Resin polymerization mechanisms

Several early interpretations of the polymerization mechanism have been proposed (1,17,29—31). Because of the complexity of this polymerization and insoluble character of the products, key intermediates have not ordinarily been isolated, nor have the products been characterized. Later work, however, on the resinification of furfural (32,33) has provided a new insight on the polymerization mechanism, particularly with respect to thermal reaction at 100—250°C in the absence of air. Based on the isolation and characterization of two intermediate products (9) and (10), stmcture (11) was proposed for the final resin. This work also explains the color produced during resinification, which always is a characteristic of the final polymer (33). The resinification chemistry is discussed in a recent review (5). 

Furfural—acetone resins have been used to form resin-aggregate mixtures referred to as organic concretes. Despite the reportedly excellent properties, there has been virtually no commercial use of such resins outside the former Soviet Union. The stmctures and polymerization mechanisms of these furfural—aldehyde—ketone polymers are discussed in a review (6). 

Phenolic novolacs, 18 760-761 Phenolic resin adhesives, 18 783-784 Phenolic resin can coatings, 18 38 Phenolic resin composites, 18 792-794 Phenolic resin drying-oil varnishes, 18 783 Phenolic resin fibers, 18 797-798 mechanical properties of, 18 798 Phenolic resin foam, 18 795-796 Phenolic resin manufacturers, U.S., 18 774 Phenolic resin polymerization, 18 760-765 alkaline catalysts in, 18 762-765 neutral catalysts in, 18 761-762 strong-acid catalysts in, 18 760-761 Phenolic resin prepregs, 18 793 Phenolic resin production unit, 18 766 Phenolic resins, 10 409 18 754-755, 756-802 22 10 26 763 in abrasive materials, 18 786-787 in air and oil filters, 18 790 additional reactants in, 18 759 analytical methods for, 18 774-779 applications of, 18 781-798 batch processes for, 18 766 from biomass and biochemical processes, 18 769-770... 

The synthesis and proposed cure mechanisms of this resin are described in reference 2. While the cure mechanism of the BCB terminated resin is not yet known, it is speculated that it reacts via one of two different routes. Initially the strained four member ring of the benzocyclobutene undergoes a thermally Induced ring opening. The opened rings then react with one another by a linear type addition to form a network type of structure or by cycloaddition to form linear polymer chains. An Illustration of the proposed polymerization mechanism of benzocyclobutene (BCB) terminated resins is shown below. 

Transformation of epoxy resins, which are viscous liquids or thermoplastic solids, into network polymers is a result of interaction with alkali or acid substances by means of to polyaddition and ionic polymerization mechanisms.10 A resin solidified by to the polyaddition mechanism, is a block copolymer consisting of alternating blocks of resin and a hardener or curing agent. A resin solidified by the ionic mechanism is a homopolymer. Molecules of both resin and hardener contain more than one active group. That is why block copolymer formation is a result of multiple reactions between an epoxy resin and a curing agent.11... 

The first step in the manufacture of fine powder resins is to prepare an aqueous colloidal dispersion by polymerization with initiator and emulsifier present.21 Although the polymerization mechanism is not a typical emulsion type, some of the principles of emulsion polymerization apply here. Both the process and the ingredients have significant effects on the product.22 The solids contents of such disper-... 

The main raw materials used in epoxy adhesive formulations (resins and curing agents) can be synthesized in a variety of ways to create many different products. Epoxies react readily via several polymerization mechanisms. The extent of crosslinking is an important determinant of the final properties of the adhesive. Crosslinking can be controlled by the choice of resin and curing agent and by the curing conditions. 

Treatment of the monomer with an acidic catalyst leads initially to polymers of low molecular weight and ultimately to crosslinked, black, insoluble, heat-resistant resin (17). Despite their reportedly excellent properties, virtually no commercial use of such resins exists outside the Soviet Union. The structure and polymerization mechanism of these furfural-ketone polymers are described in a recent study (18). An excellent combustion-resistant resin has been reported (19) from the addition of dialkylphosphites to bis(2-furfurylidene) ketone (6). Furfural condensates with other aliphatic and aromatic ketones have been reported (20,21) to provide photo-crosslinkable resins and hypergol components. 

The cationic polymerization mechanisms by which these initiators (Table 1) work were examined only in few cases. Such investigations were based on the polymerization of monoepoxides and on the analysis of the intermediate and fmal reaction products. However, the results can clarify crosslinking of technical epoxy resins only to a certain extent. It has to be taken into account that these resins are sold only in a commercial de, they all contain small amounts of by-products, catalysts etc. which can influence and alter the mechanisms as established with low-molecular epoxy compounds Nevertheless, these commonly available epoxies are useful as technical working materials. 

The basis of modern organic resin production incorporates the same principles described for their predecessors but depends upon an entirely different polymerization mechanism first applied by D Alelio in 1944, called addition or vinyl polymerization. The mechanism is one of free radical induced polymerization between reactants monomers) carrying ethenyl (or vinyl) double bonds (—GH=CH2). One of the reactants must contain at least two ethenyl double bonds to effect crosslinking. Again, an understanding of the resin synthesis is afforded by showing separately in Scheme 2.2 what are in fact simultaneously occurring complex polymerization reactions between all reactant permutations. 

PTFE is produced by free-radical polymerization mechanism in an aqueous media via addition polymerization of tetrafluoroethylene in a batch process. The initiator for the polymerization is usually a water-soluble peroxide, such as ammonium persulfate or disuccinic peroxide. A redox catalyst is used for low temperature polymerization. PTFE is produced by suspension (or slurry) polymerization without a surfactant to obtain granular resins or with a perfluori-nated surfactant emulsion polymerization) to produce fine powder and dispersion products. Polymerization temperature and pressure usually range from 0 to 100°C and 0.7 to 3.5 MPa. 

Commercially, it is polymerized by free-radical polymerization mechanism, usually in an aqueous (or nonaqueous) media via addition polymerization of TFE and hexafluoropropylene. The initiator for the polymerization is usually water-soluble peroxide, such as potassium persulfate. Chain transfer agents could be used to control the molecular weight of the resin. In general, the polymerization regime and conditions resemble those used to produce PTFE by emulsion polymerization. For melt fabrication processes, FEP is recovered, dried, and melt-extruded into cubes. It is also available in dispersion form. 

In heterophase polymeric materials such as rubber modified polystyrene or acrylonitrile-butadiene-styrene (ABS) resins, outstanding mechanical properties can be obtained only by regulating the dispersed rubber particle size and by achieving adhesion between the rubber and the resin phase. This can usually be achieved by adding block or graft copolymers, or by their formation in situ, as in industry. 

Acrylic resins used as adhesives are formed through radical or anionic polymerization [6]. Radical polymerization can be initiated by UV radiation as well as heat. The two reaction schemes are identieal in principle (Fig. 4). Cyanoacrylates are of special interest for systems with very high reaction rates. Their reaction follows an anionic polymerization mechanism. Since the polarity of the cyanoacrylates is very high, water is able to act as an initiator (Fig. 5). 

The term composite resin is applied to a group of dental restoratives that set by an addition polymerization mechanism. Originally these were based on poly(methyl... 

Since the discovery of Ziegler-Natta catalyst, isotactic polypropylene has been widely used as a commodity material due to its low cost and excellent physical properties. As the modulus of the resin is closely related to isotacticity, an understanding in polymerization mechanism is important in the chemistry of propylene polymerization as well as in the industry. 

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