Preparation and Structure of High Molecular Weight Polybutenes

Thomas, R.; Sparks, W. J.; Frolich, Per K.; Otto, Michael; Mueller-Cunradi, M.

doi:10.1021/ja01859a010

Cited by 79 publications

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“…n-Butenes are capable of reacting with isobutylene in the low temperature conditions of reaction. This results in a lowering of the molecular weight of the polymer product (Thomas et al, 1940). A similar reduction in molecular weight might reasonably be expected on copolymerization of isobutylene with acenaphthylene.…”

Section: Permittivitysupporting

confidence: 64%

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Polymers and Copolymers of Acenaphthylene

Jones¹

1951

J. Appl. Chem.

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An exploratory survey of the polymerization and copolymerization of acenaphthylene has been carried out to see whether there are possibilities of its use as an industrial monomer. Polyacenaphthy‐lene been prepared by thermal polymerization with and without peroxide‐type catalysts, by Friedel‐Crafts polymerization and by the emulsion technique. The molecular weight of a thermal polymer exceeded 100,000. Some aspects of the copolymerization of acenaphthylene with styrene have been studied and it has been shown that a substantial elevation in the softening point of polystyrene results from the incorporation of acenaphthylene units in the polymer chain. The electrical properties of the copolymers are not significantly different from those of polystyrene. Copolymers of acenaphthylene and isobutylene have been obtained by low‐temperature polymerization with Friedel‐Crafts‐type catalysts. The products were of a relatively low order of molecular weight. Examination of the ultra‐violet absorption spectra of the copolymers has revealed a tendency for the acenaphthylene units to enter the macromolecules in groups rather than randomly in single units. Butadiene and acenaphthylene which, in certain conditions, undergo a Diels‐Alder condensation to give tetrahydrofluoranthene, furnish linear copolymers by emulsion polymerization. Attempts to prepare copolymers of acenaphthylene with ethylene proved unsuccessful, acenaphthylene showing a very pronounced inhibiting effect on the polymerization.

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Section: Permittivitysupporting

confidence: 64%

“…Some of the important factors affecting molecular weight in the polymerization of isobutylene at low temperature have been discussed by Thomas, Sparks, Frolich, Otto & Mueller-Cunradi (1940). These include purity of raw materials, catalyst and catalyst concentration, temperature, and diluents.…”

Section: Permittivitymentioning

confidence: 99%

Polymers and Copolymers of Acenaphthylene

Jones¹

1951

J. Appl. Chem.

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“…With a history dating back to the very beginnings of the polymer field (i.e., terpenic resins),1 the cationic polymerization of olefins is of commercial significance, especially in the context of isobutene (IB) based polymers 2–8. Although numerous advances have been made over the years, many opportunities still exist for maximizing energy and atom efficiency while advancing the environmental characteristics of IB polymerizations 9.…”

Section: Introductionmentioning

confidence: 99%

Aqueous cationic olefin polymerization using tris(pentafluorophenyl)gallium and aluminum

Mathers

Lewis²

2011

J. Polym. Sci. A Polym. Chem.

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Tris(pentafluorophenyl)gallium (3) and aluminum (7) are active coinitiators for the production of medium‐high molecular weight (MW) polymers of styrene and isobutene (IB) under aqueous reaction conditions. Strong Brønsted acids formed in situ by reaction of these coinitiators with background moisture present in the monomer droplet (5 and 8, respectively) are believed to be responsible for inducing cationic polymerization of these monomers. Of the two, 7 is the most active for IB polymerization in both aqueous media and anhydrous aliphatic solvents. These results are in contradistinction to tris(pentafluorophenyl)boron (2), which is incapable of polymerizing IB in aqueous or aliphatic media. The MWs of the polyisobutenes (PIBs) produced under aqueous conditions by either coinitiator greatly exceed those formed under similar reaction conditions by the strongly acidic chelating diborane (1,2‐C6F4[B(C6F5)2]2, 1) or diborole (1,2‐C6F4[9‐BC12F8]2, 6). Both 3 and 7 are readily synthesized from the corresponding Group 13 halide compounds in conjunction with bis(pentafluorophenyl)zinc (4). Aqueous polymerization of IB dissolved in aliphatic solvents with 3 or 7 can yield PIBs with relatively narrow polydispersities. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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“…Higher temperature might accelerate the side reactions, such as chain transfer and termination. The inverse effect of polymerization temperature on molecular weight has been quantitatively expressed by Arrhenius equation, that is, ln M n = ln A − Δ E /RT 23–25. The overall activation energy difference (Δ E or E DP ) was calculated to be −13.5 kJ mol −1 from the slope of the linear Arrhenius plot of ln( M n ) versus 1/ T for the temperature interval from 0 to 50 °C, shown in Figure 10.…”

Section: Resultsmentioning

confidence: 99%

Cationic polymerization of isobutyl vinyl ether coinitiated with heteropolyacid or its salts in aqueous medium

Huang

Dan

2012

J. Polym. Sci. A Polym. Chem.

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The suspension cationic polymerization of isobutyl vinyl ether (IBVE) in aqueous medium could be achieved by using H3PW12O40, AlPW12O40, FePW12O40, K3PW12O40, or Na3PW12O40 as efficient water‐tolerant coinitiators in the presence of HCl. The addition reaction of IBVE with H2O occurred to form IBVE–H2O adduct and then subsequent decomposition immediately took place or turned to acetaldehyde diisobutyl acetal (A) in the presence of AlPW12O40, and (A) decomposed rapidly to form 2‐isobutanol (B) and acetaldehyde (C). Cationic polymerization of IBVE in aqueous medium was promoted greatly with increasing HCl concentration and proceeded extremely rapidly to get high polymer yield even at low concentration of AlPW12O40 of 0.3 mM. A sufficient amount of HCl was needed to decrease the hydrolysis of initiator IBVE–HCl and to accelerate the polymerization in aqueous medium simultaneously. The yield and molecular weight of poly(IBVE) increased with increasing concentrations of HCl and AlPW12O40 or with decreasing temperature. The isotactic‐rich poly(IBVE)s with m diad of around 60%, having Mn of 1200–4500 g mol−1 and monomodal molecular weight distribution could be obtained via cationic polymerization of IBVE in aqueous medium. This is the first example of cationic polymerization of IBVE in aqueous medium coinitiated by heteropolyacid and its salts. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

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Preparation and Structure of High Molecular Weight Polybutenes

Cited by 79 publications

References 0 publications

Polymers and Copolymers of Acenaphthylene

Polymers and Copolymers of Acenaphthylene

Aqueous cationic olefin polymerization using tris(pentafluorophenyl)gallium and aluminum

Cationic polymerization of isobutyl vinyl ether coinitiated with heteropolyacid or its salts in aqueous medium

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