Group transfer polymerization - polymerization of acrylic monomers

Sogah, Dotsevi Y.; Hertler, W. R.; Webster, Owen W.; Cohen, Gordon M.

doi:10.1021/ma00173a006

Cited by 524 publications

(318 citation statements)

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“…The first strategy for achieving "living" (meth)acrylate polymerization through modification of the ionic nature of the endgroup was group transfer polymerization (GTP), developed by Webster and Sogah et al at DuPont in 1983 (75)(76)(77)(78)(79)(80). This process involves initiation with a silyl ketene acetal or related compound, producing a silyl enolate propagating species.…”

Section: Group Transfer Polymerizationmentioning

confidence: 99%

“…Silyl initiators containing ether, vinyl, sulfide, cyanide, phosphonate, and phosphonium groups have been used to prepare end-functionalized poly(meth)acrylates (93,94). Diblock, triblock, and random (meth)acrylate copolymers have been prepared with both monofunctional and bifunctional silyl initiators (79,(95)(96)(97); ladder polymers (92) have also been synthesized through GTP with bifunctional initiators. Cyclopolymerizations of dknethaerylates by GTP have recently been explored (98,99).…”

Section: Group Transfer Polymerizationmentioning

confidence: 99%

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The Organometallic Polymerization of (Meth)acrylates: An Overview

Boffa

2000

ACS Symposium Series

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Metal-mediated (meth)acrylate polymerizations provide a good example of the versatility and importance of transition metal catalysis in polymer design. This chapter surveys several of these processes with respect to "living" behavior, experimental condition and monomer restrictions, and types of polymer architectures available.In addition to anionic methods, Group Transfer Polymerization (GTP) with silyl enolates or zirconocenes, organolanthanide-and aluminum porphyrin-initiated polymer ization, and Atom Transfer Radical Polymerization (ATRP) are discussed.Polymethacrylate and polyacrylate materials play an important role in our society. Almost two billion pounds of polymer products based on acrylic esters are produced each year for applications such as window plastics, dental materials, paints, contact lenses, fibers, and viscosity modifiers.Polymethacrylates-particularly poly(methyl methacrylate) (PMMA)-possess high strength, high impact resistance, excellent heat and chemical stability, and a highly amorphous nature which results in excellent optical clarity. For these reasons, they are used widely as building plastics (Plexiglas, Lucite). Polyacrylates are less rigid due to their lower glass transition temperatures, and as latex emulsions form the basis for durable automobile and house paints and coatings. Random copolymers of (meth)acrylates with vinylidene chloride (Sarari), acrylonitrile, and ethylene find applications as clothing fibers, tubing, gaskets, disposable gloves, and heat-and oil-resistant automotive elastomers.Despite the commercial utility of polymethacrylates and polyacrylates, refinements in synthetic methodology these macromolecules have lagged behind that of other polymers. The great majority of acrylic ester products in use today are still produced by radical polymerization, which allows little if any control over the fine points of the polymerization process. This is the result of the traditionally illcontrolled nature of acrylate polymerization. While chain termination and transfer side reactions may be largely eliminated for other monomers, such as styrene and dienes, through the use of controlled anionic polymerization, the (meth)acrylate ester

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Section: Group Transfer Polymerizationmentioning

confidence: 99%

Section: Group Transfer Polymerizationmentioning

confidence: 99%

The Organometallic Polymerization of (Meth)acrylates: An Overview

Boffa

2000

ACS Symposium Series

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“…Polymerization could be observed only by KHF 2 as the catalyst, and was not detected by T ASF or TBA F. This is consistent with GTP of methyl methacrylate. 10 GPC curves of the products provided by GTP of MA-PBuOZ0-11 (3) are shown in Figure I 1 gave the polymer with lower molecular weight in higher conversion (76%) (a), showing increase in the feed ratio to decrease the polymerization rate, since the higher viscosity of polymerization system brought by higher molecular weight of produced polymer should depress more strongly the diffusion of growing sites and macromonomers to retard propagation reaction. MAPBuOZ0-14 gave 4 of higher molecular weight in lower conversion compared to MA-PBuOZ0-3 at similar feed ratio (c).…”

Section: Group Transfer Polymeri:::ationmentioning

confidence: 99%

“…These termination reactions were carried out in THF at -78"C using T ASF as catalyst in amounts of more than equimolar with MTS by reference to the coupling reaction of living poly(methyl methacrylate) performed by Sogah. 10 Though the polymers of MA-PMeOZ0-14 were examined for coupling reactions in CH 3 CN using respective T ASF and KHF 2 as the catalysts at -78oc, no coupling product was detected.…”

Section: Coupling Reactions Of Poly(macromonomer)smentioning

confidence: 99%

Group Transfer Polymerization of Methacryl-Type Poly(2-oxazoline) Macromonomers

Shimano

Sato

Kobayashi

1999

Polym J

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“…Group transfer polymerization is also attractive to prepare blocked polymethacrylic copolymers. 4 These initiator systems make the block copolymerizations running at a relatively simple experimental condition. However, inducing living ability of the propagating end with currently available reagent (lower cost) and easier demand is still important in the synthetic polymer chemistry.…”

mentioning

confidence: 99%