Acrylic glass transition temperature

This chapter is focused on the synthesis and properties of acryhc-clay nanocomposite pressure-sensitive adhesives, which are an example of the use of low glass transition temperature acrylic-clay nanocomposite materials. 

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. 

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. 

T is the glass-transition temperature at infinite molecular weight and is the number average molecular weight. The value of k for poly(methyl methacrylate) is about 2 x 10 the value for acrylate polymers is approximately the same (9). A detailed discussion on the effect of molecular weight on the properties of a polymer may be found in Reference 17. 

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

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. 

Fig. 3. Elastomer properties as a function of monomer composition, butyl acrylate (BA), ethyl acrylate (FA), and methoxyethyl acrylate (MEA). (a), (—) glass-transition temperature (------------) swelling in ASTM No. 3 oil (b) (-) residual elongation at break, %, after heat aging.

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]. 

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. 

Methacrylates in general have modestly slower propagation constants, and higher glass transition temperatures than acrylates. 

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 ... 

The addition of comonomers during the polymerization enables a higher flexibility compared to PVAc-homopolymerizates. This results in a lower glass transition temperature and a lower minimum temperature of the film formation. Possible comonomers are acrylic acid esters (butylacrylate, 2-ethylhexylacrylate), dialkylfumarates, ethylene and others. 

With plastics there is a certain temperature, called the glass transition temperature, Tg, below which the material behaves like glass i.e. it is hard and rigid. As can be seen from Table 1.8 the value for Tg for a particular plastic is not necessarily a low temperature. This immediately helps to explain some of the differences which we observe in plastics. For example, at room temperature polystyrene and acrylic are below their respective Tg values and hence we observe these materials in their glassy state. Note, however, that in contrast, at room temperature, polyethylene is above its glass transition temperature and so we observe a very flexible matoial. When cooled below its Tg it then becomes a hard, brittle solid. Plastics can have several transitions. 

There are several ways in which the impact properties of plastics can be improved if the material selected does not have sufficient impact strength. One method is by altering the composition of the material so that it is no longer a glassy plastic at the operating temperature of the product (Chapter 6). In the case of PVC this is done by the addition of an impact modifier which can be a compatible plastic such as an acrylic or a nitrile rubber. The addition of such a material lowers the glass transition temperature and the material becomes a rubbery viscoelastic plastic with much improved impact properties. This is one of the methods in which PVC materials are made to exhibit superior impact properties. 

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. 

Various substituted styrene-alkyl methacrylate block copolymers and all-acrylic block copolymers have been synthesized in a controlled fashion demonstrating predictable molecular weight and narrow molecular weight distributions. Table I depicts various poly (t-butylstyrene)-b-poly(t-butyl methacrylate) (PTBS-PTBMA) and poly(methyl methacrylate)-b-poly(t-butyl methacrylate) (PMMA-PTBMA) samples. In addition, all-acrylic block copolymers based on poly(2-ethylhexyl methacrylate)-b-poly(t-butyl methacrylate) have been recently synthesized and offer many unique possibilities due to the low glass transition temperature of PEHMA. In most cases, a range of 5-25 wt.% of alkyl methacrylate was incorporated into the block copolymer. This composition not only facilitated solubility during subsequent hydrolysis but also limited the maximum level of derived ionic functionality. 

Several attempts have been made to superimpose creep and stress-relaxation data obtained at different temperatures on styrcne-butadiene-styrene block polymers. Shen and Kaelble (258) found that Williams-Landel-Ferry (WLF) (27) shift factors held around each of the glass transition temperatures of the polystyrene and the poly butadiene, but at intermediate temperatures a different type of shift factor had to be used to make a master curve. However, on very similar block polymers, Lim et ai. (25 )) found that a WLF shift factor held only below 15°C in the region between the glass transitions, and at higher temperatures an Arrhenius type of shift factor held. The reason for this difference in the shift factors is not known. Master curves have been made from creep and stress-relaxation data on partially miscible graft polymers of poly(ethyl acrylate) and poly(mcthyl methacrylate) (260). WLF shift factors held approximately, but the master curves covered 20 to 25 decades of time rather than the 10 to 15 decades for normal one-phase polymers. 

The first synthetic polymers to be used as paint varnishes were acrylic and vinylic resins. Poly(vinyl acetate) (PVAc), commercialized under the name Mowilith by Hoechst and Vinylite by Union Carbide, has been used in conservation as an adhesive since 1932 and in 1937 it was proposed as a picture varnish by Stout and Cross [63]. PVAc was soon rejected as a varnish because, despite its light stability and good solubility in organic solvents, it demonstrated poor optical properties in terms of colour saturation and the tendency to pick up dirt due to its low glass transition temperature. 

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