Polymers from multifunctional isocyanates 14. Alternating copolymers from isocyanato alkenes: Copolymerization of 2-propenyl isocyanate with trimethylsilyl methacrylate as electron acceptor monomer

Mörmann, Werner; Grimm, Axel

doi:10.1002/(sici)1099-0518(199803)36:4<611::aid-pola10>3.0.co;2-p

Cited by 5 publications

(3 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this work, RAFT polymerization was selected to synthesize silylated methacrylic polymers with controlled molecular weight distributions, well‐defined chain architectures, and low polydispersity. Some studies of trialkylsilyl methacrylate homopolymerization and copolymerization have been reported16 for applications in photoresists of polymers,17–19 in dry etch resistance of polymers,20 and in antifouling paints 21–23. However, no studies, until now, have been reported on the living radical polymerization of trialkylsilyl methacrylate monomers.…”

Section: Introductionmentioning

confidence: 99%

Controlled radical polymerization of a trialkylsilyl methacrylate by reversible addition–fragmentation chain transfer polymerization

Nguyen

Bressy

Margaillan

2005

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

The reversible addition-fragmentation chain transfer (RAFT) polymerization of a hydrolyzable monomer (tert-butyldimethylsilyl methacrylate) with cumyl dithiobenzoate and 2-cyanoprop-2-yl dithiobenzoate as chain-transfer agents was studied in toluene solutions at 70 8C. The resulting homopolymers had low polydispersity (polydispersity index < 1.3) up to 96% monomer conversion with molecular weights at high conversions close to the theoretical prediction. The profiles of the number-average molecular weight versus the conversion revealed controlled polymerization features with chain-transfer constants expected between 1.0 and 10. A series of poly (tert-butyldimethylsilyl methacrylate)s were synthesized over the molecular weight range of 1.0 Â 10 4 to 3.0 Â 10 4 , as determined by size exclusion chromatography. As strong differences of hydrodynamic volumes in tetrahydrofuran between poly(methyl methacrylate), polystyrene standards, and poly(tert-butyldimethylsilyl methacrylate) were observed, true molecular weights were obtained from a light scattering detector equipped in a triple-detector size exclusion chromatograph. The Mark-Houwink-Sakurada parameters for poly(tert-butyldimethylsilyl methacrylate) were assessed to obtain directly true molecular weight values from size exclusion chromatography with universal calibration. In addition, a RAFT agent efficiency above 94% was confirmed at high conversions by both light scattering detection and 1 H NMR spectroscopy. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5680-5689, 2005

show abstract

Section: Introductionmentioning

confidence: 99%

Controlled radical polymerization of a trialkylsilyl methacrylate by reversible addition–fragmentation chain transfer polymerization

Nguyen

Bressy

Margaillan

2005

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

show abstract

“…Zachoval reported that the ion etching rate for poly(trimethylsilyl methacrylate) in oxygen was 1/35 of that of poly(methyl methacrylate) 1. In our laboratory copolymerisation of trimethylsilyl methacrylate with methacrylic acid and other functionalised monomers like 2‐propenyl isocyanate or maleic anhydride has been investigated for application in photoresists 11–13. Nothing is known about the copolymerisation behaviour of tert ‐butyl methacrylate with trimethylsilyl methacrylate or methacrylic acid, although knowledge of reactivity ratios and properties is a prerequisite for the design of 193 nm photoresist materials.…”

Section: Introductionmentioning

confidence: 99%

Copolymers from tert‐Butyl Methacrylate with Trimethylsilyl Methacrylate or Methacrylic Acid: Models for Resist Polymers

Ferbitz

Mörmann

2003

Macro Chemistry & Physics

Self Cite

View full text Add to dashboard Cite

Free radical copolymerisation of tert‐butyl methacrylate (1) with trimethylsilyl methacrylate (2) and methacrylic acid (3) has been investigated. Reactivity ratios for methacrylic acid and tert‐butyl methacrylate indicate an azeotropic copolymerisation (r1 = 0.476 ± 0.103; r3 = 0.300 ± 0.032), whereas the two esters show preferential incorporation of 2 (r1 = 0.170 ± 0.050; r2 = 1.170 ± 0.124). Thermal cis‐elimination of isobutylene from the tert‐butyl ester and subsequent formation of six‐membered cyclic anhydride moieties has been studied. For poly(methacrylic acid‐co‐tert‐butyl methacrylate) thermogravimetry could be used to determine copolymer composition. Solvolytic desilylation of the trimethylsilyl ester groups has been investigated as an alternative route to poly(methacrylic acid‐co‐tert‐butyl methacrylate). The tert‐butyl ester is not affected under the conditions of desilylation. Sequence distribution of both copolymers has been calculated using the method introduced by Bruns and Motoc.

show abstract

“…Zachoval published an ion etching rate for poly(trimethylsilyl methacrylate) in oxygen, which was 1/35 of that for poly(methyl methacrylate) 2. In previous papers we reported on the copolymerisation of trimethylsilyl methacrylate with functional monomers like 2‐propenyl isocyanate18 and maleic anhydride 19…”

Section: Introductionmentioning

confidence: 99%

Copolymers from Methacrylic Acid and Trimethylsilyl Methacrylate ‐ Synthesis, Reactivity Ratios and Thermal Properties

Mörmann

Ferbitz

2002

Macro Chemistry & Physics

Self Cite

View full text Add to dashboard Cite

Copolymers from methacrylic acid (1) and trimethylsilyl methacrylate (2) have been synthesized by free radical copolymerisation and by controlled desilylation of poly(trimethylsilyl methacrylate) (3). The reactivity ratios were r1 = 2.75, r2 = 0.004. Differential scanning calorimetry showed a linear correlation between the peak temperature of the endotherm for the formation of cyclic anhydrides and the content of methacrylic acid in the copolymer. Obviously, the acid catalyses this reaction. The copolymers as well as poly(trimethylsilyl methacrylate) have a ceiling temperature. Sequence distributions were calculated and used to predict glass transition temperatures for comparison to the experimental results. The microstructure of the copolymers obtained by the different synthetic routes is different as shown from Tg and from their solubility. Those from desilylation are random with “reactivity ratios” of 1, those from copolymerisation seem to have longer sequences of methacrylic acid leading to formation of intermolecular aggregates. Dependence of DSC peak temperature of anhydride formation on methacrylic acid content.magnified imageDependence of DSC peak temperature of anhydride formation on methacrylic acid content.

show abstract

Polymers from multifunctional isocyanates 14. Alternating copolymers from isocyanato alkenes: Copolymerization of 2-propenyl isocyanate with trimethylsilyl methacrylate as electron acceptor monomer

Cited by 5 publications

References 2 publications

Controlled radical polymerization of a trialkylsilyl methacrylate by reversible addition–fragmentation chain transfer polymerization

Controlled radical polymerization of a trialkylsilyl methacrylate by reversible addition–fragmentation chain transfer polymerization

Copolymers from tert‐Butyl Methacrylate with Trimethylsilyl Methacrylate or Methacrylic Acid: Models for Resist Polymers

Copolymers from Methacrylic Acid and Trimethylsilyl Methacrylate ‐ Synthesis, Reactivity Ratios and Thermal Properties

Contact Info

Product

Resources

About