DOCSLIB.ORG

Polymer Reaction & Colloid Engineering

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Polymer Reaction & Colloid Engineering Institute for Chemical and Bioengineering Department of Chemistry and Applied Biosciences ETH Zurich 8093 Zurich,Switzerland LECTURE NOTES (intended to complete but not to substitute the lectures) POLYMER REACTION & COLLOID ENGINEERING Prof.Dr. M. Morbidelli October 29, 2015 AUTUMN SEMESTER 2015 Contents 1 Free-Radical Polymerization 5 1.1 Chemical Reactions . 5 1.1.1 Initiation . 5 1.1.2 Propagation . 6 1.1.3 Chain Transfer . 6 1.1.4 Bimolecular Termination . 8 1.2 Diffusion Control of Chemical Reactions . 8 1.3 Polymerization Processes . 10 1.3.1 Bulk Polymerization . 10 1.3.2 Solution Polymerization . 10 1.3.3 Suspension Polymerization . 10 1.3.4 Emulsion Polymerization . 10 1.4 Kinetics of Free-Radical Polymerization . 11 1.4.1 Involved Chemical Reactions . 11 1.4.2 Population Balance Equations in a Batch Reactor . 11 1.4.3 Rate of Monomer Consumption . 13 1.5 Pseudo Steady State Approximation . 14 1.5.1 Stiffness Ratio . 17 2 Chain Length Distribution of Polymers 19 2.1 Population Balance Equations . 19 2.1.1 Active Chains . 19 2.1.2 Dead Chains . 21 2.2 Instantaneous Chain Length Distribution . 23 2.2.1 Number Distribution and Number Average . 23 2.2.2 Weight Distribution and Weight Average . 24 2.2.3 Polydispersity . 25 2.2.4 Summary . 26 3 Cumulative Properties of Polymers 27 3.1 Cumulative Chain Length Distribution, Moments, and Properties . 27 3.1.1 Width of the Cumulative Distribution . 29 3.2 Designing Polymerization Processes with Respect to Desired CLDs . 30 3.2.1 Case I: Termination by Combination is Negligible . 30 3.2.2 Case II: Termination by Combination Dominates . 32 2 Contents 4 Copolymerization 34 4.1 Kinetics of Copolymerization . 34 4.1.1 Involved Chemical Reactions . 34 4.1.2 Long-Chain Approximation . 35 4.1.3 Rate of Monomer Consumption . 36 4.2 Chain Length Distribution of Copolymers . 37 4.2.1 Population Balance Equation . 37 4.2.2 Pseudo-Homogeneous Approach . 37 4.2.3 Kinetics of Multi-Monomer Polymerization . 38 4.3 Chain Composition Distribution of Copolymers . 40 4.3.1 Instantaneous Chain Composition . 40 4.3.2 Composition Drift . 42 4.3.3 Chain Composition Control . 43 4.3.4 Reactor Monitoring and Control . 49 5 Heterogeneous Free-Radical Polymerization 52 5.1 Concept of Micellar Particle Nucleation . 52 5.2 Radical Segregation . 53 5.3 Phase Partitioning . 55 5.3.1 Monomer . 56 5.3.2 Emulsifier . 56 5.4 Colloidal Stability . 57 5.5 Kinetic Mechanism of Emulsion Polymerization (Smith & Ewart, 1954) . 57 5.6 Kinetics of Micellar Particle Nucleation . 60 5.7 Distribution of Active Radicals in the Polymer Particles . 62 6 Stability of Colloidal Suspensions 66 6.1 Kinetic Stability of Colloidal Suspensions . 66 6.2 Interaction between two Charged Bodies . 67 6.2.1 van der Waals Forces . 67 6.2.2 Electrostatic Forces . 71 6.2.3 Total Interaction Energy . 84 6.2.4 Simple Manifestation of Electrical Double Layers: Soap Films . 85 6.3 Coagulation of Colloidal Suspensions . 85 6.3.1 Aggregation by Potential Control . 87 6.3.2 Aggregation by Electrolyte Addition . 87 6.4 Steric Interactions . 89 7 Kinetics and Structure of Colloidal Aggregates 93 7.1 Diffusion Limited Cluster Aggregation – DLCA . 93 7.1.1 Aggregation Rate Constant – DLCA . 93 7.1.2 Cluster Mass Distribution – DLCA . 95 3 Contents 7.1.3 Role of Aggregate Morphology – DLCA . 96 7.2 Reaction Limited Cluster Aggregation – RLCA . 98 7.2.1 Aggregation Rate Constant – RLCA . 98 7.2.2 Role of Cluster Morphology – RLCA . 101 7.2.3 Cluster Mass Distribution – RLCA . 103 7.3 Comparison of Aggregation Regimes – DLCA vs. RLCA . 103 7.3.1 Aggregation Rate Constant – DLCA vs. RLCA . 103 7.3.2 Cluster Mass Distribution – DLCA vs. RLCA . 104 7.3.3 Aggregate Morphology – DLCA vs. RLCA . 107 7.3.4 Comparison to Experimental Data . 108 7.4 Cluster Coalescence . 109 7.5 Solid Suspensions under Shear . 114 7.5.1 Shear induced Aggregation . 114 7.5.2 Shear induced Breakage . 119 7.6 Gelation of Colloidal Suspensions . 120 7.6.1 The Gelation Process . 120 7.6.2 Brownian-Induced Gelation . 122 7.6.3 Shear-Induced Gelation . 123 7.7 Experimental Characterization of Colloidal Suspensions . 126 7.7.1 Light Scattering . 126 7.7.2 Static Light Scattering . 127 7.7.3 Dynamic Light Scattering . 133 7.8 Zeta Potential, Electrophoretic Mobility, and Surface Charge Density . 135 8 Protein Aggregation 140 8.1 Introduction . 140 8.2 Monoclonal Antibodies . 141 8.3 Protein Colloidal Stability . 142 8.4 Protein Conformational Stability . 143 8.5 Mechanisms of Protein Aggregation . 144 8.6 Aggregation Kinetics and Reaction Order . 145 8.7 Case Studies . 146 8.7.1 Case Study 1: mAb-1 . 147 8.7.2 Case Study 2: mAb-2 . 162 8.8 Conclusion . 171 4 Chapter 1 Free-Radical Polymerization 1.1 Chemical Reactions 1.1.1 Initiation The initiation reaction produces free radicals. There are several ways to do this: • Chemical initiation The decomposition of the initiator (e.g. AIBN) forms free radicals: CH3 CH3 CH3 kd NCCN N C CN N2 + 2 NC C CH3 CH3 CH3 kd • • I2 −! I + I (rd = kdI2) • kI • I + M −! R1 dI• = 2 f k I − k I• M ≈ 0 (1.1) dt d 2 I • ) kII M = 2 f kdI2 ≡ RI (1.2) where f is the initiator efficiency, typically f = [0:5; 1]. Note that in order to ensure a continuous production of radicals all over the process, 1=kd should be larger than the characteristic time of the polymerization reaction. Examples of the decomposition characteristic time, τd for some commercial initiators are: 5 CHAPTER 1. FREE-RADICAL POLYMERIZATION τd T Acetyl peroxide 2 h 80 ◦C Cumyl peroxide 12 h 110 ◦C t-Butyl hydroperoxide 45 h 150 ◦C Since this is a first order process, τd = 1=kd. • Thermal initiation: thermal decomposition of the monomer (e.g. styrene). This represents a danger, for example during monomer transportation, since it may lead to undesired polymerization of the monomer. For this reason, inhibitors (scavengers of radicals) are usually added to the monomers before storage. This causes the occurrence of a non reproducible induction period when such monomers are polymerized. • Initiation by radiation The decomposition of the initiator is caused by light or another source of radiation. Since this method is quite expensive, it is only applied to polymerization systems oper- ating at very low temperatures. 1.1.2 Propagation Propagation is the addition of a monomer molecule to a radical chain. R R k + p n-1 n k • p • • Rn + M −! Rn+1 rp = kpRn M 1.1.3 Chain Transfer • Chain transfer to monomer • kfm • • Rn + M −! Pn + R1 r = kfmRn M The reactants are the same as for the propagation reaction, but the activation energy is 3 much larger. Accordingly, kfm is usually at least 10 times smaller than kp. This reaction 6 CHAPTER 1. FREE-RADICAL POLYMERIZATION R R k + fm + n-1 n-1 leads to the formation of a polymer chain with a terminal double bond. This can induce chain branching through the terminal double bond propagation reaction. • Chain transfer to chain transfer agent • kfs • • Rn + S −! Pn + R1 r = kfsRnS A chain transfer agent, S is a molecule containing a weak bond that can be broken to lead to radical transfer, similarly as in the case of monomer above (e.g. CCl4, CBr4, mercaptans). • Chain transfer to polymer k • fp • • Rn + Pm −! Pn + Rm r = kfpRn (mPm) • In this reaction the growing radical chain, Rn extracts a hydrogen from the dead chain, Pm. Since this extraction can occur on any of the m monomer units along the chain, the rate of this reaction is proportional to the length of Pm. General observations on the role of chain transfer reactions: - The concentration of radicals is not affected and therefore the rate of monomer con- sumption is also unchanged. - The growth of polymer chains is stopped and therefore shorter chains are produced. - Each transfer event leaves a different end-group on the chain that can be detected (NMR, titration) so as to identify and quantify the corresponding chain transfer reaction. - Nonlinear (branched) polymer chains are produced: directly by chain transfer to poly- mer or indirectly through the propagation of the terminal double bond left by a chain transfer to monomer event. 7 CHAPTER 1. FREE-RADICAL POLYMERIZATION 1.1.4 Bimolecular Termination Bimolecular termination occurs according to two different mechanisms: termination by com- bination and termination by disproportionation. Their relative importance depends upon the specific polymerization system. • Termination by combination R R R k + tc R m-1 n-1 m-1 n-1 • • ktc • • Rn + Rm −! Pn+m r = ktcRnRm This reaction results in an increase of the chain length. • Termination by disproportionation R R R R k + td + n-1 m-1 n-1 m-1 • • ktd • • Rn + Rm −! Pn + Pm r = ktdRnRm The chain length remains constant during the termination reaction. Note that also in this case chains with terminal double bond are produced, which can therefore lead to the occurrence of branching. 1.2 Diffusion Control of Chemical Reactions When dealing with macromolecules we can regard the reaction event as constituted by two steps in series: 8 CHAPTER 1. FREE-RADICAL POLYMERIZATION • a relative motion or diffusion of the two molecules in order to overlap.
Load more

Recommended publications
  • Free-Radical Photopolymerization of Acrylonitrile Grafted Onto Epoxidized Natural Rubber
    polymers Article Free-Radical Photopolymerization of Acrylonitrile Grafted onto Epoxidized Natural Rubber Rawdah Whba 1,2, Mohd Sukor Su’ait 3, Lee Tian Khoon 1,* , Salmiah Ibrahim 4, Nor Sabirin Mohamed 4 and Azizan Ahmad 1,5,* 1 Department of Chemical Sciences, Faculty of Sciences and Technology, Universiti Kebangsaan Malaysia, Bangi 43600, Malaysia; [email protected] 2 Department of Chemistry, Faculty of Applied Sciences, Taiz University, Taiz 6803, Yemen 3 Solar Energy Research Institute (SERI), Universiti Kebangsaan Malaysia, Bangi 43600, Malaysia; [email protected] 4 Centre for Foundation Studies in Science, University of Malaya, Kuala Lumpur 50603, Malaysia; [email protected] (S.I.); [email protected] (N.S.M.) 5 Research Center for Quantum Engineering Design, Faculty of Science and Technology, Universitas Airlangga, Surabaya 60286, Indonesia * Correspondence: [email protected] (L.T.K.); [email protected] (A.A.); Tel.: +60-12-7279286 (L.T.K.); +60-19-3666576 (A.A.) Abstract: The exploitation of epoxidized natural rubber (ENR) in electrochemical applications is approaching its limits because of its poor thermo-mechanical properties. These properties could be improved by chemical and/or physical modification, including grafting and/or crosslinking techniques. In this work, acrylonitrile (ACN) has been successfully grafted onto ENR- 25 by a radical photopolymerization technique. The effect of (ACN to ENR) mole ratios on chemical structure Citation: Whba, R.; Su’ait, M.S.; Tian and interaction, thermo-mechanical behaviour and that related to the viscoelastic properties of the Khoon, L.; Ibrahim, S.; Mohamed, polymer was investigated. The existence of the –C≡N functional group at the end-product of ACN-g- N.S.; Ahmad, A.
    [Show full text]
  • Dispersity Control in Atom Transfer Radical Polymerizations Through Addition of Phenyl Hydrazine
    Polymer Chemistry Dispersity Control in Atom Transfer Radical Polymerizations through Addition of Phenyl Hydrazine Journal: Polymer Chemistry Manuscript ID PY-ART-01-2018-000033.R1 Article Type: Paper Date Submitted by the Author: 04-May-2018 Complete List of Authors: Yadav, Vivek; University of Houston Hashmi, Nairah; University of Houston Ding, Wenyue; University of Houston Li, Tzu-Han; University of Houston Mahanthappa, Mahesh; University of Minnesota, Department of Chemical Engineering & Materials Science; University of Wisconsin–Madison, Department of Chemistry Conrad, Jacinta; University of Houston, Robertson, Megan; University of Houston, Chemical and Biomolecular Engineering Page 1 of 32 Polymer Chemistry Dispersity Control in Atom Transfer Radical Polymerizations through Addition of Phenyl Hydrazine Vivek Yadav,a Nairah Hashmi,a Wenyue Ding,a Tzu-Han Li,c Mahesh K. Mahanthappa,d Jacinta C. Conrad,*a and Megan L. Robertson*a,b a Department of Chemical and Biomolecular Engineering University of Houston, Houston, TX 77204-4004 b Department of Chemistry University of Houston, Houston, TX 77204-4004 c Materials Engineering Program University of Houston, Houston, TX 77204-4004d Department of Chemical Engineering and Materials Science University of Minnesota, Minneapolis, MN 55455 *Email: [email protected], [email protected] †Electronic Supplementary Information available online. 1 Polymer Chemistry Page 2 of 32 Abstract Molar mass dispersity in polymers affects a wide range of important material properties, yet there are few synthetic methods that systematically generate unimodal distributions with specifically tailored dispersities. Here, we describe a general method for tuning the dispersity of polymers synthesized via atom transfer radical polymerization (ATRP). Addition of varying amounts of phenyl hydrazine (PH) to the ATRP of tert-butyl acrylate led to significant deviations in the reaction kinetics, yielding poly(tert-butyl acrylate) with dispersities Đ = 1.08 – 1.80.
    [Show full text]
  • Oct 15, Controlled Polymerizations by Ki-Young Yoon
    Wednesday Meeting Controlled Polymerizations 10/15/2014 Ki-Young Yoon Organometallics : A Friend of Total Synthesis Total Synthesis Organometallics e.g. Barry Trost Organometallics : A Friend of Polymer Synthesis Organometallics Polymer Synthesis e.g. Bob Grubbs Organometallics : Still Blue Ocean Area Total Synthesis Organometallics Polymer Synthesis In theory, every organometallic reaction can branch out into polymerization Organometallics : Still Blue Ocean Area Hydrolytic kinetic resolution E. Jacobson Science 1997, 277, 936 J. Coates J. Am. Chem. Soc 2008, 130, 17658 Enantioselective Polymerization of Epoxides: the first person who borrows Jacobson’s catalyst for the polymerization Enantioselective Polymerization of Epoxides: Catalyst which Jacobson should have used for the polymerization 10 years ago Contents 1. Polymerization Mechanism o Step-growth polymerization o Chain-growth polymerization o Step-growth vs. Chain-growth 2. Efforts to turn Step-growth polymerization into Chain-growth polymerization o GRIM polymerization o Pd-catalyzed chain-growth polymerization Polymer is a mixture Polymer is not a pure substance. It is a mixture Organic reaction Single pure product Polymerization mixture Molecular Weight Distribution Irresponsible polymer chemist Average Molecular Weight mixture - Mn, Mw, PDI (=Mw/Mn) Polymer molecular weight Number Average Molecular Weight, Mn Danny’s Credit Grade Credit*Gr ade PhysOrg 3 4.0 (A) 12 Calculus 2 3.0 (B) 6 Weight Average Molecular Weight, Mw History 1 2.0 (C) 2 Mn (4.0+3.0+2.0) =3 SEC/3 trace
    [Show full text]
  • Effect of Chain Transfer to Polymer in Conventional and Living Emulsion Polymerization Process
    processes Article Effect of Chain Transfer to Polymer in Conventional and Living Emulsion Polymerization Process Hidetaka Tobita ID Department of Materials Science and Engineering, University of Fukui, 3-9-1 Bunkyo, Fukui 910-8507, Japan; [email protected]; Tel.: +81-776-27-8767 Received: 28 December 2017; Accepted: 5 February 2018; Published: 7 February 2018 Abstract: Emulsion polymerization process provides a unique polymerization locus that has a confined tiny space with a higher polymer concentration, compared with the corresponding bulk polymerization, especially for the ab initio emulsion polymerization. Assuming the ideal polymerization kinetics and a constant polymer/monomer ratio, the effect of such a unique reaction environment is explored for both conventional and living free-radical polymerization (FRP), which involves chain transfer to the polymer, forming polymers with long-chain branches. Monte Carlo simulation is applied to investigate detailed branched polymer architecture, including 2 the mean-square radius of gyration of each polymer molecule, <s >0. The conventional FRP shows a very broad molecular weight distribution (MWD), with the high molecular weight region conforming to the power law distribution. The MWD is much broader than the random branched 2 polymers, having the same primary chain length distribution. The expected <s >0 for a given MW is much smaller than the random branched polymers. On the other hand, the living FRP shows a much narrower MWD compared with the corresponding random branched polymers. Interestingly, 2 the expected <s >0 for a given MW is essentially the same as that for the random branched polymers. Emulsion polymerization process affects branched polymer architecture quite differently for the conventional and living FRP.
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 6,897.278 B2 Wilczek (45) Date of Patent: May 24, 2005
    USOO6897278B2 (12) United States Patent (10) Patent No.: US 6,897.278 B2 Wilczek (45) Date of Patent: May 24, 2005 (54) BRANCHED POLYOLEFIN SYNTHESIS K. Ishizu et al., Synthesis of AB Type Diblock Macromono mers, J. Poly. Sci. Polym. Chem., 29,923–927, 1991. (75) Inventor: Lech Wilczek, Wilmington, DE (US) J. J. Ma et al., Poly(ethylene-co-propylene)-g-polystyrene (73) Assignee: E. I. du Pont de Nemours and through Macomer Polymerization: Preparation, Morphol Company, Wilmington, DE (US) ogy, and Structure-Properties Relationships, J. Poly. Sci. Polym. Chem., 24, 2853–2866, 1986. (*) Notice: Subject to any disclaimer, the term of this P. Chaumont et al., Synthese Anionique de Polymeres Com patent is extended or adjusted under 35 portant Une Fonction Vinylsilane a Lune ou aux deux U.S.C. 154(b) by 184 days. extremites de la Chaine Macromoleculaire, Eur: Polym. J., 15, 537-540, 1979. (21) Appl. No.: 10/772,194 Y. Gnanou et al., The Ability of Macromonomers to Copo (22) Filed: Feb. 4, 2004 lymerize: A Critical Review with New Developments, Mak (65) Prior Publication Data romol. Chem., 190, 577–588, 1989. M. Arnold et al., On the Reactivity of Syryl-Terminated US 2004/0167305 A1 Aug. 26, 2004 Polystyrene Macromonomers in Anionic Copolymerization Related U.S. Application Data with Butadiene, Makromol. Chem., 192, 285–292, 1991. Slagowski et al., Upper Molecular Weight Limit for the (60) Division of application No. 10/316,454, filed on Dec. 11, 2002, now Pat. No. 6,740,723, which is a continuation-in Characterization of Polystyrene in Gel Permeation Chroma part of application No.
    [Show full text]
  • 1.1 Basic Polymer Chemistry 1.2 Polymer Nomenclature 1.3 Polymer
    1.1 Basic Polymer Chemistry 1.2 Polymer Nomenclature Polymers are the largest class of soft materials: over Polymer = 100 billion pounds of polymers made in US each year Monomer = Classification systems Polymer = Typical physical state? Mechanisms of chain growth Oligomer = Typical physical state? Polymerization = 1.3 Polymer Synthesis 1.4 Chain Growth Polymerization Two synthetic methods Addition polymerization Chain growth/addition polymerization One molecule adds to another with no net loss of atoms (high atom economy) Individual steps are typically rapid (msec, sec) Discrete steps Step growth polymerization Propagation rate >> termination rate What happens if the reaction runs longer? Do the chains get longer? Do you just get more chains? 1 1.5 Chain Growth Polymerization 1.6 Monomers for Chain Growth Addition polymerization Polymers form by… What’s in the polymerization mixture? Defining features Useful monomers for chain growth CH3 Cl CH2 CH CH CH Monomer Polymer H2C H2C H2C H2C ethylenepropylene styrene vinyl chloride nCH2 CH (CH2 CH)n X X O N X X C O O-CH3 CH2 O CH3 C HC C nCH2 CH (CH2 CH O)n CH C CH CH CH O H2C H2C 3 H2C H2C vinyl acetate methyl methacrylate butadiene acrylonitrile 1.7 Chain Growth Polymerization 2.1 Radical Polymerization Mechanisms to link monomers together Three steps to radical polymerization Radical Initiation Cationic (1) RO OR 2RO Anionic Transition metal catalysis (2) RO + H2C CH RO CH2 CH R R Propagation RO CH2 CH + H2C CH RO CH2 CH CH2 CH R R R R Termination 2 2.2 Radical
    [Show full text]
  • Reassessment of Free-Radical Polymerization Mechanism of Allyl Acetate Based on End-Group Determination of Resulting Oligomers by MALDI-TOF-MS Spectrometry
    #2009 The Society of Polymer Science, Japan Reassessment of Free-Radical Polymerization Mechanism of Allyl Acetate Based on End-Group Determination of Resulting Oligomers by MALDI-TOF-MS Spectrometry By Akira MATSUMOTO,Ã Takeo KUMAGAI, Hiroyuki AOTA, Hideya KAWASAKI, and Ryuichi ARAKAWA Allyl monomers polymerize only with difficulty and yield polymers of medium-molecular-weight or oligomers. This is attributable to ‘‘degradative monomer chain transfer.’’ However, the well-known allyl polymerization mechanism is based on only the kinetic data but any structural identification is not given. Allyl acetate (AAc), a most typical allyl monomer, was polymerized radically and the resultant oligomeric poly(AAc)s were characterized using MALDI-TOF-MS spectrometry in order to reassess the AAc polymerization mechanism proposed by Litt and Eirich. The induced decomposition of benzoyl peroxide by both growing polymer radical and monomeric allyl radical was presumed but it was never of importance. Then, the fate of resonance-stabilized monomeric allyl radical generated via monomer chain transfer of growing polymer radical was pursued in terms of the competition between the initiation of a new polymer chain and the chain stopping reaction of a growing polymer radical providing monomeric allyl groups as the initial and terminal end-groups, respectively. The À2 monomer chain transfer constant was estimated to be 3:73 Â 10 from the Pn value of poly(AAc) obtained at a low initiator concentration where the coupling termination of growing polymer radical with
    [Show full text]
  • Polymer Chemistry (C212)
    Polymer Chemistry (C212) Prof. Dr. Afaf M. Abdelhameed [email protected] [email protected] Anionic Addition Polymerization The mechanism of anionic polymerization is a kind of repetitive conjugate addition reaction (the "Michael reaction" in organic chemistry).This polymerization is carried out through a carbanion active species. Like all addition polymerizations, it takes place in three steps: chain initiation, chain propagation, and chain termination. Anionic polymerizations are used in the production of polydiene synthetic rubbers, solution styrene/butadiene rubbers (SBR), and styrenic thermoplastic elastomers. Monomer Characteristics In order for polymerization to occur with vinyl monomers, the substituents on the double bond must be able to stabilize a negative charge. Stabilization occurs through delocalization of the negative charge. Because of the nature of the carbanion propagating center, substituents that react with bases or nucleophiles either must not be present or be protected. Examples of vinyl monomers. Vinyl monomers with substituents that stabilize the negative charge through charge delocalization, undergo polymerization without termination or chain transfer.[2] These monomers include styrene, dienes, methacrylate, vinyl pyridine,aldehydes, epoxide, episulfide, cyclic siloxane, and lactones. Polar monomers, using controlled conditions and low temperatures, can undergo anionic polymerization. However, at higher temperatures they do not produce living stable, carbanionic chain ends because their polar substituents can undergo side reactions with both initiators and propagating chain centers. The effects of counterion, solvent, temperature, Lewis base additives, and inorganic solvents have been investigated to increase the potential of anionic polymerizations of polar monomers.[2] Polar monomers include acrylonitrile, cyanoacrylate, propylene oxide, vinyl ketone, acrolein, vinyl sulfone, vinyl sulfoxide, vinyl silane and isocyanate.
    [Show full text]
  • Dormant Polymers and Their Role in Living and Controlled Polymerizations; Influence on Polymer Chemistry, Particularly on the Ring Opening Polymerization
    polymers Review Dormant Polymers and Their Role in Living and Controlled Polymerizations; Influence on Polymer Chemistry, Particularly on the Ring Opening Polymerization Stanislaw Penczek *, Julia Pretula and Piotr Lewi ´nski Centre of Molecular and Macromolecular Studies of Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland; [email protected] (J.P.); [email protected] (P.L.) * Correspondence: [email protected]; Tel.: +48-42-681-9815 Received: 2 November 2017; Accepted: 23 November 2017; Published: 25 November 2017 Abstract: Living polymerization discovered by Professor Szwarc is well known to all chemists. Some of the living polymerizations involve dormancy, a process in which there is an equilibrium (or at least exchange) between two types of living polymers, namely active at the given moment and dormant at this moment and becoming active in the process of activation. These processes are at least equally important although less known. This mini review is devoted to these particular living polymerizations, mostly polymerizations by the Ring-Opening Polymerization mechanisms (ROP) compared with some selected close to living vinyl polymerizations (the most spectacular is Atom Transfer Radical Polymerization (ATRP)) involving dormancy. Cationic polymerization of tetrahydrofuran was the first one, based on equilibrium between oxonium ions (active) and covalent (esters) dormant species, i.e., temporarily inactive, and is described in detail. The other systems discussed are polymerization of oxazolines and cyclic esters as well as controlled radical and cationic polymerizations of vinyl monomers. Keywords: dormant polymers; living polymerization; controlled polymerization; ring-opening polymerization 1. Introduction Professor Michael (Michał in Polish) Szwarc’s contributions to the chemical science are not only related to polymers and to his discovery of living and (less known) dormant polymers [1].
    [Show full text]
  • Anionic Polymerization
    7 ANIONIC POLYMERIZATION Roderic Quirk 7.1 INTRODUCTION ion pairs (3), and solvent-separated ion pairs (4); Mt+ rep- resents a metallic counterion such as an alkali metal cation. This chapter describes the general aspects of anionic poly- In hydrocarbon media, species (1–3) would be expected merization of vinyl, carbonyl, and heterocyclic monomers, to predominate. Polar solvents tend to shift the Winstein with emphasis on alkyllithium-initiated polymerization of spectrum to the right, that is, toward more reactive, less vinyl monomers. Anionic polymerization is defined as a associated, more ionic species. With respect to the nature chain reaction polymerization in which the active centers of the bonding in organoalkali metal compounds, it is gen- for propagation are anions, which can be in the form of erally agreed that the carbon–alkali metal bond is ionic free ions, paired ions, or aggregated species [1]. The term for sodium, potassium, rubidium, and cesium. In contrast, “anion” will be considered as an atom or group of atoms experimental evidence and theoretical studies indicate that with a negative charge and an unshared pair of electrons. the carbon–lithium bond includes some covalent charac- Anions can be considered to be the conjugate bases of the ter, that is, it is a semipolar bond [3, 7]; however, there is corresponding Bronsted acids, as shown in Equation 7.1. disagreement about the relative amounts of covalent versus ionic bonding [8]. − + − − n RMt R−,Mt+ R // Mt+ R +Mt+ C H C + H (7.1) (RMt)n 1 2 3 4 5 (7.2) One unique aspect of anionic polymerization is that the The stability and reactivity of anionic species can be reactive propagating species are not transient intermediates.
    [Show full text]
  • Haloaldebyde Polymers. I. Chain Termination in Anionic Chloral Polymerization
    Polymer Journal, Vol. 7, No. 2, pp 186-194 (1975) Haloaldebyde Polymers. I. Chain Termination in Anionic Chloral Polymerization P. KusisA* and 0. VoGL Polymer Science and Engineering, University of Massachusetts, Amherst, Massachusetts 01002 (Received May 7, 1974) ABSTRACT: Anionic chloral polymerization can be carried out under certain circum­ stances in the presence of acylating agents, such as acetyl chloride and benzoyl chloride. Parts of these polymers exhibit a much improved thermal stability. Introduction of acyl end groups into the polymer permits an estimation of the molecular weight of the polymer. DTG was found to be an excellent technique with which to follow the extent of reaction, to assist in the examination of this kind of end group and to follow the thermal stability of chloral polymers. KEY WORDS Haloaldehyde Polymers I Chloral 1Anionic Polymeri- zation I Chain Transfer I Chain Termination I Acetyl Chloride 1 Benzoyl Chloride I Triphenyl Phosphine as Initiator I End Groups 1 Thermal Degradation I Our knowledge of the polymerization of chlo­ stable end groups into polychloral. It also ral has recently been greatly advanced with the provided a method for estimating the minimum development of a new technique to make homo­ number-average molecular weight of the stable and copolymers of chloral directly in a useful polychloral fraction. form. 1•2 Chloral polymerizes rapidly to high conver­ EXPERIMENTAL sion with anionic initiators. Cationic polymeri­ zation is now also well established, however, it Materials is extremely slow. 3 Chloral (obtained from the Diamond Shamrock Because chloral polymers of high chloral con­ Company) was allowed to reflux over phospho­ tent are insoluble and infusable, much of the rous pentoxide for 24 hr.
    [Show full text]
  • Redox Polymerization
    Prog. Polym. Sci. 24 (1999) 1149–1204 Redox polymerization A.S. Sarac* Department of Chemistry, Faculty of Science, Istanbul Technical University, Maslak 80626, Istanbul, Turkey Received 15 July 1996; received in revised form 23 June 1999; accepted 10 August 1999 Abstract Virtually all free-radical chain reactions require a separate initiation step in which a radical species is generated in the reaction mixture. Some types of chain reactions are initiated by adding a stable free radical, one that shows little or no tendency for self-combination, directly to the reactants, but a separate initiation step is still involved because these stable radicals are most often inorganic ions or metals. A very effective method of generating free radicals under mild conditions is by one-electron transfer reactions, the most effective of which is redox initiation. This method has found wide application for initiating polymerization reactions and has industrial importance, e.g. in low-temperature emulsion polymerizations. In this review, in addition to the classical examples of redox pairs, recently employed metal-ion–organic- compound redox systems, electrochemical regeneration of reduced metal ions, redox initiation in nonaqueous media and transition metal organic halide initiators and metal chelate initiators are all reviewed. q 1999 Elsevier Science Ltd. All rights reserved. Keywords: Free-radical chain reactions; Redox initiation; Redox pairs; Electroinduced polymerization; Vinyl polymerization; Metal ion oxidation Contents 1. Introduction ..................................................................1150
    [Show full text]