The free-radical retrograde-precipitation polymerization (FRRPP) process was introduced by the author in the early 1990s as a chain polymerization method, whereby phase separation is occurring while reactive sites are above the lower cr- ical solution temperature (LCST). It was evident that certain regions of the product polymer attain temperatures above the average ?uid temperature, sometimes rea- ing carbonization temperatures. During the early stages of polymerization-induced phase separation, nanoscale polymer domains were also found to be persistent in the reacting system, in apparent contradiction with results of microstructural coarsening from constant-temperature modeling and experimental studies. This mass con?- ment behavior was used for micropatterning, for entrapment of reactive radical sites, and for the formation of block copolymers that can be used as intermediates, surf- tants, coatings, coupling agents, foams, and hydrogels. FRRPP-based materials and its mechanism have also been proposed to be relevant in energy and environmentally responsible applications. This technology lacks intellectual appeal compared to others that have been p- posed to produce polymers of exotic architectures. There are no special chemical mediators needed. Control of conditions and product distribution is done by p- cess means, based on a robust and ?exible free-radical-based chemistry. Thus, it can readily be implemented in the laboratory and in production scale.

This monograph is a follow-up material to the first FRRPP book by Gerard Caneba in 2009. It includes additional conceptual results, implementation of the FRRPP process in emulsion media to produce various block copolymers, and other FRRPP-related supplementary topics. Conceptual topics include the application of the quantitative analysis presented in the first FRRPP monograph for the occurrence of the FRRPP process to the polysterene-styrene-ether (PS-S-Ether) and poly(methacrylic acid)-methacrylic acid-water (PMAA-MAA-Water) systems, as well as extensions through unsteady state analysis of the occurrence of flat temperature profiles. Also, the generalization of the quantitative analysis is done to consider molecular weight effects, especially based on changes of the phase envelope to an hourglass type. Topics in implementation of the FRRPP process from pre-emulsions of monomers and the solvent/precipitant are highlighted. Additional FRRPP topics are included in this monograph that pertain to more recent efforts of Gerard Caneba, such as oil spill control, oil dispersant system, and caustic sludge remediation from emulsion-based FRRPP materials, hydrolysis of vinyl acetate-acrylic acid-based copolymers, and other polymer modification studies from FRRPP-based emulsions.

This monograph is a follow-up material to the first FRRPP book by Gerard Caneba in 2009. It includes additional conceptual results, implementation of the FRRPP process in emulsion media to produce various block copolymers, and other FRRPP-related supplementary topics. Conceptual topics include the application of the quantitative analysis presented in the first FRRPP monograph for the occurrence of the FRRPP process to the polysterene-styrene-ether (PS-S-Ether) and poly(methacrylic acid)-methacrylic acid-water (PMAA-MAA-Water) systems, as well as extensions through unsteady state analysis of the occurrence of flat temperature profiles. Also, the generalization of the quantitative analysis is done to consider molecular weight effects, especially based on changes of the phase envelope to an hourglass type. Topics in implementation of the FRRPP process from pre-emulsions of monomers and the solvent/precipitant are highlighted. Additional FRRPP topics are included in this monograph that pertain to more recent efforts of Gerard Caneba, such as oil spill control, oil dispersant system, and caustic sludge remediation from emulsion-based FRRPP materials, hydrolysis of vinyl acetate-acrylic acid-based copolymers, and other polymer modification studies from FRRPP-based emulsions. "

The free-radical retrograde-precipitation polymerization (FRRPP) process was introduced by the author in the early 1990s as a chain polymerization method, whereby phase separation is occurring while reactive sites are above the lower cr- ical solution temperature (LCST). It was evident that certain regions of the product polymer attain temperatures above the average ?uid temperature, sometimes rea- ing carbonization temperatures. During the early stages of polymerization-induced phase separation, nanoscale polymer domains were also found to be persistent in the reacting system, in apparent contradiction with results of microstructural coarsening from constant-temperature modeling and experimental studies. This mass con?- ment behavior was used for micropatterning, for entrapment of reactive radical sites, and for the formation of block copolymers that can be used as intermediates, surf- tants, coatings, coupling agents, foams, and hydrogels. FRRPP-based materials and its mechanism have also been proposed to be relevant in energy and environmentally responsible applications. This technology lacks intellectual appeal compared to others that have been p- posed to produce polymers of exotic architectures. There are no special chemical mediators needed. Control of conditions and product distribution is done by p- cess means, based on a robust and ?exible free-radical-based chemistry. Thus, it can readily be implemented in the laboratory and in production scale.