Reversible Deactivation Radical Polymerization: State-Of-The-Art in 2017
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Controlled Radical Polymerization in the Dispersed Phase
CONTROLLED RADICAL POLYMERIZATION IN THE DISPERSED PHASE by MARY E. THOMSON A thesis submitted to the Department of Chemical Engineering in conformity with the requirements for the degree of Doctor of Philosophy Queen's University Kingston, Ontario, Canada December, 2010 Copyright c Mary E. Thomson, 2010 Abstract Controlled radical polymerization (CRP) has emerged as a powerful method of creating polymers with tailored molecular architectures under mild reaction conditions. However, production of these polymers efficiently at an industrial scale will likely require them to be synthesized in the dispersed phase. Three types of CRP are explored, Atom Transfer Radical Polymerization (ATRP), Nitroxide Mediated Polymerization (NMP) and Catalytic Chain Transfer (CCT) to elucidate the intricacies of creating these novel polymer colloids. Compartmentalization in an ATRP dispersed phase system is explored theoretically to understand the effects of particle size and catalyst concentration on the polymerization. The results suggest that there is an optimal range of particle sizes where the rate of poly- merization is greater than that in an equivalent bulk system while maintaining both a lower PDI (polydispersity index) and higher livingness. All three factors are desirable in ATRP but generally cannot be achieved simultaneously in bulk. Compartmentalization manifests itself differently in CCT dispersed phase systems, where the segregation of the CCT agents into different polymer particles leads to multimodal molecular weight distributions. Control over the particle size is notoriously difficult for nitroxide mediated polymeriza- tion, as it is challenging to decouple an increase in the particle size with an increase in target molecular weight using a two stage emulsion polymerization approach. -
Poly( Ethylene-Co-Methyl Acrylate)-Solvent- Cosolvent Phase Behaviour at High Pressures
Poly( ethylene-co-methyl acrylate)-solvent- cosolvent phase behaviour at high pressures Melchior A. Meilchen, Bruce M. Hasch, Sang-Ho Lee and Mark A. McHugh* Department of Chemical Engineering, Johns Hopkins University, Baltimore, MD 21278, USA (Received 5 April 7991; accepted 75 July 1997 ) Cloud-point data to 160°C and 2000 bar are presented showing the effect of cosolvents on the phase behaviour of poly(ethylene-co-methyl acrylate) (EMA) (64 mo1%/36 mol%) with propane and chlorodifluoromethane (F22). Ethanol shifts the EMA-propane cloud-point curves to lower temperatures and pressures, but above _ 10 wt% ethanol, the copolymer becomes insoluble. Up to 40 wt% acetone monotonically shifts the EMA-propane cloud-point curves to lower temperatures and pressures. Acetone and ethanol both shift the cloud-point curves of EMA-F22 mixtures in the same monotonic manner for cosolvent concentrations of up to 40 wt%. (Keywords: copolymer; cosolvent; high pressures) INTRODUCTION or diethyl ether, so it is necessary to operate at elevated temperatures and pressures to dissolve high molecular Within the past 20 years there has been a great deal of weight polystyrene in either solvent. Adding acetone to effort invested in trying to understand and model the PS-diethyl ether mixtures monotonically reduces the solubility behaviour of polar polymers in liquid cosolvent pressure needed at a given temperature to obtain a single mixtures’-9. Polymer solubility is usually related to phase. whether the cosolvent preferentially solvates or adsorbs There has also been a number of viscometric and light to certain segments of the polymer chain as determined scattering studies on the solution behaviour of polar by light scattering, viscosity measurements or cloud- copolymers in liquid cosolvent mixtures’4*‘5. -
End-Functional Styrene-Maleic Anhydride Copolymers Via Catalytic
Article pubs.acs.org/Macromolecules End-Functional Styrene−Maleic Anhydride Copolymers via Catalytic Chain Transfer Polymerization † ‡ † § § Gemma C. Sanders, , Robbert Duchateau, Ching Yeh Lin, Michelle L. Coote, † and Johan P. A. Heuts ,* † Laboratory of Polymer Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands ‡ Dutch Polymer Institute (DPI), John F. Kennedylaan 2, 5612 AB Eindhoven, The Netherlands § ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia *S Supporting Information ABSTRACT: Styrene−maleic anhydride copolymers have been successfully synthesized using catalytic chain transfer polymerization employing the low spin [bis(difluoroboryl)- dimethylglyoximato]cobalt(II) (COBF) complex. By partially replacing styrene with α-methylstyrene (while maintaining the amount of maleic anhydride at 50 mol %) over a range of ratios, it was shown that the rate of reaction and molar mass decreases with increasing α-methylstyrene content. The polymers were characterized using MALDI−ToF−MS and 1H−13C gHMQC NMR to determine the end groups, which in the presence of α-methylstyrene was an α-methylstyrene unit with a vinylic functionality. For styrene−maleic anhydride copolymers, the end group was determined to be predom- inantly maleic anhydride with a vinylic functionality. Considering the fact that in a styrene−maleic anhydride copolymerization the propagating radicals are predominantly of a styrenic nature, this was a very surprising result, suggesting that the maleic anhydride radicals undergo a chain transfer reaction, which is orders of magnitude faster than that of styrenic radicals. This conclusion was supported by high-level ab initio quantum chemical calculations, which showed that hydrogen abstraction from the maleic anhydride radical is 40 kJ/mol more exothermic than that from a styrene radical. -
Living Free Radical Polymerization with Reversible Addition – Fragmentation
Polymer International Polym Int 49:993±1001 (2000) Living free radical polymerization with reversible addition – fragmentation chain transfer (the life of RAFT) Graeme Moad,* John Chiefari, (Bill) YK Chong, Julia Krstina, Roshan TA Mayadunne, Almar Postma, Ezio Rizzardo and San H Thang CSIRO Molecular Science, Bag 10, Clayton South 3169, Victoria, Australia Abstract: Free radical polymerization with reversible addition±fragmentation chain transfer (RAFT polymerization) is discussed with a view to answering the following questions: (a) How living is RAFT polymerization? (b) What controls the activity of thiocarbonylthio compounds in RAFT polymeriza- tion? (c) How do rates of polymerization differ from those of conventional radical polymerization? (d) Can RAFT agents be used in emulsion polymerization? Retardation, observed when high concentra- tions of certain RAFT agents are used and in the early stages of emulsion polymerization, and how to overcome it by appropriate choice of reaction conditions, are considered in detail. Examples of the use of thiocarbonylthio RAFT agents in emulsion and miniemulsion polymerization are provided. # 2000 Society of Chemical Industry Keywords: living polymerization; controlled polymerization; radical polymerization; dithioester; trithiocarbonate; transfer agent; RAFT; star; block; emulsion INTRODUCTION carbonylthio compounds 2 by addressing the following In recent years, considerable effort1,2 has been issues: expended to develop free radical processes that display (a) How living is RAFT polymerization? -
Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature
polymers Article Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature Aziz Ben-Miled 1 , Afshin Nabiyan 2 , Katrin Wondraczek 3, Felix H. Schacher 2,4 and Lothar Wondraczek 1,* 1 Otto Schott Institute of Materials Research (OSIM), Friedrich Schiller University Jena, D-07743 Jena, Germany; [email protected] 2 Institute of Organic Chemistry and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, D-07743 Jena, Germany; [email protected] (A.N.); [email protected] (F.H.S.) 3 Leibniz Institute of Photonic Technology (Leibniz IPHT), D-07745 Jena, Germany; [email protected] 4 Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, D-07743 Jena, Germany * Correspondence: [email protected]; Tel.: +49-3641-9-48500 Abstract: A quartz crystal microbalance with dissipation monitoring (QCM-D) was employed for in situ investigations of the effect of temperature and light on the conformational changes of a poly (triethylene glycol acrylate-co-spiropyran acrylate) (P (TEGA-co-SPA)) copolymer containing 12–14% of spiropyran at the silica–water interface. By monitoring shifts in resonance frequency and in acoustic dissipation as a function of temperature and illumination conditions, we investigated the evolution of viscoelastic properties of the P (TEGA-co-SPA)-rich wetting layer growing on the sensor, Citation: Ben-Miled, A.; Nabiyan, A.; from which we deduced the characteristic coil-to-globule transition temperature, corresponding to Wondraczek, K.; Schacher, F.H.; the lower critical solution temperature (LCST) of the PTEGA part. -
ICSHAM Acrylic Esters Safe Handling Guide
ACRYLATE ESTERS A SUMMARY OF SAFETY AND HANDLING 3RD EDITION Compiled by ATOFINA Chemicals, Inc. BASF Corporation Celanese, Ltd. The Dow Chemical Company ROHM AND HAAS2002 COMPANY TABLE OF CONTENTS 1 INTRODUCTION.....................................................................................................................................................................1 2 NAMES AND GENERAL INFORMATION......................................................................................................................2 2.1 ODOR..............................................................................................................................................................................................2 2.2 REACTIVITY.....................................................................................................................................................................................2 3 PROPERTIES AND CHARACTERISTICS OF ACRYLATES........................................................................................3 4 SAFETY AND HANDLING MANAGEMENT TRAINING..........................................................................................5 4.1 GENERAL CONSIDERATIONS.......................................................................................................................................................5 4.2 SAFETY, HEALTH AND ENVIRONMENTAL REVIEWS...................................................................................................................5 4.3 WRITTEN OPERATING PROCEDURES...........................................................................................................................................5 -
Visible-Light-Mediated, Additive-Free, and Open-To-Air Controlled Radical Polymerization Cite This: Polym
Polymer Chemistry View Article Online PAPER View Journal | View Issue Visible-light-mediated, additive-free, and open-to-air controlled radical polymerization Cite this: Polym. Chem., 2019, 10, 1585 of acrylates and acrylamides† Jessica R. Lamb, K. Peter Qin and Jeremiah A. Johnson * Oxygen tolerance in controlled radical polymerizations has been an active field of study in recent years. Herein, we report a photocontrolled, additive-free iniferter polymerization that operates in completely open vials utilizing the “polymerizing through oxygen” mechanism. Trithiocarbonates are directly activated with high intensity 450 nm light to produce narrowly dispersed (Mw/Mn = 1.1–1.6) polyacrylates and poly- acrylamides. Living behavior is demonstrated through chain extension, block copolymer synthesis, and control over molecular weight through varying the monomer : iniferter ratio. A slight increase in induction Received 7th January 2019, period is observed for the open vial polymerization compared to the air-free reaction, but polymers with Accepted 7th February 2019 similar Mn and Mw/Mn values are produced after 30–60 minutes of irradiation. This system will provide a Creative Commons Attribution 3.0 Unported Licence. DOI: 10.1039/c9py00022d convenient platform for living additive manufacturing because of its fast reaction time, air tolerance, wide rsc.li/polymers monomer scope, and lack of any additives beyond the monomer, iniferter, and DMSO solvent. Introduction generally avoided by performing the polymerizations under inert conditions; however, degassing techniques such as freeze– Controlled radical polymerization (CRP) techniques have trans- pump–thaw cycles, sparging, or performing experiments in a formed macromolecular synthesis by enabling access to poly- glovebox can be impractical for certain applications. -
Recent Advances in RAFT Polymerization: Novel Initiation Mechanisms and Optoelectronic Applications
polymers Review Recent Advances in RAFT Polymerization: Novel Initiation Mechanisms and Optoelectronic Applications Xiangyu Tian 1 ID , Junjie Ding 1 ID , Bin Zhang 1 ID , Feng Qiu 2, Xiaodong Zhuang 2,3,* ID and Yu Chen 1,* 1 Key Laboratory for Advanced Materials and Shanghai Key Laboratory of Functional Materials Chemistry, Institute of Applied Chemistry, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China; [email protected] (X.T.); [email protected] (J.D.); [email protected] (B.Z.) 2 The State Key Laboratory of Metal Matrix Composites & Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Dongchuan Road 800, Shanghai 200240, China; [email protected] 3 Center for Advancing Electronics Dresden (CFAED) & Department of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany * Correspondence: [email protected] (X.Z.); [email protected] (Y.C.); Tel.: +86-021-6425-3765 (X.Z.) Received: 24 February 2018; Accepted: 12 March 2018; Published: 14 March 2018 Abstract: Reversible addition-fragmentation chain transfer (RAFT) is considered to be one of most famous reversible deactivation radical polymerization protocols. Benefiting from its living or controlled polymerization process, complex polymeric architectures with controlled molecular weight, low dispersity, as well as various functionality have been constructed, which could be applied in wide fields, including materials, biology, and electrology. Under the continuous research improvement, main achievements have focused on the development of new RAFT techniques, containing fancy initiation methods (e.g., photo, metal, enzyme, redox and acid), sulfur-free RAFT system and their applications in many fields. -
Adhesion to Plastic
Adhesion to Plastic Marcus Hutchins Scientist I TS&D Industrial Coatings-Radcure Cytec Smyrna, GA USA Abstract A plastic can be described as a mixture of polymer or polymers, plasticizers, fillers, pigments, and additives which under temperature and pressure can be molded into various items1. Plastic materials have become a staple of our everyday life in applications ranging from food packaging to home construction. In automotive applications alone, over four billion pounds2 of plastic were used in cars and light trucks and that figure is expected to grow 30 percent by 2011. The demand for plastic is growing at a rate faster than metal because of advantages such as reduced weight, reduced material cost, corrosion resistance and increased durability over metal. As the demand for plastic increases, the need to effectively and efficiently coat plastic parts will also increase. For most plastics, that will mean starting with a good primer coating. This paper will present three new ultraviolet (UV) curable resins that may be used to formulate primers for a variety of plastic substrates. ©RadTech e|5 2006 Technical Proceedings Introduction Once a plastic part is formed, a coating is usually applied for decorative or protective purposes. Typically, that starts with a primer coating. There are many factors that positively affect the adhesion of the primer to the substrate, and several will be discussed here. One of the more important properties in achieving adhesion is the ability of the coating to wet the substrate3. In order for wetting to occur, the surface tension of the coating must be less than the surface energy of the substrate. -
Methyl Acrylate
METHYL ACRYLATE Data were last reviewed in IARC (1986) and the compound was classified in IARC Monographs Supplement 7 (1987). 1. Exposure Data 1.1 Chemical and physical data 1.1.1 Nomenclature Chem. Abstr. Serv. Reg. No.: 96-33-3 Chem. Abstr. Name: 2-Propenoic acid, methyl ester IUPAC Systematic Name: Acrylic acid, methyl ester Synonym: Methyl propenoate 1.1.2 Structural and molecular formulae and relative molecular mass O H2 C CH C O CH3 C4H6O2 Relative molecular mass: 86.09 1.1.3 Chemical and physical properties of the pure substance (a) Description: Liquid with an acrid odour (Budavari, 1996) (b) Boiling-point: 80.6°C (American Conference of Governmental Industrial Hygienists, 1992) (c) Melting-point: –76.5°C (Budavari, 1996) (d) Solubility: Slightly soluble in water (6 g/100 mL at 20°C, 5 g/100 mL at 40°C); soluble in ethanol, diethyl ether, acetone and benzene (American Conference of Governmental Industrial Hygienists, 1992) (e) Vapour pressure: 9.3 kPa at 20°C; relative vapour density (air = 1), 3.0 (Ver- schueren, 1996) ( f ) Flash point: –2.8°C, closed cup; 6.7°C, open cup (American Conference of Governmental Industrial Hygienists, 1992) (g) Explosive limits: upper, 25%; lower, 2.8% by volume in air (American Con- ference of Governmental Industrial Hygienists, 1992) (h) Conversion factor: mg/m3 = 3.52 × ppm –1489– 1490 IARC MONOGRAPHS VOLUME 71 1.2 Production and use Production of methyl acrylate in the United States was reported to be 14 100 tonnes in 1983 (United States National Library of Medicine, 1997). -
Red List Microplastic Ingredients
Products on this list have been found to contain ingredients which are commonly considered to be microplastic ingredients. These include but are not limited to Polyethylene (PE), Polypropylene (PP), Polymethyl methacrylate (PMMA), Nylon (PA), Polyurethane, and Acrylates Copolymer. No. Polymer Source 1 Acetophenone/Oxymethylene Copolymer ECHA 2 Acetylenediurea/Formaldehyde/Tosylamide Crosspolymer ECHA 3 Acrolein/Acrylic Acid Copolymer ECHA 4 Acrylamide/Ammonium Acrylate Copolymer ECHA 5 Acrylamide/Ethalkonium Chloride Acrylate Copolymer ECHA 6 Acrylamide/Ethyltrimonium Chloride Acrylate/Ethalkonium Chloride ECHA Acrylate Copolymer 7 Acrylamide/Sodium Acrylate Copolymer ECHA 8 Acrylamide/Sodium Acryloyldimethyltaurate Copolymer ECHA 9 Acrylamide/Sodium Acryloyldimethyltaurate/Acrylic Acid Copolymer ECHA 10 Acrylamides/DMAPA Acrylates/Methoxy PEG Methacrylate Copolymer ECHA 11 Acrylamidopropyltrimonium Chloride/Acrylates Copolymer ECHA 12 Acrylates Copolymer ECHA; UNEP; 13 Acrylates Crosspolymer ECHA 14 Acrylates Crosspolymer-3 ECHA 15 Acrylates Crosspolymer-4 ECHA 16 Acrylates/Acetoacetoxyethyl Methacrylate Copolymer ECHA 17 Acrylates/Acrylamide Copolymer ECHA 18 Acrylates/Aminoacrylates/C10-30 Alkyl PEG-20 Itaconate Copolymer ECHA 19 Acrylates/Ammonium Methacrylate Copolymer ECHA 20 Acrylates/Beheneth-25 Methacrylate Copolymer ECHA 21 Acrylates/Beheneth-25 Methacrylate/Steareth-30 Methacrylate ECHA Copolymer 22 Acrylates/Behenyl Acrylate/Dimethicone Methacrylate Copolymer ECHA 23 Acrylates/Behenyl Methacrylate/Dimethicone Methacrylate -
Stereochemistry of Acrylate Polymerization in Toluene Using N-Buli
Polymer Journal. Vol. 31, No.5. pp 479-481 (1999) NOTES Stereochemistry of Acrylate Polymerization in Toluene Using n-BuLi Weihong Lru,t Tamaki NAKANO,* and Yoshio 0KAMOTo*-tt Joint Research C'emer for Precision Polymeri::.ation (JRC' P P)-Japan Chemical Innovation Institute (JC'Il), Graduate School of EnJ;ineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan *Department of Applied Chemistry, Graduate School of Engineerin[;, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan (Received November 18, 1998) KEY WORDS Anionic Polymerization / Tacticity I Acrylate I Methacrylate I Lithium Hydroxide / Stereospecific Polymerization / The stereostructure of a vinyl polymer often sig our previous reports. 13· 14 nificantly affects its physical and chemical properties. Therefore, stereocontrol of vinyl polymerizations is an RESULTS AND DISCUSSION important topic in macromolecular science, and various stereospecific polymerizations using Ziegler-Natta, me Temperature Effect tallocene. or anionic catalysts (initiators) have been The conditions and results of the polymerizations are examined. 1 •2 As to anionic polymerization, methacrylate summarized in Table I. In the MA polymerization, the polymerization has been most systematically investigat yield of the MeOH-insoluble polymer decreased as re ed, and both highly isotactic and syndiotactic polymers action temperature increased, while in the tBA polym have been synthesized. 2 •3 However, the stereocontrol of erizations, polymer yield was over 90% at all temper acrylate polymerization is generally difficult probably atures. This suggests that some side reactions including because of the absence of the ex-methyl group which may the carbonyl attack, which is less likely for tBA having a greatly contribute to the formation of a propagation bulky side group, took place in the MA polymeriza center with a high stereospecificity.