Novel monomer synthesis

We first discuss the materials research which includes monomer synthesis, growth of monomer crystalline structures and polymerization in the solid state, yielding the requisite polymer structures. Next, the nonlinear optical experimental research is discussed which includes a novel experimental technique to measure x (w). Linear and nonlinear optical data obtained for the polydiacetylene films is subsequently presented. Detailed theoretical analysis relating the data to x (< >) and subsequently to its molecular basis will be discussed in a later publication. 

The development of novel hyperbranched synthesis strategies now offers new options for assembling old commodity monomers into unique, unprecedented polymeric architectures. There are high expectations that these new architectures will produce substantially different properties that will be utilized in a variety of... 

More industrial polyethylene copolymers were modeled using the same method of ADMET polymerization followed by hydrogenation using catalyst residue. Copolymers of ethylene-styrene, ethylene-vinyl chloride, and ethylene-acrylate were prepared to examine the effect of incorporation of available vinyl monomer feed stocks into polyethylene [81]. Previously prepared ADMET model copolymers include ethylene-co-carbon monoxide, ethylene-co-carbon dioxide, and ethylene-co-vinyl alcohol [82,83]. In most cases,these copolymers are unattainable by traditional chain polymerization chemistry, but a recent report has revealed a highly active Ni catalyst that can successfully copolymerize ethylene with some functionalized monomers [84]. Although catalyst advances are proving more and more useful in novel polymer synthesis, poor structure control and reactivity ratio considerations are still problematic in chain polymerization chemistry. 

The synthesis of the novel monomers was accomplished using the successful Grignard chemistry for the functionalization of carbosilanes. We present here three types of unsaturated organodisilanes which were prepared by alkenylation of Me4Si2Cl2. The alkenyldisilanes 4, 5, and 6 are isomers with different positions of the C=C bond (Scheme 1) [7],... 

Synthesis of polydiacetylenes from novel monomers having two diacetylene units linked by an arylene group were characterized by solid-state NMR. ... 

Figure 2.18 Synthesis of novel monomers by integration of bio-and chemo-catalysis. Source adapted from Wubbolts [154],...

Christensen, N. K., Petersen, M., Nielsen, R, Jacobsen, J. R, Olsen, C. E., Wengel, J. (1998). A novel class of oligonucleotide analogues containing 2 -0,3, C-linked [3.2.0]-bicycloarabinonucleoside monomers Synthesis, thermal affinity studies, and molecular modeling, J. Am. Chem. Soc., 120 5458. 

Friedel-Crafts alkylation of aromatics with CMF to give rise to benzyl derivatives 34a and 34b was first demonstrated in 1909 [139] and reprised by Rauchfuss and co-worker in 2013 to provide feedstock 34c for hydrodeoxygenation to diesel-range hydrocarlxMis [140]. Similar reactions have been used to produce a range of novel monomers and polymers. Thus, Szmant et al. reported as far back as 1981 the application of CMF to the synthesis of polymeric building blocks 35 and 36, among others (Fig. 1) [141]. 

Finally, the diverse PHA monomers are a rich pool for novel polymer synthesis (Taguchi et al. 2008 Rieth et al. 2(X)2). Copolymerization of PHA monomers with commercially available polymer monomers will generate limitless new copolymers. This is an area that has not yet started to attract attention, possibly owing to the high cost of PHA monomer production. However, copolymer of lactide and 3-hydroxy-butyrate (3HB) has recently been reported, signifying the start of the PHA monomer-based new polymer era. 

Li, H. and C. Lambert. 2005. 3,4-Methylenedithiopyrrole Convenient synthesis and application as a novel monomer for electroactive polymers. / Mater Chem 15 1235-1237. 

Associated with vegetable oils, their fatty acids and their derivatives, efforts concentrated on preparation of novel monomers for the synthesis of materials with interesting properties, based primarily on renewable resources. 

Only a few studies on oleochemistry have been reported until now. Similar to the effects seen with the thiol-ene reaction, one can take advantage of this interesting tool for the synthesis of novel monomers to be polymerised further by classical methods. Also, the possibility of two thiol groups reacting with one ethynyl group via two-step addition makes thiol-yne click polymerisation an interesting method for the preparation of hyperbranched polymers. 

Roumanet, PJ Lafleche, F Jarroux, N Raoul, Y Claude, S Guegan, P. Novel aliphatic polyesters from na oleic acid based monomer. Synthesis, epoxidation, cross-linking and biodegradation. European Polymer Journal, 2013, v. 49 (4), 813-822. 

The emphasis in research and technological development of new products in the polymer industry has changed from synthesis of novel monomers to blending polymers in order to obtain desirable performance properties at a dial-in cost. Polymer blends offer improved performance/cost ratios and flexibility to tailor-make the product to suit customer needs. Polymer blends are intimate mixtures of two or more polymers. The individual components may be melt-mixed, solution blended, co-precipitated, controlled devolatilized, or coagulated before final processing. Finished articles are converted from blends by extrusion or molding processing operations. 

Recent work from our laboratory developed new methodology for the preparation of novel bis-functionalized ferrocene complexes (Scheme I). The synthetic strategy gave us the ability to functionalize the cyclopentadienyl rings in a sequential manner. The strategy proved to be invaluable for ferrocene monomer synthesis and permits an array of novel complexes to be prepared. 

Emily Pentzer is currently a postdoctoral assodate with Prof. Todd Emrick at the University of Massachusetts Amherst Polymer Sdence and Engineering Department. She received her BS in chemistry with highest honors from Butler University in 2005. In 2010, she earned her PhD in oi anic chemistry from Northwestern University where she was an NSF fellow and worked on the design and polymerization of novel monomers for ROMP. Her current research efforts focus on the synthesis of orgarric and inoigaruc semiconducting materials and their electronic communication with each other. 

---