Homopolymers glass transition temperature

The stracture-property correlation of different copolymers with n-butyl acrylate and isobomyl acrylate units have been studied. The primary goal was to compare thermomechanical properties of block, gradient and statistical copolymers of nBA and IBA with various acrylate homopolymers (Scheme 1). The choice of nBA and IBA was dictated by very different thermal properties of the resulting homopolymers, glass transition temperature (Tg) of PnBA is -54°C while the Tg of PIBA is 94°C. Thus, their copolymerization with carefully selected ratios should result in polymers with thermal properties, i.e., Tg similar to acrylate homopolymers poly(t-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA) and poly(n-propyl acrylate) (PPA). 

Analysis of Copolymer Tg Data. The Tg data of the copolymers can be fit to appropriate models to determine the values of the homopolymer glass transition temperatures of the individual monomers. Since the Tg of butyl acrylate and vinyl acetate are well known, we hoped to use this analysis to determine the Tg of a VEC homopolymer. We chose a linear model (also known as the Gibbs-DeMarzio theory) ... 

Tgj and = Homopolymers glass transition temperatures M and = Threshold masses of atoms Df = Macromolecular coil fractal dimension. 

Consider the partially miscible blend of polycarbonate and styrene acrylonitrile copolymer (SAN). The two glass transition temperatures were found to be 110°C and 150°C. Discuss the change in entropy of mixing at the glass transition of the blend. The homopolymer glass transition temperature of PC is 165°C and SAN at azeotropic composition of 25% AN is 103°C. 

Table VI. Michael Adduct Homopolymer Glass Transition Temperatures...

Below T polymers are stiff, hard, britde, and glass-like above if the molecular weight is high enough, they are relatively soft, limp, stretchable, and can be somewhat elastic. At even higher temperatures they flow and are tacky. Methods used to determine glass-transition temperatures and the reported values for a large number of polymers may be found in References 7—9. Values for the T of common acrylate homopolymers are found in Table 1. 

In methacrylic ester polymers, the glass-transition temperature, is influenced primarily by the nature of the alcohol group as can be seen in Table 1. Below the the polymers are hard, brittle, and glass-like above the they are relatively soft, flexible, and mbbery. At even higher temperatures, depending on molecular weight, they flow and are tacky. Table 1 also contains typical values for the density, solubiHty parameter, and refractive index for various methacrylic homopolymers. 

As shown in Table 3, the glass-transition temperatures of the amorphous straight-chain alkyl vinyl ether homopolymers decrease with increasing length of the side chain. Also, the melting points of the semicrystalline poly(alkyl vinyl ether)s increase with increasing side-chain branching. 

The glass-transition temperature in amorphous polymers is also sensitive to copolymerization. Generally, T of a random copolymer falls between the glass-transition temperatures of the respective homopolymers. For example, T for solution-polymerized polybutadiene is —that for solution-polymerized polystyrene is -HlOO°C. A commercial solution random copolymer of butadiene and styrene (Firestone s Stereon) shows an intermediate T of —(48). The glass-transition temperature of the random copolymer can sometimes be related simply as follows ... 

T and are the glass-transition temperatures in K of the homopolymers and are the weight fractions of the comonomers (49). Because the glass-transition temperature is directly related to many other material properties, changes in T by copolymerization cause changes in other properties too. Polymer properties that depend on the glass-transition temperature include physical state, rate of thermal expansion, thermal properties, torsional modulus, refractive index, dissipation factor, brittle impact resistance, flow and heat distortion properties, and minimum film-forming temperature of polymer latex... 

Whereas random copolymers exhibit one T described by equation 38, block copolymers, because of this microphase separation, exhibit two glass-transition temperatures. The T of each block is close to, if not the same as, the homopolymer from which it was formed. Polymer properties are also affected by the arrangement of the blocks. This is shown for high styrene-containing or high molecular-weight styrene resias of various block arrangements ia Table 3. 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

The glass transition temperature of a random copolymer usually falls between those of the corresponding homopolymers since the copolymers will tend to have intermediate chain stiffness and interchain attraction. Where these are the only important factors to be considered a linear relationship between Tg and copolymer composition is both reasonable to postulate and experimentally verifiable. One form of this relationship is given by the equation... 

As is commonly the case with crystalline polymers the glass transition temperature is of only secondary significance with the aliphatic polyamide homopolymers. There is even considerable uncertainty as to the numerical values. Rigorously dried polymers appear to have TgS of about 50°C, these figures dropping towards 0°C as water is absorbed. At room temperature nylon 66 containing the usual amounts of absorbed water appears to be slightly above the T ... 

The glass transition temperatures of the nylons appear to be below room temperature so that the materials have a measure of flexibility in spite of their high crystallinity under general conditions of service. The polymers have fairly sharply defined melting points and above this temperature the homopolymers have low melt viscosities. Some thermal properties of the nylons are given in Table 18.4. 

The TMC polycarbonate homopolymer has a glass transition temperature of 238°C, nearly 100°C above that of the bis-phenol A polycarbonate. Therefore, copolymers will have intermediate glass transitions depending on the relative proportions of TMC and bis-phenol A. Commercial grades (marketed by Bayer as Apec HT) have Vicat softening points from 158 to... 

As shown in Table 3, the glass transition temperature of the acrylate homopolymers is very much dependent on the nature of the alcohol that was used to make the acrylate ester. Typically, the Tg is the lowest when the number of carbons in the alkyl group (R in the formula above) is about 8-12. 

Mixtures of monomers can be used to balance properties. This is possible due to the ease of copolymer formation via free-radical polymerization. The glass transition temperature of acrylic copolymers can be predicted from the weight fraction of the component monomers and the glass transition temperatures of the respective homopolymers [20]. Eq. 3 (commonly known as the Fox equation) is reported ... 

A major development in fluoroplastks is the recent small scale production of Teflon AF, a noncrystaUme (amorphous) fluorocarbon polymer with a high glass transition temperature (240 °C) This optically transparent TFE copolymer is soluble m certan fluorocabons and has the same chemical and oxidative stability as crystallme TFE homopolymers [5]... 

Although each of these cyclic siloxane monomers can be polymerized separately to synthesize the respective homopolymers, in practice they are primarily used to modify and further improve some specific properties of polydimethylsiloxanes. The properties that can be changed or modified by the variations in the siloxane backbone include the low temperature flexibility (glass transition temperature, crystallization and melting behavior), thermal, oxidation, and radiation stability, solubility characteristics and chemical reactivity. Table 9 summarizes the effect of various substituents on the physical properties of resulting siloxane homopolymers. The... 

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