411317 Polymer Chemistry (2/2552) by Dr. WalaipornPrissanaroon-Ouajai Dept. of Industrial Chemistry, KMUTNB 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 2 POLYMER CHEMISTRY- WHAT IS IT ? Chemistry of large molecules 1980 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 3 What are polymers ? Why are polymersimportant ? Extraordinary range of physical properties Many (not all)are cheap 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 4 Polymer contains repeating units Polymers vs. Macromolecules A polymer is a macromolecule.but a macromolecule may not be a polymer Polypropylene (PP) n Macromolecules contain no repeating units Ex. Protein, DNA 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 5 Packaging/films (PE, PP, PET) Everyday household stuff Paint (Polyacrylate, Epoxy) Adhesives (Epoxy resin, Acrylic resin) Auto's,aerospace,etc. Fibres (polyester, nylon) Electronic applications Elastomers (Rubber, Butadiene) Applications ABS 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 6 Plastics and the Environment ? FromThe Poison Plasticpublished by Greenpeace (www.greenpeace.org): Most common plastics pose serious threats to human health and the environment. extreme pollution fromproduction toxic chemical exposure during use hazards fromfires (C x H y +O 2 CO 2 +H 2 O) their contribution to the worlds growing waste crisis. http://www.pcd.go.th/info_serv/waste_rubbish.htm(!"#$%#&""'()*) 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 7 Ages agoNatural fibers Ex. wool, silk and cotton 1492Columbusdiscovered South America and found the use of natural rubber (Heveabrasiliensis) Historical background Uses: Latex coating Polyisoprene Crying trees Para rubber 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 8 Vulcanizationtransformation of hevearubber to elastomer (valcanizedrubber) 1839Charles Goodyear 1 st synthetic plastic made from natural polymer 1843Nelson Goodyear Ebonite High % vulcanization (rubber:S=100:32) S 8 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 9 1848 - Menard Cellulose Nitrate Synthetic polymers started!! 1 st artificial thermoplastic 1846Parkesand Hyatt Celluloid Cellulose Nitrate +Camphor (as plasticizer) use in photographic industry highly flammable compound 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 10 1905- Baekeland Bakelite 1st truly synthetic plastic not soften by heat Phenol Formaldehyde Phenol-Formaldehyde resin 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 11 1920s - Staudinger Macromolecule hypothesis Nobel prize - Chemistry 1953 Demonstrations of Both natural & synthetic polymers Polymer is Giant molecule not aggregate like colloid or cyclic compound long chain-like molecule formulated a polymericstructure for rubber, based on a repeating isoprene unit 1927 PVC 1931 PMMA & Neoprene 1938 Nylon 1941 LDPE 1943 Silicone 1947 Epoxy resins 1948 ABS 1957 HDPE Development of commercial polymers 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 12 Classification of polymers 1. By source 1.1 Natural polymers (including macromolecules) cis-polyisoprene(natural rubber) glycosidiclinkage PolysaccharideEx. starch, glycogen, cellulose, chitin, chitosan (C 6 H 10 O 5 ) n-1 where n = 300 and 3000. -NHCO-CH 2 for chitin -NH 2 for chitosan Protein (Polyamide) Ex. plastics, synthetic rubbers, synthetic fibers ect. 1.2 Synthetic polymers 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 13 2.1 Condensation polymerization (frombi/polyfunctional monomers) 2. By polymerization reaction (for synthetic polymers) Dimer Monomer Ester bond [C-(CH 2 ) n -C-O-(CH 2 ) m -O] O O polyester Ex. Polyamide, polyurethane, polycarbonate, ect. Step-growth polymerization 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 14 2.2 Chain-growth polymerization (fromunsaturated hydrocarbons or olefins ) Ex. poly(vinyl alcohol), PTFE, poly(vinyl acetate), PMMA ect. X X X X X [CH 2 -CH 2 ] [CH-CH 2 ] n n [CH-CH 2 ] Cl n 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 15 3. By composition 3.1 Homopolymers (contain one type of repeat unit) [CH 2 -CH 2 ] [CH-CH 2 ] OH n n 3.2 Copolymers (contain at least 2 repeat units) Ex. Styrene-Butadiene-Styrene block copolymer (SBS) Thermoplastic Elastomer Ex. Acrylonitrile-butadiene-styrene copolymer (ABS) 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 16 4.1 Linear chain with 2 ends 4.2 Cyclic- chain with no end 4.3 Branchedpolymers have side chains 4.4 Dendritic(or dendrimer) - tree-like molecule 4.5 Network (or crosslinked) 3D structures which each chain is connected to others 4. By skeletal structure 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 17 Strain () = L L 0 Deformation ......... Stress ....... Strain .-..... 5. By application In case solidSee mechanical properties-............. Strain Stress Flexible plastics Fiber Rigid plastics Elastomer Emulsion 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 18 6.1 Thermoplastics - Soft (and melt) and formable when heated - Rigid when cooled - Can be re-heated and re-formed into different shapes 6. By thermal behavior Recycled plastics 6.2 Thermosetting plastics- Initially form a X-linked solidwith by heating - Soft (not melt) when 2 nd heated but cannot re-shaped Melamine-formaldehyde resins Epoxy resins 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 19 Biodegradable polymers Conducting polymers Specific classes of polymers PLA PHB PCL 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 20 Nomenclature of Polymers Source-based name: base on name of monomer Structure-based name: base on structure of repeat unit Poly + name of monomer Note:use ( ) if monomer has a multi-worded name Poly(nameof structure of repeat unit) CH 2 =CH 2 CH=CH 2 OH CH=CH 2 CH 3 Monomer Polymer Source-based name Structure-based name In UK called polythene 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 21 IUPAC recommendation for source-based names of polymers 1. Homopolymer Poly+nameof monomer For multi-worded monomer name Poly(nameof monomer) or Polyethylene (PE) Polypropylene (PP) Polystyrene (PS) Poly(vinyl chloride) (PVC) Polytetrafluoroethylene (Teflon) 1.1) Addition polymers Most common polymer.Used in bags, wire insulation,and squeeze bottles Fibers,indoor-outdoor carpets,bottles Styrofoam,molded objects such as tableware (forks,knives and spoons), trays,videocassette cases. Clear food wrap,bottles,floor covering, synthetic leather,water and drain pipe Nonstick surfaces,plumbing tape, chemical resistant containers and films (or ethylene) (or propylene) 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 22 1.1) Addition polymers (continued) Polyacrylonitrile (Acrilan,Orlon,Creslan) Polychlorprene (neoprene rubber) Poly(vinyl acetate) (PVA) Polyisoprene Natural rubber Styrene butadiene rubber (SBR) Poly(methyl methacrylate) (Lucite, Plexiglas) Glass replacement,paints,and household products Fibers used in knit shirts,sweaters, blankets,and carpets Adhesives (Elmers glue),paints, textile coatings,and chewing gum Rubber bands,gloves,tires,conveyor belts,and household materials Oil and gasoline resistant rubber Non-bounce rubber used in tires (or isoprene) (or chloroprene) (2-chloro-1,3-butadiene) (copolymer) 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 23 1.2) Condensation polymers Polyamides (nylon) Polyesters (Dacron,Mylar,Fortrel) Polyesters (Glyptal resin) Polyesters (Casting resin) Fibers,molded objects Linear polyesters,fibers, recording tape Cross-linked polyester,paints Cross-linked with styrene and benzoyl peroxide,fiberglass boat resin,casting resin (fromcondensation polymerization) (Thermoset) (Thermoset) (Thermoplastic) 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 24 Phenol-formaldehyde (Bakelite) Cellulose acetate Silicones Polyurethanes Mixed with fillers,molded electrical cases,adhesives,laminates, varnishes Photographic film Water-repellent coatings, temperature-resistant fluids and rubber Foams,rigid and flexible,fibers Note :Same repeat units and names can exhibit different chemical and physical characteristics,e.g.MWor MWD. 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB) 25 2. Copolymer Poly(nameof monomer A-co-name of monomer B) Poly(propene-co-methacrylonitrile) Polyacrylonitrile-block-polybutadiene-block-polystyrene Poly[(acrylic acid)-ran-(ethyl acrylate)] Polyisoprene-graft-poly(methacrylic acid) Ex. Copoly(propene/methacrylonitrile) Block-copoly(acrylonitrile/butadiene/styrene) Ran-copoly(acrylic acid/ethyl acrylate) Graft-copoly(isoprene/methacrylic acid) Alternative Format (Random) 411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB)