2025 Lecture 1 Part A With Assignment PDF

14th January 2025 Giant -Nylon- 尼龙 Contact details: Dr Jianyong Jin Associate Professor School of Chemical Sciences CHEM100/G Course director Office hour: make appointment PhD 2005 Polymer Chemistry Newmarket Campus Building 902 Room 227 Clemson Universi...

14th January 2025 Giant -Nylon- 尼龙 Contact details: Dr Jianyong Jin Associate Professor School of Chemical Sciences CHEM100/G Course director Office hour: make appointment PhD 2005 Polymer Chemistry Newmarket Campus Building 902 Room 227 Clemson University, USA Phone: +64 9 3737599 ext 86624 Email: [email protected] WeChat： 高分子  Textbook Resources Chapter 6 in Napoleon’s Buttons Napoleon's Buttons: How 17 Molecules Changed History Author: Penny Le Couteur A major wardrobe malfunction in December 1812 helped cause Napoleon's army of 600,000 to return from Russia with only 10,000 men. Up until that time, Napoleon's army was unbeaten. What happened? They had to fight the elements—the cold Russian winter as well as the element tin (Sn). Tin was a major ingredient in the buttons used to hold up the soldiers' pants. Tin changes from shiny metal to gray dust when the temperature drops, in this case, causing their clothing to drop as well. Textbook Resources Chapter 1 in Fundamentals of Polymer Sciences Author: Stoyko Fakirov Stoyko Fakirov was visiting professor at the University of Auckland, New Zealand. He studied chemistry at the University of Sofia, Bulgaria, and received his PhD from the Lomonossov State University in Moscow. Stoyko Fakirov is member of the editorial board of 12 international journals on polymers and advanced materials. He has published more than 300 peer- reviewed papers, edited or co-edited and always contributed to 15 books on polymer science and holds nine US patents. July 2021  What is NYLON ? 尼龙是一种高分子材料. Nylon is a type of synthetic polymer. It was first developed in the 1930s and is known for its strength, elasticity, and resistance to abrasion and chemicals. Nylon is commonly used in a variety of applications, including textiles, automotive parts, and industrial components. The term Plastics versus Polymer The word “plastic” is derived from the Greek meaning "capable of being shaped or molded or reshaping“ by the applications of heat and/or pressure. It was during the 1920’s that the term “plastics” became popular. In layman’s terms, polymers are often referred to as plastics. However, from today onward, in this class, we will use the term 'polymer' instead of 'plastic.' It not only sounds more precise but also reflects a deeper understanding of the subject, making you sound more knowledgeable! In North America, polymers are also referred to as macromolecules. Why on earth should I bother to learn anything At all about polymers? Long chain molecules Extraordinary Range of physical properties Many (not all) are cheap They are just damn interesting !!!!! They are everywhere and play a vital role in our everyday lives. In this NYLON week, we have four stories today (14th Jan) Just one word - Polymer Wednesday (15th Jan) On the flip side of the coin Plastics and Environment Thursday (16th Jan) pre-Nylon days Friday (17th Jan) Nylon - a textile fashion revolution Polymer’s storyline Introduction to Polymers Types of Polymers Polymerization Processes Properties of Polymers Enjoyable stories Molecules from small to large (Polymer) A water molecule is about 0.27 nanometer across DNA is about 2 nanometers across and can stretch out to meters in length. Nylon is giant molecule (aka polymer) This is polymer.  Introduction to Polymers Polymers are long chain molecules (It is important to understand how these chains are oriented and folded. Some chains are very flexible (e.g. -CH2-CH2- CH2-) and can fold and entangle easily. Some chains are very rigid (e.g polyphenylene, polyaniline, etc) and don’t really fold at all. Shrunken Random walk stretched out  Introduction to Polymers Poly.....mer many units Polymers are very large long chain molecules —M—M—M—M—M—M— (macromolecules) that are comprised or built up of or smaller units or monomers. — (M) — n n is the number of repeating units n ranges from 10 to a few million Therefore, polymer For man-made polymer, n is the chains can vary degree of polymerization (DP) significantly in length, ranging from a few nanometers to several micrometers. Some Basic Definitions POLYMER A large molecule made up of small building blocks MONOMERS The building blocks HOMO-POLYMER What you get if the building blocks are all the same CO-POLYMER A polymer made up of different monomers BLEND (Alloy) A mixture of different polymers  Monomer  Polymer Polymer Name(s) Abbreviation Monomer Ethylene Polyethylene low density LDPE CH2=CH2 HDPE Ethylene Currently, we have Polyethylene high density CH2=CH2 thousands of different Polypropylene Propylene PP monomers, which CH2=CHCH3 result in the Poly(vinyl chloride) creation of thousands of Vinyl chloride PVC unique polymers !!! CH2=CHCl Polystyrene Styrene PS CH2=CHC6H5  What is polymer ? Poly.....mer many units Polymers are very large long chain molecules —M—M—M—M—M—M— (macromolecules) that are comprised or built up of or smaller units or monomers. — (M) — n n is the number of repeat units n ranges from 10 to a few million Question; if a polymer chain is made from A. 1320 nm 8570 monomers, each monomer is 0.154 B. 1.32 micron nm size, can you calculate the length of C. 0.0132 mm this polymer chain ? D. I don’t know and I don’t care! Polymer-in-a-can [video] Polymer-in-a-can [video]  Polymer’s storyline Introduction to Polymers Types of Polymers Polymerization Processes Properties of Polymers Enjoyable stories  Types of Polymers Classification by Sources Natural polymer Semi-synthetic polymer Synthetic polymer Classification by Architecture Linear Branched Crosslinked Classification by behaviour upon heating Thermoplastics thermosets  Classification by Sources  From the earliest times - NATURAL PLASTICS Plastics have existed in natural form in plants and animal since life began. Man has exploited and used naturally occurring plastics throughout recorded human history  In the nineteenth century - SEMI-SYNTHETIC PLASTICS chemical modification of natural plastics Charles Goodyear - rubber vulcanization Isaiah Hyatt Celluloid …. ….  After 1930s to present - Totally SYNTHETIC PLASTICS man-made materials, fossil fuel based, and coal based  Naturally Occurring Plastics Harvest from Nature - used throughout recorded history Cotton / cellulose / bamboo Natural rubber hog bristles Horn, Ivory Naturally occurring polymers are everywhere. Such as cellulose, cotton, starch, DNA, RNA, protein. Cotton/Cellulose Starch Repeating unit Repeating unit Naturally occurring polymers are everywhere. Such as cellulose, cotton, starch, DNA, RNA, protein. Orders of protein structure 29 Pfizer mRNA vaccine contains polymer Rubber in Mesoamerica Ancient Mesoamericans were the first people to invent rubber balls (Nahuatl languages: ōllamaloni), sometime before 1600 BCE, and used them in a variety of roles. Ancient rubber was made from latex of the rubber tree, which is indigenous to the tropical areas of southern Mexico and Central America. The latex was made into rubber by mixing it with the juice of what was likely Ipomoea alba (a species of morning glory), a process which preceded Goodyear's vulcanization by several millennia. Rubber vulcanization -1839 Charles Goodyear  Semi Synthetic Plastics Celluloid from Cellulose - 1856 synthetic ivory substitute for horn, ivory, tortoise shell "horn-like material"  Semi Synthetic Plastics Regenerated Cellulose (Viscose) - 1905 Cellophane HO OH from the words cellulose and diaphane ("transparent") O O CH 2 OH NaOH OH HO O O CH 2 ONa CS 2 OH HO O O CH 2 OCSNa S H+ HO OH cellophane wrap for hampers O O CH 2 OH Semi Synthetic Plastics Rayon and Celanese ~1920 Rayon Hawaiian Shirt The First 100% Synthetic Plastics -1910s Baekeland and Bakelite A Bakelite telephone Leo Baekeland 1907 A Bakelite camera A Bakelite radio  Fully Synthetic Plastics From unlikely raw materials of oil and coal, chemists derived synthetic plastics for thousands of everyday products. refinery monomers polymerisation Processing 37 Fully Synthetic Plastics [video]  Classification by Architecture Polymer architecture in polymer science relates to the way branching leads to a deviation from a strictly linear polymer chain. https://en.wikipedia.org/wiki/Polymer_architecture  HIGH DENSITY POLYETHYLENE STRUCTURE MOLTEN STATE FROZEN STATE Density 0.965 g/mL Very long linear chains 80 – 90% Crystallinity Very little branching Melting Point 135 oC 40 40  LOW DENSITY POLYETHYLENE STRUCTURE MOLTEN STATE Easy processing – the effect FROZEN STATE Low Density 0.92 g/mL of Long Chain Branching 50-60% Crystallinity Melting Point 98 -120 oC 41 41 Classification by behavior upon heating Classification by behavior upon heating [video] Classification by behavior upon heating [video]  Interlocked polymer chains Thermosets are crosslinked polymer Professor Colin Raston with his invention, the vortex fluidic device, which can 'uncook' egg whites.  Recycling of thermoset is big big deal in next 20 years!!!!! Recyclable thermoset plastics are one of 10 emerging technologies of 2015 highlighted by the World Economic Forum’s Meta-Council on Emerging Technologies. Thermosets are highly cross-linked, which means the molecules have extremely strong chemical bonds. Once you’ve initially heated them up to set them into the shape you want – hence the name “thermoset” – they’re irreversibly bound. That means they’re much stronger than thermoplastics, but also that heating them up again won’t break down the bonds in a way that enables you to usefully reshape them, as with thermoplastics. It’ll just char them and crack them instead. Dentist is making thermosets everyday. Polymer’s storyline Introduction to Polymers Types of Polymers Polymerization Processes Properties of Polymers Enjoyable stories POLYMERIZATION : A chemical reaction that converts monomers (building blocks) to polymers (large molecules). Polymerization Polymer Monomer Single units many units —M—M—M—M—M—M— M Hundreds of paper clips hook together to form a chain POLYMERIZATION PROCESSES Addition Polymerization [video] Addition Polymerization [video]  Two common types of POLYMERIZATION PROCESSES Fast ! Slow ! Exponential Decay (increasing form)  Condensation Polymerization Polyesters (PET) STRUCTURE HOOC COOH H2O O O diacid n HO OH polyester diol Applications Packaging (cheese) Bottles, containers Optical film Fibre, fabrics, textiles  Condensation Polymerization Polyamide (aka Nylon) Nylon is a generic word representing a class of polymers as polyamides. STRUCTURE HOOC COOH H2O O H N diacid n H2N NH2 polyamide diamine  PET Polyethylene terephthalate - Fizzy drink bottles, oven-ready meal trays... HDPE High-density polyethylene - Bottles for milk and washing-up liquids… PVC Polyvinyl chloride - Food trays, cling film, bottles for squash, mineral water and shampoo. LDPE Low density polyethylene - Carrier bags and bin liners. Polypropylene - Margarine tubs, PP microwaveable meal trays. Polystyrene - Yoghurt pots, foam meat or PS fish trays, hamburger boxes and egg cartons, vending cups, plastic cutlery, protective packaging for electronic goods and toys. OTHER Any other plastics that do not fall into any of the above categories. Coding by Society of Plastic Industry (1980s) [video]  [video] https://www.youtube.com/watch?v=jJlqyTb-oy0  Remember these common polymers: 1. Polyester (PET) 2. High Density Polyethylene ( HDPE) 3. Polyvinyl Chloride (PVC or vinyl) Account for 80% of 4. Low Density Polyethylene ( LDPE) all polymers !! 5. Polypropylene (PP) 6. Polystyrene (PS) 7. All Other Plastics : such as acrylics, NYLON ,rubber, Polycarbonate and TEFLON, degradable polymers, electronics plastics, etc… Note: This assignment is slightly different from last year! Exemplary photos of the product Here are some examples of synthetic polymers; this is not a complete list, but it is provided for your reference. ABS Acrylonitrile-Butadiene-Styrene PI Polyimide CPVC Chlorinated Polyvinyl Chloride PMMA Polymethyl methacrylate (acrylic) EVA Ethylene-Vinyl Acetate PMP Polymethyl Pentene (TPX) FEP Fluorinated Ethylene Propylene POM Polyoxymethylene (acetal) HDPE High-Density Polyethylene (2) PP Polypropylene (5) LCP Liquid Crystal Polymer PPE Polyphenylene Ether, Modified LDPE Low-Density Polyethylene (4) PPS Polyphenylene Sulfide LLDPE Linear Low-Density Polyethylene PS Polystyrene (6) MDPE Medium-Density Polyethylene PSU Polysulfone PA Polyamide (nylon) PTFE Polytetrafluoroethylene PAS Polyarylsulfone PU/PUR Polyurethane PB Polybutylene PVC Polyvinyl Chloride (3) PBT Polybutylene Terephthalate PVDF Polyvinylidene Fluoride PC Polycarbonate PVF Polyvinyl Fluoride PE Polyethylene SAN Styrene Acrylonitrile PEEK Polyetheretherketone SMA-PC Blends Styrene Maleic Anhydride and PEI Polyetherimide Polycarbonate PES Polyethersulfone TPE Thermoplastic Elastomer PET/PETE Polyethylene Terephthalate (1) UHMW-PE Ultra High Molecular Weight PETG Glycol Modified Polyester Terephthalate Polyethylene https://pslc.ws/~pslcws/macrog/level2.htm https://pslc.ws/~pslcws/macrog/level1.htm Assignment #2 on the topic of “Nylon” due by 11:59pm Friday 31st January 2025 Polymer’s storyline Introduction to Polymers Types of Polymers Polymerization Processes Properties of Polymers Enjoyable stories To be continued…