Session Y42: Renewable and Sustainable Polymers

Sustainable epoxy and oxetane thermosets from photo-initiated cationic polymerization.

A group of sustainable materials are proposed and produced from multifunctional epoxides and oxetanes obtained from renewable sources. Monomers are photopolymerized using diaryliodonium salts designed and synthesized by our group as initiator. A detailed investigation of the network formation of epoxidized linseed oil revealed that crosslinks is markedly dependent to the thickness and viscosity of substrate. Copolymerization studies of difunctional oxetane showed that limonene dioxide was effective in increasing the reaction rates and shorten the inherent induction period, also known as kick-starting effect. Such oxetane thermoset can achieve desirable curing rates and Tg compared to petroleum based epoxy used in applications such as large scale surface coatings.   

Structure and Dynamics of Cellulose Molecular Solutions

Molecular dissolution of microcrystalline cellulose has been achieved through mixing with ionic liquid 1-Ethyl-3-methylimidazolium acetate (EMIMAc), and organic solvent dimethylformamide (DMF). The mechanism of cellulose dissolution in tertiary mixtures has been investigated by combining quasielastic and small angle neutron scattering (QENS and SANS). As SANS data show that cellulose chains take Gaussian-like conformations in homogenous solutions, which exhibit characteristics of having an upper critical solution temperature, the dynamic signals predominantly from EMIMAc molecules indicate strong association with cellulose in the dissolution state. The mean square displacement quantities support the observation of the stoichiometric 3:1 EMIMAc to cellulose unit molar ratio, which is a necessary criterion for the molecular dissolution of cellulose. Analyses of dynamics structure factors reveal the temperature dependence of a slow and a fast process for EMIMAc’s bound to cellulose and in DMF, respectively, as well as a very fast process due possibly to the rotational motion of methyl groups, which persisted to near the absolute zero.   

Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers.

Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene-$b$-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues---such as poly(styrene-$b$-butadiene-$b$-styrene) (SBS)---in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.   

Mechanochemical modification of lignin and application of the modified lignin for thermoplastics and thermosets

In this work, mechanochemical modification of lignin and use of the modified lignin in thermoplastics and thermosets were studied. Oleated lignin was successfully prepared by transesterification between lignin and methyl, and the oleation reaction was performed in a solvent-free and room temperature ball milling process with a relatively short time. PLA/lignin blends were prepared through melt extrusion. Compared with the PLA/lignin blends, the PLA/oleated lignin blends exhibited finer dispersion of lignin in the blends, increased glass transition temperature and higher tensile properties, suggesting improved compatibility between lignin and PLA.~Carboxylic and anhydride groups were also introduced into the structure of lignin via mechanochemical modification, and the resulting lignin derivatives were~used as curing agents for epoxies. The dynamic mechanical properties and thermal stability of the cured epoxy resins were studied using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA).   

Alignment of Fatty Acid-Derived Triblock Copolymers under Large Amplitude Oscillatory Shear

Linear ABA triblock copolymers find widespread utilization as thermoplastic elastomers (TPEs): materials which exhibit elastomeric behavior at room temperature and can be readily processed at elevated temperatures. Traditional TPEs are derived from fossil fuels; however, the finite availability of petroleum and the environmental impact of petroleum processing has led to an increased interest in developing alternative sources for polymers. Vegetable oils and their fatty acids are promising replacements for petroleum sources due to their abundance, low cost, lack of toxicity, biodegradability and ease of functionalization that provides convenient routes to polymerization. In this study, triblock copolymer TPEs were synthesized containing lauryl and stearyl acrylate, derived from fatty acids found in vegetable oils. Small-angle X-ray scattering experiments revealed highly aligned triblock copolymer morphologies after the application of large amplitude oscillatory shear. The temperature and frequency dependence of the degree of alignment was investigated. In contrast to prior studies on shear-aligned morphologies in bulk and thin film block copolymers, hexagonal close packed and face centered cubic spherical structures were observed.   

PLA branching with anhydrides and tri-functional aziridine

Branched PLA was prepared by melt blending with tri-functional aziridine (T-Az) and pyromellitic dianhydride (PMDA). $^{1}$HNMR, gel permeation chromatography (GPC) and rheology were used to characterize the topological structures of branched PLA. Fast reaction between PLA carboxyl end group and T-Az resulted in 3-arm stars and increased the molecular weight. However, the 3-arm stars did not show strain hardening behavior under extensional flow. After modifying PLA hydroxyl end group with PMDA, PLA can react with T-Az on both chain ends and form long chain branched structure, which showed strain hardening in extension. It was found that that only 10{\%} of the PLA hydroxyl end groups reacted with PMDA.   

\textbf{The influence of starch oxidization and aluminate coupling agent on interfacial interaction, rheological behavior, mechanical and thermal properties of poly(propylene carbonate)/starch blends}

Poly(propylene carbonate) (PPC) is a kind of new biodegradable polymer that is synthesized by copolymerization of propylene oxide and carbon dioxide. In this work, PPC end-capped with maleic anhydride (PPCMA)/thermoplastic starch (TPS), PPCMA/thermoplastic oxidized starch (TPOS) and PPCMA/AL-TPOS (TPOS modified by aluminate coupling agent) blends were prepared by melt blending to improve its thermal and mechanical properties. FTIR results showed that there existed hydrogen-bonding interaction between PPCMA and starch. SEM observation revealed that the compatibility between PPCMA and TPOS was improved by the oxidation of starch. The enhanced interfacial interactions between PPCMA and TPOS led to a better performance of PPC blends such as storage modulus (G'), loss modulus (G"), complex viscosity ($\eta $*), tensile strength and thermal properties. Furthermore, the modification of TPOS by aluminate coupling agent (AL) facilitated the dispersion of oxidized starch in PPC matrix, and resulted in increasing the tensile strength and thermal stability.