Nonterminated polymeric anions: The initiation of polymerization of certain polar monomers

Graham, Roger; Panchak, John R.; Kampf, Mary J.

doi:10.1002/pol.1960.1204414412

Cited by 43 publications

(7 citation statements)

References 8 publications

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“…The composition was determined by carbon and hydrogen analyses, and the density was measured at 20°C by the flotation method with aqueous solutions of calcium chloride. The number-average molecular weight (Mn) was determined by GPC with a Waters Model R-4 as based on a calibration curve of monodisperse polystyrenes (Waters Table I According to the method by Graham, et al, 14 the block copolymers, Z-1 and Z-2, were produced by the addition of CDA to living polystyrene anions initiated with n-butyllithium-tetrahydrofuran in toluene as solvent under highly reduced pressure mmHg) at room temperature. The obtained block copolymers were purified and dried by the same methods as used in the case of the random copolymers.…”

Section: Preparation Of Random Copolymersmentioning

confidence: 99%

“…A block copolymer presents a contrast to a random copolymer in the sequential distributions. Graham, et a!., 14 noted that isopropyl acrylate could give a AB-type block copolymer with living polystyrene anions initiated by nbutyllithium-tetrahydrofuran, but other acrylates such as ethyl and cyclohexyl acrylates had not polymerized well. In our laboratory, however, a AB-type block copolymer of cyclododecyl acrylate and styrene could be obtained according to the Graham's method.…”

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confidence: 99%

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Glass Transition Behaviors of Random and Block Copolymers and Polymer Blends of Styrene and Cyclododecyl Acrylate. I. Glass Transition Temperatures

Daimon

Okitsu

Kumanotani

1975

Polym J

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Glass transition temperatures have been studied for the random and block copolymers of styrene and cyclododecyl acrylate. The random copolymers showed a single glass transition temperature, which provided a concave glass transition temperature-composition curve. This concave relationship was fairly well represented by the modified Gibbs-Dimarzio equation of Uematsu and Honda, which includes the influence of the specific character of cyclododecyl acrylate as a monomeric unit. Each of the block copolymers as well as the blends of their component homopolymers showed two separated glass transition temperatures corresponding to the respective ones of poly(cyclododecyl acrylate) and polystyrene; these were independent of the total composition, owing to the incompatibility of the components.

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Section: Preparation Of Random Copolymersmentioning

confidence: 99%

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confidence: 99%

Glass Transition Behaviors of Random and Block Copolymers and Polymer Blends of Styrene and Cyclododecyl Acrylate. I. Glass Transition Temperatures

Daimon

Okitsu

Kumanotani

1975

Polym J

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“…Anions of polystyrene (from butyllithium in THF) and of poly(MMA) (from 9-fluorenyllithium) have been shown to initiate the polymerization of alkyl methacrylates (hexyl, butyl), methacrylonitrile, isopropyl acrylate, and acrylonitrile. This authors (38) found that the poly (MMA) anion was unable to initiate the polymerization of styrene. 9-Fluorenyllithium, although sufficiently basic to initiate the polymerization of MMA, was also found to be unable to initiate the polymerization of styrene, and no styrene was found in copolymerizations initiated by this catalyst involving both monomers.…”

Section: «-Buli-et3aimentioning

confidence: 96%

Lithium Catalysis in Industrial Polymerization

Kamienski¹

1965

Ind. Eng. Chem.

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A penetrating analysis of this new and increasingly important area-addition, condensa- INDUSTRIAL AND ENGINEERING CHEMISTRYLIT HI U M -containing catalysts are critical to production of hundreds of millions of pounds of polymers per year in plants such as this one for polymerizing ethylene were also the best for propylene polymerization. Within the optimum range of 1.8 to 2.5, high yields of isotactic polypropylenes were obtained. Evans and Owen (27) used the appearance of the yellow color characteristic of the TiCl4-benzene complex to show the presence of excess TiCl.i in the titration of w-butyllithium. The (LiBu)/(TiCl4) ratio at which a color change occurred was between 1.13

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“…In contrast, chain transfer is facile for acrylates due to the presence of an acidic proton at the carbonyl a-position (10,13,(33)(34)(35)(36). Again, only bulky monomers such as isopropyl and f-butyl acrylate (*BuA), may be polymerized anionically to high conversion with even moderate degrees of control.…”

Section: Side Reactionsmentioning

confidence: 99%

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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Nonterminated polymeric anions: The initiation of polymerization of certain polar monomers

Cited by 43 publications

References 8 publications

Glass Transition Behaviors of Random and Block Copolymers and Polymer Blends of Styrene and Cyclododecyl Acrylate. I. Glass Transition Temperatures

Glass Transition Behaviors of Random and Block Copolymers and Polymer Blends of Styrene and Cyclododecyl Acrylate. I. Glass Transition Temperatures

Lithium Catalysis in Industrial Polymerization

The Organometallic Polymerization of (Meth)acrylates: An Overview

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