Urethane Modification

Abrasion and impact resistance of acrylic coatings can be improved with the addition of up to 30% of a water borne polyurethane. The addition of a polyurethane dispersion as a physical blend improves the inherent film strength and film formation of the aciylic latices. Polyurethanes generally have better film forming properties because of their lower MFFT at identical surface hardness. 

Improvements in mar resistance can be found through the use of silicone or wax-based additives. In certain applications where the surface appearance needs to be improved, specific flow agents may prove worthwhile. 

Freeze / thaw resistance of the wet paint is usually modified with methyl carbitol. However, this will give a corresponthng increase in the open time of the wet film. Although propylene and ethylene glycol are more efficient, both are hygroscopic and will retard film formation and decrease corrosion resistance. 

Many of the properties imparted by the additives are interdependent, e.g. the addition of a silicone defoamer will often require a flow agent to counteract cissing. The balance of these minor ingredients is crucial and on many occasions the key to a successful waterborne formulation. Some commonly used ad tives are given in Table 7-10. 

TABLE 7-10 SOME COMMONLY USE DEFOAMERS, WETTING AND LEVELUNG AIDS. 

---

Principles of Urethane Modification. The flame retardance and temperature resistance (or flame endurance) of modified isocyanurate foams are affected by the following factors ... 

In the case of urethane-modification, two kinds of catalysts, i.e., urethane-formation catalysts and isocyanate-trimerization catalysts, are usually used. Major trimerization catalysts are listed in Table 11 and major urethane catalysts are listed in Tables 8 through 10. 

Preparation. Urethane-modified isocyanurate foams are mostly fH epared by the one-shot process based on the jH inciple discussed previously in the urethane modification section. The semi-prepolymer process is used only in limited cases because of viscosity problems. This section describes several examples of formulations for producing block foams, slabstock foams, laminate foams, and spray foams. 

Modification of cellular polymers by incorporating amide, imide, oxa2ohdinone, or carbodiimide groups has been attempted but only the urethane-modified isocyanurate foams are produced in the 1990s. PUIR foams often do not require added fire retardants to meet most regulatory requirements (34). A typical PUIR foam formulation is shown in Table 6. 

Stmctural and chemical modification of urethane containing polymer matri-ces with macrocycles - calixarenes having reactive hydrazide groups have been carried out and stmcture, physico chemical and sensor properties of polyure-thanesemicarbazides (PUS) synthesised have been studied. The polymers obtained (on the base of polypropylene glycol MM 1000 and polysiloxane diol MM 860, hexamethylene diisocyanate and calixarene dihydrazide) are identified by IR-spectroscopy, size exclusion chromatography (SEC), DSC, WAXS and SAXS methods. 

In one projected commercial modification of the process the phosgenation stage is replaced by one in which the nitro compounds are reacted with CO and an alcohol to form a urethane. This is then split to form an isocyanate in the second step. 

Not only are these reactions of importance in the development of the cross-linked polyurethane networks which are involved in the manufacture of most polyurethane products but many are now also being used to produce modified isocycuiates. For example, modified TDI types containing allophanate, urethane and urea groups are now being used in flexible foam manufacture. For flexible integral foams and for reaction injection moulding, modified MDIs and carbodi-imide MDI modifications cU"e employed. 

Urethane linkages between amino groups of a protein and PEG provide a stable attachment, more resistant to hydrolytic cleavage (13). In fact, it was demonstrated on radioactively labeled PEG-derivatives that urethane links are completely stable under a variety of physiological conditions (14). The attachment of PEG to a protein via carbamate was obtained (15,16) using carbonyldiimidazole activated PEG. However, the polymer activated in this manner is not very reactive and therefore very long reaction times (48-72 h at pH 8.5) were required to achieve sufficient modifications. 

The protection of amino groups of amino sugars benefits particularly from the use of new blocking groups introduced for peptide synthesis. In this context, light-sensitive urethans and amides that can be utilized for the protection of amino groups in amino sugars are of particular interest in saccharide synthesis and modification. 

The majority of resins are composed of two dimethacrylate monomers, 2,2 -bis [4(2-hydroxy-3-methacryloyloxypropyloxy)phenyl] propane (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA) [22-28]. Typically, TEGDMA or other methacrylate monomers are added as viscosity modifiers to Bis-GMA to make the solution less viscous and more appropriate for clinical use. These diluents also allow for better distribution of the components during manufacture of these composite systems. Another common monomer used to make dental composites, especially those manufactured in Europe, is urethane dimethacrylate [24,29, 30], Ethoxy bisphenol A dimethacrylate is another modification of the Bis-GMA monomer that can be used to make a more hydrophobic polymer that would better withstand the wet oral environment. Other diluents include low viscosity diacrylates and dimethacrylates. Table 1 lists some of these monomers [31-37]. 

The three secondary hydroxyl groups in the 12-posihon are somewhat slow to react with diisocyanates and generally require heat for the completion of reaction. This can be of advantage or disadvantage depending upon the specific application. Modifications of CO and particularly of ricinoleic acid through esterification results in products that are of considerable interest as polyols for various urethane applications [88, 89]. 

Although blending with other coating resins provides a variety of ways to improve the performance of alkyds, or of the other resins, chemically combining the desired modifier into the alkyd structure eliminates compatibility problems and gives a more uniform product. Several such chemical modifications of the alkyd resins have gained commercial importance. They include vinylated alkyds, silicone alkyds, urethane alkyds, phenolic alkyds, and polyamide alkyds. 

---