Polymerization, crosslinking during

We can create crosslinks during chain growth polymerization by copolymerizing dienes with vinyl monomers. When the two vinyl functions of the diene are incorporated into separate chains, a crosslink is formed. This process is shown in Fig. 2.18. When we use a low concentration of dienes, we produce a long chain branched polymer, while high concentrations of dienes create a highly crosslinked polymer network... 

To the synthetic thermoplastics and thermosets of Figure 3, the synthetic rubbers and elastomers may be added. In 1972 they amounted to more than 15 billion pounds worldwide. SBR has been the workhorse of the rubber industry since World War II. Being used in tires, it amounts to over half of all rubber production. G. M. Burnett and G. G. Cameron have investigated the way its crosslinking during polymerization affects its properties and processability. For years it... 

A super-hydrophilic absorbing polymer was synthesized from acrylic monomers and chemically crosslinked during the polymerization reaction to optimize barrierdressing properties ... 

When the intrinsic viscosity of a polymer solution is reduced by changing the solvent or by introducing crosslinks during polymerization,... 

Crosslinked Polystyrene. Polystyrene lightly crosslinked during polymerization by 0.01-0.25% divinylbenzene provides foams, expanded by carbon dioxide or other gases, with greater expandability and resistance to collapse at elevated temperatures (102, 103). Other divinylbenzene copolymers are reported, employing as blowing agent saturated aliphatic or fluoroaliphatic volatile liquids, tetramethylsilane, and azobis-isobutyronitrile (99,106, 108). 

Inaba et al. prepared a series of model styrene/butyl acrylate copolymer latexes with glass transition temperatures at room temperature. The functional monomer 2-(3-isopropenylphenyl)-2-methylethylisocyanate (TMI) was used as monomer/crosslinking agent for further film formation. A small amount of methacrylic acid was introduced in some formulations in order to enhance the crosslinking reaction. A redox initiation system was used to reduce premature crosslinking during the polymerization [82]. 

Pre-crosslinked Latex Blends. In these materials the individual latexes are crosslinked during synthesis, then blended, and a film is formed. Because of limited deformation and/or interdiffusion capabilities, such films tend to be weak, and only used for special purposes [Zosel and Lay, 1993 Lesko and Sperry, 1997], However, light crosslinking, as occurs in SBR latexes, may be tolerated. Pre-crosslinked latex blends materials are actually not IPNs, because the definition requires that at least one of the polymers be polymerized and/or crosslinked in the immediate presence of the other. An application of pre-crosslinked suspension-polymerized blends, in anionic and cationic form, is as ion-exchange resins. In suspensions, the particles are larger, usually of the order of 10-200 pm. 

EGDMA is also a clear liquid which is insoluble in water, and has a boiling point of 260 °C (at 1 atm) [50]. As an example of the application of EGDMA in emulsion polymerization systems, Tobita et al. recently modelled the kinetics of homogeneous crosslinking during the emulsion copolymerization of EGDMA with methyl methacrylate, and described the evolution of crosslink density with time (i.e., conversion) [51]. 

During emulsion polymoization proccesses crosslinking can occur due to the presence of radicals and unsaturation in the polymer chain. Chain transfer agents are often used to decrease the level of crosslinking during polymerization. The gel content of a crosslinkable polymo is d ned as the fraction of material of infinite MM experimental criteria are usually more aibitraiy, and strongly depend on the experimental procedure. The same holds for the gel point, Le. the conversion at which the first insoluble polymer network makes its appearance. For example, in ABS gel content can be based on the toluene extraction of the soluble fraction of the polybutadioie. Hie insoluble residue is the gel fraction by definition. 

With plasma treatment, surface wettability can be readily induced on a variety of normally non-wettable materials as shown in Table P. 5. Certain polymeric surfaces, such as the polyolefins, become crosslinked during plasma treatment. The surface skin of polyethylene, for example, will become crosslinked so that if the polymer were placed on a hot plate of sufficient heat, the interior would turn to a molten liquid while the crosslinked outer skin held a solid shape. Other polymers have their critical surface energy affected in different ways. Plasma-treated polymers usually form adhesive bonds that are two to four times the strength of nontreated polymers. Table P.5 presents bond strength of various plastic adherends pretreated with activated gas and bonded with an epoxy or urethane adhesives. 

Solomon recently reviewed the subject of vinyl and acrylic modified oils and alkyds. While his emphasis is on the grafting reactions, of course all of these materials are semi-IPNs, since the oil or alkyd crosslinks during polymerization. 

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