High-temperature polymerization

Chemical reaction or polymerization High-temperature coking Corrosion Buildup on internal reactor surfaces, and in crude-oil storage tanks, is often encountered Carbonaceous material is deposited on walls of furnace tubes Common problem in heat exchangers... 

Laurox Lauroyl peroxide Laurydoi LYP 97 LYP 97F NSC 670 Peroxide, bis(l-oxododecyl)- Peroxide, didodecanoyl Peroxyde de lauroyle. Initiator for bulk, solution, and suspension polymerization, high-temperature curing of polyester resins, and cure of acrylic syrup. White plates mp = 49 insoluble in H2O, soluble in CHCI3. Elf Atochem N. Am. 

Formed commercially by the polymerization of S, NajCOj and PhX in a sealed container at 275--370 C, substituted derivatives are known but not fully evaluated. Used as high-temperature adhesives, for laminates and in coatings. 

An alternative approach envisages the stimulating idea to produce an all-carbon fullerene polymer in which adjacent fullerenes are linked by covalent bonds and align in well characterized one-, two- and tliree-dimensional arrays. Polymerization of [60]fullerene, with the selective fonnation of covalent bonds, occurs upon treatment under pressure and relatively high temperatures, or upon photopolymerization in the absence of a triplet quencher,... 

A schematic of a continuous bulk SAN polymerization process is shown in Figure 4 (90). The monomers are continuously fed into a screw reactor where copolymerization is carried out at 150°C to 73% conversion in 55 min. Heat of polymerization is removed through cooling of both the screw and the barrel walls. The polymeric melt is removed and fed to the devolatilizer to remove unreacted monomers under reduced pressure (4 kPa or 30 mm Hg) and high temperature (220°C). The final product is claimed to contain less than 0.7% volatiles. Two devolatilizers in series are found to yield a better quaUty product as well as better operational control (91,92). 

Acrylonitrile has contributed the desirable properties of rigidity, high temperature resistance, clarity, solvent resistance, and gas impermeabiUty to many polymeric systems. Its availabiUty, reactivity, and low cost ensure a continuing market presence and provide potential for many new appHcations. 

Polydextrose (Pfizer) is prepared by high temperature polymerization of glucose in the presence of a catalyst. It is a water-soluble, amorphous soUd used primarily as a hulking agent (52). Dried fmit, including pmnes, and dried plum, date, and grape juice is used for similar appUcations (53). 

When pure needle-like crystals of -aminobenzoyl chloride are polymerized in a high temperature, nonsolvent process, or alow temperature, slurry process, polymer is obtained which maintains the needle-like appearance of monomer. PBA of inherent viscosity, 4.1 dL/g, has been obtained in a hexane slurry with pyridine as the acid acceptor. Therefore PBA of fiber-forming molecular weight can be prepared in the soHd state. 

Because high temperatures are required to decompose diaLkyl peroxides at useful rates, P-scission of the resulting alkoxy radicals is more rapid and more extensive than for most other peroxide types. When methyl radicals are produced from alkoxy radicals, the diaLkyl peroxide precursors are very good initiators for cross-linking, grafting, and degradation reactions. When higher alkyl radicals such as ethyl radicals are produced, the diaLkyl peroxides are useful in vinyl monomer polymerizations. 

Ja.cketingMa.teria.ls. Besides the metallic protective coverings (based on aluminum, copper and copper alloys, lead, steel, and zinc), the most popular jacketing materials are based on polymeric materials that can be either thermoplastic (with limited high temperature use) or thermosetting. 

The most common water-soluble initiators are ammonium persulfate, potassium persulfate, and hydrogen peroxide. These can be made to decompose by high temperature or through redox reactions. The latter method offers versatility in choosing the temperature of polymerization with —50 to 70°C possible. A typical redox system combines a persulfate with ferrous ion ... 

Most chromium-based catalysts are activated in the beginning of a polymerization reaction through exposure to ethylene at high temperature. The activation step can be accelerated with carbon monoxide. Phillips catalysts operate at 85—110°C (38,40), and exhibit very high activity, from 3 to 10 kg HDPE per g of catalyst (300—1000 kg HDPE/g Cr). Molecular weights and MWDs of the resins are controlled primarily by two factors, the reaction temperature and the composition and preparation procedure of the catalyst (38,39). Phillips catalysts produce HDPE with a MJM ratio of about 6—12 and MFR values of 90—120. 

Eastman Chemical has utilized a unique, high temperature solution process for propylene polymerization. Polymerization temperatures are maintained above 150°C to prevent precipitation of the isotactic polypropylene product in the hydrocarbon solvent. At these temperatures, the high rate of polymerization decreases rapidly, requiring low residence times (127). Stereoregularity is also adversely affected by high temperatures. Consequentiy, the... 

Thermal polymerization is not as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that caimot be induced to react by catalysts. The process consists of the vapor-phase cracking of, for example, propane and butane, followed by prolonged periods at high temperature (510—595°C) for the reactions to proceed to near completion. Olefins can also be conveniendy polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst, such as sulfuric acid, copper pyrophosphate, or phosphoric acid, at 150—220°C and 1035—8275 kPa (150—1200 psi), depending on feedstock and product requirement. 

Several crystalline condensed phosphates may also be formed by the dehydration of monosodium phosphate (MSP). Maddrell s salt exists as Form 11 (high temperature MaddreU, NaPO -ll, insoluble metaphosphate-11) and Form 111 (low temperature MaddreU, NaPO -lll, insoluble metaphosphate-111). Both forms are highly polymerized and difficult (slow) to dissolve in water. Mixtures of the two forms are marketed as a dental abrasive for toothpaste formulations containing soluble fluoride. Maddrell s salt is also used with disodium phosphate as a cheese emulsifying aid. 

Surface Modification. Plasma surface modification can include surface cleaning, surface activation, heat treatments, and plasma polymerization. Surface cleaning and surface activation are usually performed for enhanced joining of materials (see Metal SURFACE TREATMENTS). Plasma heat treatments are not, however, limited to high temperature equiUbrium plasmas on metals. Heat treatments of organic materials are also possible. Plasma polymerization crosses the boundaries between surface modification and materials production by producing materials often not available by any other method. In many cases these new materials can be appHed directly to a substrate, thus modifying the substrate in a novel way. 

A number of papers and patents describe polymerization processes to poly(tetramethylene ether) glycols having a narrow molecular weight distribution = 1.2—1.4). In principle, this can be achieved by having all chains grow quickly at one time, either by high temperature initiation (33)... 

Although examples in the Kureha patent Hterature indicate latitude in selecting hold times for the low and high temperature polymerization periods, the highest molecular weight polymers seem to be obtained for long polymerization times. The addition of water to PPS polymerizations has been reported to effect polymer stabilization (49), to improve molecular weight (50,51), to cause or enhance the formation of a second Hquid phase in the reaction mixture (52), and to help reprecipitate PPS from NMP solution (51). It has also been reported that water can be added under pressure in the form of steam (53). 

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