Synthesis and Property Comparison of Silicone Polymers

Synthesis and Property Comparison of Silicone-Based and Polyvinyl Acetate-Based Polymers
Abstract Polymers are large molecules with high molecular weights made from smaller molecules. Cross-linking imparts higher mechanical properties such as strength, modulus, and elasticity. The effects of cross-linking are varied for different polymers and give a focus of the study. Silicone polymers are commonplace and their physical properties can change rapidly with crosslinking. The driving force behind these reactions was thermodynamic stability and increased entropy. The cross-linked silicone polymer exhibited high elasticity with resistance to deformation, while the poly(vinyl acetate) polymer flowed more like a liquid exhibiting characteristics of a non-Newtonian fluid.
INTRODUCTION During World War II there was a shortage of natural rubber in the United States. The shortage drove scientific effort to create a substitute. It was during this period that James Wright mixed boric acid with silicone oil, creating a silicone polymer with unusual properties. The putty could be stretched further than rubber, and when rolled into a ball it would bounce. Today, we refer to this invention as Silly Putty.1 A polymer is defined as a large molecule built up by the repetition of small, simple chemical units.2 Silicone polymers consist of Si-O linkages, and unlike carbon, tend to only form single bonds. Known for their high thermal stability, silicone polymers have applications from water repellents to breast implants.2 Organic polymers typically consist of alkene monomers. During polymerization the alkenes form single bonds to form chains. Cross-linking of polymers by boric acid creates strong linkages from one chain to another, resulting in a boronic ester with strong B-O bonds by transesterification.3 Cross-linking has profound effects on the physical properties of polymers, increasing strength and modulus. RESULTS AND DISCUSSION Dichlorodimethylsilane is a bifunctional molecule which is very reactive and easily hydrolyzed. Hydrolysis of dichlorodimethylsilane in ether results in dimethylsilanediol, providing the -OH groups necessary for the intermolecular condensation reaction that produces silicone polymers.2 The final result is mixture of high-molecular-weight elastomers that exist in both linear and cyclic forms. Heating the mixture provides energy while also evaporating off the solvent. This increases the concentration of the silicone and favors
Figure 1: Hydrolysis of dichlorodimethylsilane.
linearization of the polymer. The process is known as equilibration and results in a thermodynamically stable conformation. Adding the trifunctional boric acid initiates a crosslinking reaction forming boronic esters between the siloxane chains with Si-O-B linkages.3
Figure 2: Intermolecular condensation of silanols.
Poly(vinyl acetate) is an organic polymer and the main constituent in Elmers Glue. Crosslinking the poly(vinyl acetate) with borax turns it from a liquid into a solid. For every two polymer chains that are cross-linked there is a loss of two acetic acid molecules.
Figure 3: Cross-Linking of Poly(vinyl acetate) by Borax.
EXPERIMENTAL Poly(dimethylsiloxane). A mixture of diethyl ether (2 mL) and dichlorodimethylsilane (1 mL, 1.064 g, 8.24 mmol) was added to a flask. Water (2 mL) was added dropwise to the solution over 2 min. The reaction mixture was allowed to sit at room temperature. The lower aq phase was removed and discarded. A soln of sodium bicarbonate (0.1M, 1 mL) was added to the reaction mixture dropwise. The lower aq phase was removed and tested with litmus paper for the
presence of acid. The neutralized organic phase was washed with water (2 mL) and the aq phase removed and discarded. Anhy sodium sulfate was added to the organic phase to dry. The organic phase was concentrated on a hotplate resulting in a clear silicone fluid (0.1217 g). Boric acid (0.0061 g, 0.09 mmol) was added to the fluid and stirred for 5 min. The resulting mixture was heated on a hotplate for 10 min, producing the desired product, a clear stiff gum (0.1266 g). Poly(vinyl acetate). Elmers glue (2.9894 g) and Borax (0.4655 g) were added to a beaker and hand mixed for 2 min. This resulted in an off-white putty (3.4504 g). Comparison of the two polymers. Each polymer was rolled into a ball and dropped on a hard surface to compare the elastic properties. The polymers were pulled sharply on to compare the cleavage. The polymers were stretched apart for comparison of elasticity and resistance to deformation. Lastly, the polymers were placed on a hard surface and monitored to compare the flow characteristics. CONCLUSION Polymers are large molecules with high molecular weights made from smaller molecules. Cross-linking imparts higher mechanical properties such as strength, modulus, and elasticity. Silicone polymers are commonplace and their physical properties can change rapidly with crosslinking. The driving force behind these reactions was thermodynamic stability and increased entropy. The cross-linked silicone polymer exhibited high elasticity with resistance to deformation, while the poly(vinyl acetate) polymer flowed more like a liquid exhibiting characteristics of a non-Newtonian fluid.
REFERENCES (1) Inventor of the Week Archive, MIT http://web.mit.edu/invent/iow/sillyputty.html Accessed 9-13-12 (2) Billmeyer, Jr., F. Textbook of Polymer Science, 3rd edition; Wiley-Interscience.: New York, 1984, p 3. (3) Jones, Jr., M. Organic Chemistry, 3rd Edition; W.W. Norton & Co.: New York, 2005, pp 399, 896-898

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Synthesis and Property Comparison of Silicone-Based and Polyvinyl Acetate-Based Polymers

Figure 2: Intermolecular condensation of silanols.

Figure 3: Cross-Linking of Poly(vinyl acetate) by Borax.

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