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Anionic synthesis of narrow molecula...

University of Southern California.

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Anionic synthesis of narrow molecular weight distribution poly(methyl methacrylate), poly(n-butyl acrylate), and poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymers at elevated temperatures.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Anionic synthesis of narrow molecular weight distribution poly(methyl methacrylate), poly(n-butyl acrylate), and poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymers at elevated temperatures./
Author:	Zagala, Angela Pascual.
Description:	144 p.
Notes:	Adviser: Thieo Hogen-Esch.
Contained By:	Dissertation Abstracts International57-03B.
Subject:	Chemistry, Organic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9621735

Anionic synthesis of narrow molecular weight distribution poly(methyl methacrylate), poly(n-butyl acrylate), and poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymers at elevated temperatures.
Zagala, Angela Pascual.

Anionic synthesis of narrow molecular weight distribution poly(methyl methacrylate), poly(n-butyl acrylate), and poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymers at elevated temperatures. - 144 p.

Adviser: Thieo Hogen-Esch.

Thesis (Ph.D.)--University of Southern California, 1995.

The anionic polymerization of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) initiated by the tetraphenylphosphonium salt of triphenylmethyl anion (Ph$\sb3Subjects--Topical Terms:

516206
Chemistry, Organic.

Anionic synthesis of narrow molecular weight distribution poly(methyl methacrylate), poly(n-butyl acrylate), and poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymers at elevated temperatures.
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005 20101007
008 101007s1995 ||||||||||||||||| ||eng d
035 $a (UMI)AAI9621735
035 $a AAI9621735
040 $a UMI $c UMI
100 1 $a Zagala, Angela Pascual. $3 1058157
245 1 0 $a Anionic synthesis of narrow molecular weight distribution poly(methyl methacrylate), poly(n-butyl acrylate), and poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymers at elevated temperatures.
300 $a 144 p.
500 $a Adviser: Thieo Hogen-Esch.
500 $a Source: Dissertation Abstracts International, Volume: 57-03, Section: B, page: 1837.
502 $a Thesis (Ph.D.)--University of Southern California, 1995.
520 $a The anionic polymerization of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) initiated by the tetraphenylphosphonium salt of triphenylmethyl anion (Ph$\sb3 $c $\sp{-} $p h$\sb4 $p $\sp{+})$ in THF at ambient temperatures gives narrow molecular weight distribution poly(methyl methacrylate) (PMMA) and poly(n-butyl acrylate) (PBA) in quantitative yields. Poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymers (PMMA-PBA) are similarly synthesized by sequential anionic polymerization of MMA and n-BuA at $0 \sp\circ $c . Ph$\sb3 $c $\sp{-} $p h$\sb4 $p $\sp{+}$ formed by cation exchange of triphenylmethyl potassium (Ph$\rm\sb3 C\sp{-}K\sp{+})$ with tetraphenylphosphonium chloride (Ph$\sb4 $p Cl) in THF rapidly initiates polymerization as evident from an instantaneous disappearance of the Ph$\rm\sb3 C\sp{-}Ph\sb4P\sp{+}$ absorption maximum $(\lambda\sb\max=506$ nm). Polymerizations are complete in less than two seconds and produce high molecular weight polymers (DP $\le$ 300) with relatively narrow molecular weight distributions (MWD $\le$ 1.2) The initiator efficiency is found to be between 30-70% based on the original Ph$\rm\sb3 C\sp{-}K\sp{+}$ concentration due to decomposition of the initiator (t$\sb{1/2}$ - $\sim $2 00 seconds at $2 2\sp\circ $c ). The initiator system may also be applied to the polymerization of 2-vinyl pyridine. The stereochemistry of the PMMA generated is similar to that reported for Group Transfer Polymerization (GTP).
520 $a NMR and FT-IR studies of the Ph$\sb4 $p $\sp{+}$ salt of the methyl isobutyrate enolate anion were carried out as model of the propagating center. These investigations were consistent with the predominant structure being an ylide (4), which was in rapid equilibrium with a low concentration of the active species, Ph$\sb4 $p $\sp+ $m IB$\sp-.$ The success of the anionic polymerization of (meth)acrylates in THF ambient temperatures attributed to a decrease in the rate of termination relative to the rate of propagation due to the presence of a bulky and kinetically stable cation. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)
590 $a School code: 0208.
650 4 $a Chemistry, Organic. $3 516206
650 4 $a Chemistry, Polymer. $3 1018428
650 4 $a Plastics Technology. $3 1023683
690 $a 0490
690 $a 0495
690 $a 0795
710 2 $a University of Southern California. $3 700129
773 0 $t Dissertation Abstracts International $g 57-03B.
790 $a 0208
790 1 0 $a Hogen-Esch, Thieo, $e advisor
791 $a Ph.D.
792 $a 1995
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9621735