation of the prepolymer.     

Nitroxide-mediated photo-living radical polymerization of methyl methacrylate in solution

The photoradical polymerization of methyl methacrylate (MMA) was performed in an acetonitrile solution at room temperature using (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator, and (4-tert-butylphenyl)diphenylsulfonium triflate as the photo-acid generator. This solution polymerization showed a non-steady-state during the very early stage followed by a steady-state. The polymerization produced oligomers with several thousand molecular weights at a very low conversion under the non-steady-state. It was confirmed that the polymerization proceeded in accordance with a living mechanism under the steady-state based on the linear correlations for both the first-order time-conversion plots and the conversion–molecular weight plots. The molecular weight distributions of the polymers obtained in the steady-state were approximately 1.8. The block copolymerization with isopropyl methacrylate ( ⁱ PMA) demonstrated that the growing polymer chain ends of the MMA prepolymer were stabilized even at a high conversion and efficiently initiated the ⁱ PMA polymerization.     

Synthesis and thermal properties of poly(methyl methacrylate)-graft-(cellobiosylamine-C15)

Model experiments for synthesis of a comb-shaped copolymer with cellulose side-chains were performed with cellobiose derivatives. A novel cellobiose monomer, N-(15-methacryloyloxypentadecanoyl)-2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-β-d-glucopyranosylamine (2) was prepared from heptaacetylcellobiosyl- amine. Homopolymerization of cellobiose monomer 2 and copolymerization of monomer 2 with methyl methacrylate (MMA) were performed using 2,2′-azobis(isobutyronitrile) (AIBN) as an initiator to obtain homopolymers 3-i (i = 1–4) and copolymers 3-i (i = 5–7), poly(methyl methacrylate)-graft-(heptaacetylcellobiosylamine-C15). The size exclusion chromatography—multi-angle laser light scattering (SEC-MALS) measurements revealed that comb-shaped homopolymers 3-i (i = 1–4) had more compact structures compared to copolymers 3-i (i = 5–7) at the same elution volume. Selective deacetylation of polymers 3-i (i = 1–7) gave novel cellobiose polymers 4-i (i = 1–7), poly(methyl methacrylate)-graft-(cellobiosylamine-C15). The amide linkages between cellobiose moiety and long-chain alkyl group, and the ester linkages between PMMA main-chain and long-chain alkyl group remained after deprotection. The differential scanning calorimetry (DSC) measurements revealed that the T _gs of the polymers 4-i (i = 1, 5, 6, 7) increased with increasing cellobiose composition in the polymers. It was indicated that cellobiose moieties of polymers 4-i (i = 1, 5, 6, 7) reduced the mobility of PMMA main-chain.     

Effect of azoinitiators on nitroxide-mediated photo-living radical polymerization of methyl methacrylate

In order to clarify the initiator factor dominating the molecular weight distribution of the resulting polymer, the nitroxide-mediated photo-living radical polymerization of methyl methacrylate was performed using eight different kinds of azoinitiators: i.e., 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), racemic-(2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile), meso-(2RS,2′SR)-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis(2-methylpropionate), and 2,2′-azobis(N-butyl-2-methylpropionamide). The bulk polymerization was carried out at room temperature for 3 h using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator in the presence of bis(alkylphenyl)iodonium hexafluorophosphate as the photo-acid generator. All the initiators provided a molecular weight distribution below 1.7 for the MTEMPO/initiator ratio of 2, although at the ratio of unity, about half of the initiators produced the molecular weight distribution around 2.3–3.4. The UV analysis revealed that the initiators having a higher ε value tended to more strictly control the molecular weight and provide a higher initiator efficiency. The half-lives of the initiators had little effect on the molecular weight control and initiator efficiency.     

Photo-controlled/living radical polymerization of 2-(dimethylamino)ethyl methacrylate using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a mediator

The photo-controlled/living radical polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) was attained using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator and (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) (r-AMDV) as the initiator. The bulk polymerization of DMAEMA produced a polymer with a comparatively narrow molecular weight distribution below 1.6. The first-order time conversion plots showed a linear increase. The molecular weight of the resulting polymer also increased with an increase in the monomer conversion. The molecular weights of the resulting polymers were in good agreement with the theoretical molecular weights. A linear correlation was also obtained for the plots of the molecular weight vs. the reciprocal of the initial concentration of r-AMDV. The GPC analysis demonstrated the living nature of the polymerization based on the fact that the curves were shifted to the higher molecular weight side without deactivation as the conversion increased.     

Homogeneous and multiphase poly(methyl methacrylate) graft polymers via the macromonomer method

Anionic and group transfer polymerization processes were used to synthesize controlled molecular weight methacryloyloxy functionalized poly(dimethylsiloxane) and poly(methyl methacrylate) macromonomers having a narrow molecular weight distribution and high percent functionality. These macromonomers were anionically copolymerized with methyl methacrylate (MMA) to afford poly(methyl methacrylate)-graft-poly(methyl methacrylate) (PMMA-g-PMMA) and poly(methyl methacrylate)-graft-poly(dimethylsiloxane) (PMMA-g-PDMS) polymers having not only narrow molecular weight distribution graft parts but also backbone parts. The PMMA-g-PDMS system was fractionated using supercritical chlorodifluoromethane to determine its chemical composition distribution (CCD). The CCD for the PMMA-g-PDMS copolymerized in a living manner was substantially more narrow than the free radically copolymerized material. The PMMA-g-PMMA system was used to study the dilute solution properties of branched homopolymers. The appropriateness of the universal calibration gel permeation chromatography (GPC) method for branched systems exhibiting long chain branching was reaffirmed.     

Photo-controlled/living radical polymerization mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl in inert atmospheres

The photo-controlled/living radical polymerization of methyl methacrylate using a nitroxide mediator was established in an inert atmosphere. The bulk polymerization was performed at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator and (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate as the accelerator by irradiation with a high-pressure mercury lamp. The photopolymerization in a N₂ atmosphere produced a polymer with a comparatively narrow molecular weight distribution; however, the experimental molecular weight was slightly different from the theoretical molecular weight. The Ar atmospheric polymerization also provided a polymer with the molecular weight distribution similar to that of the polymer obtained by the N₂ atmospheric polymerization. These inert atmospheric polymerizations more rapidly proceeded to produce polymers with narrower molecular weight distributions than the vacuum polymerization. The livingness of the Ar atmospheric polymerization was confirmed on the basis of the first-order time–conversion plots and conversion–molecular weight plots.     

Effects of concentration of nonionic surfactant and molecular weight of polymers on the morphology of anisotropic polystyrene/poly(methyl methacrylate) composite particles prepared by solvent evaporation method

The effects of the concentration of polyoxyethylene octylphenyl ether (OP-10) as a nonionic surfactant and the molecular weight of polymers (polystyrene (PS) and poly(methyl methacrylate) (PMMA)) on the morphology of anisotropic PS/PMMA composite particles were investigated. In the case of polymers with lower molecular weight (M _w ≈ 6.0 × 10⁴ g/mol), the PS/PMMA composite particles have dimple, via acorn, to hemispherical shapes along with the increase of the OP-10 concentration. On the other hand, when the polymers have higher molecular weight (M _w ≈ 3.3 × 10⁵ g/mol), the morphology of PS/PMMA composite particles changed from dimple, via hemispherical, to snowman-like structure while the concentration of OP-10 was increased. Furthermore, thermodynamic analysis was first simply made by spreading coefficients, and the results indicated that both the concentration of OP-10 aqueous solution and the molecular weight of polymers were very important to the final morphology of anisotropic composite particles.     

Manifestation of side-chain interactions in solution properties of “loose” PI-graft-PMMA molecular brushes

The molecular properties of polymer brushes composed of polyimide with polymerization degree 50 and loosely grafted poly(methyl methacrylate) chains of variable length (PI-graft-PMMA) were studied by viscometry, dynamic light scattering, and equilibrium electro-optical Kerr effect methods in a diluted solution. It was established that the intrinsic viscosity and hydrodynamic dimension of PI-graft-PMMA copolymers increase when the electro-optical Kerr constant decreases with the elongation of PMMA side chains in the range of 40–110 monomer units. The observed difference in the solution properties of the copolymers was explained by their side-chain interactions in spite of a large distance between the neighboring grafting points typical of “loose brushes.” A strong effect of the chain rigidity and dipole structure on solution properties of the studied samples was demonstrated. The Kuhn segment lengths for PI-graft-PMMA copolymers were estimated to vary in the range 3.8–12.1?nm.     

Synthesis of well‐defined multigraft copolymers by a two‐step living radical polymerization with nitroxyl‐functionalized poly(methyl methacrylate)

Novel multigraft copolymers of poly(methyl methacrylate‐graft‐polystyrene) (PMMA‐g‐PS) in which the number of graft PS side chains was varied were prepared by a subsequent two‐step living radical copolymerization approach. A polymerizable 4‐vinylbezenyl 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) monomer (STEMPO), which functioned as both a monomer and a radical trapper, was placed in a low‐temperature atom transfer radical polymerization (60°C) process of methyl methacrylate with ethyl 2‐bromopronionate (EPNBr) as an initiator to gain ethyl pronionate‐capped prepolymers with TEMPO moieties, PMMA‐STEMPOs. The number of TEMPO moieties grafted on the PMMA backbone could be designed by varying STEMPO/EPNBr, for example, the ratios of 1/2, 2/3, or 3/4 gained one, two, or three graft TEMPO moieties, respectively. The resulting prepolymers either as a macromolecular initiator or a trapper copolymerized with styrene in the control of stable free‐radical polymerization at an elevated temperature (120 °C), producing the corresponding multigraft copolymers, PMMA‐g‐PSs. The nitroxyl‐functionalized PMMA prepolymers produced a relatively high initiation efficiency (>0.8) as a result of the stereohindrance and slow diffusion of TEMPO moieties connected on the long PMMA backbone. The polymerization kinetics in two processes showed a living radical polymerization characteristic. The molecular structures of these prepolymers and graft copolymers were well characterized by combining Fourier transform infrared spectroscopy, gel permeation chromatography, chemical element analysis, and ¹H NMR. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1876–1884, 2002     

Synthesis of poly(methyl methacrylate)‐b‐polystyrene containing a crown ether unit at the junction point via combination of atom transfer radical polymerization and nitroxide mediated radical polymerization routes

Poly(methyl methacrylate)‐b‐polystyrene (PMMA‐b‐PS) containing a benzo‐15‐crown‐5 unit at the junction point was prepared by combining atom transfer radical polymerization and nitroxide‐mediated radical polymerization. For this purpose, 6,7,9,10,12,13,15,16‐octahydro‐5,8,11,14,17‐pentaoxa‐benzocyclopentadecene‐2‐carboxylic acid 3‐(2‐bromo‐2‐methyl‐propionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yloxy)‐ethoxycarbonyl]‐propyl ester ( 3 ) was synthesized and used as an initiator in atom transfer radical polymerization of methyl methacrylate in the presence of CuCl and pentamethyldiethylenetriamine at 60°C. A linear behavior was observed in both plots of ln([M]₀/[M]) versus time and M_n,_GPC versus conversion indicating that the polymerization proceeded in a controlled/living manner. Thus obtained PMMA precursor was used as a macroinitiator in nitroxide‐mediated radical polymerization of styrene (St) at 125°C to give well‐defined PMMA‐b‐PS with crown ether per chain. Kinetic data were also obtained for copolymerization. Moreover, potassium picrate (K⁺ picrate) complexation of 3 and PMMA‐b‐PS copolymer was studied. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3242–3249, 2006     

SYNTHESIS OF POLY(METHYL METHACRYLATE)-SILICA NANO-COMPOSITE

ABSTRACT

Transparent organic/pre-ceramic composite films of poly(methyl methacrylate) [PMMA] and perhydropolysilazane [PHPS] were synthesized by blending poly(methyl methacrylate-co-2-hydroxyethyl methacrylate) [P(MMA-co-HEMA)] random copolymers and PHPS. In the blend films, P(MMA-graft-PHPS) graft copolymers were formed, PMMA and PHPS were microscopically phase-separated in the solid state. Morphology of the microphase separation was investigated by transmission electron microscopy by changing HEMA content of the random copolymers and blend ratio of PHPS to HEMA. To convert PHPS to silica glass, the blend films were calcinated at 100°C. The morphology of the microphase separation of the films was not changed by the calcinations; the calcinated films were transparent. When the molar content of HEMA of P(MMA-co-HEMA) and the molar content of PHPS to HEMA in feed were 14.5% and 150%, respectively, the morphology was well ordered lamellae of PMMA and silica.