Acrylics modification

When used as substitutes for asbestos fibers, plant fibers and manmade cellulose fibers show comparable characteristic values in a cement matrix, but at lower costs. As with plastic composites, these values are essentially dependent on the properties of the fiber and the adhesion between fiber and matrix. Distinctly higher values for strength and. stiffness of the composites can be achieved by a chemical modification of the fiber surface (acrylic and polystyrene treatment [74]), usually produced by the Hatschek-process 75-77J. Tests by Coutts et al. [76] and Coutts [77,78] on wood fiber cement (soft-, and hardwood fibers) show that already at a fiber content of 8-10 wt%, a maximum of strengthening is achieved (Fig. 22). 

The checkers found that some product codistilled with ethyl acrylate under these conditions, lowering their yield of pure ethyl 2-iodo-3-nitropropionato to 85-87%. They were able to obtain the submitters yield, however, by introducing a slight modification. The flask containing the residue was fitted with an ice water condenser, and vacuum was applied at the top of the condenser. Evacuation at room temperature (0.5 mm.) for 3 hours removed the ethyl acrylate completely with no loss of product. 

Owing to multi-functionahty, physical properties such as solubihty and the glass transition temperature and chemical functionahty the hyperbranched (meth) acrylates can be controlled by the chemical modification of the functional groups. The modifications of the chain architecture and chemical structure by SCV(C)P of inimers and functional monomers, which may lead to a facile, one-pot synthesis of novel functionahzed hyperbranched polymers, is another attractive feature of the process. The procedure can be regarded as a convenient approach toward the preparation of the chemically sensitive interfaces. 

In their original form these cements came as a zinc oxide powder and a concentrated solution of poly(acrylic acid) (Wilson, 1975b). Since then they have been subject to a number of chemical modifications. 

Not all modified starches are suitable for removal by aqueous dissolution alone. Such modifications of natural starches are carried out to reduce solution viscosity, to improve adhesion and ostensibly to enhance aqueous solubility. Commercial brands vary [169], however, from readily soluble types to those of limited solubility. Indeed, some may be as difficult to dissolve as potato starch if they have been overdried. It is thus very important to be sure of the properties of any modified starch present. If there are any doubts about aqueous dissolution, desizing should be carried out by enzymatic or oxidative treatment. Even if the size polymer is sufficiently soluble, it is important to ensure that the washing-off range is adequate. Whilst the above comments relate to modified starches, other size polymers such as poly(vinyl acetate/alcohol) and acrylic acid copolymers vary from brand to brand with regard to ease of dissolution. 

Recently, nitrilases have been applied to polymer modification, specifically to the modification of polyacrylonitrile (PAN). Nearly 3 x 106 tons of PAN are produced per annum and used in the textile industry. However, there is a great need to improve moisture uptake, dyeability with ionic dyes, and feel of this acrylic fiber. The cyano moieties of PAN have been successfully modified to carboxylates with the commercial Cyanovacta nitrilase, thus enhancing the aforementioned properties of PAN [98]. Nitrilase action on the acrylic fabric was improved... 

Matama, T., Cameiro, F., Caparros, C. et al. (2007) Using a nitrilase for the surface modification of acrylic fibers. Biotechnology Journal, 2, 353-360. 

Many other functional silane coupling agents are available from commercial suppliers, including hydroxyl, aldehyde, acrylate and methacrylate, and anhydride compounds. Substrate modification procedures similar to those discussed above can be used with these reagents to link a biomolecule to an inorganic surface or particle. 

The carboxylated types (XNBR) contain one, or more, acrylic type of acid as a terpolymer, the resultant chain being similar to nitrile except for the presence of carboxyl groups which occur about every 100 to 200 carbon atoms. This modification gives the polymer vastly improved abrasion resistance, higher hardness, higher tensile and tear strength, better low temperature brittleness, and better retention of physical properties after hot-oil and air ageing when compared to ordinary nitrile rubber. 

Furthermore FERRIPHOS ligands bearing alkyl groups instead of dimethy-lamino substituents proved to be excellent ligands in the asymmetric hydrogenation of a-acetamidoacrylic acids[34] and acetoxy acrylic esters[35l Their air stability and the easy modification of their structure make the FERRIPHOS ligands particularly useful tools for asymmetric catalysis. 

Arylation of activated double bonds with diazonium salts in the presence of copper catalysts is known as the Meerwin reaction. The reaction is postulated to either proceed through an organocopper intermediate or through a chlorine atom transfer from chiral CuCl complex to the a-acyl radical intermediate. Brunner and Doyle carried out the addition of mesityldiazonium tetrafluoroborate with methyl acrylate using catalytic amounts of a Cu(I)-bisoxazoline ligand complex and were able to obtain 19.5% ee for the product (data not shown) [79]. Since the mechanism of the Meerwin reaction is unclear, it is difficult to rationalize the low ee s obtained and to plan for further modifications. 

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