Acyclic Azoester Modification of 1,4- and 1,2-Polybutadienes. Structure and Properties

Schulz, D. N.; Spiewak, J. W.; Valaitis, J. K.; Mochel, V. D.; Barzan, M. L.

doi:10.1021/ma60078a008

Cited by 15 publications

(6 citation statements)

References 11 publications

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“…The close correspondence between the T g 's and the good fit for the data to the modified GTW equation suggest that these polymers were random “copolymers of copolymers”, that is, random copolymers of ECO and SCO units. Although the mechanism of polymerization predicts that ethylene, styrene, and CO ought to incorporate as a copolymer of copolymers,7 this is the first application of polymer science principles to demonstrate this fact.…”

Section: Resultsmentioning

confidence: 94%

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Synthesis and properties of copolymers of ethylene/carbon monoxide with styrene/carbon monoxide

Kacker

Sissano

Schulz

2000

J. Polym. Sci. A Polym. Chem.

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The terpolymerization of ethylene, styrene, and carbon monoxide was accomplished by two different palladium‐based catalysts: a phosphine‐based ligand system and a nitrogen‐based ligand system. The range of possible compositions and the composition dependence of the properties of the resulting polymers were determined. These polymers were essentially carbon monoxide versions of the ethylene styrene interpolymers recently presented by Dow. A comparison between the two families of polymers is attempted. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 752–757, 2000

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Section: Resultsmentioning

confidence: 94%

“…Because of the high crystallinity of 100% ECO copolymer, this T g was difficult to determine experimentally. Consequently, we used the modified GTW equation7 (eq 3) and plotted the T g of the copolymers versus a derived term based upon the composition to predict the T g of the ECO copolymer (Fig. 1).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and properties of copolymers of ethylene/carbon monoxide with styrene/carbon monoxide

Kacker

Sissano

Schulz

2000

J. Polym. Sci. A Polym. Chem.

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“…These phenomena have also been observed for isopropyl azodicarboxylate-modified polybutadiene obtained by the ene reaction. 8,10 Figure 2 also illustrates that, when the concentration of COOH is less than 6 mol %, the relationship between T g 's and COOH% can be described by the Fox equation…”

Section: T G Of Synthesized Cpbdsmentioning

confidence: 92%

“…The chemical modification of polybutadienes is a useful method for altering and optimizing their physical and chemical properties. 1,[7][8][9][10][11][12][13][14][15] This topic has been the subject of many studies. A few examples of the chemical reactions used include hydrogenation, 7,[13][14][15] hydrohalogenation, 7,12 and ene reactions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of high molecular weight carboxylated polybutadiene

Gong

Wool

Friend

et al. 1999

J. Polym. Sci. A Polym. Chem.

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High molecular weight carboxylated polybutadienes (cPBDs) with number‐average molecular weight (Mn) from 98,000 to 200,000 and carboxylic acid (COOH) contents of 0.5–10 mol % were successfully synthesized through hydrocarboxylation of polybutadienes (PBDs) at temperatures of 140–150°C using PdCl2(PPh3)2 and SnCl2 · 2H2O catalysts. At low extents of hydrocarboxylation (COOH < 6 mol %), glass transition temperatures (Tg's) of the resulting cPBDs did not change considerably (<10°C). Significant chain scission and crosslinking was not detected during the chemical modification process. Characterization of the microstructures of cPBDs by FTIR, 13C‐NMR, and Raman spectroscopy showed that the carboxylic groups were incorporated on the pendant (1,2) PBD double bonds as well as the backbone (1,4) double bonds, indicating the hydrocarboxylation reaction did not solely occur at the terminal carbons of the pendant double bonds. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3129–3138, 1999

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“…These results are congruous with an earlier study that found the 1,4 modification with IAD to be significantly faster than the IAD reaction with l,2-PB. 3 It was also shown therein that the IAD addition to high vinyl polybutadiene occurs randomly. Since the microstructure of the 85% 1,2-PB used here is random,58 the IAD-modified polymer produced is also random, even though in this case the attachment is to the 1,4 units.…”

Section: Microstructure and Propertiesmentioning

confidence: 92%

The structure of azoester-modified polybutadiene elastomers

Roland¹,

Böhm²,

Sadhukhan³

1985

J. Appl. Polym. Sci.

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SynopsisIt is demonstrated that the improved tack and green strength accompanying the IAD modification of polybutadiene arise strictly from the introduction of bulky, polar groups. The fact that addition of 1,4-PB occurs in a blocked arrangement is not a factor in the development of high green strength, as can be seen by the large increase in strength of modified 1,2-PB, wherein the IAD groups are randomly attached. The tack is also elevated through random IAD addition; however, the relevance of blocked vs. random structure in this regard cannot be completely judged since it depends as well on the absolute IAD level and the polymer's T,, as well as the test temperature. At high levels of IAD (about 38 mol %), the modified PB becomes a phase-separated material, exhibiting high stiffness and brittleness. This heterm geneous system is quite unlike the PB modified with only 15 mol % IAD. These latter elastomeric materials are homogenous, and remain so during deformation. The attainment-of high tack and green strength relies upon maximal addition of the IAD groups, provided the molecules retain their flexibility. In blending the modified PB with other rubbers, optimum behavior in the blends appears to be achieved when the IAD-PB is present as a continuous phase.

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Acyclic Azoester Modification of 1,4- and 1,2-Polybutadienes. Structure and Properties

Cited by 15 publications

References 11 publications

Synthesis and properties of copolymers of ethylene/carbon monoxide with styrene/carbon monoxide

Synthesis and properties of copolymers of ethylene/carbon monoxide with styrene/carbon monoxide

Synthesis and characterization of high molecular weight carboxylated polybutadiene

The structure of azoester-modified polybutadiene elastomers

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