Search NASASearch

SEARCH · Search NASA

Results for “POLYBUTADIENE”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records

Low-Temperature Chemiluminescence From cis-1,4-Polybutadiene, 1,2-Polybutadiene, and trans-Polypentenamer at Temperatures Near Ambient

The chemiluminescence emission at 25-60 C was measured from films of cis-1,4-polybutadiene, 1,2-polybutadiene, and trans-polypentenamer. The polymers were autoxidized previously in air 100 C, or allowed to react with singlet molecular oxygen in solution, and then cast into films. Values of beta(or k(sub d,((1)O2 yields (3)03)/k(sub r)((1)O2 + polymer yields products)) were determined in benzene for cis-1,4-polybutadiene and cis-1,4-polyisoprene, and for model compounds cis-3-hexene and cis-3-methyl-3-hexene by independent methods. The chemiluminescence emission from irradiated films of the polymers containing a dye sensitizer showed a complicated time dependence, and the results depended on the length of irradiation.

Nathan, Richard A.

Thermal Rearrangements of Polybutadienes with Different Vinyl Contents

A study was made of the loss of double bonds in equibinary (1,4-1,2) polybutadiene (EB) and in polybutadienes with 30% 1,2, 70% 1,4 (FI), and 10% 1,2, 90% 1,4 (DI) double-bond content, when heated in vacuum under nonpyrolitic conditions (temperature range 220-280 C). These polymers were found to undergo second-order loss of 1,2 unsaturation with similar activation energies (E(sub a) = 34.0 +/- 3 kcal/mole), by analogy to the previously reported thermally induced loss of double bonds in 1,2-polybutadiene (VB) (E(sub a) = 33.6 +/- 3 kcal/mole). Moreover, EB and Fl exhibited also second-order loss of 1,4 unsaturation, with E(sub a) ca. 36 and 40 kcal/mole, respectively, while DI showed negligible loss of 1,4 unsaturation below 260 C, in common with cis-1,4-polybutadiene (CB) (with 2% 1,2 double bonds) examined earlier. The loss of 1,2 double bonds in the various polybutadienes with different vinyl contents is accompanied by substantial methyl production, ranging from about one methyl group formed for every 4-5 vinyl units lost in VB, to one methyl for every two vinyls lost in EB,and to almost one methyl for each vinyl lost in DI or CB. Mechanisms are proposed for the thermally induced loss of 1,2 and 1,4 unsaturation in various polybutadienes and for the accompanying methyl production.

Golub, Morton A.

Reactions of Atomic Oxygen (O(3P)) with Polybutadienes and Related Polymers

Thin films of the following polymers were exposed at ambient temperature to ground-state oxygen atoms (O(3P)), generated by a radio-frequency glow discharge in O2: cis- and trans-1,4-polybutadienes (CB and TB), amorphous 1,2-polybutadiene (VB), polybutadienes with different 1,4/1,2 contents, trans polypentenamer (TP), cis and trans polyoctenamers (CO and TO), and ethylene-propylene rubber (EPM). Transmission infrared spectra of CB and TB films revealed extensive surface recession, or etching, unaccompanied by any microstructural changes within the films, demonstrating that the reactions were confined to the surface layers. Contrary to the report by Rabek, Lucki, and Ranby (1979), there was no O(3P)-induced cis-trans isomerization in CB or TB. From weight-loss measurements, etch rates for polybutadienes were found to be markedly dependent on vinyl content, decreasing by two orders of magnitude from CB (2% 1,2) to structures with 30 to 40% 1,2 double bonds, thereafter increasing by half an order of magnitude to VB (97% 1,2). Relative etch rates for EMP and the polyalkenamers were in the order: EMP is greater than CO (or TO) is greater than TP is greater than CB. The sole non-elastomer examined, TB, had an etch rate about six times that of CB, ascribable to a morphology difference. Cis/trans content had a negligible effect on the etch rate of the polyalkenamers. Mechanisms involving crosslinking through units are proposed for the unexpected protection imparted to polybutadienes by the 1,2 double bonds.

Golub, Morton A.

Radiation-induced loss of unsaturation in 1,2-polybutadiene

The radiation induced loss of unsaturation and methyl production in 1,2-polybutadiene (VB) was studied using IR spectroscopy. It was found that G(-1,2), which depends on the initial vinyl content, decreased from approximately 550 for VB with 98.5% 1,2 initially, to approximately 270 for VB with 85% 1,2 initially. G(-trans-1,4) ranged from approximately 21 for VB with 14% trans-1,4 to nearly zero for VB with less than 1% trans-1,4 initially. Methyl production was found to equal one methyl group formed for every 4-5 vinyl units consumed in the radiation-cyclized VB, in contrast to one methyl formed for every two vinyls reacted during cationic cyclization to give monocyclic structures. The IR spectra of gamma-irradiated VB were very similar to the spectra of UV-irradiated or thermally-treated VB at the same residual vinyl contents. It is suggested that the radiation-induced cyclization of VB occurs by a nonionic, nonradical 'energy chain' mechanism, which apparently holds for the cyclization of VB, whether induced by gamma-rays, UV radiation, or heat.

Golub, M. A.

Mechanical and swelling behaviour of well characterized polybutadiene networks

Endlinking of hydroxyl-terminated polybutadiene with the appropriate isocyanate has been used to prepare well characterized networks. Two networks have been studied with molecular weights of the prepolymers being 6100 and 2400 g/mole by g.p.c. Cylindrical specimens were prepared and the derivatives of the stored energy function with respect to the stretch invariants were determined by torque and normal force measurements in torsion. From these data the Valanis-Landel (1967) stored energy function derivatives w-prime(lambda) were determined for both networks. The stored energy function for the junction constraint model of Flory (1953, 1977, 1979, 1985) which is a special form of the Valanis-Landel function, has been fitted to that determined from the experiments. The contributions to the stored energy function from the phantom network and from the junction constraints respectively do not agree with predictions from the topologies of the networks. In spite of this, the form of w-prime(lambda) for the junction constraint model gives an excellent 'curve fit' to the data. Comparison is also made with equilibrium swelling.

Mckenna, Gregory B.

Reactions Of Atomic Oxygen {O(3P)} With Polybutadienes

Report describes experimental study of chemical reactions of atomic oxygen in ground state {O(3P)} with polybutadienes and related polymers. Attention focused on such reactions because of adverse effects of environmental atomic oxygen on polymeric materials in low orbits around Earth.

Golub, Morton A.

Thermal cis-trans isomerization of cis,cis-3,7-decadiene - A model for cis-1,4-polybutadiene

The thermal cis-trans isomerization of cis,cis-3,7-decadiene (DD), a model compound for cis-PBD, is reported. It is demonstrated that the rather low E for the polyalkenamer isomerizations compared with that for the 2-olefins is not an artifact of the solid polymer structures, but rather is characteristic of both small and large molecules possessing pairs of nonconjugated vinylene double bonds in a suitable arrangement.

Golub, M. A.

Polybutadiene (Jumping Rubber)

This laboratory procedure starts with a violet suspension of an 'alfin' catalyst being added to a bottle containing a solution of 1,3-butadiene in pentane. The bottle is corked and shaken for several seconds. The mixture sets to a gel, and within 2 minutes the contents erupt from the bottle.

Fine, Leonard W.

NMR and Infrared Study of Thermal Oxidation of cis-1, 4-Polybutadiene

A study of the microstructural changes occuring in CB during thermal, uncatalyzed oxidation was carried out. Although the oxidation of CB is accompanied by extensive crosslinking with attendant insolubilization, it was found possible to follow the oxidation of solid CB directly with C-13 NMR spectroscopy. The predominant products appearing in the C-13 NMR spectra of oxidized CB are epoxides. The presence of lesser amounts of alcohols, peroxides, and carbonyl structures was adduced from complementary infrared and NMR spectra of soluble extracts obtained from the oxidized, crosslinked CB. This distribution of functional groups contrasts with that previously reported for the autooxidation of 1,4-polyisoprene. The difference was rationalized in terms of the relative stabilities of intermediate radical species involved in the autoxidation of CB and 1,4-polyisoprene.

Gemmer, Robert V.

Polyolefin-Based Aerogels

An organic polybutadiene (PB) rubberbased aerogel insulation material was developed that will provide superior thermal insulation and inherent radiation protection, exhibiting the flexibility, resiliency, toughness, and durability typical of the parent polymer, yet with the low density and superior insulation properties associated with the aerogels. The rubbery behaviors of the PB rubber-based aerogels are able to overcome the weak and brittle nature of conventional inorganic and organic aerogel insulation materials. Additionally, with higher content of hydrogen in their structure, the PB rubber aerogels will also provide inherently better radiation protection than those of inorganic and carbon aerogels. Since PB rubber aerogels also exhibit good hydrophobicity due to their hydrocarbon molecular structure, they will provide better performance reliability and durability as well as simpler, more economic, and environmentally friendly production over the conventional silica or other inorganic-based aerogels, which require chemical treatment to make them hydrophobic. Inorganic aerogels such as silica aerogels demonstrate many unusual and useful properties. There are several strategies to overcoming the drawbacks associated with the weakness and brittleness of silica aerogels. Development of the flexible fiber-reinforced silica aerogel composite blanket has proven one promising approach, providing a conveniently fielded form factor that is relatively robust toward handling in industrial environments compared to silica aerogel monoliths. However, the flexible silica aerogel composites still have a brittle, dusty character that may be undesirable, or even intolerable, in certain applications. Although the cross-linked organic aerogels such as resorcinol-formaldehyde (RF), polyisocyanurate, and cellulose aerogels show very high impact strength, they are also very brittle with little elongation (i.e., less rubbery). Also, silica and carbon aerogels are less efficient radiation shielding materials due to their lower content of hydrogen element. The present invention relates to maleinized polybutadiene (or polybutadiene adducted with maleic anhydride)- based aerogel monoliths and composites, and the methods for preparation. Hereafter, they are collectively referred to as polybutadiene aerogels. Specifically, the polybutadiene aerogels of the present invention are prepared by mixing a maleinized polybutadiene resin, a hardener containing a maleic anhydride reactive group, and a catalyst in a suitable solvent, and maintaining the mixture in a quiescent state for a sufficient period of time to form a polymeric gel. After aging at elevated temperatures for a period of time to provide uniformly stronger wet gels, the micro porous maleinized polybutadiene- based aerogel is then obtained by removing interstitial solvent by supercritical drying. The mesoporous maleinized polybutadiene-based aerogels contain an open-pore structure, which provides inherently hydrophobic, flexible, nearly unbreakable, less dusty aerogels with excellent thermal and physical properties. The materials can be used as thermal and acoustic insulation, radiation shielding, and vibration-damping materials. The organic PB-based rubber aerogels are very flexible, no-dust, and hydrophobic organics that demonstrated the following ranges of typical properties: densities of 0.08 to 0.255 grams per cubic centimeters, shrinkage factor (raerogel/rtarget) = 1.2 to 2.84, and thermal conductivity values of 20.0 to 35.0 mW/m-K.

Lee, Je Kyun

Thermal rearrangements in polypentenamer and polyoctenamer

Experiments were conducted to show that polypentenamer and polyoctenamer, in common with 1,4-polybutadiene, undergo anaerobic thermal cis-trans isomerization at temperatures as low as 200 degrees C. Their activation energies for isomerization are comparable to that of polybutadiene. The relative rate constants are found to decrease in the order: polybutadiene, polypentenamer, polyoctenamer. When heated in a vacuum at 200 to 270 degrees C, polypentenamer exhibits a loss of double bonds. This disappearance of unsaturation has no counterpart in polybutadiene or polyoctenamer. In polypentenamer, a mechanism for a thermally-induced ring closure that is different from the one shown for the cyclization-depolymerization of various unsaturated polymers is evident. The cyclization-depolymerization process does cause a loss of double bonds in polybutadiene and polyoctenamer at temperatures greater than or equal to 275 degrees C.

Golub, M. A.