Ch E 1 Engineering Polymers How Plastics are

Ch. E #1: Engineering Polymers: How Plastics are Made The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Plexiglas, or Polymethyl Methacrylate (PMMA) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

A “Bubble Chair” An Aquarium THEY’RE BOTH MADE OF PMMA. WHY? The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

PMMA Properties ØExtremely transparent. ØHard & Shatterproof. ØThermoplastic: mold, melt, & remold again. ØHighly weather resistant. ØDoesn’t yellow over time. The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

PMMA Production Ø Made in sheets, rods, tubes, or beads. Ø Methyl Methacrylate(MMA) + Initiator. Ø Benzoyl Peroxide(BP). Ø Principles of Polymer Systems. Rodriguez et al. Ø PMMA sheet: bulk polymerization in a batch reactor(BR) sheet mold. The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

PMMA REACTOR DESIGN We calculated that 100 aquariums (15 L each) require 740 kg of PMMA to make. Polymerization t: 54 hrs MMA + Benzoyl Peroxide T=60°C 740 kg PMMA Reactor Volume=780 L Mold @ t=0 MMA: 9. 43 mol/L BP: 1. 0 x 10 -7 mol/L Mold @ t=54 hrs The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Polyether Ether Ketone (PEEK) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Polyether ketone (PEEK) ØAn advanced engineering plastic ØHigh resistance to abrasion, chemicals, fire, hydrolysis, and radiation ØApplications: aviation, automobile, manufacturing, electronic apparatuses, and food and beverage industries The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

PEEK in Comparison to other Plastics ØSuperior ductility ØHigh electrical resistance ØLow moisture absorption ØHigh thermal resistance http: //www. quadrantplastics. com/na-en/products/injection-moldedsolutions/working-together/material-selection. html ØHigh Young’s Modulus The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Sulfonation of PEEK H 2 SO 4 ØSulfonated PEEK (SPEEK) has improved solubility that allows it to be subjected to size exclusion chromatography, which gives it a better molar mass distribution ØCompared to the original PEEK, SPEEK has a longer molecular chain, which gives it superior mechanical properties The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Reaction Kinetics Source: Mechanism and kinetics of poly(ether ketone) sulfonation in concentrated sulfuric acid at room temperature by D Daoust, J Devaux, and P Godard Where C 0 is the initial concentration and Ct is the concentration at reaction time t of the unsulfonated –Oф. O– groups, and k 2 and k 3 are the apparent rate constants at 20°C shown below: Concentrations of sulfuric acid (wt %) k 2 ka(h-1) k 3 95. 9 4. 9 x 10 -3 2. 7 x 10 -3 96. 8 7. 2 x 10 -3 3. 2 x 10 -3 97. 7 19. 3 x 10 -3 10. 3 x 10 -3 98. 6 48. 0 x 10 -3 19. 8 x 10 -3 The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Results Ø 97. 7% of H 2 SO 4 @ 20°C and a goal of 99. 9% sulfonation: 26. 4 days (extremely long time) Ø 98. 6% H 2 SO 4 @ 20°C and a goal of 99% sulfonation: 8. 7 days (shorter, but still very long time) ØThus, the relatively shorter time to run the batch to sulfonate PEEK would be 8. 7 days within 98. 6% H 2 SO 4 and 99% sulfonation ØMay be possible to increase the speed with increased temperature The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Polyoxymethylene (POM) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Introduction • Polyacetal/Polyformaldehyde • Monomer: Formaldehyde HISTORY • 1920: Staudinger unsuccessfully researched • 1959: Delrin (POM) introduced into the market MARKET • Global Demand: 808 kt • Price: $1. 29 – $1. 38/ lb The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Main Properties • • Wear Resistant Impact Resistant Moisture Resistant to Most Organic Solvents High Creep Resistant to Low Temperatures Low Friction Coefficient The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Uses Buckles Conveyor Belt Gears Snowboard Buckles The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Production Process Carbon monoxide methanol formaldehyde Carbon Monoxide + Hydrogen produce methanol Methanol oxidizes to formaldehyde Formaldehyde chain polymerizes to polyoxymethylene Solution Polymerization (Solvent: Heptane) Insoluble Polymer polyoxymethylene The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Air 34, 000 kg Production Process of Formaldehyde Reactor 1 : Silver Catalyst Vaporizer Reactor 2: Copper Catalyst 2, 800 kg Water Methanol 5000 kg Polymerization reactor 1 million POM Gears Air Compressor Valve Heat exchanger Pure Formaldehyde 4, 000 kg Water + Methanol Distillation System Absorber CO 2 Methyl Formate 335 kg 13 kg U. S. Patent: 6, 147, 263 The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Polyphthalamide (PPA) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Polyphthalamide (PPA) • Comprised of HMD, TPA, IPA, and adipic acid. Hexamethylenediamine Terephthalic acid • Raw material: Castor bean plant • Used to make PA 10 T type of PPA Isophthalic acid Adipic acid • Provides the diamine portion of the polymer • Renewable resource The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Properties Uses • high T • automotive resistance components • chemical • plumbing resistance • electronic • low creep connectors • harmless • Meta. Cork to the body • lamp sockets • flexible • fuel system • dimensionally components stable Oica. com (accessed July 19, 2011). “World Motor Vehicle Production by Country and Type”. • Demand has increased with the increase of production of motor vehicles (Desirable alternative to metal) • $2. 72 -3. 18 per lb (fairly high price) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Polymerization Reactor Design • Interfacial • Multiple reactors involved to polycondensation reaction achieve a high molecular weight of between 1000 g/mol • Solution polymerization and 3000 g/mol (aqueous) • Batch reactor • Results: Multiple 2. 14 L reactors running for 13. 5 hours (based on Malluche et al. , Polymer Engineering and Science, 2007) • Predicted design not very efficient, likely to switch to a different reactor configuration The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

POLYCARBONATE (PC) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

POLYCARBONATE (PC) - PC is a high quality engineering plastic. - PC was invented by Dr. Fox and Dr. Schnell in 1953. - A thermoplastic that has Øexcellent heat resistance Øgood electrical insulation properties Øhigh transparency. Figure 1: PC has a high impact strength compared to those of other plastics The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

THERE IS PC ALL AROUND US PC is found in: -bottles -CDs & DVDs -tableware -containers -electrical shavers -cell phone cases -computers -vehicle lights -tubes -sheets -food mixers -glasses The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

THE DEMAND FOR POLYCARBONATE -In 2011, America’s demand for polycarbonate reached 1, 780 million pounds. -From 1995 to 2011 there was a large increase in the demand (1, 320 million pounds of PC) (Source: The Freedonia Group, Inc. “Polycarbonate demand to increase 5. 2 percent annually” http: //www. theiapdmagazine. com ©The Freedonia Group, Inc. 2002. ) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

PRODUCTION PROCESS Polymerization Mechanism: Step Growth Figure 3: Direct phosgenation (left) and transesterification (right) methods Type Of Polymerization: Bulk Polymerization Methods of Production: -Direct Phosgenation -Transesterification Materials Used For Direct Phosgenation: -Bisphenol A (BPA) -Phosgene Materials Used For Transesterification: -Bisphenol A (BPA) (Source: Green Industry“Examples of Safer Reactions” -Dimethyl Carbonate http: //www. greener industry. org. uk. ) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

BULK POLYMERIZATION IN A BATCH REACTOR § The overall objective is to design a batch reactor to produce a specified amount of polycarbonate via the transesterification of DPC with BPA. § Both the volume of the reactor and the time required to run the reactor are essential to design a chemical plant. Figure 4: This is a diagram of a bulk polymerization The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

SPORTS BOTTLE PRODUCTION Make 1000 Sports Bottles: (450, 000 g) TIME REQUIRED TO RUN A REACTOR: (Rate Constants were obtained from Hersh, and Choi. , J. Appl. Polym. Sci. , 1990) -It takes 0. 34 -0. 71 seconds depending on the target chain length, which is really fast. VOLUME OF THE REACTOR: - The volume for the reactor would be 390 L. The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Kevlar Poly(para-phenylene terephthalamide) PPTA The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Applications and Properties • Bulletproof vests • Car tires • Ropes and cables • • High tensile strength Lightweight Flexible Flame-resistant The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Synthesis and Production • • Para-phenylenediamine Terephthaloyl chloride Condensation reaction Polymer is spun into fibers, then woven into fabric PPD TCL Kevlar The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Reactor Design and Optimization • Highly reactive and exothermic → solution polymerization • Stirred batch reactor with a cooling water jacket N batches per day Batch reactor downtime • Cleaning tank • Filling tank for next batch N(t + td) = 86, 400 seconds td = a. V + b Thermodynamic data: Zhang, Tao, et al. A novel scalable synthesis process of PPTA by coupling n-pentane evaporation for polymerization heat removal. Chinese Chemical Letters, 2011. Kinetic data: Gupta, J. S. , et al. Polymerization Kinetics of Rodlike Molecules under Quiescent Conditions. AICh. E Journal , 2001, 1, p. 177. The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Reactor Design and Optimization For 30 bulletproof vests per day (~10, 000 per year): • • 90 kg of Kevlar N = 8 batches per day V = 11, 000 L t = 3800 s (~1 hr) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Poly (lactic acid) PLA By Nika Sabasteanski and George Kaufer The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Poly (lactic acid) PLA -Feedstock: Lactic Acid Lactide (isomers) -Polymerization: Ring Opening Polymerization -Benefits -Biodegradable Figure 1: Yogurt -Applications containers -Biomedical: Sutures -Food: Yogurt containers -Market -Cargill Dow Nature Works -Projections: 7% growth per year Figure 2: Sutures The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Production Process -Production -Bulk Polymerization -Batch Reactor -Volume ≈ 2, 400 L -Synthesis: Chain Growth Figure 3: Synthesis -Initiator, Catalysts -Found Information -Kinetic Parameters (used in program) -Chemical Properties -Method of Solution -MATLAB: Euler’s Method The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

MATLAB Program for Reactor Design clear all format long %Clears all stored variables %Displays numbers at double precision D = 0. 02; N = 500; kp=0. 901; ki=1; kt=1*10^-6; %Step size in minutes %Number of steps %l/mol*min M 0=9. 16; M=zeros(1, N); M(1)=M 0; %Found initial concentration by dividing density of L-Lactide by the molecular weight of L-Lactide, L/mol %Initialize array of monomer concentrations %Picking the inital value of M to be M 0 I 0=1*10^-8; I=zeros(1, N); I(1)=I 0; %L/mol, chosen %Initialize array of initator concentrations %Picking the inital value of I to be I 0 P=zeros(1, N); P(1)=(kp*M 0)/((kp*M 0)+(2*kt*ki*I 0*M 0)^. 5); t 0 = 0; t=zeros(1, N); t(1)=t 0; %Initial time in minutes %Initialize array of times %Picking the inital value of t to be t 0 for i = 1: N dmdt = -kp*M(i)*(((ki/kt)*I(i)*M(i))^. 5); didt=-ki*I(i)*M(i); t(i+1)=t(i)+D; M(i+1)=M(i)+D*dmdt; I(i+1)=I(i)+D*didt; P(i+1)=(kp*M(i+1))/(kp*M(i+1)+((2*kt*ki*I(i+1)*M(i+1))^. 5)); end The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

Emissions and Byproducts -Emission -Byproduct -Carbon Dioxide -Normal Butanol (n-butanol) Figure 4: Carbon Dioxide Emissions from leading plastics The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

THANK YOU VERY MUCH The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011