Poly -1,2-Propanediol

Plasticizers can be classified according to their chemical nature. The most important classes of plasticizers used in rubber adhesives are phthalates, polymeric plasticizers, and esters. The group phthalate plasticizers constitutes the biggest and most widely used plasticizers. The linear alkyl phthalates impart improved low-temperature performance and have reduced volatility. Most of the polymeric plasticizers are saturated polyesters obtained by reaction of a diol with a dicarboxylic acid. The most common diols are propanediol, 1,3- and 1,4-butanediol, and 1,6-hexanediol. Adipic, phthalic and sebacic acids are common carboxylic acids used in the manufacture of polymeric plasticizers. Some poly-hydroxybutyrates are used in rubber adhesive formulations. Both the molecular weight and the chemical nature determine the performance of the polymeric plasticizers. Increasing the molecular weight reduces the volatility of the plasticizer but reduces the plasticizing efficiency and low-temperature properties. Typical esters used as plasticizers are n-butyl acetate and cellulose acetobutyrate. 

The Poly methane Polymer of 2,5-Dinitraza-1,6-Hexane Diisocyanate and 2,2-Din it ro-1,3-Propanediol. 

Maleic anhydride, 98 g (1.0 mol), 148 g (1.0 mol) of phthalic anhydride, and 160 g (2.1 mol) of 1,2-propanediol are poly condensed in a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a distillation head connected to a condenser and a receiver flask. The flask is placed in a salt bath preheated at 160°C. Water begins to distill and the temperature is then raised gradually to 190°C. The polycondensation is stopped (after about 15 h) when the reaction mixture has an acid number of 50 (see Section 2.3.8.4.1) (Scheme 2.54). A slightly different procedure is described in ref. 423. 

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. 

Simple physical entanglements can be sufficient to produce a structurally stable gel if the polymer has a sufficiently great molecular weight and if the polymer is of only modest hydrophilicity. In this case, the polymer will swell in water without dissolving, even in the absence of covalent cross-links. Poly(2-hydroxyethyl methacrylate) (PHEMA) is a prominent example of this type of hydrogel when uncross-linked, it will dissolve in 1,2-propanediol but only swell in water. 

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. 

PTT is made by the melt polycondensation of PDO with either terephthalic acid or dimethyl terephthalate. The chemical structure is shown in Figure 11.1. It is also called 3GT in the polyester industry, with G and T standing for glycol and terephthalate, respectively. The number preceding G stands for the number of methylene units in the glycol moiety. In the literature, polypropylene terephthalate) (PPT) is also frequently encountered however, this nomenclature does not distinguish whether the glycol moiety is made from a branched 1,2-propanediol or a linear 1,3-propanediol. Another abbreviation sometimes used in the literature is PTMT, which could be confused with poly(tetramethylene terephthalate),... 

Propanediol. Both the diol and the dicarboxylic acid components of poly-trimethylene-terephthalate, a high performance polyester fiber with extensive applications in textile apparel and carpeting, are currently manufactured from petrochemical raw materials. 

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. 

Hydroxypropanal. 3-Hydroxypropanal can be formed by fermentation of glucose and is thus an attractive starting material for production of 1,3-propanediol, which can be polymerized with /ere-phthalic acid to produce poly trimethylene terephthalate (PTT). PTT is used in the fibers industry in the production of stain resistant carpets etc. 

Aliphatic Glycidyl Ethers. Aliphatic epoxy resins have been synthesized by glycidylation of difunclional or poly functional polyols such as a 1.4-butanediul. 2.2-dimethyl-1.3-propanediol (neopentyl glycol), polypropylene glycols, glycerol, irimethylolpropane. and pentaerythritol. 

The superior properties of polypropylene terephthalate) (PPT) polymer and fibers over the chemically analogous poly(ethylene terephthalate) (PET, used for soda bottles) and poly(butylene terephthalate) (PBT) have been well known for several decades PPT fibers are much more elastic and less brittle than PET and offer better recovery from stretching than PBT they are also easier to dye than either PET or PBT. Compared to the intermediate for PET, ethylene glycol, which is available inexpensively from ethylene oxide, and to that for PBT, butanediol, likewise available inexpensively from butene or butadiene, the intermediate for PPT, 1,3 propanediol (1,3-PPD or PDO), was not - and on a large scale is still not - available. Three processes, two chemical ones and one biotechnological, compete to change this situation (Figure 20.10). 

Recently, a,co-bis-hydroxy-terminated poly(l,3-propylene succinate) has been chain-extended to yield high molecular weight poly(ester-carbonates) [44] using a bischloroformate route. Thus, using a molar ratio of 1,3-propanediol to succinic acid of 1.02, an oligomer having Mn of 2,200 and Mw of 3,000 was ob-... 

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... 

PrOH 1,3-propanediol SA succinic acid CHDM 1,4-cyclohexanedimethanol PEG poly(ethylene glycol)... 

Hydroxy-propionic acid 1,3-Propanediol, acrylamide, acrylic acid, acrylonitrile, ethyl-3-hydroxypropionic acid, L-alanine, L-serine, malonic acid, propiolactone, poly(3-HP), poly(3-hydroxybutyric acid-co-3-hydroxypropionic acid) Polymers, fine chemicals Cao et al., 1999 Werpy and Petersen, 2004 Zhang etal., 2004 Patel etal., 2006... 

C3 Lactic acid 3-Hydroxypropionic acid Glycerol 1.2- Propanediol 1.3- Propanediol Propionic acid Acetone L-lsoleucine L-Leucine L-Proline L-Serine L-Valine L-Arginine L-Tryphophane L-Aspartic acid Cyanophycin Gellan Heparin Hyaluronic acid Poly-gamma-Glutamic acid Poly-epsilon-lysine Polyhydroxyalkanoates Pullulan... 

Propanediol (1,3PD) is also undergoing a transition from a small-volume specialty chemical into a commodity. The driving force is its application in poly (trimethylene terephthalate) (PTT), which is expected to partially replace polyethylene terephthalate) and polyamide because of its better performance, such as stretch recovery. The projected market volume of PTT under the trade-names CORTERRA (Shell) and Sorona 3GT (Dupont) is 1 Mt a-1 within a few years. In consequence, the production volume of 1,3PD is expected to expand from 55kta-1 in 1999 to 360 kt a-1 in the near future. 1,3PD used to be synthesized from acrolein by Degussa and from ethylene oxide by Shell (see Fig. 8.8) but a fermentative process is now joining the competition. 

Preparation of Poly(isocitric Acid Lactone-co-Propanediol)... 

Preparation of Poly[(Isocitric Acid Lactone-co-Propanediol)-fe/oc -(Glycolide-co-Lactide)]... 

DuPont is instead producing 1,3-propanediol (PDO) from corn sugar rather than petroleum feedstocks. PDO is a key component of DuPont s new Sorona 3GT polymer. Other examples of microbial polymers under study are polyhydroxyalk-anoates and Y-poly(glutamic acid). 

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