Copolymer transition temperatures

Table 1 shows that most acryflcs have low glass-transition temperatures. Therefore, in copolymers they tend to soften and flexibHize the overall composition. Plasticizers also lower the transition temperature. However, unlike incorporated acryflc comonomers, they can be lost through volatilization or extraction. 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

Improved Hot—Wet Properties. Acryhc fibers tend to lose modulus under hot—wet conditions. Knits and woven fabrics tend to lose their bulk and shape in dyeing and, to a more limited extent, in washing and drying cycles as well as in high humidity weather. Moisture lowers the glass-transition temperature T of acrylonitrile copolymers and, therefore, crimp is lost when the yam is exposed to conditions requited for dyeing and laundering. 

The Ts of methacryhc polymers may be regulated by the copolymerization of two or more monomers as illustrated in Figure 1. The approximate T value for the copolymer can be calculated from the weight fraction of each monomer type and the T (in K) of each homopolymer (15). Acrylates with low transition temperatures are frequently used as permanent plasticizers (qv) for methacrylates. Unlike plasticizer additives, once polymerized into the polymer chain, the acrylate cannot migrate, volatilize, or be extracted from the polymer. 

Measurement of modulus over an extensive temperature range offers more information than T alone (16). Typical modulus—temperature curves are shown in Figure 1. Assuming that the reference temperature is the transition temperature of the copolymer, then curve A of Figure 1 is that of a softer polymer and curve B is that of a harder polymer. Cross-linking of the polymer elevates and extends the mbbery plateau Htde effect on T is noted until extensive cross-linking has been introduced. In practice, cross-linking of methacryhc polymers is used to decrease thermoplasticity and solubihty and to increase residence. 

Polymers of Styrene Derivatives. Many styrene derivatives have been synthesized and the corresponding polymers and copolymers prepared (61). Glass-transition temperatures for a series of substituted styrene polymers are shown in Table 3. The highest T is that of... 

Fig. 3. Effect of comonomer stmcture on the glass-transition temperature of VDC copolymers (72), where A represents acrylonitrile B, methyl acrylate ...

The dynamic mechanical properties of VDC—VC copolymers have been studied in detail. The incorporation of VC units in the polymer results in a drop in dynamic modulus because of the reduction in crystallinity. However, the glass-transition temperature is raised therefore, the softening effect observed at room temperature is accompanied by increased brittleness at lower temperatures. These copolymers are normally plasticized in order to avoid this. Small amounts of plasticizer (2—10 wt %) depress T significantly without loss of strength at room temperature. At higher levels of VC, the T of the copolymer is above room temperature and the modulus rises again. A minimum in modulus or maximum in softness is usually observed in copolymers in which T is above room temperature. A thermomechanical analysis of VDC—AN (acrylonitrile) and VDC—MMA (methyl methacrylate) copolymer systems shows a minimum in softening point at 79.4 and 68.1 mol % VDC, respectively (86). 

In cases where the copolymers have substantially lower glass-transition temperatures, the modulus decreases with increasing comonomer content. This results from a drop in crystallinity and in glass-transition temperature. The loss in modulus in these systems is therefore accompanied by an improvement in low temperature performance. However, at low acrylate levels (< 10 wt %), T increases with comonomer content. The brittle points in this range may therefore be higher than that of PVDC. 

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 ... 

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... 

Ethylene-norbomene copolymers of interest as thermoplastics were discussed in Section 11.6.2. It is however to be noted that copolymers with a norbomene content of about 30 wt% have a glass transition temperature of about 0°C and that copolymers with norbomene contents up to this amount are being evaluated as thermoplastic elastomers... 

In the 1960s materials became available which are said to have been obtained by chlorination at lower temperatures. In one process the reaction is carried out photochemically in aqueous dispersion in the presence of a swelling agent such as chloroform. At low temperatures and in the presence of excess chlorine the halogen adds to the carbon atom that does not already have an attached chlorine. The product is therefore effectively identical with a hypothetical copolymer of vinyl chloride and symmetrical dichloroethylene. An increase in the amount of post-chlorination increases the melt viscosity and the transition temperature. Typical commercial materials have a chlorine content of about 66-67% (c.f. 56.8% for PVC) with a Tg of about 110% (c.f. approx. 80°C for PVC). 

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... 

Because the polymer degrades before melting, polyacrylonitrile is commonly formed into fibers via a wet spinning process. The precursor is actually a copolymer of acrylonitrile and other monomer(s) which are added to control the oxidation rate and lower the glass transition temperature of the material. Common copolymers include vinyl acetate, methyl acrylate, methyl methacrylate, acrylic acid, itaconic acid, and methacrylic acid [1,2]. 

We present here a simple experiment, conceived to test both the reptation model and the minor chain model, by Welp et al. [50] and Agrawal et al. [51-53]. Consider the HDH/DHD interface formed with two layers of polystyrene with chain architectures shown in Fig. 5. In one of the layers, the central 50% of the chain is deuterated. This constitutes a triblock copolymer of labeled and normal polystyrene, which is, denoted HDH. In the second layer, the labeling has been reversed so that the two end fractions of the chain are deuterated, denoted by DHD. At temperatures above the glass transition temperature of the polystyrene ( 100°C), the polymer chains begin to interdiffuse across the... 

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