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Feng, Dingsong.

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Synthesis and characterization of polyisobutylene based block copolymers containing poly(methacrylates) as hard blocks.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Synthesis and characterization of polyisobutylene based block copolymers containing poly(methacrylates) as hard blocks./
Author:	Feng, Dingsong.
Description:	117 p.
Notes:	Adviser: Rudolf Faust.
Contained By:	Dissertation Abstracts International68-09B.
Subject:	Chemistry, Polymer. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3285263
ISBN:	9780549270379

Synthesis and characterization of polyisobutylene based block copolymers containing poly(methacrylates) as hard blocks.
Feng, Dingsong.

Synthesis and characterization of polyisobutylene based block copolymers containing poly(methacrylates) as hard blocks. - 117 p.

Adviser: Rudolf Faust.

Thesis (Ph.D.)--University of Massachusetts Lowell, 2007.

The synthesis of polyisobutylene (PIB)-based block copolymers containing poly(methacrylates) as a second block has been achieved by a combination of living cationic and anionic polymerizations. Specifically, the second block could be poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), P(MMA-co-HEMA) with different MMA/HEMA ratios, poly( tert-butyl methacrylate) (PtBMA) and poly(methacrylic acid) (PMAA). The obtained triblock copolymers comprised of PIB as a central block and poly(methacrylate) as side blocks demonstrate characteristics of thermoplastic elastomers and are potential candidates for application as drug-eluting stent coatings.

ISBN: 9780549270379Subjects--Topical Terms:

1018428
Chemistry, Polymer.

Synthesis and characterization of polyisobutylene based block copolymers containing poly(methacrylates) as hard blocks.
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020 $a 9780549270379
035 $a (UMI)AAI3285263
035 $a AAI3285263
040 $a UMI $c UMI
100 1 $a Feng, Dingsong. $3 1280741
245 1 0 $a Synthesis and characterization of polyisobutylene based block copolymers containing poly(methacrylates) as hard blocks.
300 $a 117 p.
500 $a Adviser: Rudolf Faust.
500 $a Source: Dissertation Abstracts International, Volume: 68-09, Section: B, page: 5985.
502 $a Thesis (Ph.D.)--University of Massachusetts Lowell, 2007.
520 $a The synthesis of polyisobutylene (PIB)-based block copolymers containing poly(methacrylates) as a second block has been achieved by a combination of living cationic and anionic polymerizations. Specifically, the second block could be poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), P(MMA-co-HEMA) with different MMA/HEMA ratios, poly( tert-butyl methacrylate) (PtBMA) and poly(methacrylic acid) (PMAA). The obtained triblock copolymers comprised of PIB as a central block and poly(methacrylate) as side blocks demonstrate characteristics of thermoplastic elastomers and are potential candidates for application as drug-eluting stent coatings.
520 $a 1. Synthesis and Characterization of P(MMA- co-HEMA)-b-PIB- b-P(MMA-co-HEMA) Triblock Copolymers. P(MMA-co-HEMA)-b-PIB- b-P(MMA-co-HEMA) triblock copolymers with different compositions were prepared by a synthetic methodology involving the transformation from living cationic to anionic polymerization. Anionic copolymerization of MMA and 2-[(trimethylsilyl)oxy]ethyl methacrylate (protected HEMA) resulted in random copolymers exhibiting close to theoretical M ns and low polydispersities (PDI<1.1). 1,1-Diphenylethylene end-functionalized PIB (DPE-PIB-DPE) was prepared by the reaction of living difunctional PIB and 1,4-bis(1-phenylethenyl)benzene (PDDPE), followed by the methylation of the resulting diphenyl carbenium ion with dimethylzinc (Zn(CH3)2). The DPE ends were quantitatively metalated with n-butyllithium in tetrahydrofuran at room temperature, and the resulting macroanion initiated the polymerization of methacrylates yielding triblock copolymers with high blocking efficiency. Microphase separation of the thus prepared triblock copolymers was evidenced by the two glass transitions at -64 and +120°C observed by differential scanning calorimetry (DSC). These new block copolymers exhibit typical stress-strain behavior of thermoplastic elastomers. Surface characterization of the samples was accomplished by angle-resolved X-ray photoelectron spectroscopy (XPS), which revealed that the surface is richer in PIB compared to the bulk. However, a substantial amount of P(MMA-co-HEMA) remains at the surface. The presence of hydroxyl functionality at the surface provides an opportunity for further modification.
520 $a 2. Facile Synthesis of PIB-DPE and Its Application for the Synthesis of PIB-based Blcok Copolymers Containing Poly(methacrylates). The convenient synthesis of methoxy-free 1,1-diphenylethylene end-functionalized polyisobutylene (PIB-DPE) has been accomplished by capping living PIB with 1,4-bis (1-phenylethenyl)benzene, followed by hydride transfer reaction with tributylsilane. This process avoids methylation with large excess of dimethylzinc, which results in a large amount of inorganic salt contamination. The obtained PIB-DPE was quantitatively metalated with 1.5-fold excess n-butyllithium in tetrahydrofuran at room temperature. The acidic methine proton at the chain end remained intact during lithiation procedure. The resulting macroanion efficiently initiated the polymerization of methacylate monomer.
520 $a PMMA-b-PIB-b-PMMA, (PHEMA)- b-PIB-b-PHEMA and PtBMA-b-PIB- b-PtBMA have been prepared with high blocking efficiency. Complete hydrolysis of PtBMA-b-PIB- b-PtBMA into PMAA-b-PIB- b-PMAA was realized in tetrahydrofuran/1,4-dioxane using HCl aqueous solution. The complete hydrolysis was confirmed by 1H-NMR, FTIR and DSC measurements.
520 $a 3. Synthesis of PIB-b-PMMA by a Novel Coupling Reaction. The synthesis of poly(isobutylene- b-methyl methacrylate) (PIB-b-PMMA) has been accomplished by a novel coupling reaction via a combination of living cationic and anionic polymerizations. Chloroallyl chain-end functionalized PIB (PIB-AllylCl) was prepared by capping living PIB with 1,3-butadiene. Living PMMA was prepared in situ for coupling reaction. However, PIB-AllylCl is unreactive toward living PMMA in tetrahydrofuran at -78°C. The more reactive bromoallyl end-functionalized PIB (PIBAllylBr) could be prepared by a quantitative halogen exchange reaction using an excess of lithium bromide. The PIB-AllylBr could be coupled with living PMMA in tetrahydrofuran at -78 °C with high efficiency (> 95%).
590 $a School code: 0111.
650 4 $a Chemistry, Polymer. $3 1018428
690 $a 0495
710 2 $a University of Massachusetts Lowell. $3 1017839
773 0 $t Dissertation Abstracts International $g 68-09B.
790 $a 0111
790 1 0 $a Faust, Rudolf, $e advisor
791 $a Ph.D.
792 $a 2007
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3285263