MacromolecularMacromolecular ChemistryChemistry
Paul J Flory 1910 -1985 Wallace H. Carothers 1896 -1937
Chemistry 367L/392N NomenclatureNomenclature MethodsMethods
Source name (more common use)
– based on monomer name (polystyrene)
IUPAC, constitutional repeating unit
– used in both source and structure names…messy!
Abbreviations and acronyms
– PMMA [poly(methyl methacrylate)]…also common
Trade names
– marketing and technological literature Chemistry 367L/392N ExamplesExamples
CHCH2 1. Poly(1-acetoxyethylene) - structure 2. Poly(vinyl acetate) - source OCCH3 O 1. Poly(but-1-ene-1,4-diyl) CHCHCH CH 2 2 2. Polybutadiene a CHCH 2 1. Poly(1-cyanoethylene) CN 2. Polyacrylonitrile
CH2 1. Poly(methylene) 2. Polyethene; polyethylene O O O 1. Poly[(2,5-dioxotetrahydrofuran- CH 2 3,4-diyl)(1-phenylethylene)] 2. Poly(maleic anhydride-alt -styrene) Ph Chemistry 367L/392N IndustrialIndustrial Influence:Influence: TradeTrade NamesNames
PVC poly (vinylidene chloride) Saran wrap PVC poly (vinyl chloride) Pipe and records PET poly (ethylene teraphthalate) Coke bottles, Dacron Polystyrene Cups and packaging Delrin Bushings and engineering parts Lexan Bullet proof glass Teflon Non stick pans PVDF speakers and microphones Kevlar bullet proof vests Nylon Rope and fiber
Chemistry 367L/392N CommonCommon AbbreviationsAbbreviations Selected examples ABS (acrylonitrile butadiene styrene) LLDPE (linear low density polyethylene) PA66 [polyamide (Nylon) 66] PC (polycarbonate) PET [poly(ethylene terephthalate)] PMMA [poly(methyl methacrylate)] PS (polystyrene) PVC [poly(vinyl chloride)] TP (thermoplastic elastomer polyolefin) PVF2 [poly(vinlylidine fluoride)]
(www.plasticsusa.com/tradename.html)
Chemistry 367L/392N ClassClass NamesNames
Polyolefin Polyester Polyamide Polycarbonate Polyurethane
NamingNaming ““classesclasses ”” ofof polymerspolymers
Chemistry 367L/392N NameName ‘‘emem oror drawdraw ‘‘emem
Cl Br Cl Br Cl Br
CH2-O -CH-CCl-CH2-O-CH-CHCl-CH2-O-CH-CHCl
CH3 CH3 CH3 Poly(ethylene-alt-carbon monoxide) Poly(1-oxopropanediyl)
Poly(vinyl alcohol)
Poly(1-methyl-1-phenylethylene) Chemistry 367L/392N Wallace Hume Carothers 1896 -1937
Carothers, W.H., J. Am. Chem. Soc . 1929, 51 , 2548-58
Chemistry 367L/392N CarothersCarothers PaperPaper
Chemistry 367L/392N AdditionAddition polymerpolymer
Polystyrene
H H H HHH C C ( ) H C CCC n HH
Chemistry 367L/392N AdditionAddition PolymerPolymer
Polyvinylchloride
H Cl HHHH CC CCCC H H HHCl Cl chloroethene poly(chloroethene) aka polyvinylchloride (pvc)
Chemistry 367L/392N CondensationCondensation PolymerPolymer Dacron
O O
n HO C C OH + n HO CH2 CH2 OH heat with an acid catalyst
O O
H2O + C C OCH2 CH2 O n
poly(ethan-1,2-diyl benzene-1,4-dicarboxylate) Chemistry 367L/392N CondensationCondensation PolymerPolymer Nylon 6,6
H H O O N (CH ) N 2 6 C (CH2)4 C H H HO OH 1,6-diaminohexane hexanedioic acid
O O ( N (CH ) N C (CH ) C H2O + 2 6 2 4 )n H H part of a nylon polymer chain
Chemistry 367L/392N Chemistry 367L/392N ProblemsProblemsCarothersCarothers withwith CarothersCarothers DefinitionDefinition DefinitionDefinition
A d d itio n
CO2H O
-H2O OH O ( + HO O H HO2C HO( O Condensation
O NCO H OCN N O Ar OH O N + HO O H NCO Condensation?
OO O O O Addition? O Condensation? Chemistry 367L/392N AnotherAnother ProblemProblem
O O
OC ORC R
Polyester from lactone
O
OH R CO2H ORC + H2O
from ωωω-hydroxycarboxylic acid
Chemistry 367L/392N PaulPaul JJ FloryFlory 19101910 --19851985
The Nobel Prize in Chemistry 1974
"for his fundamental achievements, both theoretical and experimental, in the physical chemistry of the macromolecules"
Chemistry 367L/392N FloryFlory ClearsClears ThingsThings UpUp Polymer Structure is distinct from Polymerization Process.
Addition Condensation Polymerization Polymerization O O O H H HO O O HO O
Condensation Polymer
Process Structure
Addition Similar connections Same composition Ring-opening (monomer = polymer) No by-products Condensation New functional groups Release of small molecules Degradation gives different composition Chemistry 367L/392N BasicBasic TypesTypes ofof PolymerizationPolymerization MechanismsMechanisms
Dimer Tetramer Octamer Hexamer Step-growth O ... O HOC CH2 CH2 OHH OC CH2 CH2 OH
H2O
Chain-growth
O
O- O Ring-opening O - RO RO + O O H Chemistry 367L/392N ChainChain growthgrowth systemsystem
TheThe characteristiccharacteristic ofof aa chainchain polymerpolymer isis thatthat polymerpolymer growthgrowth takestakes placeplace byby monomermonomer reactingreacting onlyonly withwith thethe reactivereactive centerscenters .. MonomerMonomer doesdoes notnot reactreact withwith monomermonomer andand thethe differentdifferent --sizedsized speciesspecies suchsuch asas dimerdimer ,, trimertrimer ,, andand nn--mermer dodo notnot reactreact withwith eacheach other.other. TheThe polymerizationpolymerization ceasesceases whenwhen thethe activeactive centercenter isis destroyeddestroyed byby terminationtermination reaction(sreaction(s ).).
Chemistry 367L/392N StepStep GrowthGrowth systemsystem
AA condensationcondensation takestakes placeplace betweenbetween twotwo polyfunctionalpolyfunctional moleculesmolecules toto produceproduce oneone largerlarger polyfunctionalpolyfunctional moleculemolecule withwith thethe possiblepossible eliminationelimination ofof aa smallsmall moleculemolecule suchsuch asas water.water. TheThe reactionreaction continuescontinues untiluntil oneone ofof thethe reagentsreagents isis usedused up.up.
Chemistry 367L/392N TheThe chainchain growthgrowth vs.vs. stepstep growthgrowth
Step Chain
Chemistry 367L/392N