Co-monomers

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Reduction in the stereo-regularity by adding co-monomers, reducing the crystallization tendency of the polychloroprene. 

Thousands of technical papers and many books have been written on the subject of phenolic resins. The polymer is used in hundreds of diverse applications and in very large volumes. It is used worldwide. In fact the term phenolic resin encompasses a wide variety of materials based on a broad range of phenols and co-monomers. In this short article, we cannot expect complete coverage. Our hope is that we can provide an understanding of the fundamental chemistries, uses, and values of these materials as well as enough references to permit the interested reader to begin his own exploration of the topic. 

Kunitake, Yamaguchi and Aso149 studied the copolymerization of 2-furaldehyde with olefins and vinyl ethers using BF3 Et20 in methylene chloride or toluene at —78 °C. No copolymers were obtained with olefins, but p-tolyl vinyl ether or 2,3-dihydropyran gave polyethers. With the former co-monomer the values of the reactivity ratios were rx = 0.15 0.15 and r2 = 0.25 0.05 (Mj = 2-furaldehyde). 

Non-crystalline polymers are those which include high levels of irregularity within their structure. Typical sources of such irregularity are copolymerisation with significant amounts of at least two co-monomers and also complete absence of stereoregularity, i.e. atactic polymers. 

Improved co-monomer incorporation. Metallocene catalysts are very efficient at co-monomer incorporation, which means that co-monomer use can be reduced by a factor of ten or more. This has some cost advantages but, more importantly, there is less unincorporated comonomer in the final product, improving efficiency and mass balance and reducing VOCs. 

The hazards of a rigid classification of substances which may modify the course of a free radical polymerization are well illustrated by the examples of inhibitors and retarders which have been cited. The distinction between an inhibitor or retarder, on the one hand, and a co-monomer or a transfer agent, on the other, is not sharply defined. Moreover, if the substance is a free radical, it is potentially either an initiator or an inhibitor, and it may perform both functions as in the case of triphenylmethyl. If the substance with which the chain radicals react is a molecule rather than a radical, three possibilities may arise (i) The adduct radicals may be completely unreactive toward monomer. They must then disappear ultimately through mutual interaction, and we have a clear-cut case of either inhibition or retarda-... 

Copolymerization of butadiene with another monomer such as acrylonitrile, methacrylonitrile, styrene, or methyl vinyl ketone increases perceptibly the proportion of 1,4 units at the expense of 1,2. The ratio of cis to trans is not materially altered, however. One is obliged to conclude that the co-monomer shows a greater preference for addition to the terminal carbon (i.e., to carbon 4) of the resonating chain radical than does the butadiene Foster and... 

Binder correlated this selectivity with differences in polarity of the co-monomers. 

Figure 1. Sketch of the primary structure (vide infra) of cross-linked polystyrene (a) and of a typical cross-linked poly-vinyil co-monomer-functional co-monomer-cross-linker (b) [14].

Pol5uireas were among the first polycondensation pol-5mers to be employed as catal dic supports for heterogeneous metal catalysts. The first report about palladium on polyurea, by Zhang and Neckers [99] dates back to 1979. They obtained their catalyst in a two step preparation, where the co-monomers (2,4- toluendiisocyanate, TDI, and the complex between palladium acetate and 4,4 -di-amino-2,2 -bip5Tiridine) were condensed together and... 

The use of copolymers is essentially a new concept free from low-MW additives. However, a random copolymer, which includes additive functions in the chain, usually results in a relatively costly solution yet industrial examples have been reported (Borealis, Union Carbide). Locking a flame-retardant function into the polymer backbone prevents migration. Organophosphorous functionalities have been incorporated in polyamide backbones to modify thermal behaviour [56]. The materials have potential for use as fire-retardant materials and as high-MW fire-retardant additives for commercially available polymers. The current drive for incorporation of FR functionality within a given polymer, either by blending or copolymerisation, reduces the risk of evolution of toxic species within the smoke of burning materials [57]. Also, a UVA moiety has been introduced in the polymer backbone as one of the co-monomers (e.g. 2,4-dihydroxybenzophenone-formaldehyde resin, DHBF). 

This depolymerisation is inherent in the polymer structure and can be prevented by either making a copolymer (such that when un-zipping reaches the co-monomer moiety it is stopped from going any further (e.g., POM (polyoxymethylene) in which a few percent of ethylene oxide has been incorporated), or by using free radical traps (see anti-oxidants). 

The most successful examples of commercialized non-metallocene catalysts are the constrained geometry complexes such as (29) developed at Dow and Exxon.109-112 The open nature of the titanium center favors co-monomer uptake. Hence, o-oleflns such as propene, 1-butene, 1-hexene... 

Sterically bulky P,0-donor ligands have been used to prepare highly active catalysts, many of which are also capable of incorporating polar co-monomers. For example, complex (115) has... 

The diimine palladium compounds are less active than their nickel analogs, producing highly branched (e.g., 100 branches per 1,000 carbons) PE. However, they may be used for the copolymerization of Q-olefins with polar co-monomers such as methyl acrylate.318,319 Cationic derivatives, such as (121), have been reported to initiate the living polymerization of ethylene at 5°C and 100-400 psi.320 The catalyst is long-lived under these conditions and monodisperse PE (Mw/Mn= 1.05-1.08) may be prepared with a linear increase in Mn vs. time. 

Well-defined nanoclusters (w 10-100 A diameter) of several metals have been prepared via the polymerization of metal-containing monomers. The synthetic approach involves the block copolymerization of a metallated norbornene with a hydrocarbon co-monomer which is used to form an inert matrix. Subsequent decomposition of the confined metal complex affords small clusters of metal atoms. For example, palladium and platinum nanoclusters may be generated from the block copolymerization of methyl tetracyclododecane (223) with monomers (224) and (225) respectively. 10,611 Clusters of PbS have also been prepared by treating the block copolymer of (223) and (226) with H2S.612 A similar approach was adopted to synthesize embedded clusters of Zn and ZnS 613,614... 

The synthesis and properties of heat-resistant polyazomethines containing 2,5-disubstituted oxadiazole fragments, being insulators convertible into semiconductors by doping with iodine, have been described. The radical copolymerization of alkenes with the fluorescent co-monomer 2-/-butyl-5-(4 -vinyl-4-biphenylyl)-l,3,4-oxadiazole has resulted in useful macromolecular scintillators. Anionic polymerization of 2-phenyl-l,3,4-oxadiazolin-5-one has produced a nylon-type product <1996CHEC-II(4)268>. 

Sclair A process for polymerizing ethylene. Depending on the co-monomer used, the product can be linear low-density polyethylene (LLDPE) or high-density polyethylene (HDPE). Developed by DuPont in 1960 and widely licensed. Engineered by Uhde under the name Sclairtech. Nova Chemicals (Alberta) acquired the technology in 1994. 

UNIPOL [Union Carbide Polymerization] A process for polymerizing ethylene to polyethylene, and propylene to polypropylene. It is a low-pressure, gas-phase, fluidized-bed process, in contrast to the Ziegler-Natta process, which is conducted in the liquid phase. The catalyst powder is continuously added to the bed and the granular product is continuously withdrawn. A co-monomer such as 1-butene is normally used. The polyethylene process was developed by F. J. Karol and his colleagues at Union Carbide Corporation the polypropylene process was developed jointly with the Shell Chemical Company. The development of the ethylene process started in the mid 1960s, the propylene process was first commercialized in 1983. It is currently used under license by 75 producers in 26 countries, in a total of 96 reactors with a combined capacity of over 12 million tonnes/y. It is now available through Univation, the joint licensing subsidiary of Union Carbide and Exxon Chemical. A supported metallocene catalyst is used today. 

Another significant cooperativity effect in preferential helical screw sense optically active copolymers is the majority rule phenomenon.18bl8q In this case, the screw sense of a helical main chain with unequal proportions of opposite chirality enantiopure chiral side groups is controlled by the enantiomeric excess only. Since this phenomenon was first reported from poly-a-olefins made of vinyl co-monomers bearing nonenantiopure chiral moieties by Green et al.8b and Pino et al.,16b this majority rule has been established in... 

Synthetic methods include the use of silanes bearing a chiral group for silylating the surface of the porous sol-gel silica, the use of such silanes as monomers or co-monomers in the polycondensation, the physical entrapment of chiral molecules, the imprinting of SG materials with chiral templates and the creation of chiral pores, and the induction of chirality in the matrix skeleton itself 48... 

---