Polymerization of methyl α-(trifluoromethyl)acrylate and .alpha.-trifluoromethylacrylonitrile and copolymerization of these monomers with methyl methacrylate

Itô, Hiroshi; Miller, Dolores C.; Willson, C. Grant

doi:10.1021/ma00231a043

Cited by 61 publications

(45 citation statements)

References 12 publications

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“…In the present study, the polymerization reactivity of α-trifluoromethacrylic acid derivatives, that had a trifluoromethyl group at α-position of acrylic acid, was markedly low compared with that of MMA. Figure 2 summarizes the results obtained in this study and reported in previously published papers 7,9) . Trifluoromethyl methacrylate (A in Fig.…”

Section: Discussionsupporting

confidence: 65%

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Basic Study on the Application of Novel Functional Monomers to a Denture Base Resin

et al. 2008

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To improve the mechanical properties and to reduce the water sorption amount of denture base resins, the polymerization characteristics of three novel fluoro-substituted monomers (MAF-TBN, MAF-MAE, MAF-TBN) and three styrene-type monomers (PTBS, PEES, PACS) were studied, as well as the copolymerization of these monomers with MMA. Subsequently, the mechanical properties and water sorption of the copolymers prepared from these monomers and MMA were evaluated. The polymerization reactivity of the monomers by BPO was lower than MMA, except for PACS. However, the copolymerization reactivity of the monomers with MMA was good, except for MAF-TBN. The copolymer of MAF-MAE and MMA in three fluoro-substituted monomers and PACS and MMA in three styrene-type monomers showed similar mechanical properties and extremely low water sorption compared with those of PMMA.Keywords: Functional monomer, Polymerization, Mechanical Property INTRODUCTION Poly(methyl methacrylate) (PMMA) is widely used in denture base resins. However, PMMA has posed several problems in clinical applications, such as poor water resistance, decrease in mechanical strength by water absorption, polymerization shrinkage, and monomer volatility. Against this background, novel resins with good mechanical properties and lower water sorption in the place of PMMA are required. To circumvent the abovementioned drawbacks, we have studied some monomers to date. For example, to improve the water resistance of PMMA, hydrophobic alkyl methacrylate and bis(methacryloyloxy) dimethylsiloxane oligomer were synthesized, and the mechanical properties of the copolymers of these monomers and MMA were evaluated 1,2) . The mechanical properties and water resistance of the copolymers were improved in comparison with PMMA, and the polymerization shrinkage was decreased. Increase in the monomer content for the copolymers was able to renders resin with the required hardness, but there was also increase in brittleness 1) . Decrease in the monomer content, on the other hand, did not improve water resistance and mechanical properties. In the case of the siloxane oligomer, the water resistance of the copolymer was improved, but the mechanical properties were poor compared with those of PMMA 2) . To improve the mechanical properties and to decrease the water sorption of resins, it has been proposed to introduce fluorine groups to the resins. Octafluoropentyl and 2,2,2-trifluoroethyl methacrylate have been investigated as resin binders of direct filling resins 3) and denture base resins 4) respectively. As for fluoroalkyl methacrylates, they were applied as visible light-cured soft resins 5) or as a modifier to the surface of denture base resins 6) to inhibit bacterial adherence. However, the mechanical properties of the resins were not improved. The poor strength might be due to decrease in interaction, such as van der Waals' force and the orientation of polar groups, among the polymer molecules by the substitution of the methyl group by long fluoroalkyl group at the ester position. Unfort...

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Section: Discussionsupporting

confidence: 65%

“…124 and 134℃ respectively 7) . As for methyl α-(trifluoromethyl)acrylate (D), it had very low reactivity in polymerization 9) . On the reactivity of methyl β-(difluoro)methacrylate (E) and the mechanical properties of the polymer thereof, they were still unknown.…”

Section: Discussionmentioning

confidence: 99%

Basic Study on the Application of Novel Functional Monomers to a Denture Base Resin

et al. 2008

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“…Electron-deficient 2-trifluoromethylacrylic monomers (Alfrey-Price e value for methyl 2-trifluoromethylacrylate is 2.5 [13]) and electronrich norbornene derivatives undergo radical copolymerization with a common initiator such as AIBN (Scheme II) [2], although neither monomer produces homopolymer under normal radical polymerization conditions [14]. The copolymer composition has been found to be acrylate/norbornene=''2/ 1 through quantitative NMR analysis of copolymers and through in situ kinetics analysis by 'H NMR.…”

Section: Lithographic Characterizationmentioning

confidence: 99%

“…The NB monomer reacts with the TBTFMA polymer radical six times (1/0.17) faster than TBTFMA when the penultimate group is TBTFMA. Thus, TBTFMA can form a trimer (k111#0) while its radical homopolymerization is very sluggish [14].…”

Section: Lithographic Characterizationmentioning

confidence: 99%

Fluoropolymers for 157/193 nm Lithography: Chemistry, New Platform, Formulation Strategy, and Lithographic Evaluation.

Itô

Truong

Okazaki

et al. 2002

J. Photopol. Sci. Technol.

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A copolymer of t-butyl 2-trifluoromethylacrylate (TBTFMA) and norbornene bearing hexafluoroisopropanol (NBHFA) as an acid group, which is prepared by radical copolymerization, is employed in our 157 nm resist. The radical copolymerization of 2-trifluoromethylacrylic monomers with norbornene derivatives has been shown to follow the penultimate model much better than the commonly employed terminal model. These copolymers (containing >50 mol% TBTFMA) are too lipophilic to provide good imaging. Blending a NBHFA homopolymer with an optical density (OD) of 1.7/µm at 157 nm into the copolymers (OD=2.5-2.7/µm) results in increased hydrophilicity and reduced OD (2.2-2.0/µm) and provides high resolution images. A copolymer of TBTFMA with vinyl ethers has been identified as a new platform, which can be prepared facilely by common radical polymerization. Certain vinyl ether copolymers are also compatible with the NBHFA homopolymer and thus blending improves their OD and aqueous base development. Because these fluoropolymers are highly transparent at 193 nm as well, they are evaluated as 157/193 dual wavelength resists.

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“…1 The fluoroalkyl moiety in ester group was synthesized by the hydrolysis of the compound from the radical addition of 2-benzoxypentafluoropropene [CF 2 ¼C(CF 3 )OCOC 6 H 5 ] with tetrahydrofuran (THF). Radical and anionic polymerization of the monomer were examined to afford a polymer of 1.1 Â 10 4 as the highest molecular weight initiated by benzoyl peroxide (BPO) at 60 C in spite of low yield of the polymer.…”

mentioning

confidence: 99%

Synthesis and polymerization of novel fluoroalkyl 2‐trifluoromethylacrylate possessing tetrahydrofuran moiety

Hosoya¹,

Hamana²,

Takani³

et al. 2011

J. Polym. Sci. A Polym. Chem.

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Polymerization of methyl α-(trifluoromethyl)acrylate and .alpha.-trifluoromethylacrylonitrile and copolymerization of these monomers with methyl methacrylate

Cited by 61 publications

References 12 publications

Basic Study on the Application of Novel Functional Monomers to a Denture Base Resin

Basic Study on the Application of Novel Functional Monomers to a Denture Base Resin

Fluoropolymers for 157/193 nm Lithography: Chemistry, New Platform, Formulation Strategy, and Lithographic Evaluation.

Synthesis and polymerization of novel fluoroalkyl 2‐trifluoromethylacrylate possessing tetrahydrofuran moiety

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