Propanediol Monomer

A new route with the potential of further lowering PDO cost is the enzymatic fermentation [17, 18] of glycerol and alcohol. This process is still under development by Du Pont and Genecore International. With advances in biogenetic engineering, new strains of engineered bacteria have improved the yield and selectivity of the process to the point where this route is ready for pilot plant scale-up. 

PDO chemistry, technology, the relative merits and the manufacturing economics of the above three routes have been reviewed by Chen et al. [19], Wu [20] and by SRI International in its Process Economic Progress report [21], Therefore, PDO will not be further elaborated in this article. 

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Glycerol is a by-product of the biodiesel production 1 ton biodiesel production produces 100 kg of glycerol. Glycerol is a 1.2.3-triol that is used in personal care and pharmaceutical products and as feed additive, but there are also a variety of derived chemicals such as propanediols (monomers in polyester and polyurethane materials), oUgoglycerols (cosmetics and biodegradable lubricants), epichlorohydrin (polymers), and glycerol carbonate (solvent). 

There are numerous possible monomers that can be used in the backbone of the polyester prepolymer. However, typical monomers are 1,2-propanediol, as just mentioned, with maleic acid (usually added as the anhydride) to provide the sites of unsaturation, and phthalic acid (again usually added as the anhydride) to act as the second of the two diacid species. The structures of these latter two substances are shown in Figure 4.1. 

Poly(trimethylene terephthalate) (PTT) is a polymer with very useful properties. As a textile fibre it has excellent softness, stretch and recovery. As a resin it has excellent barrier properties. Developed over 60 years ago, PTT has not been very widely used compared to poly(ethylene terephthalate) (PET) as one of the key monomers 1,3-propanediol (PDO) has been expensive. 

The blend is partially crosslinked with a vinyl monomer when dissolved in an organic aprotic solvent and has a pH of 5.0 or lower. The first block copolymer is prepared by polycondensing a bis-hydroxyalkyl ether, such as dipropylene glycol, diethylene glycol, and the like, with propylene oxide. Next, the resulting propoxylated diol is reacted with ethylene oxide to produce the block copolymer. The second copolymer is prepared by polycondensing 2-amino-2-hydroxymethyl-1,3-propanediol, commonly known as TRIS, with... 

The hydrogenation of 3-hydroxy propan al (HPA) to 1,3-propanediol (PD) over Ni/SiOi/AEO, catalyst powder was studied by Professor Hoffman s group at the Friedrich-Alexander University in Erlagen, Germany (Zhu et al., 1997). PD is a potentially attractive monomer for polymers like polypropylene terephthalate. They used a batch stirred autoclave. The experimental data were kindly provided by Professor Hoffman and consist of measurements of the concentration of HPA and PD (Chpa< Cpd) versus time at various operating temperatures and pressures. 

Poly(trimethylene terephthalate) (PTT) is a newly commercialized aromatic polyester. Although available in commercial quantities only as recently as 1998 [1], it was one of the three high-melting-point aromatic polyesters first synthesized by Whinfield and Dickson [2] nearly 60 years ago. Two of these polyesters, polyethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT), have become well-established high-volume polymers. PTT has remained an obscure polymer until recent times because one of its monomers, 1,3-propanediol (PDO), was not readily available. PDO was sold as a small-volume fine chemical at more than 10/lb., and was therefore not suitable as a raw material for commercial polymers. 

DuPont and Shell have developed a new polyester, poly(trimethylene terephthalate) (PTT) (structure 19.38) that is structurally similar to PET, except that 1,3-propanediol (PDO) is used in place of ethylene glycol. The extra carbon in Sorona allows the fiber to be more easily colored giving a textile material that is softer with greater stretch. Further, it offers good wear and stain resistance for carpet use. The ready availability of the monomer PDO is a major consideration with efforts underway to create PDO from the fermentation of sugar through the use of biocatalysts for this conversion. Sorona and Lycra blends have already been successfully marketed. Sorona is also targeted for use as a resin and film. 

Among the polycarbonates, PTMC in particular has been studied for biomedical use. PTMC is commonly derived by ring-opening polymerization (Fig. 9). The monomer, l,3-dioxan-2-one,is obtained by refluxing 1,3-propanediol in an excess of diethyl carbonate. Albertsson et al. have reported on the polymerization in bulk and solution using a number of initiators and catalysts [120,279, 280]. PTMC is aliphatic and has a low Tg (approximately -17 °C), it is thus in its... 

Keywords. Monomers from renewable resources, Polymers from renewable resources, 1,3-Propanediol, Succinic acid, Lactones, Cyclohexanedimethanol, Polyethyleneglycol, Chain-extension, Poly(ester-urethane)s, Poly(ester-carbonate)s... 

This -ketoadipate pathway produces e.g., succinic acid, a compound used as monomer for the production of aliphatic polyesters. Already in 1881, the production of e.g., 1,3-propanediol by the fermentation of glycerol was reported [8],... 

One way of improving the physical and mechanical properties of the polymeric materials produced was to copolymerize the original monomers with stiffer comonomers, whose corresponding homopolymers are endowed with high thermal and mechanical properties. Therefore, 1,4-cyclohexanedimetha-nol was copolymerized with 1,3-propanediol and succinic acid. Segmented copolymers between oligofpropylene succinate)s and PEG were also produced in order to modify their hydrophilic/hydrophobic properties. 

Less useful was the synthetic strategy based on the ROP of lactones deriving from 1,3-propanediol, due to the high cost (low yield) of the starting monomer. 

All of the isophthalate-based polyether-ester copolymers which were prepared using various diols are slow to crystallize. Those copolymers that eventually do crystallize exhibit excellent tensile strength and tear strength. All of the 2,6-naphthalenedicarboxylate copolymers prepared using linear ,o>-diols exhibit excellent tensile strength and tear strength. Phase separation in the melt is encountered with 4,4 -biphenyldicarboxyl-ate-based copolymer at the 50-wt % ester level when 1,4-butanediol is used as the diol monomer but not when 1,3-propanediol, 1,5-pentanediol, and 1,6-hexanediol are used. 

Propanediol is a monomer with potential utility in the production of polyester fibers and in the manufacture of polyurethanes and cyclic compounds. A variety of chemical... 

Polypropylene terephthalate, sold as Sorona by the DuPont Corporation, is made into fibers used in clothing and other materials. Although 1,3-propanediol, one of the monomers needed for its synthesis, has been prepared from petroleum feedstocks in the past, it is now available from a renewable plant source such as corn. 

An intriguing report by Steinke et al. [ 17] describes the creation of molecularly imprinted anisotropic polymer monoliths . Optically transparent blocks of MIP using either methacrylic acid (MAA) or 2-(acrylamido)-2-methylpropanesulphonic acid (AMPSA) as functional monomers and TRIM (trimethylolpropane trimethacrylate 2-ethyl-2-(hydroxymethyl)-l,3-propanediol trimethacrylate) as the cross-linker were synthesised using the photoactive template Michler s ketone... 

Figure 35. Rate of polymerization as a function of free energy change (-AGet) for photoinitiated CQ-NPG systems. Polymerizing monomer mixture 2-ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate (TMPTA) and ethylated bisphenol-A dimethacrylate (bis-EMA) (1 1). Polymerization was initiated by an argon-ion laser beam. Data from Ref. [175].

Polycarbonate synthesis by lipase-catalyzed polycondensation was demonstrated. Activated dicarbonate, 1,3-propanediol divinyl dicarbonate, was used as the monomer for enzymatic synthesis of polycarbonates.222 Lipase CA-catalyzed polymerization with a,co-alkylene glycols produced the polycarbonates with Mw up to 8.5 x 103. Aromatic polycarbonates with DP larger than 20 were enzymatically obtained from the activated dicarbonate and xylylene glycols in bulk.211... 

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