Synthesis and thermal properties of poly(cycloalkyl methacrylate)s bearing bridged‐ and fused‐ring structures

Matsumoto, Akikazu; Mizuta, Keiichiro; Otsu, Takayuki

doi:10.1002/pola.1993.080311014

Cited by 78 publications

(55 citation statements)

References 19 publications

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“…Various poly(meth)acrylates bearing bulky ester groups, such as bornyl, 1 isobornyl, 1-3 adamantyl [4][5][6][7] and its derivatives, [4][5][6][8][9][10][11] have been synthesized to improve the thermal properties, such as the glass transition temperature and the thermal degradation temperature, of poly(methyl methacrylate) (PMMA). For example, the incorporation of adamantyl groups into polymer structures generally produces not only a high thermal stability but also an improvement in other physical and chemical properties, such as transparency to ultraviolet light, low dielectric constant, hydrophobicity, high oxidation resistance, low surface energy and high density.…”

Section: Introductionmentioning

confidence: 99%

Precise synthesis of poly(1-adamantyl methacrylate) by atom transfer radical polymerization

Fuchise

Sone

Miura

et al. 2010

Polym J

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1-Adamantyl methacrylate (AdMA) was polymerized using the atom transfer radical polymerization (ATRP) method with methyl a-bromoisobutyrate (MBiB), copper(I) bromide (CuBr), copper(II) bromide (CuBr 2 ) and 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) in toluene at 60 1C, producing well-defined poly(1-adamantyl methacrylate) (PAdMA). Simultaneous control of the molecular weight and tacticity of PAdMA was successfully achieved by the ATRP method using the MBiB/CuBr/CuBr 2 / tris[2-(dimethylamino)ethyl]amine-initiating system in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) at À20 1C. Block copolymerization of AdMA and methyl methacrylate (MMA) was successfully achieved by the poly(methyl methacrylate) macroinitiator/CuBr 2 /HMTETA/tin(II) 2-ethylhexanoate-initiating system based on activators generated by electron transfer (AGET) ATRP method. Differential scanning calorimetry revealed the relationship between the glass transition temperature, molecular weight and tacticity of the obtained PAdMA.

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Section: Introductionmentioning

confidence: 99%

Precise synthesis of poly(1-adamantyl methacrylate) by atom transfer radical polymerization

Fuchise

Sone

Miura

et al. 2010

Polym J

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“…12 However, it has been revealed that k 1 decreases with an increase in bulkiness of the substituent. Consequently, those monomers with smaller k 1 values polymerize rapidly to high molecular weight.…”

Section: Polymerizationmentioning

confidence: 99%

“…A significant decrease in k 1 of methacrylic ester by introduction of a bulky and rigid cycloalkyl ester group has been reported, 12 and a bulky ester substituent of tX-ethylacrylates was expected to decrease the termination rate. If the tX-ethylacrylate bearing the bulky ester alkyl group has similar kP and smaller k 1 values than those of MEA, the tX-ethylacrylate could polymerize to high molecular weight as a result of a favorable balance between the slow propagation and termination rates.…”

mentioning

confidence: 98%

Sterically Hindered Elementary Reactions in Radical Polymerization of α-Ethylacrylic Esters as Studied by ESR Spectroscopy

Kobatake

Yamada

1996

Polym J

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ABSTRACT:Radical polymerizations of methyl a-ethylacrylate (MEA) and cyclohexyl a-ethylacrylate (CHEA) in bulk were kinetically investigated on the basis of the absolute rate constants of elementary reactions evaluated by ESR spectroscopy. ESR spectra of the propagating radicals from MEA and CHEA were observed as five-line spectra by accumulation of a few scans during the slow polymerization of MEA and CHEA to low molecular weight (Mn= 1000---4000). The rate constants of propagation and termination (k 0 and k,) were determined based on quantification of propagating radicals from the a-ethylacrylates: k 0 = 8.6 and k, 2.1 x 10 7 L mol-1 s for MEA, and kP = 1.6 and k, = 1.8 x 10 6 L mol-1 s for CHEA. The steric hindrance of the ethyl group was found to bring about slower propagation and slightly slower termination rates of MEA in comparison with methyl methacrylate (MMA). The detailed structural analysis of the end group in the polymer indicates that replacement of the a-methyl group of MMA with the ethyl group of MEA results in termination involving mainly combination (76%). The steric hindrance seems to affect the termination mode.KEY WORDS Radical Polymerization I a-Ethylacrylate I a-Substituted Acrylic Ester I Propagation Rate Constant I Termination Rate Constant I Electron Spin Resonance Spectroscopy I Among 1, 1-disubstituted ethylenic monomers, a variety of IX-substituted acrylates except for the acrylates bearing a large alkyl group and functioning as a chain transfer agent through the addition-fragmentation are polymerizable. 1 Recent studies of radical polymerization of the IX-( substituted methyl)acrylates have drawn much attention because slight changes in the structure of the IX-substituent greatly affect the polymerizability. The IX-( substituted methyl)acrylates bearing alkoxymethyl, 2 acyloxymethy1,3 fluoromethyl, 4 and carboalkoxymethyl groups 5 as the IX-substituent readily polymerize to high molecular weight in spite of the presence of the bulky substituent. The absolute rate constants of propagation and termination (kp and k 1 ) for the alkoxymethyl, acyloxymethyl and carboalkoxymethyl derivatives have been determined based on quantification of the respective propagating radicals by the ESR method, 2 • 3 • 5 and it has been rationalized that the balance between the slow propagation and termination rates allows polymer formation from the IX-(substituted methyl)acrylates. Therefore, it is convinced that the steric hindrance of the IX-substituent provides steric hindrance-assisted polymerization of IX-(substituted methyl)acrylates.

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“…The most striking feature of the polymer properties is the strong increase in glass transition temperature (T A) as a function of IBMA concentration. [8] The IBMA homopolymer has a T 8 above 200°C. Polymers with appreciable levels of IRMA have T 6's above ISO°C.…”

Section: Introductionmentioning

confidence: 99%

Single layer resists with enhanced etch resistance for 193 nm lithography.

Allen

Wallraff

DiPietro

et al. 1994

J. Photopol. Sci. Technol.

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The quest for a high performance positive chemically amplified (CA) resist for 193 nm lithography is a significant challenge. We have recently developed the first high resolution positive resist for 193 nm lithography.[ 1 J Our work now centers on improving etch resistance while maintaining imaging quality.In this paper we will discuss structure/property relationships of methacrylate polymers with increased etch resistance over our first generation resist. Modifications which improve etch resistance often negatively impact aqueous solubility and polymer thermal properties. Several approaches will be discussed which attempt to address competing considerations in positive resist design.

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Synthesis and thermal properties of poly(cycloalkyl methacrylate)s bearing bridged‐ and fused‐ring structures

Cited by 78 publications

References 19 publications

Precise synthesis of poly(1-adamantyl methacrylate) by atom transfer radical polymerization

Precise synthesis of poly(1-adamantyl methacrylate) by atom transfer radical polymerization

Sterically Hindered Elementary Reactions in Radical Polymerization of α-Ethylacrylic Esters as Studied by ESR Spectroscopy

Single layer resists with enhanced etch resistance for 193 nm lithography.

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