Revised polymer 2011

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  • Revised polymer 2011

    1. 1. POLYMERS
    2. 2. TopicsIntroduction PANClassification PETPhysical Properties Poly amidesTypes of Polymerization PolyethyleneCopolymers PolypropyleneVulcanization Resins(Phenol-Formaldehyde)PVC PolymethylmethacrylatePolyurethane
    3. 3. POLYMERSContents:Types of polymersPhysical propertiesTypes of polymerisationSome important polymers
    4. 4. Terminology 1.Polymer: A long molecule made up from lots of small molecules called monomers.  A + A + A + A  -A-A-A-A- Eg. Ethene polyethene styrene  polystyrene Vinyl chloridePolyvinyl chloride
    5. 5. Eg. PE ( Polyethene )
    6. 6. Terminology…
    7. 7. Homopolymer AAAAAAAAAAARandom CCACBBACABAAAlternating ABCABCABCABCBlock AAAABBBBCCCCGraftCross link polymer
    8. 8. a)Homopolymerb)Copolymerc) Block copolymerd) Graft copolymer 8
    9. 9. The number of repeating units in chain formed in a polymer is known as the "degree of polymerization(DP)
    10. 10. Degree of polymerisation: The number of repeating units in a polymer molecule. 5,000 – 2,00,000 malecular mass range.
    11. 11. The configuration of monomeric units in apolymer molecule
    12. 12. Isomerism/Polymer TacticityIsotacticSindiotacticRandom
    13. 13. FunctionalityThe number of bonding sites/active sites
    14. 14. Types of PolymerisationAddition or Chain PolymerisationCondensation or step- PolymerisationCopolymerisation
    15. 15. Addition or chain polymerisation
    16. 16. Example of addition polymers 16
    17. 17. 1st group 2nd group Product ExampleHydroxyl Carboxyl Polyester Polyethylenetere--OH -COOH -OOC- phthalate(terylene)Amino Carboxyl Polyamide Nylon-6:6_NH2 -COOH _NH-CO-Hydroxyl Isocyanate Polyurethane Spandex fibre-OH OCN- -OC-NH-
    18. 18. Types of polymers On the basis of source: a) Natural ----- which are found in nature in animals and plants starch(polymer of α-D-glucose, cellulose(polymer of β-D-glucose), proteins(polypeptides,polyamides),nucleic acids, natural rubber(a polymer of cis-iso prene) Gutta percha (polymer of trans isoprene) b) Synthetic……PE, PP, PS, PVC,nylon,terylene,bakelite
    19. 19. On the basis of structureLinear polymers:posess high m.p,density,and tensile strength due to close packing of polymer chain High density polythene(HDPE) Nylons, polyester Branched chain polymers: posess low m.p density,and tensile strength due to poor packing of polymer chain in the presence of branches. low density polyethene(IDPE),glycogen,amylopectinThree dimensional network polymers: Hard,rigid,brittle,donot melt but burn on strong heating due to the presence of cross links bakelite,urea-formaldehyde ,melamine-formaldehyde
    20. 20. On the basis of molecular forces: a) Thermoplastic polymers: Linear long chain polymers which can be softened on heating and hardened on cooling Hardness is temporary property Can be prosessed again and again PE, PP, PVC, PS, Teflon, Nylonb) Thermosetting polymers: Permanent setting polymers Three dimensional cross linked structure with strong covalent bonds Cannot be reprocessed
    21. 21. Polyester,bakelite,epoxy resins,urea formaldehyde resinElastomers: (or synthetic rubber)Any rubber like structure which can be stretched at least thrice its lengthFibres: whose chains are held together by strong intermolecular forces like hydrogen bonding. Cryatalline,High tensile strength
    22. 22. Thermoplastics vs. Thermosetting plastics
    23. 23. Thermoplastics (80%) No cross links between chains. Weak attractive forces between chains broken by warming. Change shape - can be remoulded. Weak forces reform in new shape when cold.
    24. 24. Thermosets Extensive cross-linking formed by covalent bonds. Bonds prevent chains moving relative to each other. What will the properties of this type of plastic be like?
    25. 25. Addition polymerisationMonomers contain C=C bondsDouble bond opens to (link) bond to next monomer moleculeChain forms when same basic unit is repeated over and over.Modern polymers also developed based on alkynes R- C C - R’
    26. 26. Copolymerisationwhen more than one monomer is used. An irregular chain structure will result eg propene/ethene/propene/propene/etheneWhy many polymers designers want to design a polymer in this way?(Hint) Intermolecular bonds!
    27. 27. ..RO: MechanismH2C CHCH3 •
    28. 28. ..RO: MechanismH2C CHCH3 • H2C CHCH3
    29. 29. ..RO: MechanismH2C CHCH3 H2C CHCH3 •
    30. 30. ..RO: MechanismH2C CHCH3 H2C CHCH3 • H2C CHCH3
    31. 31. ..RO: MechanismH2C CHCH3 H2C CHCH3 H2C CHCH3 •
    32. 32. ..RO: MechanismH2C CHCH3 H2C CHCH3 H2C CHCH3 • H2C CHCH3
    33. 33. Free-Radical AdditionPolymerization of Ethylene H2C CH2 200 °C O2 2000 atm peroxidesCH2 CH2 CH2 CH2 CH2 CH2 CH2 polyethylene
    34. 34. Free-Radical Polymerization of Propene H2C CHCH3 CH CH CH CH CH CH CH CH3 CH3 CH3 CH3 CH3 CH3 CH3 polypropylene
    35. 35. ..RO • Mechanism .. H2C CHCH3
    36. 36. ..RO: MechanismH2C CHCH3 H2C CHCH3 H2C CHCH3 •
    37. 37. Likewise... •H2C=CHCl polyvinyl chloride •H2C=CHC6H5 polystyrene •F2C=CF2 Teflon
    38. 38. Chain growth polymerization• Addition polymerization• All the atoms in monomer is used to produce a polymer.• Steps in chain reaction:• initiation• propagation• termination
    39. 39. Step growth polymerizationPolymerization mechanism in which bi-functional ormultifunctional monomers react to form first dimers,then trimers, longer oligomers and eventually longchain polymers.•Eg: polyesters, polyamides, polyurethanes. Etc•Polymer+molecule with low molecular weight.
    40. 40. Differences between step-growth polymerization and chain-growth polymerizationStep growth Chain growth Growth throughout matrix Growth by addition of monomer only at one end of chain Rapid loss of monomer early Some monomer remains even at in the reaction long reaction times Similar steps repeated Different steps operate at throughout reaction process different stages of mechanism. Average molecular weight Molar mass of backbone chain increases slowly at low increases rapidly at early stage conversion and high extents and remains approximately the of reaction are required to same throughout the obtain high chain length. polymerization Ends remain active (no Chains not active after termination) termination No initiator necessary Initiator required
    41. 41. Free radical polymerizationInitiation: active center created.2 stepsRadicals from initiatorsTransfer to monomerTypes of initiation:Thermal decompositionPhotolysisRedox reactionsPersulfate
    42. 42. Propagation:Termination :Combination of two active chain endsCombination of an active chain end with an initiator radical
    43. 43. Cationic polymerization• Cationic initiator binds & transfers charge to monomer.• Reactive monomer reacts with other monomer to form a polymer.• Active site: carboniumion , oxonium, sulfonium or phosphonium ion• Monomers: alkoxy. phenyl, vinyl, 1,1-dialkyl-substituted alkene monomers.• Initiator: provide electrophile eg: bronsted acids(acetic acid,HCL), Lewis acids+electron donor.• Application :polyisobutylene.
    44. 44. Cationic polymerization
    45. 45. Anionic polymerizationCarried out through carbanion active species.Monomer: vinyl monomers with substituents on double bond able to stabilise a –ve charge. Eg: styrene, dienes, methacrylate, vinyl pyridine, aldehydes, epoxide, episulfide cyclic siloxane, and lactonesPolar monomers: eg: acrylonitrile, cyanoacrylate, propylene oxide, vinyl ketone, acrolein, vinyl sulfone, vinyl sulfoxide, vinylsilane andisocyanate..
    46. 46. Solvents- polar solvents decrease stability.initiation : electron transfer, strong acids.Propagation: very fast,low temp, heat is released.Termination: quenching, water, alcohol, chain transfer.Application :polydiene synthetic rubbers, solution styrene/butadiene rubbers (SBR), and styrenic thermoplastic elastomers
    47. 47. Polymerization techniquesBulk polymerizationSolution polymerizationSuspension polymerizationEmulsion polymerization
    48. 48. Bulk polymerization• Mass or bulk polymerization: Polymerization of the undiluted monomer.• carried out by adding a soluble initiator to pure monomer into liquid state.• Viscosity increases dramatically during conversion• 2 types Quiescent bulk polymerization Eg: phenol- formaldehyde condensation Stirred bulk polymerization Eg: nylon 66.
    49. 49. Advantages Disadvantages • The system is simple and • Heat transfer and mixing requires thermal insulation. become difficult as the • The polymer is obtained pure. viscosity of reaction mass increases. • Large castings may be • Highly exothermic. prepared directly molecular weight distribution can be • The polymerization is easily changed with the use of obtained with a a chain transfer agent. broad molecular weight distribution due to the high viscosity and lack of good heat transfer. • Very low molecular weights are obtained.
    50. 50. Solution polymerizationMonomer dissolved in solvent, formed polymer staysdissolved. Depending on concentration of monomer thesolution does not increase in viscosity.Advantages Disadvantages* Product sometimes * Contamination with solvent directly usable* Controlled heat release * Chain transfer to solvent * Recycling solventApplicationsAcrylic coating, fibrespinning, film casting
    51. 51. Suspension polymerizationLiquid or dissolved monomer suspended in liquid phase.Suspending agent- PVA, methyl cellulose.InitiatorParticle size 10-500µm.
    52. 52. Emulsion polymerization• Water• Monomer• SurfactantExamples:• Synthetic rubber-styrene- butadiene (SBR), Polybutadiene, Polychloroprene.• Plastics-PVC, polystyrene, Acrylonitrile-butadiene-styrene terpolymer (ABS).• Dispersions-polyvinyl acetate, polyvinyl acetate copolymers, latexacrylic paint, Styrene-butadiene, VAE
    53. 53. Advantages Disadvantages Surfactants andHigh molecular polymerization adjuvants - weight polymers difficult to removefast polymerization rates. For dry (isolated) polymers,allows removal of heat from water removal is an energy- the system. intensive process viscosity remains close to Designed to operate at high that of water and is not conversion of monomer to dependent on molecular polymer. This can result in weight. significant chain transfer toThe final product can be used polymer. as such ,does not need to be Can not be used for altered or processed condensation, ionic or Ziegler-Natta polymerization.
    54. 54. PolyethyleneThe liquid gases under high pressure is pumped into a heated pressure vessel maintained 150 to 250c .By the catalytic effect of traces of oxygen present ethylene is polymerized in to poly ethylene.Properties:A rigid waxy solid white, transulent non polar meterialChemically resistant to strong acids, alkalies and salt solutionsGood insulator of electricirty
    55. 55. Swollen and permeable to most oils and organic solvents particularly to keroseneDue to its high symmetrical structure polyethylene crystallizes very easilyPolyethylene produced by high pressure process has a branched structure and therefore flexible and toughLow pressure process results in a completely linear PE having high density and better chemical resistanceCommercial PE is divided in to 3 typesType I or low density PE (0.91-0.925g/cm3)Type II or medium density PE(0.925 -0.940 g/cm3)Type III or high density PE (0.941- 0.965 g /cm3)
    56. 56. USESFor making high frequency insulator partsBottle capsFlexible bottlesKitchen and domestic appliancesToysSheets for packing materialsTubes pipesCoated wires and cablesBags for packing
    57. 57. Poly propyleneIsomer of propylene by Zeigler natta reactionPropertiesStereo regular ( iso tactic)Highly crystalline polymer (M.P 160-170 c)Better hardnessStrengthStiff than PEMore resistant than PE
    58. 58. USESIn producing moulded parts and fibersIts fibers are used in making ropes(extremely strong by weight)CarpetsFurniture upholstery,Blankets,Hand bags, etcWater pipesWashing machine partsSterilizable hospital equipment
    59. 59. Poly Vinyl ChlorideIs obtained by heating a water emulsion of Vinyl chloride in presence of small amounts of benzyl peroxide or hydrogen peroxide in an auto clave under pressureVinyl chlodire so needed is prepared by treating acetylene at 1 to 1.5 atm with hydrogen chloride at 60- 80 °C in the presence of metal chloride as catalyst
    60. 60. PropertiesPVC is acolourless ,Odourless ,inflammable chemically inert ,resistant to light,atmospheric oxygen,inorganic acids,alkalies but soluble in hot chlorinated hydrocarbons such as ethyl chlorideGreater stiffness and rigidity compared to PE but is brittleMost widely used synthetic plastic
    61. 61. USESRigid PVC has superior chemical resistance and high rigidity but is brittleUsed for making sheets which are employed for tank liningLight fittings, safety helmetsRefrigerator componentsTyresCycle and motor cycle mudguards
    62. 62. Poly vinyl AcetatePropertiesIt is colorless, transparent materialResistant to water, atmospheric oxygen and chemicalsIt is fairly soluble in organic solventsGood heat resistance but slight yellowing takes place after prolonged storage above 120 CIt is harmless if taken orally
    63. 63. USESUnder the influence of compressive or tensile forces articles made from polyvinyl acetate are distorted, even at room temperature, so it is not used for moulding purposesHowever used for making records,chewing gumssurgical dressings,paints, lacquors,
    64. 64. plastic emulsions,coatings, card-boards,wrap-ping papers,finishing textiles and other fabric andbonding paper,leather,textiles
    65. 65. Poly StyreneIt is transparentLightExcellent moisture-resistantIt can be nitrated by fuming nitric acid and sulphonated by Conc.sulphuric acid, at 100 C it yields water soluble emulsionsIt is highly electric insulatingHighly resistant to acids and good chemical resistantBrittleIt has a unique property of transmitting light through curved sections
    66. 66. UsesIn moulding articles like toys, combs,Buttons, buckles, radio and television patrsRefrigerator parts, battery casesHigh frequency electrical insulators,Lenses,Indoor lightening panels
    67. 67. Poly methyl methacrylate orLucite or plexiglassIs obtained by the polymerisation of methyl methacryalate (ester of methyl acrylic acid) in presence of acetyl peroxide or hydrogen peroxide.It is an acrylic polymer
    68. 68. PropertiesPMMA is hard fairly rigid material with high softening point of about 130-140 C but it becomes rubbber like at 65 CThis relatively wide span of temperature from its rigid state to viscous consistency accounts for outstanding shape forming properties of PMMA.It has high optical transperancyHigh resistance to sun light and ability of transmitting light accurately even in curved sections
    69. 69. UsesFor making lenses Artificial eyesAir craft light fixtures DenturesBomber noses EmulsionsGun turrets PaintsCockpit canopies AdhesivesTransparent models of Automotive appliances complicated Jewellery mechanisms Wind screensBone splints T.V screens guards
    70. 70. Poly acrylonitrileI t is obtained by the polymerisation of acrylonitrile in the presence of a peroxideIt is an acrylic polymerProperties:It is a high melting , hard and horny solid.
    71. 71. UsesAs a substituent for wool for making fibres like acrilan. Thus it is used for making warm clothes, carpets , blankets etc
    72. 72. Phenolic resins or PhenoplastsThey are the condensation polymerisation products of phenolic derivatives(like phenol, resorcinol) with aldehydes (like formaldehyde).Most important member of this class is BakeliteIt is prepared by condensing phenol with formaldehyde in presence of acidic/alkaline catalystThe initial reaction results in the formation of o- and P-hydroxy methyl phenol, which reacts to form liner polymer navolac
    73. 73. During moulding hexamethylene tetra amine is added , this provides formaldehyde, which converts the soluble , fusible navolac in to a hard infusible and insoluble solid of cross linked structureProperties:RigidHardScratch resistantInfusibleWater resistantInsoluble solid
    74. 74. Resistant to non oxidising acids, salts and many organic solvents but are attached by alkaliesbecause of the presence of free hydroxy group in their structureThey posses excellent insulating character
    75. 75. UsesFor making electrical insulating partslike switches, plugs, switch boars, heater handles etcFor making moulded articles like telephone parts, cabinets of radio and televisionAs adhesives for grinding wheels used in propeller shafts for paper industry for rolling mills
    76. 76. PropertiesPolycarbonates are charecteriseed by impact and tensile strength over a wide a range of tempetature.They are soluble in organic solvents and alkaliesUses:For preparing moulded domestic wareElectric insulators in electronics and electrical industries.

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