Molecular weight of polyurethane

Polymers. The molecular weights of polymers used in high energy electron radiation-curable coating systems are ca 1,000—25,000 and the polymers usually contain acryUc, methacrylic, or fumaric vinyl unsaturation along or attached to the polymer backbone (4,48). Aromatic or aUphatic diisocyanates react with glycols or alcohol-terrninated polyether or polyester to form either isocyanate or hydroxyl functional polyurethane intermediates. The isocyanate functional polyurethane intermediates react with hydroxyl functional polyurethane and with acryUc or methacrylic acids to form reactive p olyurethanes. 

This process is based on the very high reactivity of the isocyanate group toward hydrogen present ia hydroxyl groups, amines, water, etc, so that the chain extension reaction can proceed to 90% yield or better. Thus when a linear polymer is formed by chain extension of a polyester or polyether of molecular weight 1000—3000, the final polyurethane may have a molecular weight of 100,000 or higher (see Urethane polymers). 

The thermoplastic polyurethane (TPU) adhesives must, of necessity, contain low gel content because they must be processable in an extruder. Most adhesives are relatively linear, with a functionality of 2.0, although small amounts of branching may be introduced, usually at the expense of a lower melt flow. Good physical properties of TPU s are obtained when the thermoplastic urethanes have molecular weights of 100,000 or higher (see p. 56 in [63]). Most TPU adhesives are based on symmetrical polyesters with a fast crystallizing backbone or a backbone slightly modified to increase the open time. 

Modified alkyd resins In this group one finds styrenated alkyds, vinyl toluenated alkyds, oil-modified vinyl resins, acrylic alkyds, silicone alkyds and polyurethane alkyds. The modifying component usually has a number of effects. It always increases the molecular weight of the alkyd polymer, and may impart hardness, durability, or chemical resistance. It also affects the solubility of the polymer in solvents. 

Figure 25.3 b) shows a generic polyester-based polyurethane. The most common polyester repeat units are derived from the polycondensation of adipic acid and a diol, such as ethylene glycol, which results in the structure shown in Fig, 25.4. The average molecular weight of the polyester sequences between urethane links commonly ranges between 400 and 6,000 g/mol. 

As the reaction proceeds beyond the gel point, the molecular weight of EANCs decreases and the fraction of material in the EANCs increases. The fraction of material in dangling chains passes through a maximum but their molecular weight decreases. Figure 5.5 characterizes the behavior of simple polyurethane systems. 

Another approach was attempted by Seppala and Kylma who reported the synthesis of poly(ester-urethane)s by condensation of hydroxyl terminated tel-echelic poly(CL-co-LA) oligomers with 1,6-hexamethylene diisocyanate (Scheme 33) [94]. The diisocyanate acts as chain extender producing an increase in molecular weight of the preformed oligomers. The authors claim that some of the copolymers present elastomeric properties. Using a similar method. Storey described the synthesis of polyurethane networks based on D,L-LA, GA, eCL,... 

Figure T. Effects of molecular weight of PCL-diol parts on the hydrolysis of polyurethanes by R. delemar lipase. Each reaction mixture for biodegradability assay contained 15.6-37.2 mg of polyurethane film (i4.U-2T.1 mg as polyester moiety) on the cover glass (3.2 cm ) in a total volume of 10 ml. In this condition, no effect of amount of polyurethane was observed. (Mn)s of PCL-diols parts of polyurethanes I, II, III and IV were 530, 1250, 2000, 3000 respectively. The dashed lines show PCL-diol (Mn 2000) ( ) and PCL-diol (Mn 3000) ( ).

Polymerization of the oxiranes is typically propagated from a starter molecule that is chosen to define the functionality if) of the final polyol. The functionality and the molecular weight of polyols are the main design features that define the polyurethane properties in the end-use applications. Additionally, the balance of EO and PO in the polyether polyols, mainly for flexible foam polyols, is tailored to enhance the compatibility of formulations and the processability of the foam products. The exact composition of the polyols defines the crucial performance features of the final polyurethane product. Even seemingly small differences in polyol composition can result in changes to polyol processabihty and polyurethane performance. This becomes a crucial issue when replacing conventional petrochemical polyols with polyols from different feedstocks. To demonstrate the sensitivity of commercial formulations to changes in feedstocks, a simple example is offered below. 

If polyurethanes are used to entrap cells, the diffusion wiU depend on the polyol used to build the polyurethane since the polyol defines equilibrium moisture. Later in this chapter, we will discuss a number of entrapment systems, including acrylates and polysaccharides. Each has its own equilibrium moisture and therefore unique diffusion constant. Only polyurethanes, however, offer the opportunity to affect changes in the constants. Conventional hydrophilic polyurethanes have equilibrium moisture levels around 70%. It is possible, however, to increase the molecular weight of a polyol (an ethylene glycol of 1000 molecular weight) to 3000 or more. This increases the equilibrium moisture to greater than 90%. 

Polyolefins. Ultra-High-Molecular-Weight Polyethylene.TIus is easily made by conventional low-pressure coordination polymerization. Hercules Hi-fax 1900 has a molecular weight of 2.5-5.0 million. Its outstanding properties are low coefficient of friction (0.11) abrasion-resistance superior to nylon, polyurethane, and steel unbreakable in the Izod notched impact test and high resistance to most inorganic and many organic chemicals. 

The most efficient intermediate layers are polyurethane adhesives or glues.175 In this case, the correct choice of molecular weight of the polyester and its ratio to diisocyanate is very important. The dependence of the adhesive strength on the molecular weight and the isocyanate-to-diol ratio is shown in Fig. 4.13. The best adhesion to metal is achieved when an intermediate layer based on low-molecular-weight polyester and at a ratio of NCO OH = 2.5 is used. 

As the molecular weight of the polyurethane chains increases, the physical properties will change. Preparation of a prepolymer will allow the formation... 

Incorporated HRP into polyelectrolyte complexes with chitosan of different molecular weights (MW 5-150 kDa) The complex formed by 0.001% chitosan with a molecular weight of 150 kDa was most stable when immobilized on foamed polyurethane, it retained at least 50% of the initial activity for 550 days [43]... 

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