Solvent-Free Synthesis by Free-Radical Frontal Polymerization

Fortenberry, Dionne I.; Lewis, Lydia L.; Simmons, Chris; Ilyashenko, Victor M.

doi:10.1021/bk-1998-0713.ch009

Cited by 5 publications

(6 citation statements)

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“…Additionally, there is a ''burning out'' effect of radicals at high temperature. [1,5] The lower conversions and molar masses observed are therefore along expected lines.…”

Section: Productsupporting

confidence: 60%

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Water‐Triggered Frontal Polymerization

Pujari

Inamdar²,

Ponrathnam

et al. 2007

Macromol. Rapid Commun.

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A totally new mode of frontal polymerization (FP) of acrylamide is established which is triggered by the simple addition of a minute, specific volume of water. Experimental conditions under which this mode of polymerization yields linear and water‐soluble polyacrylamide were carefully established, paving the way to synthesize commercially pertinent homo‐ and copolymers. A new redox couple was identified to circumvent the imidization and the ensuing gelation, hitherto associated with FP of acrylamide. Effects of reaction variables such as type and concentration of redox couple and volume of water on measurable parameters of FP such as front velocity, front temperature, shape of front and yield have been studied. Two types of redox couples are reported. Nonplanar frontal regime was observed in few redox couples. We could visually observe helical patterns with naked eyes, while layered patterns were observable under SEM. Additionally, micro‐phase separation and heterogeneity in the polymer matrix was observed due to unreacted pockets of monomer which evolve via bulk mode. This nonlinear phenomenon is described.magnified image

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“…Additionally, there is a ''burning out'' effect of radicals at high temperature. [1,5] The lower conversions and molar masses observed are therefore along expected lines.…”

Section: Productsupporting

confidence: 60%

“…[2] Pojman et al [1,3,4] have since extensively examined the phenomenon. In recent years, three classes of FP such as: thermal FP, [5] isothermal FP [1,6] and UV initiated (photo) FP [7,8] have emerged.…”

Section: Introductionmentioning

confidence: 99%

Water‐Triggered Frontal Polymerization

Pujari

Inamdar²,

Ponrathnam

et al. 2007

Macromol. Rapid Commun.

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“…The general reaction scheme used for the synthesis of GMA-EGDM copolymers is presented in figure 1. Free radical FP is triggered by the complete decomposition of initiator followed by Arrhenius reaction kinetics (Pojman et al 1996b(Pojman et al , 1998. Reaction continues in a localized re-gion and propagates as a thermal wave (front) using the heat of polymerization.…”

Section: Resultsmentioning

confidence: 99%

“…Russian workers studied the phenomenon extensively after the first observations were reported by Chechilo in 1972(Chechilo et al 1972Enikolopyan et al 1974;Khaunkaev et al 1974;Chechilo and Enikolopyan 1975;Davtyan et al 1975Davtyan et al , 1976Davtyan et al , 1977Davtyan et al , 1984Davtyan et al , 1985Davtyan et al , 1986Davtyan et al , 1989White andKim 1992, 1993). Pojman et al (Pojman 1991;Pojman et al 1992Pojman et al , 1993Pojman et al , 1995aPojman et al ,b, 1996aPojman et al ,b, 1997Pojman et al , 1998Pojman et al , 2000Pojman et al , 2003 triggered considerable excitement in both fundamental and applied aspects of frontal polymerization. The use of this mode of polymerization has many applications including rapid curing of polymers without external heating (White andKim 1992, 1993), uniform curing of thick samples, solventless preparation of polymers such as thermochromic material (Pojman et al 1995a,b), hydrogels (Washington and Steinbock 2001), polyurethane (Fiori and Mariani 2003), functionalized crosslinked polymer networks (Pujari et al 2004), GRIN material (Koike et al 1988;Zhang et al 1997;Masere et al 2001) (by isothermal FP) and in synthesizing copolymers (Tredici et al 1998;Perry et al 2003).…”

Section: Introductionmentioning

confidence: 99%

Functionalized polymer networks: synthesis of microporous polymers by frontal polymerization

et al. 2004

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A series of glycidyl methacrylate (GMA)-ethylene dimethacrylate (EGDM) copolymers of varying compositions were synthesized by free-radically triggered thermal frontal polymerization (FP) as well as by suspension polymerization (SP) using azobisisobutyronitrile [AIBN] as initiator. The two sets of copolymers were characterized by IR spectroscopy and mercury intrusion porosimetry, for determination of epoxy number and specific surface area. Frontal polymerization was more efficient, yielding greater conversions at much shorter reaction times. The self-propagating frontal polymerization also generates microporous material with narrow pore size distribution. It yields higher internal pore volume and surface area than suspension polymerization, surface morphologies are, however, inferior.

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“…Thermally initiated frontal polymerization has been intensively studied since 1967 7. Typically, the monomer in a test tube is heated applying an electric iron at the top, polymerization starts and the reaction frontal wave keeps advancing toward the bottom until all the monomer is thoroughly converted into polymer.…”

Section: Introductionmentioning

confidence: 99%

Study on spatial–temporal kinetics of photo‐initiated frontal polymerization in stacked reaction cells

Tao

Yang

Zeng

et al. 2006

Polymer International

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The spatial–temporal kinetics for photo‐initiated frontal polymerization(PFP) of isobornyl acrylate with 2,4,6‐trimethylbenzoyldiphenyl phosphine oxide (TPO) as photobleaching initiator was studied experimentally in stacked reaction cells. FTIR and NMR spectroscopy were employed to measure the polymerization conversion, which is dependent on the exposure time, sample depth, light intensity and photo‐initiator concentration. The experimental results are consistent with the theoretical model prediction and show that prolonged irradiation time, higher light intensity and lower photo‐initiator concentration are favorable in enhancing the advance of the polymerization front. The depth‐resolved GPC analysis shows that the average molecular weight of the PFP product dramatically increases with sample depth, while the molecular weight polydispersity reduces steadily with increase in sample depth. Copyright © 2006 Society of Chemical Industry

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Solvent-Free Synthesis by Free-Radical Frontal Polymerization

Cited by 5 publications

References 0 publications

Water‐Triggered Frontal Polymerization

Water‐Triggered Frontal Polymerization

Functionalized polymer networks: synthesis of microporous polymers by frontal polymerization

Study on spatial–temporal kinetics of photo‐initiated frontal polymerization in stacked reaction cells

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