13 Addition Polymerization: Preparation of Polystyrene Using Two Types of Initiators
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Oligomeric A2 + B3 Approach to Branched Poly(Arylene Ether Sulfone)
“One-Pot” Oligomeric A 2 + B 3 Approach to Branched Poly(arylene ether sulfone)s: Reactivity Ratio Controlled Polycondensation A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science By ANDREA M. ELSEN B.S., Wright State University, 2007 2009 Wright State University WRIGHT STATE UNIVERSITY SCHOOL OF GRADUATE STUDIES June 19, 200 9 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Andrea M. Elsen ENTITLED “One-Pot” Oligomeric A2 + B3 Approach to Branched Poly(arylene ether sulfone)s: Reactivity Ratio Controlled Polycondenstation BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science . _________________________ Eric Fossum, Ph.D. Thesis Director _________________________ Kenneth Turnbull, Ph.D. Department Chair Committee on Final Examination ____________________________ Eric Fossum, Ph.D. ____________________________ Kenneth Turnbull, Ph.D. ____________________________ William A. Feld, Ph.D. ____________________________ Joseph F. Thomas, Jr., Ph.D. Dean, School of Graduate Studies Abstract Elsen, Andrea M. M.S., Department of Chemistry, Wright State University, 2009. “One-Pot” Oligomeric A 2 + B 3 Approach to Branched Poly(arylene ether sulfone)s: Reactivity Ratio Controlled Polycondensation The synthesis of fully soluble branched poly(arylene ether)s via an oligomeric A 2 + B 3 system, in which the A 2 oligomers are generated in situ, is presented. This approach takes advantage of the significantly higher reactivity toward nucleophilic aromatic substitution reactions, NAS, of B 2, 4-Fluorophenyl sulfone, relative to B 3, tris (4-Fluorophenyl) phosphine oxide. The A 2 oligomers were synthesized by reaction of Bisphenol-A and B 2, in the presence of the B 3 unit, at temperatures between 100 and 160 °C, followed by an increase in the reaction temperature to 180 °C at which point the branching unit was incorporated. -
Cationic/Anionic/Living Polymerizationspolymerizations Objectives
Chemical Engineering 160/260 Polymer Science and Engineering LectureLecture 1919 -- Cationic/Anionic/LivingCationic/Anionic/Living PolymerizationsPolymerizations Objectives • To compare and contrast cationic and anionic mechanisms for polymerization, with reference to free radical polymerization as the most common route to high polymer. • To emphasize the importance of stabilization of the charged reactive center on the growing chain. • To develop expressions for the average degree of polymerization and molecular weight distribution for anionic polymerization. • To introduce the concept of a “living” polymerization. • To emphasize the utility of anionic and living polymerizations in the synthesis of block copolymers. Effect of Substituents on Chain Mechanism Monomer Radical Anionic Cationic Hetero. Ethylene + - + + Propylene - - - + 1-Butene - - - + Isobutene - - + - 1,3-Butadiene + + - + Isoprene + + - + Styrene + + + + Vinyl chloride + - - + Acrylonitrile + + - + Methacrylate + + - + esters • Almost all substituents allow resonance delocalization. • Electron-withdrawing substituents lead to anionic mechanism. • Electron-donating substituents lead to cationic mechanism. Overview of Ionic Polymerization: Selectivity • Ionic polymerizations are more selective than radical processes due to strict requirements for stabilization of ionic propagating species. Cationic: limited to monomers with electron- donating groups R1 | RO- _ CH =CH- CH =C 2 2 | R2 Anionic: limited to monomers with electron- withdrawing groups O O || || _ -C≡N -C-OR -C- Overview of Ionic Chain Polymerization: Counterions • A counterion is present in both anionic and cationic polymerizations, yielding ion pairs, not free ions. Cationic:~~~C+(X-) Anionic: ~~~C-(M+) • There will be similar effects of counterion and solvent on the rate, stereochemistry, and copolymerization for both cationic and anionic polymerization. • Formation of relatively stable ions is necessary in order to have reasonable lifetimes for propagation. -
Photopolymerization Reactions Under Visible Lights: Principle, Mechanisms and Examples of Applications J.P
Progress in Organic Coatings 47 (2003) 16–36 Photopolymerization reactions under visible lights: principle, mechanisms and examples of applications J.P. Fouassier∗, X. Allonas, D. Burget Département de Photochimie Générale, UMR n◦7525, Ecole Nationale Supérieure de Chimie, 3 Rue Alfred Werner, 68093 Mulhouse Cedex, France Received 22 June 2002; received in revised form 19 November 2002; accepted 20 December 2002 Abstract A general overview of visible light photoinduced polymerization reactions is presented. Reaction mechanisms as well as practical efficiency in industrial applications are discussed. Several points are investigated in detail: photochemical reactivity of photoinitiating system (PIS), short overview of available photoinitiators (PIs) and photosensitizers (PSs), mechanisms involved in selected examples of dye sensitized polymerization reactions, examples of applications in pigmented coatings usable as paints, textile printing, glass reinforced fibers, sunlight curing of waterborne latex paints, curing of inks, laser-induced polymerization reactions, high speed photopolymers for laser imaging, PISs for computer-to-plate systems. © 2003 Elsevier Science B.V. All rights reserved. Keywords: Photopolymerization; Visible light; Radiation curing 1. Introduction Radical, cationic and anionic polymerizations can be ini- tiated by the excitation of suitable photoinitiating systems Radiation curing technologies provide a number of eco- (PISs) under lights. Most of these systems were originally nomic advantages over the usual thermal operation among sensitive to UV lights but by now a large number of various them: rapid through cure, low energy requirements, room systems allows to extend the spectral sensitivity to visible temperature treatment, non-polluting and solvent-free for- lights. According to the applications which are developed, mulations, low costs. -
Trade Names and Manufacturers
Appendix I Trade names and manufacturers In this appendix, some trade names of various polymeric materials are listed. The list is intended to cover the better known names but it is by no means exhaustive. It should be noted that the names given may or may not be registered. Trade name Polymer Manufacturer Abson ABS polymers B.F. Goodrich Chemical Co. Acrilan Polyacrylonitrile Chemstrand Corp. Acrylite Poly(methyl methacrylate) American Cyanamid Co. Adiprene Polyurethanes E.I. du Pont de Nemours & Co. Afcoryl ABS polymers Pechiney-Saint-Gobain Alathon Polyethylene E.I. du Pont de Nemours & Co. Alkathene Polyethylene Imperial Chemical Industries Ltd. Alloprene Chlorinated natural rubber Imperial Chemical Industries Ltd. Ameripol cis-1 ,4-Polyisoprene B.F. Goodrich Chemical Co. Araldite Epoxy resins Ciba (A.R.L.) Ltd. Arnel Cellulose triacetate Celanese Corp. Arnite Poly(ethylene terephthalate) Algemene Kunstzijde Unie N.Y. Baypren Polychloroprene Farbenfabriken Bayer AG Beetle Urea-formaldehyde resins British Industrial Plastics Ltd. Ben vic Poly(vinyl chloride) Solvay & Cie S.A. Bexphane Polypropylene Bakelite Xylonite Ltd. Butacite Poly( vinyl butyral) E.I. du Pont de Nemours & Co. Butakon Butadiene copolymers Imperial Chemical Industries Ltd. Butaprene Styrene-butadiene copolymers Firestone Tire and Rubber Co. Butvar Poly(vinyl butyral) Shawinigan Resins Corp. Cap ran Nylon 6 Allied Chemical Corp. Carbowax Poly(ethylene oxide) Union Carbide Corp. Cariflex I cis-1 ,4-Polyisoprene Shell Chemical Co. Ltd. Carina Poly(vinyl chloride) Shell Chemical Co. Ltd. TRADE NAMES AND MANUFACTURERS 457 Trade name Polymer Manufacturer Carin ex Polystyrene Shell Chemical Co. Ltd. Celcon Formaldehyde copolymer Celanese Plastics Co. Cellosize Hydroxyethylcellulose Union Carbide Corp. -
Polymer Dynamics
Polymer Dynamics 2017 School on Soft Matters and Biophysics Instructor: Alexei P. Sokolov, e-mail: [email protected] Text: Instructor's notes with supplemental reading from current texts and journal articles. Please, have the notes printed out before each lecture. Books (optional): M.Doi, S.F.Edwards, “The Theory of Polymer Dynamics”. Y.Grosberg, A.Khokhlov, “Statistical Physics of Macromolecules”. J.Higgins, H.Benoit, “Polymers and Neutron Scattering”. 1 Course Content: I. Introduction II. Experimental methods for analysis of molecular motions III. Vibrations IV. Fast and Secondary Relaxations V. Segmental Dynamics and Glass Transition VI. Chain Dynamics and Viscoelastic Properties VII. Rubber Elasticity VIII. Concluding Remarks 2 INTRODUCTION Polymers are actively used in many technologies Traditional technologies: Even better perspectives for use in novel technologies: Example: Light-weight materials Boeing-787 “Dreamliner” 80% by volume is plastic Materials for energy generation Example: polymer solar cells Materials for energy storage Example: Polymer-based Li battery Polymers have huge potential for applications in Bio-medical field “Smart” materials, stimuli-responsive, self-healing … 3 Polymers Polymers are long molecules They are constructed by covalently bonded structural units – monomers Main difference between properties of small molecules and polymers is related to the chain connectivity Advantages of Polymeric Based Materials: Easy processing, relatively cheap manufacturing Light weight (contain mostly light elements like C, H, O) Unique viscoelastic properties (e.g. rubber elasticity) Extremely broad tunability of macroscopic properties 4 Definitions o Monomer – repeat unit, structural block of the polymer chain o Oligomer – short chains, ~ 3-10 monomers o Polymers – long chains, usually hundreds of monomers o Degree of polymerization – number of monomers in the polymer chain Molecular weight: Weight of the molecule M [g/mol]. -
Polymer Exemption Guidance Manual POLYMER EXEMPTION GUIDANCE MANUAL
United States Office of Pollution EPA 744-B-97-001 Environmental Protection Prevention and Toxics June 1997 Agency (7406) Polymer Exemption Guidance Manual POLYMER EXEMPTION GUIDANCE MANUAL 5/22/97 A technical manual to accompany, but not supersede the "Premanufacture Notification Exemptions; Revisions of Exemptions for Polymers; Final Rule" found at 40 CFR Part 723, (60) FR 16316-16336, published Wednesday, March 29, 1995 Environmental Protection Agency Office of Pollution Prevention and Toxics 401 M St., SW., Washington, DC 20460-0001 Copies of this document are available through the TSCA Assistance Information Service at (202) 554-1404 or by faxing requests to (202) 554-5603. TABLE OF CONTENTS LIST OF EQUATIONS............................ ii LIST OF FIGURES............................. ii LIST OF TABLES ............................. ii 1. INTRODUCTION ............................ 1 2. HISTORY............................... 2 3. DEFINITIONS............................. 3 4. ELIGIBILITY REQUIREMENTS ...................... 4 4.1. MEETING THE DEFINITION OF A POLYMER AT 40 CFR §723.250(b)... 5 4.2. SUBSTANCES EXCLUDED FROM THE EXEMPTION AT 40 CFR §723.250(d) . 7 4.2.1. EXCLUSIONS FOR CATIONIC AND POTENTIALLY CATIONIC POLYMERS ....................... 8 4.2.1.1. CATIONIC POLYMERS NOT EXCLUDED FROM EXEMPTION 8 4.2.2. EXCLUSIONS FOR ELEMENTAL CRITERIA........... 9 4.2.3. EXCLUSIONS FOR DEGRADABLE OR UNSTABLE POLYMERS .... 9 4.2.4. EXCLUSIONS BY REACTANTS................ 9 4.2.5. EXCLUSIONS FOR WATER-ABSORBING POLYMERS........ 10 4.3. CATEGORIES WHICH ARE NO LONGER EXCLUDED FROM EXEMPTION .... 10 4.4. MEETING EXEMPTION CRITERIA AT 40 CFR §723.250(e) ....... 10 4.4.1. THE (e)(1) EXEMPTION CRITERIA............. 10 4.4.1.1. LOW-CONCERN FUNCTIONAL GROUPS AND THE (e)(1) EXEMPTION................. -
Chain-Growth Polymerization, Version of 1/5/05
Chapter Three, Chain-growth polymerization, Version of 1/5/05 3 Chain-growth polymerization 3.1 Introduction We indicated in Chapter 1 that the category of addition polymers is best characterized by the mechanism of the polymerization reaction, rather than by the addition reaction itself. This is known to be a chain mechanism, so in the case of addition polymers we have chain reactions producing chain molecules. One thing to bear in mind is the two uses of the word chain in this discussion. The word chain continues to offer the best description of large polymer molecules. A chain reaction, on the other hand, describes a whole series of successive events triggered by some initial occurrence. We sometimes encounter this description of highway accidents in which one traffic mishap on a fogbound highway results in a pileup of colliding vehicles that can extend for miles. In nuclear reactors a cascade of fission reactions occurs which is initiated by the capture of the first neutron. In both of these examples some initiating event is required. This is also true in chain-growth polymerization. In the above examples the size of the chain can be measured by considering the number of automobile collisions that result from the first accident, or the number of fission reactions which follow from the first neutron capture. When we think about the number of monomers that react as a result of a single initiation step, we are led directly to the degree of polymerization of the resulting molecule. In this way the chain mechanism and the properties of the polymer chains are directly related. -
Worksheet: Addition Polymerization
Worksheet: Addition Polymerization In this worksheet, we will practice defining an addition polymerization and determining the structure of an addition polymer from the monomer reactant. Q1: Addition polymers may be made from many types of monomer. What is the most common type of monomer used to make addition polymers? A Alcohols B Carboxylic acids C Alkanes D Alkenes E Alkynes Q2: Which of the following is the best description of an addition polymer? A A polymer that can be easily added to other polymers B A polymer made by linking monomers together, without forming by-products C A polymer made by linking different monomers in a well-defined sequence D A polymer made by linking monomers together and releasing water or other small molecules E A polymer that can be linked to itself to form a longer polymer Q3: Poly(styrene) is an addition polymer made from the monomer styrene. If 100 kg of styrene reacts completely to form polystyrene, what mass of polystyrene is produced? Q4: Which of the following molecules can be polymerized? H H O H H H H H H C C C A C C C C H B H CC H H H O H H H H H H H O H H D H C C CC H E HHC H HH H Q5: Which of the following chemicals is used as a monomer for the following polymer? A Butanol H H CC B But-1-ene H C H C Butane 2 5 n D Butanoic acid E But-2-ene Q6: Which of the following chemicals is used as a monomer for the following polymer? A 1, 1, 2 -Trichloroethene Cl H B 1, 1, 1 -Trichloroethene CC C 1, 2-Dichloroethene Cl H n D Chloroethene E 1, 1-Dichloroethene Q7: Which of the following diagrams shows two -
Aim: to Prepare Block Copolymers of Methyl Methacrylate (MMA) and Styrene
Conducting A Reversible-Deactivation Radical Polymerization (RDRP) Aim: To Prepare Block Copolymers of Methyl Methacrylate (MMA) and Styrene. Polymers are ubiquitous in the modern world. They provide tremendous value because the chemical and physical properties of these materials are determined by the monomers that are used to put them together. One of the most powerful methods to construct polymers is radical-chain polymerization and this method is used in the commercial synthesis of polymers everyday. Methyl methacrylate is polymerized to form poly(methyl methacrylate) (PMMA) which is also known as acrylic glass or Plexiglas (about 2 billion pounds per year in the US). This material is lightweight, strong and durable. The polymer chains are rigid due to the tetrasubstituted carbon atom in the polymer backbone and they have excellent optical clarity. As a consequence, these materials are used in aircraft windows, glasses, skylights, signs and displays. Polystyrene (PS), which can also be synthesized from radical chain polymerization, has found extensive use as a material (also approximately 2 billion pounds per year in the US). One of the forms of PS, Styrofoam, is used extensively to make disposable cups, thermal insulation, and cushion for packaging. Scheme 1. Radical polymerization of methyl methacrylate or styrene. While there are extensive uses for these polymers, when synthesizing any material using a free-radical polymerization, samples are obtained with limited control over molecular weight and molecular weight distribution. New methods have been developed directly at Carnegie Mellon (https://www.cmu.edu/maty/) which lead to improved control in this process. This new method is a reversible-deactivation of the polymerization reaction where highly reactive radicals toggle back and forth between an active state, where the polymer chain is growing, and a dormant state, where the polymer chain is capped (Scheme 2). -
Biodegradable Polymeric Biomaterials in Different Forms for Long-Acting
University of Tennessee Health Science Center UTHSC Digital Commons Theses and Dissertations (ETD) College of Graduate Health Sciences 5-2017 Biodegradable Polymeric Biomaterials in Different Forms for Long-acting Contraception and Drug Delivery to the Eye and Brain Dileep Reddy Janagam University of Tennessee Health Science Center Follow this and additional works at: https://dc.uthsc.edu/dissertations Part of the Pharmaceutics and Drug Design Commons Recommended Citation Janagam, Dileep Reddy (http://orcid.org/0000-0002-7235-7709), "Biodegradable Polymeric Biomaterials in Different Forms for Long-acting Contraception and Drug Delivery to the Eye and Brain" (2017). Theses and Dissertations (ETD). Paper 425. http://dx.doi.org/10.21007/etd.cghs.2017.0429. This Dissertation is brought to you for free and open access by the College of Graduate Health Sciences at UTHSC Digital Commons. It has been accepted for inclusion in Theses and Dissertations (ETD) by an authorized administrator of UTHSC Digital Commons. For more information, please contact [email protected]. Biodegradable Polymeric Biomaterials in Different Forms for Long-acting Contraception and Drug Delivery to the Eye and Brain Document Type Dissertation Degree Name Doctor of Philosophy (PhD) Program Pharmaceutical Sciences Track Pharmaceutics Research Advisor Tao L. Lowe, Ph.D. Committee Joel Bumgardner, Ph.D. James R. Johnson, Ph.D. Bernd Meibohm, Ph.D. Duane D. Miller, Ph.D. ORCID http://orcid.org/0000-0002-7235-7709 DOI 10.21007/etd.cghs.2017.0429 Comments Two year embargo expires -
Heats of Combustion and Solution of Liquid Styrene and Solid Polystyrene, and the Heat of Polymerization of Styrenel by Donald E
U. S. Department of Commerce Research Paper RP1801 National Bureau of Sta ndards Volume 38, June 1947 Part of the Journal of Research of the National Bureau of Standards Heats of Combustion and Solution of Liquid Styrene and Solid Polystyrene, and the Heat of Polymerization of Styrenel By Donald E. Roberts, William W . Walton, and Ralph S. Jessup Bomb-calorimetric m easurements have yielded for the heats of combustion (-t:"Hc0) at 25° C of liquid styrcne and solid polystyrene to form gaseous carbon dioxide and liquid watcr the values 4394.88 ± 0.67 into kj/mole (1050.58 ± 0.14 kcal/mole) , and 4325.09 ± 0.42 int. kj/CsH s-unit (1033.89 ± 0.10 kcal/CsHs-unit), resp ectively, and for the heat of polymerization of liquid styrene to solid polystyrene at 25° C the value 69.79 ± 0.66 into kj/mole (16.68 ± 0.16 kcal/mole) . The results obtained on two samples of polystyrcne of different molecular weight were in agreement within the p'recision of the measurements. M easurements of the heat of olution of solid polystyrenc in liquid monomeric styrene gave the value 3.59 ± 0.21 l,nt. kj (0.86 ± 0.05 kcal) evolved per CsH s-unit of polystyrene at 25 ° C. Addition of this to the value for the heat of polymerization of liquid styrene to solid polystyrene gives the value 73.38 ± 0.69 into kj (17.54 ± 0.16 kcal) per mole of styrenc for the heat of polymerization of liquid styrene at 25° C, when the final product is a solution of polystyrene in styrene containing 6.9 percent by weight of polystyrene. -
TEST - Alkenes, Alkadienes and Alkynes
Seminar_2 1. Nomenclature of unsaturated hydrocarbons 2. Polymerization 3. Reactions of the alkenes (table) 4. Reactions of the alkynes (table) TEST - Alkenes, alkadienes and alkynes. Polymerization • Give the names • Write the structural formula • Write all isomeric compounds • The processes explanation 1. NOMENCLATURE OF UNSATURATED HYDROCARBONS ALKENE NOMENCLATURE We give alkenes IUPAC names by replacing the -ane ending of the corresponding alkane with -ene . The two simplest alkenes are ethene and propene. Both are also well known by their common names ethylene and propylene. Ethylene is an acceptable synonym for ethene in the IUPAC system. Propylene, isobutylene, and other common names ending in -ylene are not acceptable IUPAC names. 1. The longest continuous chain that includes the double bond forms the base name of the alkene. 2. Chain is numbered in the direction that gives the doubly bonded carbons their lower numbers. 3. The locant (or numerical position) of only one of the doubly bonded carbons is specified in the name; it is understood that the other doubly bonded carbon must follow in sequence. 4. Carbon-carbon double bonds take precedence over alkyl groups and halogens in determining the main carbon chain and the direction in which it is numbered. 5. The common names of certain frequently encountered alkyl groups, such as isopropyl and tert-butyl, are acceptable in the IUPAC system. Three alkenyl groups--vinyl, allyl, and isopropenyl--are treated the same way: 6. When a CH 2 group is doubly bonded to a ring, the prefix methylene is added to the name of the ring: 7. Cycloalkenes and their derivatives are named by adapting cycloalkane terminology to the principles of alkene nomenclature: No locants are needed in the absence of substituents; it is understood that the double bond connects C-1 and C 2.