Plastics condensation polymers

TriaUyl Gyanurate Gure of Preformed Polymers. TAC and TAIC are often used in smaU amounts with vinyl-type and condensation polymers for cured plastics, mbber and adhesive products of high strength, and heat and solvent resistance. In some cases, chemical stabUity is also... 

Since the last edition several new materials have been aimounced. Many of these are based on metallocene catalyst technology. Besides the more obvious materials such as metallocene-catalysed polyethylene and polypropylene these also include syndiotactic polystyrenes, ethylene-styrene copolymers and cycloolefin polymers. Developments also continue with condensation polymers with several new polyester-type materials of interest for bottle-blowing and/or degradable plastics. New phenolic-type resins have also been announced. As with previous editions I have tried to explain the properties of these new materials in terms of their structure and morphology involving the principles laid down in the earlier chapters. 

The molecular chains of plastics are formed by condensation or addition polymerization,. V condensation polymer forms by stepwise reacting molecules with each other and eliminating small molecules such as water. Addition polymer forms chains by the linking without elimin.ating small molecules,... 

Condensation polymers tend to exist below their Tg at room temperature. They typically form fairly ordered structures with lots of strong interactions between the various chains giving strong materials with some, but not much, elongation when stretched. They are normally used as fibers and plastics. They have high stress/strain ratios. 

A number of plastics are condensation polymers and include polyesters and nylons that are not as highly oriented as the same materials but in fiber form. Other plastics have been developed that have outstanding heat stability, strength, and other properties that allow their wide use. These plastics include polycarbonates, polyimides, polybenzimidazoles, polysulfides, polyethers, polysulfones, and polyketones. 

Highly cross-linked condensation materials form the basis for a number of important adhesives and bulk materials, especially phenolic and amino plastics. Most of these products have formaldehyde as one of their starting reactants. These materials are thermosets that decompose prior to melting, and are therefore more difficult to recycle than most condensation polymers that are thermoplastics and do melt prior to decomposition. 

We begin by exploring the two major types of synthetic polymers used today—addition polymers and condensation polymers. This provides a good background for the discussion of plastics in Chapter 18. 

Physical Stabilization Process. Cellular polystyrene, the outstanding example polytvinyl chloride) copolymers of styrene and acrylonitrile (SAN copolymers) and polyethylene can be manufactured by this process, Chemical Stabilization Processes. This method is more versatile and thus has been used successfully for more materials than the physical stabilization process. Chemical stabilization is more adaptable for condensation polymers than for vinyl polymers because of the fast yet controllable curing reactions and the absence of atmospheric inhibition. Foamed plastics produced by these processes include polyurethane foams, polyisocyanurates. and polyphenols. 

A very useful group of adhesives and plastics is based on condensation polymers of bisphenol A and chloromethyloxacyclopropane (epichlorohydrin, CH2—CHCH2C1). The first step in the formation of epoxy resins is to form a... 

As a second example, there is a wide variety of breakdown products and oligomeric products that may be formed from the reactive monomers that are the building blocks of plastics. For plastics, the general assumption has been that any side-reaction products and breakdown products are likely to be significantly less toxic than the monomers, and so restricting the migration of the monomer was accepted as an indirect way to limit any hazard from the oligomers also. Whilst this approach is probably acceptable for addition polymers, such as those made from the unsaturated monomers vinyl chloride, butadiene and acrylonitrile where the unsaturated monomer is far more noxious than their products, the validity of this means of indirect control is questionable for condensation polymers such as polyesters and for polyethers formed from epoxide monomers. 

Fig. 13.42 Simulation results of the RIM process involving a linear step polymerization T0 = Tw = 60°C, kf— 0.5L/moles, t(lii = 2.4 s. (a) Conversion contours at the time of fill, (h) Temperature contours at the time of fill. [Reprinted hy permission from J. D. Domine and C. G. Gogos, Computer Simulations of Injection Molding of a Reactive Linear Condensation Polymer, paper presented at the Society of Plastics Engineers, 34th Armu. Tech. Conf, Atlantic City, NJ, 1976. (Also published in the Polym. Eng. Sci., 20, 847-858 (1980) volume honoring Prof. B. Maxwell).]...

The broadest classification for plastics is the old thermoplastic and thermosetting . Examples of the former group are polyethylene, polystyrene, and poly-(methyl methacrylate) examples of the latter are urea-formaldehyde condensation polymers, powder coatings based on polyesters, epoxy resins, and vulcanized synthetic elastomers. 

Pyrolysis treatments are interesting regarding the aforementioned plastic refuse makeup. Other successful treatments for feedstock recycling of condensation polymers (PET, ABS, etc.), that allows for the depolymerization and recovery of their constituent monomers (e.g. hydrolysis, alcoholysis, methanolysis, etc.), cannot be applied for polyolefin plastics recycling. In contrast, pyrolysis of polyolefins yields valuable hydrocarbon mixtures of... 

Provided that the condensation of the silanol end groups is well controlled, the polymers obtained are all flowable. A Si NMR spectrum of a typical, partially condensed polymer is shown in Fig. 1. The polymers can be compounded wilh appropriate fillers, plasticizers, and other additives. 

The repeating units of the engineering plastics also identify these as being predominantly condensation polymers, the class discussed in Chaps. 20 and 21. The commodity plastics are prime examples of the utility of the vinyl-type or chain reaction, polymers to be discussed here. 

Since the plastics are produced from petrochemicals derived from hydrocarbons, the motivation to reuse, recycle, or reprocess for energy recovery is primarily driven by an interest in conservation of petroleum resources. Economic factors are also important, but the potential saving of landfill space is more a perception rather than a reality [9]. Most of the categories of vinylic polymers discussed in this chapter are melt-formable, that is, they are thermoplastic materials, rather than nonmelting or thermosetting as are several of the condensation polymers discussed in Chapters 20 and 21. Thus,... 

Plastics with a carbonyl group can be converted to monomers by hydrolysis or glycolysis. Condensation polymers such as polyesters and nylons can be depolymerized to form monomers. For Polyurethanes (PURs), what is obtained is not the initial monomer, but a reaction product of the monomer diamine, which can be converted to diisocyanate. For PURs. hydrolysis is attractive as they can be easily broken down to polyols and diamines. The only issue is to separate them later. Steam-assisted hydrolysis has been shown to yield 60 to 80 percent recovery of polyols from PUR foam products. A twin screw extruder can be used as a reactor for hydrolysis. Glycolysis of PURS, yields mixture of polyols that can be reused directly. 

I he first commercially successful plastic, or synthetic resin as it was called in those days, was bakelite. This was a condensation polymer produced from formaldehyde and phenol, with the elimination of water as shown below ... 

The major disadvantage of chemical depolymerization is that it is almost completely restricted to the recycling of condensation polymers, and is of no use for the decomposition of most addition polymers, which are the main components of the plastic waste stream. Condensation polymers are obtained by the random reaction of two molecules, which may be monomers, oligomers or higher molecular weight intermediates, which proceeds with the liberation of a small molecule as the chain bonds are formed. Chemical depolymerization takes place by promoting the reverse reaction of the polymer formation, usually through the reaction of those small molecules with the polymeric chains. Several resins widely used on a commercial scale are based on condensation polymers, such as polyesters, polyamides, polyacetals, polycarbonates, etc. However, these polymers account for less than 15% of the total plastic wastes (see Chapter 1). 

Depending on the chemical agent used to break down the polymer, different depolymerization routes can be envisaged glycolysis, methanolysis, hydrolysis, ammonolysis, etc. In the following sections of this chapter, these alternatives are reviewed for those condensation polymers having the most significant commercial applications. It must be pointed out that a majority of the studies on chemical depolymerization of plastic wastes is reported in patents works published in the scientific literature are relatively scarce. 

This section describes the chemical recycling, via chemolysis, of certain condensation polymers which, although being produced in significantly lower amounts than polyesters and polyurethanes, are used in important applications, and so also contribute to the plastic waste stream. 

Thermal processes are mainly used for the feedstock recycling of addition polymers whereas, as stated in Chapter 2, condensation polymers are preferably depolymerized by reaction with certain chemical agents. The present chapter will deal with the thermal decomposition of polyethylene, polypropylene, polystyrene and polyvinyl chloride, which are the main components of the plastic waste stream (see Chapter 1). Nevertheless, the thermal degradation of some condensation polymers will also be mentioned, because they can appear mixed with polyolefins and other addition polymers in the plastic waste stream. Both the thermal decomposition of individual plastics and of plastic mixtures will be discussed. Likewise, the thermal coprocessing of plastic wastes with other materials (e.g. coal and biomass) will be considered in this chapter. Finally, the thermal degradation of rubber wastes will also be reviewed because in recent years much research effort has been devoted to the recovery of valuable products by the pyrolysis of used tyres. 

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