Free-radical crosslinking polymerization of unsymmetrical divinyl compounds, 1 Gelation in the polymerization of allyl methacrylate

Matsumoto, Akira; Asai, Satoru; Aota, Hiroyuki

doi:10.1002/1521-3935(20001201)201:18<2735::aid-macp2735>3.3.co;2-6

Cited by 15 publications

(23 citation statements)

References 11 publications

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“…Figure 11 shows a plot of the deviation of the actual gel points from the calculated gel points versus the primary chain length of the resulting prepolymers. For comparison, the figure includes similar ones for the conventional free‐radical polymerization of AMA that were obtained by Matsumoto et al21 (in bulk at 50 °C and with the same equation described previously). The deviation becomes clearly smaller with a decrease in the primary chain length.…”

Section: Resultsmentioning

confidence: 82%

“…AMA has two different types of double bonds (a conjugated methacryloyl group and an unconjugated allyl group), and its preferential free‐radical polymerization occurs in the methacryloyl group because of its fairly higher reactivity in comparison with that of the other unsaturated functional group. Studies on the free‐radical polymerization of AMA have been performed in emulsion and homogeneous systems, in bulk and in solution 18–22. Thus, the early stage of this polymerization leads to the formation of poly(allyl methacrylate) (PAMA) prepolymers with abundant pendant allyl groups.…”

Section: Introductionmentioning

confidence: 99%

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Bulk atom transfer radical polymerization of allyl methacrylate

París

Fuente

2005

J. Polym. Sci. A Polym. Chem.

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A detailed investigation of the polymerization of allyl methacrylate, a typical unsymmetrical divinyl compound containing two types of vinyl groups, methacryloyl and allyl, with quite different reactivities, was performed with atom transfer radical polymerization (ATRP). Homopolymerizations were carried out in bulk, with ethyl-2-bromoisobutyrate as the initiator and with copper halide (CuX, where X is Cl or Br) with N,N,N 0 ,N@,N@-pentamethyldiethylenetriamine as the catalyst system. Kinetic studies demonstrated that during the early stages of the polymerization, the ATRP process proceeded in a living manner with a low and constant radical concentration. However, as the reaction continued, the increased diffusion resistance restricted the mobility of the catalyst system and interrupted the equilibrium between the growing radicals and dormant species. The obtained poly(allyl methacrylate)s (PAMAs) were characterized with Fourier transform infrared, 1 H NMR, and size exclusion chromatography techniques. The dependence of both the gel point conversion and molecular characteristics of the PAMA prepolymers on different experimental parameters, such as the initiator concentration, polymerization temperature, and type of halide used as the catalyst, was analyzed. These real gel points were compared with the ones calculated according to Gordon's equation under the tentative assumption of equal reactivity for the two types of vinyl groups. Moreover, the microstructure of the prepolymers was the same as that exhibited by those homopolymers prepared by conventional free-radical polymerization; the fraction of syndiotactic arrangements increased as the reaction temperature was lowered. # 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: [2395][2396][2397][2398][2399][2400][2401][2402][2403][2404][2405][2406] 2005

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Section: Resultsmentioning

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Bulk atom transfer radical polymerization of allyl methacrylate

París

Fuente

2005

J. Polym. Sci. A Polym. Chem.

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“…The polymer yield at different reaction time was illustrated in Figure 1. The copolymerization systems of equimolar ratio allyl maleimide and propyl maleimide were very active, and reached 100 wt % gel conversion in 5 h. This might be because that intermolecular crosslinking predominantly occurred rather than intramolecular crosslinking 16. However, this is good for the outward development of a dendritic structure, because gelling usually occurs by way of hyperbranched intermediates, thus the high gelation activity on the other hand implies high degree of branching.…”

Section: Resultsmentioning

confidence: 99%

A novel feed‐stock recyclable hyperbranched polymaleimide: Synthesis and characterization

Wei

Liu

et al. 2006

J of Applied Polymer Sci

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Hyperbranched polymaleimide can be readily obtained by copolymerization of allyl maleimide and propyl maleimide. A hyperbranched polymaleimide was obtained in a yield of 56 wt % in 3 h at 50°C, whose weight average molecular mass and polydispersity index were measured by size-exclusion chromatography to be 59,000 and 4.1, respectively. TGA showed a one-step mass loss process in the decomposition of the hyperbranched polymaleimide. The dominant pyrolysis mechanism was revealed by gas chromatography/mass spectrometry to be depolymerization. The major pyrolysates of the hyperbranched polymaleimide were allyl maleimide, propyl succinimide, and other volatile monomeric units.

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“…Using conventional synthesis methods, it has been previously reported that the allyl group has a lower reactivity, which results in a large amount of unaltered allyl groups during conventional polymerization and leads to less crosslinked material. [6][7][8][9] The goal of this study is to take a step toward the understanding of the mechanisms involved during plasma polymerization of organic precursors, and in particular, understanding the impact of unsaturations contained in a precursor on the deposition rate and quality of the coatings. Therefore, we selected two precursors with the same general molecular structure as AMA, namely n-propyl methacrylate (nPMA) and propyl isobutyrate (PiB), which only differ by their number of carbon-carbon doublebonds.…”

Section: Introductionmentioning

confidence: 99%

The Impact of Double Bonds in the APPECVD of Acrylate-Like Precursors

Batan

Nisol

Kakaroglou

et al. 2013

Plasma Process. Polym.

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In this study, we investigated the atmospheric plasma polymerization of allyl methacrylate (AMA), n-propyl methacrylate (nPMA), and propyl isobutyrate (PiB), whose chemistry mainly differs by their number of unsaturations. The resulting material is characterized using X-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRRAS) while the thickness of the coatings is determined by visible spectroscopic ellipsometry (Vis-SE). The results show that the concentration of ester groups at the surface of the plasma polymers, as well as their deposition rate strongly depends on the surrounding unsaturations present in the precursor. A stabilization of the ester groups and an increase in the deposition rate due to the carbon-carbon double bonds is suggested.

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Free-radical crosslinking polymerization of unsymmetrical divinyl compounds, 1 Gelation in the polymerization of allyl methacrylate

Cited by 15 publications

References 11 publications

Bulk atom transfer radical polymerization of allyl methacrylate

Bulk atom transfer radical polymerization of allyl methacrylate

A novel feed‐stock recyclable hyperbranched polymaleimide: Synthesis and characterization

The Impact of Double Bonds in the APPECVD of Acrylate-Like Precursors

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