Photopolymerization in dispersed systems

Abstract Zero-VOC technologies combining ecological and economic efficiency are destined to occupy a growing place in the polymer economy. Today, Polymerization in dispersed systems and Photopolymerization are the two major key players. The hybrid technology based on photopolymerization in dispersed systems has emerged as the next technological frontier, not only to make processes even more efficient and eco-friendly, but also to expand the range of polymer products and properties. This review summarizes the current knowledge in research relevant to this field in an exhaustive way. Firstly, fundamentals of photoinitiated polymerization in dispersed systems are given to show the favourable context for developing this emerging technology, its specific features as well as the distinctive equipment and materials necessary for its implementation. Secondly, a state-of-the-art and critical review is provided according to the seven main processing methods in dispersed systems: emulsion, microemulsion, miniemulsion, dispersion, precipitation, suspension, and aerosol.

[1]  J. Pinto,et al.  Suspension Polymerization Processes , 2013 .

[2]  C. Esen,et al.  Preparation of Monodisperse Polymer Particles by Photopolymerization , 1996 .

[3]  R. Partch,et al.  Preparation of polymer colloids by chemical reactions in aerosols. I. Poly(p-tertiarybutylstyrene)† , 1983 .

[4]  A. Cox,et al.  An experiment to measure Mie and Rayleigh total scattering cross sections , 2002 .

[5]  Ying Zhang,et al.  Efficient synthesis of monodisperse, highly crosslinked, and “living” functional polymer microspheres by the ambient temperature iniferter‐induced “living” radical precipitation polymerization , 2013 .

[6]  S. Pratsinis,et al.  Particle formation in gases: A review , 1996 .

[7]  J. Asua,et al.  Miniemulsion Polymerization Using Oil-Soluble Initiators , 1994 .

[8]  L. Johnston,et al.  Surface photochemistry: generation of benzyl radical pairs on dry silica gel , 1984 .

[9]  Stephanie E. Sigmund,et al.  Defined polymer shells on nanoparticles via a continuous aerosol-based process , 2014, Journal of Nanoparticle Research.

[10]  Jianwen Yang,et al.  Photoinitiated dispersion polymerization of methyl methacrylate: A quick approach to prepare polymer microspheres with narrow size distribution , 2008 .

[11]  Reinhold Schwalm,et al.  UV Coatings: Basics, Recent Developments and New Applications , 2007 .

[12]  I. Capek Photopolymerization of Butyl Acrylate Microemulsion. Effect of Reaction Conditions and Additives on Fates of Desorbed Radicals , 1996 .

[13]  Koichi Takamura,et al.  Polymer Dispersions and Their Industrial Applications , 2002 .

[14]  J. Bolton,et al.  Determination of the Quantum Yield for the Photochemical Generation of Hydroxyl Radicals in TiO2 Suspensions , 1996 .

[15]  R. Partch,et al.  Preparation of polymer colloids by chemical reactions in aerosols. III. Polyurea and mixed polyurea-metal oxide particles☆☆☆ , 1985 .

[16]  J. Asua,et al.  Redox initiator systems for emulsion polymerization of acrylates , 2009 .

[17]  T. Otsu Iniferter concept and living radical polymerization , 2000 .

[18]  M. Winnik,et al.  Synthesis of PMMA Microparticles with a Narrow Size Distribution by Photoinitiated RAFT Dispersion Polymerization with a Macromonomer as the Stabilizer , 2014 .

[19]  A. Shchukarev,et al.  A cation-exchange material for protein separations based on grafting of thiol-terminated sulfopropyl methacrylate telomers onto hydrophilized monodisperse divinylbenzene particles. , 2008, Journal of separation science.

[20]  E. Pişkin,et al.  Microemulsion photopolymerization of methacrylates stabilized with sodium dodecyl sulfate and poly(N-acetylethylenimine) macromonomers , 2002 .

[21]  E. Oliveros,et al.  Flash Latex Production in a Continuous Helical Photoreactor: Releasing the Brake Pedal on Acrylate Chain Radical Polymerization , 2016 .

[22]  R. Lazzaroni,et al.  Dispersion Photopolymerization of Acrylated Oligomers Using a Flexible Continuous Reactor , 2016 .

[23]  S. Armes,et al.  Aqueous dispersion polymerization: a new paradigm for in situ block copolymer self-assembly in concentrated solution. , 2011, Journal of the American Chemical Society.

[24]  F. Candau,et al.  Inverse microemulsion polymerization of acrylamide: characterization of the water-in-oil microemulsions and the final microlatexes , 1984 .

[25]  K. Irgum,et al.  Monodisperse Polymeric Particles by Photoinitiated Precipitation Polymerization , 2007 .

[26]  J. Asua,et al.  Designing tubular reactors to avoid clogging in high solids miniemulsion photopolymerization , 2013 .

[27]  L. Gan,et al.  Microemulsion polymerizations and reactions , 2005 .

[28]  D. Baigl,et al.  Photo-actuation of liquids for light-driven microfluidics: state of the art and perspectives. , 2012, Lab on a chip.

[29]  J. Vanderhoff,et al.  Microemulsion polymerization of styrene , 1989 .

[30]  Thomas D. Donnelly,et al.  Particle size determination: An undergraduate lab in Mie scattering , 2001 .

[31]  E. Oliveros,et al.  Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry , 2006 .

[32]  N. Turro,et al.  Magnetic field and magnetic isotope effects on photoinduced emulsion polymerization , 1983 .

[33]  Jianbo Tan,et al.  Photoinitiated RAFT Dispersion Polymerization: A Straightforward Approach toward Highly Monodisperse Functional Microspheres , 2012 .

[34]  E. Oliveros,et al.  Absorption and Scattering in Concentrated Monomer Miniemulsions: Static and Dynamic Investigations , 2014 .

[35]  K. Irgum,et al.  Polymerization of Divinylbenzene and Divinylbenzene-co-Glycidyl Methacrylate Particles by Photoinitiated Precipitation Polymerization in Different Solvent Mixtures , 2009 .

[36]  C. Boyer,et al.  RAFT iniferter polymerization in miniemulsion using visible light , 2017 .

[37]  M. Antonietti,et al.  Evidence for the preservation of the particle identity in miniemulsion polymerization. , 1999 .

[38]  Jianbo Tan,et al.  Photoinitiated dispersion polymerization using polyurethane based macrophotoinitiator as stabilizer and photoinitiator , 2010 .

[39]  R. Liska Photoinitiators with functional groups. V. New water‐soluble photoinitiators containing carbohydrate residues and copolymerizable derivatives thereof , 2002 .

[40]  Etienne Goovaerts,et al.  Highly sensitive setup for tunable wavelength hyper-Rayleigh scattering with parallel detection and calibration data for various solvents. , 2009, Optics express.

[41]  J. Asua Challenges for industrialization of miniemulsion polymerization , 2014 .

[42]  Yan Lu,et al.  Preparation of polystyrene-poly(N-isopropylacrylamide) (PS-PNIPA) core-shell particles by photoemulsion polymerization , 2006 .

[43]  P. Kubelka,et al.  New contributions to the optics of intensely light-scattering materials. , 1954, Journal of the Optical Society of America.

[44]  S. Krishnan,et al.  Polymer Microspheres Prepared by Water-Borne Thiol-Ene Suspension Photopolymerization. , 2012, ACS macro letters.

[45]  Mehmet Toner,et al.  Multifunctional Encoded Particles for High-Throughput Biomolecule Analysis , 2007, Science.

[46]  Biggs,et al.  Ultrasonic initiation of polystyrene latex synthesis , 2000, Ultrasonics sonochemistry.

[47]  D. Fischer,et al.  Continuous flow reactor for miniemulsion chain photopolymerization: Understanding plugging issue , 2016 .

[48]  Kai Li,et al.  Synthesis of monodisperse poly(divinylbenzene) microspheres , 1993 .

[49]  C. Chern,et al.  Principles and Applications of Emulsion Polymerization , 2008 .

[50]  N. Turro,et al.  An efficient, high conversion photoinduced emulsion polymerization. Magnetic field effects on polymerization efficiency and polymer molecular weight , 1980 .

[51]  Li Zhang,et al.  Room temperature synthesis of poly(poly(ethylene glycol) methyl ether methacrylate)-based diblock copolymer nano-objects via Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA) , 2016 .

[52]  M. Meier,et al.  Green polymerization methods : renewable starting materials, catalysis and waste reduction , 2011 .

[53]  Zhiqiang Gao,et al.  Synthesis of monodisperse polymer microspheres by photopolymerization of microdroplets , 2007 .

[54]  Mingguang Yu,et al.  Facile Preparation of Monodisperse Poly(2‐hydroxyethyl acrylate)‐Grafted Poly(methyl methacrylate) Microspheres via Photoinitiated RAFT Dispersion Polymerization , 2016 .

[55]  A. Ovsianikov,et al.  Highly efficient water‐soluble visible light photoinitiators , 2016 .

[56]  Xueliang Li,et al.  Rapid synthesis of well-defined all-acrylic diblock copolymer nano-objects via alcoholic photoinitiated polymerization-induced self-assembly (photo-PISA) , 2017 .

[57]  Steven L. Murov,et al.  Handbook of photochemistry , 1973 .

[58]  J. Fouassier,et al.  Photoinitiators for Polymer Synthesis: Scope, Reactivity, and Efficiency , 2012 .

[59]  A. Braun,et al.  Radical Photopolymerization in Miniemulsions. Fundamental Investigations and Technical Development , 2011 .

[60]  A. V. Chernyshev,et al.  Observation of magnetic field effect on polymer yield in photoinduced dispersion polymerization of styrene , 2003 .

[61]  T. Allen,et al.  Photochemical polymerization of acrylamide aerosol particles , 1987 .

[62]  C. Boyer,et al.  Photoinitiated Polymerization‐Induced Self‐Assembly (Photo‐PISA): New Insights and Opportunities , 2017, Advanced science.

[63]  Derek L. Patton,et al.  Functional, composite polythioether nanoparticles via thiol-alkyne photopolymerization in miniemulsion. , 2015, Chemical communications.

[64]  P. Roose,et al.  UV-nanoparticles: Photopolymerized polymer colloids from aqueous dispersions of acrylated oligomers , 2014 .

[65]  Woong‐Ryeol Yu,et al.  Dispersion polymerization of styrene using poly(4-vinylpyridine) macro-RAFT agent under UV radiation , 2012, Fibers and Polymers.

[66]  T. Imae,et al.  Microemulsion polymerization of styrene , 1991 .

[67]  P. Kubelka,et al.  New Contributions to the Optics of Intensely Light-Scattering Materials. Part I , 1948 .

[68]  E. Oliveros,et al.  Continuous-flow synthesis of polymer nanoparticles in a microreactor via miniemulsion photopolymerization , 2014 .

[69]  Danni Wang,et al.  Dispersion polymerization of n‐butyl acrylate , 2002 .

[70]  C. Croutxé-Barghorn,et al.  Photopolymerizable Monomer Miniemulsions: Why Does Droplet Size Matter? , 2013 .

[71]  Vishnu Pareek,et al.  Light Intensity Distribution in a Photocatalytic Reactor Using Finite Volume , 2004 .

[72]  J. Fouassier,et al.  Kinetics of photopolymerization of butyl acrylate in direct micelles , 1997 .

[73]  F. Grieser,et al.  Emulsion polymerization synthesis of cationic polymer latex in an ultrasonic field. , 2002, Journal of colloid and interface science.

[74]  Leonie Barner,et al.  Ambient temperature synthesis of well‐defined microspheres via precipitation polymerization initiated by UV‐irradiation , 2007 .

[75]  Frank N. Jones,et al.  Organic Coatings: Science and Technology , 1992 .

[76]  Xueliang Li,et al.  Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects. , 2017, Macromolecular rapid communications.

[77]  José M. Asua,et al.  Emulsion polymerization: From fundamental mechanisms to process developments , 2004 .

[78]  M. Fischer Industrial Applications of Photochemical Syntheses , 1978 .

[79]  P. Zetterlund Controlled/living radical polymerization in nanoreactors: compartmentalization effects , 2011 .

[80]  C. Ober,et al.  Monodispersed, micron‐sized polystyrene particles by dispersion polymerization , 1985 .

[81]  J. Asua,et al.  Kinetics of the photoinitiated inverse microemulsion polymerization of 2-methacryloyl oxyethyl trimethyl ammonium chloride , 1998 .

[82]  C. Boyer,et al.  Visible Light-Mediated Polymerization-Induced Self-Assembly in the Absence of External Catalyst or Initiator. , 2016, ACS macro letters.

[83]  Lifen Zhang,et al.  A surfactant-free emulsion RAFT polymerization of methyl methacrylate in a continuous tubular reactor , 2015 .

[84]  Markus Antonietti,et al.  Polyreactions in miniemulsions , 2002 .

[85]  P. Marote,et al.  Response surface optimization of miniemulsion: application to UV synthesis of hexyl acrylate nanoparticles , 2015, Colloid and Polymer Science.

[86]  G. Will,et al.  Photo-initiated miniemulsion polymerization as a route to the synthesis of gold nanoparticle encapsulated latexes , 2010 .

[87]  M. Pishko,et al.  Release of protein from highly cross-linked hydrogels of poly(ethylene glycol) diacrylate fabricated by UV polymerization. , 2001, Biomaterials.

[88]  W. Cook,et al.  Photoinitiated Cationic Polymerization of Mono and Divinyl Ethers in Aqueous Medium Using Ytterbium Triflate as Lewis Acid , 2008 .

[89]  D. Koo,et al.  Photo-induced emulsion polymerization of vinyl acetate in the presence of poly(oxyethylene) nonyl phenyl ether, a nonionic emulsifier (II) , 2002 .

[90]  Yang Jianwen,et al.  Synthesis of Highly Monodisperse Surface-Functional Microspheres by Photoinitiated RAFT Dispersion Polymerization Using Macro-RAFT Agents , 2013 .

[91]  W. Steen Absorption and Scattering of Light by Small Particles , 1999 .

[92]  D. Koo,et al.  Photo‐induced emulsion polymerization of vinyl acetate in the presence of poly(oxyethylene)10 nonyl phenyl ether ammonium sulfate, an anionic emulsifier (I) , 2002 .

[93]  J. Asua,et al.  Miniemulsion Photo-Copolymerization of Styrene/Butyl Acrylate in a Continuous Tubular Reactor , 2014 .

[94]  M. Schmutz,et al.  Thiol–Ene Linear Step-Growth Photopolymerization in Miniemulsion: Fast Rates, Redox-Responsive Particles, and Semicrystalline Films , 2016 .

[95]  Qiuping Yu,et al.  Use of Polyion Complexation for Polymerization-Induced Self-Assembly in Water under Visible Light Irradiation at 25 °C. , 2015, ACS Macro Letters.

[96]  Sabine Beuermann,et al.  Rate coefficients of free-radical polymerization deduced from pulsed laser experiments , 2002 .

[97]  M. Wörner,et al.  Photoinitiated miniemulsion polymerization in microfluidic chips on automated liquid handling stations: Proof of concept , 2016 .

[98]  J. Pojman,et al.  Neutron scattering study of the structural change induced by photopolymerization of AOT/D2O/dodecyl acrylate inverse microemulsions. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[99]  J. Crivello,et al.  Synthesis and modification of epoxy‐ and hydroxy‐functional microspheres , 2005 .

[100]  Y. Gnanou,et al.  Dispersion Ring-Opening Metathesis Polymerization of Norbornene Using PEO-Based Stabilizers , 2002 .

[101]  Jianbo Tan,et al.  Monodisperse highly cross-linked “living” microspheres prepared via photoinitiated RAFT dispersion polymerization , 2015 .

[102]  Li Zhang,et al.  Photosynthesis of poly(glycidyl methacrylate) microspheres: a component for making covalently cross-linked colloidosomes and organic/inorganic nanocomposites , 2016, Journal of Materials Science.

[103]  N. Turro,et al.  Photoinitiated polymerization of styrene in microemulsions , 1987 .

[104]  Qiuping Yu,et al.  The direct synthesis of interface-decorated reactive block copolymer nanoparticles via polymerisation-induced self-assembly , 2015 .

[105]  E. Davis,et al.  Photochemical initiated polymerization of single microdroplets , 1996 .

[106]  S. Whitaker,et al.  Concepts and design of chemical reactors , 1986 .

[107]  Wei Li,et al.  Janus and ternary particles generated by microfluidic synthesis: design, synthesis, and self-assembly. , 2006, Journal of the American Chemical Society.

[108]  Li Zhang,et al.  Alcoholic Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA): A Fast Route toward Poly(isobornyl acrylate)-Based Diblock Copolymer Nano-Objects. , 2016, ACS macro letters.

[109]  Yoshio Suzuki,et al.  Radical polymerization of miniemulsions induced by compressed gases , 2016 .

[110]  Alberto E. Cassano,et al.  Cylindrical photocatalytic reactors. Radiation absorption and scattering effects produced by suspended fine particles in an annular space , 1997 .

[111]  F. Schork,et al.  Emulsion and miniemulsion polymerizations with an oil‐soluble initiator in the presence and absence of an aqueous‐phase radical scavenger , 2002 .

[112]  I. Capek Photopolymerization of butyl acrylate microemulsions 1. Post-polymerization , 1996 .

[113]  Wantai Yang,et al.  Preparation of transparent polystyrene nano-latexes by an UV-induced routine emulsion polymerization , 2009 .

[114]  K. Landfester Miniemulsion polymerization and the structure of polymer and hybrid nanoparticles. , 2009, Angewandte Chemie.

[115]  S. Armes,et al.  A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly , 2016, Macromolecules.

[116]  S. Shim,et al.  Living-Free-Radical Emulsion Photopolymerization of Methyl Methacrylate by a Surface Active Iniferter (Suriniferter) , 2003 .

[117]  Jean-Pierre Fouassier,et al.  Photoinitiation, Photopolymerization, and Photocuring: Fundamentals and Applications , 1995 .

[118]  Jianbo Tan,et al.  Photoinitiated precipitation polymerization in liquid CO2: Fast formation of crosslinked poly(acrylic acid-co-methoxy polyethylene glycol acrylate) microspheres , 2011 .

[119]  Li Zhang,et al.  Low-Temperature Synthesis of Thermoresponsive Diblock Copolymer Nano-Objects via Aqueous Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA) using Thermoresponsive Macro-RAFT Agents. , 2016, Macromolecular rapid communications.

[120]  S. Armes,et al.  Non-aqueous Isorefractive Pickering Emulsions , 2015, Langmuir : the ACS journal of surfaces and colloids.

[121]  X. Kong,et al.  A green protocol to prepare monodisperse poly(TMPTMA–styrene) microspheres by photoinitiated precipitation polymerization in low-toxicity solvent , 2013, Colloid and Polymer Science.

[122]  Kevin I Booker-Milburn,et al.  Flow photochemistry: Old light through new windows , 2012, Beilstein journal of organic chemistry.

[123]  R. Partch,et al.  Preparation of polymer colloids by chemical reactions in aerosols: II. Large particles , 1984 .

[124]  Alexander Penlidis,et al.  An Updated Review on Suspension Polymerization , 1997 .

[125]  R. Liska,et al.  Photoinitiators with functional groups. IX. Hydrophilic bisacylphosphine oxides for acidic aqueous formulations , 2006 .

[126]  Y. Yagcı,et al.  Photoinduced Electron Transfer Reactions for Macromolecular Syntheses. , 2016, Chemical reviews.

[127]  A. Chiriac,et al.  Magnetic field polymerisation , 2000 .

[128]  Markus Antonietti,et al.  Preparation of polymeric nanocapsules by miniemulsion polymerization. , 2001 .

[129]  Michael Grätzel,et al.  Photophysical and Photochemical Processes in Micellar Systems , 1980 .

[130]  J. Lalevée,et al.  Visible-Light Emulsion Photopolymerization of Styrene. , 2018, Angewandte Chemie.

[131]  J. Buchanan,et al.  Thiol-ene polymer microbeads prepared under high-shear and their successful utility as a heterogeneous photocatalyst via C 60 -capping , 2016 .

[132]  G. González,et al.  Emulsion polymerization in a microwave reactor , 1998 .

[133]  I. Capek Radical polymerization of polar unsaturated monomers in direct microemulsion systems , 1999 .

[134]  T. I. Quickenden,et al.  The ultraviolet absorption spectrum of liquid water , 1980 .

[135]  M. Winnik,et al.  PMMA Microspheres with Embedded Lanthanide Nanoparticles by Photoinitiated Dispersion Polymerization with a Carboxy-Functional Macro-RAFT Agent , 2015 .

[136]  Petr Chýlekt,et al.  Light scattering by small particles in an absorbing medium , 1977 .

[137]  P. Lovell,et al.  Chain transfer to polymer in free-radical bulk and emulsion polymerization of vinyl acetate studied by NMR spectroscopy , 1998 .

[138]  Stuart C. Thickett,et al.  Emulsion polymerization : State of the art in kinetics and mechanisms , 2007 .

[139]  M. L. Satuf,et al.  Experimental Method to Evaluate the Optical Properties of Aqueous Titanium Dioxide Suspensions , 2005 .

[140]  Snowballing radical generation leads to ultrahigh molecular weight polymers. , 2012, Macromolecular rapid communications.

[141]  Y. Ding,et al.  Synthesis of Hydrogen-Bonded Pore-Switchable Cylindrical Vesicles via Visible-Light-Mediated RAFT Room-Temperature Aqueous Dispersion Polymerization. , 2016, ACS macro letters.

[142]  T. Tadros,et al.  Preparation of microlatex dispersions using oil-in-water microemulsions , 1991 .

[143]  C. Croutxé-Barghorn,et al.  Two Routes Towards Photoinitiator‐Free Photopolymerization in Miniemulsion: Acrylate Self‐Initiation and Photoactive Surfactant , 2011 .

[144]  Robert G. Gilbert,et al.  Emulsion polymerization : a mechanistic approach , 1995 .

[145]  Qiuyu Zhang,et al.  Fast and facile fabrication of porous polymer particles via thiol–ene suspension photopolymerization , 2014 .

[146]  D. Shipp,et al.  Suspension “click” polymerizations: thiol-ene polymer particles prepared with natural gum stabilizers , 2015, Colloid and Polymer Science.

[147]  H. Takayanagi,et al.  Mechanisms of the Photochemical Rearrangement of Diphenyl Ethers. , 1996, The Journal of organic chemistry.

[148]  Tao Chen,et al.  UV light-initiated RAFT polymerization induced self-assembly , 2015 .

[149]  M. Cheung Formation of Porous Polymeric Structures by the Polymerization of Single-phase Microemulsions Formulated with Methyl Methacrylate and Acrylic Acid , 1991 .

[150]  Ulrich Fehrenbacher,et al.  Kinetics of the early stage of dispersion polymerization in supercritical CO2 as monitored by turbidimetry. 2. Particle formation and locus of polymerization , 2002 .

[151]  J. Asua,et al.  Synthesis of high solids content low surfactant/polymer ratio nanolatexes. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[152]  J. Pojman,et al.  Humidity-responsive polymeric films based on AOT-water reverse microemulsions , 2007 .

[153]  J. Rieger,et al.  Polymerization-Induced Self-Assembly: From Soluble Macromolecules to Block Copolymer Nano-Objects in One Step , 2012 .

[154]  Hao Sun,et al.  Photo-PISA: Shedding Light on Polymerization-Induced Self-Assembly. , 2015, ACS macro letters.

[155]  G. Hadziioannou,et al.  Microfluidic synthesis and assembly of reactive polymer beads to form new structured polymer materials , 2008 .

[156]  Z. Kam,et al.  Absorption and Scattering of Light by Small Particles , 1998 .

[157]  E. Oliveros,et al.  The use of chemical actinometry for the evaluation of the light absorption efficiency in scattering photopolymerizable miniemulsions , 2015, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[158]  M. Wörner,et al.  Perspectives of aerosol-photopolymerization: organic-inorganic hybrid nanoparticles , 2014, Colloid and Polymer Science.

[159]  C. Croutxé-Barghorn,et al.  Photoinduced miniemulsion polymerization , 2010 .

[160]  K. Matyjaszewski,et al.  Photoinitiated ATRP in Inverse Microemulsion , 2013 .

[161]  Y. Yagcı,et al.  Photoinitiated Bulk and Emulsion Polymerization of Styrene – Evidence for Photo-Controlled Radical Polymerization , 2011 .

[162]  Xueliang Li,et al.  Facile Preparation of CO2 -Responsive Polymer Nano-Objects via Aqueous Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA). , 2017, Macromolecular rapid communications.

[163]  Caio L. Firme,et al.  Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory. , 2013, The journal of physical chemistry. A.

[164]  Jianbo Tan,et al.  One-stage photoinitiated RAFT dispersion polymerization - Reaction parameters for achieving high particle size uniformity , 2014 .

[165]  K. Salikhov Magnetic Isotope Effect in Radical Reactions: An Introduction , 1996 .

[166]  M. Sangermano,et al.  Cationic Aerosol Photopolymerization , 2015 .

[167]  I. Capek Photopolymerization of alkyl(meth)acrylates and polyoxyethylene macromonomers in fine emulsions , 2000 .

[168]  E. Kaler,et al.  Microemulsion Polymerization of Styrene: The Effect of Salt and Structure , 1996 .

[169]  T. P. Davis,et al.  Chain Transfer to Monomer in the Free-Radical Polymerizations of Methyl Methacrylate, Styrene, and α-Methylstyrene , 1998 .

[170]  X. Allonas,et al.  Acrylate nanolatex via self‐initiated photopolymerization , 2014 .

[171]  John C. Dixon,et al.  The shock absorber handbook , 2007 .

[172]  Gerald Scott,et al.  Polymer Degradation and Stabilisation , 1988 .

[173]  F. Sun,et al.  Photo‐Initiated Dispersion Polymerization of Copolymer Microspheres in a Closed System: Poly(MMA‐co‐MAA) , 2010 .

[174]  Jiangtao Xu,et al.  A Polymerization-Induced Self-Assembly Approach to Nanoparticles Loaded with Singlet Oxygen Generators , 2016 .

[175]  Xueliang Li,et al.  Enzyme-Assisted Photoinitiated Polymerization-Induced Self-Assembly: An Oxygen-Tolerant Method for Preparing Block Copolymer Nano-Objects in Open Vessels and Multiwell Plates , 2017 .

[176]  Jie Yao,et al.  Synthesis of silane monomer-modified styrene–acrylate microemulsion coatings by photopolymerization , 2008 .

[177]  Stuart C. Thickett,et al.  Controlled/Living Radical Polymerization in Dispersed Systems: An Update. , 2015, Chemical reviews.

[178]  J. Asua,et al.  Hybrid miniemulsion photopolymerization in a continuous tubular reactor—A way to expand the characteristics of polyurethane/acrylics , 2012 .

[179]  J. Asua Polymeric dispersions : principles and applications , 1997 .

[180]  R. Giudici,et al.  Synthesis of Core-Shell Particles of Polystyrene and Poly(methyl methacrylate) Using Emulsion Photopolymerization , 2013 .

[181]  P. Lacroix-Desmazes,et al.  Synthesis of mono functional carboxylic acid poly(methyl methacrylate) in aqueous medium using sur-iniferter. Application to the synthesis of graft copolymers polyethylene-g-poly(methyl methacrylate) and the compatibilization of LDPE/PVDF blends , 2003 .

[182]  P. Lacroix-Desmazes,et al.  Synthesis of Poly(vinyl acetate)-block-poly(dimethylsiloxane)-block-poly(vinyl acetate) Copolymers by Iodine Transfer Photopolymerization in Miniemulsion , 2009 .

[183]  F. Taghipour,et al.  Irradiance modeling in annular photoreactors using the finite-volume method , 2010 .

[184]  D. H. Napper,et al.  Studies of the steric stabilization of colloidal particles , 1971 .

[185]  Zhou Zhou,et al.  Photo-induced polymerization in ionic liquid medium: 1. Preparation of polyaniline nanoparticles , 2009 .

[186]  H. D. H. Stöver,et al.  Growth Mechanism of Poly(divinylbenzene) Microspheres in Precipitation Polymerization , 1999 .

[187]  Toivo T. Kodas,et al.  Aerosol Processing of Materials , 1998 .

[188]  Stuart W. Prescott,et al.  Miniemulsion copolymerization of methyl methacrylate and butyl acrylate by ultrasonic initiation , 2005 .

[189]  Leonie Barner,et al.  Reversible Addition−Fragmentation Chain Transfer Polymerization Initiated with Ultraviolet Radiation , 2002 .

[190]  G. Gescheidt,et al.  Simple one-pot syntheses of water-soluble bis(acyl)phosphane oxide photoinitiators and their application in surfactant-free emulsion polymerization. , 2015, Macromolecular rapid communications.

[191]  Xueliang Li,et al.  Expanding the Scope of Polymerization-Induced Self-Assembly: Z-RAFT-Mediated Photoinitiated Dispersion Polymerization. , 2018, ACS macro letters.

[192]  Lijuan Wang,et al.  Synthesis and Evaluation of a Surface-Active Photoinitiator for Microemulsion Polymerization , 1998 .

[193]  J. Durand,et al.  Polymerization of acrylamide in nonionic microemulsions: Characterization of the microlatices and polymers formed , 1987 .

[194]  D. Shipp,et al.  Suspension thiol-ene photopolymerization: Effect of stabilizing agents on particle size and stability , 2014 .

[195]  E. Oliveros,et al.  Colloidal and Supported TiO2: Toward Nonextractable and Recyclable Photocatalysts for Radical Polymerizations in Aqueous Dispersed Media , 2016 .

[196]  K. Moussa,et al.  A new method for monitoring ultra‐fast photopolymerizations by real‐time infra‐red (RTIR) spectroscopy , 1988 .

[197]  M. Cunningham,et al.  Living Ab Initio Emulsion Polymerization of Methyl Methacrylate in Water Using a Water-Soluble Organotellurium Chain Transfer Agent under Thermal and Photochemical Conditions. , 2018, Angewandte Chemie.

[198]  F. Candau,et al.  Inverse microemulsion polymerization , 1982 .

[199]  C. Croutxé-Barghorn,et al.  Light-Mediated Thiol-Ene Polymerization in Miniemulsion: A Fast Route to Semicrystalline Polysulfide Nanoparticles. , 2014, ACS macro letters.

[200]  Jiangtao Xu,et al.  Visible-Light-Regulated Controlled/Living Radical Polymerization in Miniemulsion. , 2015, ACS macro letters.

[201]  H. Lasa,et al.  TiO2 absorption and scattering coefficients using Monte Carlo method and macroscopic balances in a photo-CREC unit , 2011 .

[202]  I. Capek,et al.  On kinetics of microemulsion copolymerization of butyl acrylate and acrylonitrile , 1996 .

[203]  José M. Asua,et al.  Challenges and Opportunities in Continuous Production of Emulsion Polymers: a Review , 2016 .

[204]  Peter G. Odell,et al.  SUSPENSION POLYMERIZATION PROCESSES , 2010 .

[205]  Moses O. Tadé,et al.  Light intensity distribution in heterogenous photocatalytic reactors , 2008 .

[206]  Shlomo Magdassi,et al.  High-performance 3D printing of hydrogels by water-dispersible photoinitiator nanoparticles , 2016, Science Advances.

[207]  C. Pan,et al.  The photo-controlled polymerization-induced self-assembly and reorganization process for fabrication of polymeric nanomaterials , 2017 .

[208]  Qiuyu Zhang,et al.  Magnetic nanoparticles encapsulated latexes prepared with photo-initiated miniemulsion polymerization , 2010 .

[209]  T. Corrales,et al.  Photoinitiated polymerization in bicontinuous microemulsions: Fluorescence monitoring , 2006 .

[210]  Mingguang Yu,et al.  Z-type and R-type macro-RAFT agents in RAFT dispersion polymerization – another mechanism perspective on PISA , 2016 .

[211]  Chia‐Chi Ho,et al.  Polymerization in Bicontinuous Microemulsion Glasses , 2006 .

[212]  Gregory T. Russell,et al.  Modeling of termination in intermediate and high conversion free radical polymerizations , 1994 .

[213]  Yi Cheng,et al.  UV-Enhanced Gas-Solid Chlorination of Polyvinyl Chloride for Cleaner Production of Chlorinated Polyvinyl Chloride , 2016 .

[214]  M. Wörner,et al.  Perspectives of aerosol-photopolymerization: Nanoscale polymer particles , 2013 .

[215]  Weishan Li,et al.  Poly (styrene-co-maleic anhydride) microspheres prepared in ethanol/water using a photochemical method and their application in Ni2+ adsorption , 2013 .

[216]  K. Matyjaszewski A Commentary on “Role of Initiator-Transfer Agent-Terminator (Iniferter) in Radical Polymerizations: Polymer Design by Organic Disulfides as Iniferters” by T. Otsu, M. Yoshida (Macromol. Rapid Commun. 1982, 3, 127–132) , 2005 .

[217]  Kiyoshi Suzuki,et al.  A new kinetic interpretation of the styrene microemulsion polymerization , 1997 .

[218]  A. Scranton,et al.  Photopolymerization of butyl acrylate-in-water microemulsions: Polymer molecular weight and end-groups , 2005 .

[219]  M. Wörner,et al.  Perspectives of Aerosol-Photopolymerization: Nanostructured Polymeric Particles , 2014 .

[220]  Jiangtao Xu,et al.  Visible Light Photocatalytic Thiol–Ene Reaction: An Elegant Approach for Fast Polymer Postfunctionalization and Step-Growth Polymerization , 2015 .

[221]  J. Asua,et al.  High performance pressure sensitive adhesives by miniemulsion photopolymerization in a continuous tubular reactor , 2014 .

[222]  K. Jensen,et al.  Synthesis of micro and nanostructures in microfluidic systems. , 2010, Chemical Society reviews.

[223]  S. Shim,et al.  Living radical dispersion photopolymerization of styrene by a reversible addition–fragmentation chain transfer (RAFT) agent , 2003 .

[224]  E. Oliveros,et al.  Optimization of the photochemically initiated polymerization of methyl methacrylate , 2006 .

[225]  M. Podgórski,et al.  Monodispersity/Narrow Polydispersity Cross-Linked Microparticles Prepared by Step-Growth Thiol–Michael Addition Dispersion Polymerizations , 2015 .