We synthesized six polyurethane networks from 4,4Ј-diphenylmethane diisocyanate and polyols based on midoleic sunflower, canola, soybean, sunflower, corn, and linseed oils. The differences in network structures reflected differences in the composition of fatty acids and number of functional groups in vegetable oils and resulting polyols. The number average molecular weights of polyols were between 1120 and 1300 and the functionality varied from 3.0 for the midoleic sunflower polyol to 5.2 for the linseed polyol. The functionality of the other four polyols was around 3.5. Canola, corn, soybean, and sunflower oils gave polyurethane resins of similar crosslinking density and similar glass transitions and mechanical properties despite somewhat different distribution of fatty acids. Linseed oil-based polyurethane had higher crosslinking density and higher mechanical properties, whereas midoleic sunflower oil gave softer polyurethanes characterized by lower T g and lower strength but higher elongation at break. It appears that the differences in properties of polyurethane networks resulted primarily from different crosslinking densities and less from the position of reactive sites in the fatty acids.

The kinetics of the epoxidation of soybean oil and the extent of side reactions were studied at 40, 60 and 80°C. Epoxidation was carried out in toluene with "in situ " formed peroxoacetic and peroxoformic acid and in the presence of an ion exchange resin as the catalyst. The reaction was found to be first-order with respect to the double bond concentration. At higher temperatures and at higher conversions a deviation from the first-order kinetics was observed. The rate constants for the epoxidation with peroxoacetic acid were 0.118 (h -1 ) at 40°C, 0.451 (h -1 ) at 60°C and 1.278 (h -1 ) at 80°C, while those for peroxoformic acid were 0.264, 0.734, and 1.250 (h -1 ). The activation energy was found to be 54.7 kJ/mol for the epoxidation with peroxoacetic acid and 35.9 kJ/mol for that with peroxoformic acid. Three factors indicated that side reactions did not occur on a large scale: The absence of an OH band in the IR spectra, the formation of less than 2% of higher molecular weight products from gel permeation chromatography and the selectivity values between 0.9 and 1.

Polyurethane networks based on vegetable oils have very heterogeneous composition, and it is difficult to find a close correlation between their structure and properties. To establish benchmark structure-properties relationships, we have prepared model polyurethane networks based on triolein and 4,4'-diphenylmethane diisocyanate (MDI). Cross-linking in the middle of fatty acid chains leaves significant parts of the triglyceride as dangling chains. To examine their effect on properties, we have synthesized another polyurethane network using triolein without dangling chains (removed by metathesis). The structure of polyols was studied in detail since it affects the structure of polyurethane networks. The network structure was analyzed from swelling and mechanical measurements and by applying network and rubber elasticity theories. The cross-linking density in both networks was found to be close to theoretical. The triolein-based model network displayed modulus (around 6 MPa), tensile strength (8.7 MPa), and elongation at break (136%), characteristic of hard rubbers. Glass transition temperatures of the networks from triolein and its metathesis analogue were 25 and 31.5 degrees C, respectively.

Vegetable oils are very heterogeneous materials with a wide distribution of triacylglycerol structures and double-bond contents. The hydrogenation of epoxidized soybean oil (ESO) produces polyols having a functionality distribution related to that of soybean oil. Therefore, these polyols are convenient substances for studying the impact of structural heterogeneity on network formation and properties. Polyols of hydroxyl numbers ranging from 225 to 82 mg KOH/g and weight-average functionalities ranging from 4.4 to 2.7 were obtained by the variation of the time of hydrogenation of ESO. An analysis of the functionality distribution in polyols shows that gel points with diisocyanates vary from 54 to 76% conversion. The molecular weights of the network chains of polyurethanes prepared from these polyols and diphenyl methane diisocyanate varied from 688 to 1993. Polyols with hydroxyl numbers above 200 mg KOH/g gave glassy polymers, whereas those below that value gave rubbers. The heterogeneity of polyols had a negative effect on the elastic properties only at low crosslinking densities.

While incorporation of only a few mol % of diphenylsiloxy-, DiPhS, repeat units into polydimethylsiloxane, PDMS, chains is enough to completely suppress their crystallization, it also leads, in polymers obtained by silanolate-initiated ring-opening polymerization, to a puzzling and yet unexplained chain branching which significantly distorts polymer molecular weight distributions and affects their chain conformation. In contrast to this, we found that introduction of comparable amounts (ca. 5 mol %) of diethylsiloxy-, DiEtS, units into the same type of polymers also suppresses polymer crystallization but does not lead to any detectable branching, yielding polymers with the most probable molecular weight distribution and typical random coil conformation in a thermodynamically good solvent, such as toluene. On the basis of the results of a 29 Si NMR and SEC-MALS study, we propose that branching in DiPhS-containing polymers is caused by a nucleophilic attack of initiating silanolate anions on their Si−C Ar side bonds and a resulting formation of phenyltrisiloxysilane T-branches. We also propose that because branching may seriously disrupt mechanical properties of elastomers if such DiPhS-containing PDMSs are used for cross-linking, the DiEtS-modified derivatives represent polymers of choice if applications of such elastomers at extremely low temperatures are desired.

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Photocuring and vat photopolymerization (VP) additive manufacturing (AM) is reported for two families of fully amorphous poly(dimethyl siloxane) (PDMS) terpolymers containing either diphenylsiloxy (DiPhS) or diethylsiloxy (DiEtS) repeating units. A thiol‐functionalized PDMS crosslinker enables rapid crosslinking in air using efficient thiol–ene addition. Differential scanning calorimetry and dynamic mechanical analysis (DMA) confirm the absence of crystallinity for the DiPhS‐containing systems, while DMA shows a rubbery plateau extending to greater than 200 °C for the DiEtS‐containing system. VP‐AM of both photopolymer systems afford well‐defined 3D geometries, including high aspect ratio structures, which demonstrate feasibility of these photopolymers for the 3D printing of unique geometric objects that require elastomeric performance to temperatures as low as −120 °C.

The composition of crude algal oil was analyzed and determined by several methods. Oil was converted to polyols by ozonolysis, epoxidation, and hydroformylation. Ozonolysis gave a polyol with lighter color but a low OH number and was unsuitable for polyurethane applications. Epoxidation also improved the color and gave a polyol with an OH number around 150 mg KOH/g, which with diphenylmethane diisocyanate gave a homogeneous, rubbery, transparent sheet. Desirable rigid foams were prepared with the addition of water to the formulation. Hydroformylation was carried out successfully giving an OH number of about 150 mg KOH/g, but the polyol was black. Casting the polyurethane sheet was difficult due to the very high reactivity of the polyol. Polyurethane foam of lower quality than from epoxidation polyol was obtained. More work on optimization of the foaming system would improve the foam. Crude algal oil is a viable starting material for the production of polyols. Better results would be obtained from refined algal oils.