Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1995-11-28
1998-07-14
Schofer, Joseph L.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526942, 526 89, 526203, 5263184, 526281, C08F 200
Patent
active
057805652
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention describes organic synthesis reactions performed under superatmospheric conditions.
2. Background Information
Dispersion polymerization involves the polymerization of at least one monomer that is soluble in the reaction mixture. Monomer, initiator, and solvent form a homogeneous medium in which polymerization takes place. In this medium, an oligomeric or polymeric radical grows until it attains such a high molecular weight that it is no longer soluble in the reaction mixture. At this point, the polymer phase separates into particles. A stabilizer or dispersing agent prevents particle aggregation or flocculation, i.e., a kinetically stable dispersion is formed.
Dispersion polymerization differs from emulsion, microemulsion, and suspension polymerization in that the starting monomers are soluble in the polymerization solvent or diluent and do not require emulsification (i.e., the formation of monomer-containing micelles or droplets). Further, unlike emulsion polymerization, the overall rate of polymer propagation in dispersion polymerization is not dependent on particle number. (All of these differ from solution polymerizations where all materials remain soluble in the polymerization medium throughout the course of the polymerization and from precipitation polymerization where the polymer product precipitates from the polymerization medium and aggregates.)
Dispersion polymerizations can be carried out in aqueous or non-aqueous media. Non-aqueous (usually organic) dispersion polymerizations were developed in an effort to provide thin films of vinyl or acrylic polymers without having to resort to multiple applications of dilute polymer solutions. Although this goal was accomplished, the continued use of volatile organic compounds (VOCs) remains a significant problem. Coating VOC-dispersed polymers, while an improvement over solution polymerization, does not eliminate the problem of disposing of the organic medium itself.
Dispersion polymerizations performed in non-aqueous diluents can produce monodisperse particles with diameters ranging from 80 nm to 10 .mu.m. These particles, once separated from the reaction medium, have potential use as, for instance, chromatography packing materials and controlled-release matrices.
In dispersion polymerizations performed in organic diluents, suppression of flocculation through the use of a polymeric stabilizer (i.e., dispersing agent) is known as steric stabilization. Traditional stabilizers have distinct segments, one segment being soluble in and the other incompatible with the polymerization medium. The incompatible segment sorbs onto the surface of the polymer particle to be dispersed, while the soluble segment forms a sheath around the polymer particle to be dispersed. Typically, such stabilizers have been block or graft copolymers.
Olefin metathesis reactions are generally carried out neat (i.e., without solvent). Because metathesis catalysts are often organometallic complexes, insolubility of the catalyst can be a problem. This can lead to incomplete conversion of the olefins undergoing the metathesis reaction.
The use of supercritical fluids or liquids that are gases at standard temperature and pressure (STP, 25.degree. C. and 1 atm) as reaction fluids has been studied. In particular, carbon dioxide, either as a liquid or as a supercritical fluid, has been reported as a polymerization medium. Solution polymerizations (PCT Publication WO 93/20116), suspension and emulsion polymerizations (U.S. Pat. No. 5,312,882), microemulsion polymerizations (U.S. Pat. No. 4,933,404) and precipitation polymerizations (U.S. Pat. No. 3,471,463) have been described previously. Dispersion polymerization in superatmospheric fluids has not been taught or suggested heretofore.
SUMMARY OF THE INVENION
Briefly, the present invention provides a process of making a polymer, comprising the steps of: gas at STP and that is held at a pressure greater than atmospheric pressure such that the fluid is a liquid or a supercritica
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Clough Robert S.
Gozum John E.
Senger Cheryl L.
Burleson David G.
Little Douglas B.
Minnesota Mining and Manufacturing Company
Sarofim N.
Schofer Joseph L.
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