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Heldana
Heldana
05/24/2023 1
Today’s discussion:-
1. what does it mean by polymer?
2. what is polymerization and types?
3. What is the difference between homoploymer and copolymer?
05/24/2023 2
INTRODUCTION
POLYMER
• Polymer (Greek poly-, "many" + -mer, "part") is a substance or material consisting of very
large molecules called macromolecules, composed of many repeating subunits, held together
by covalent bonds.
• Covalent bonds: sharing of valence electrons to complete an octet around atoms.
• Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers
such as DNA and proteins that are fundamental to biological structure and function.
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• Polymerization:- a process whereby smaller molecules, called monomer molecules (building
blocks) react together chemically to form either linear chains or a three-dimensional network
of polymer chains.
• Monomers add to one another in such a way that the polymer contains all the atoms of the
starting monomers.
• At the end of the addition polymerization reaction, only one product is formed. This product is
the polymer chain.
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https://status.libretexts.org.
Example:- poly(ethene), formed by lots of ethene monomers.
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2. Condensation polymerization:-
• The part that is eliminated is usually a small molecule like water or HCl gas. Such
small molecules (which are like by-products of a reaction) condense on things as tiny
droplets.
• The molecules should have one or two functional groups (like alcohol, amine, or
carboxylic acid groups).
• The reaction takes place between two similar or different functional groups or
monomers.
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Advantages of polymers:-
• Relative cheapness,
• ease of fabrication,
• low density,
• chemical inertness,
• biodegradability
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General naming rules
1) In the case of addition polymers or in other cases where a single monomer species is
used, the prefix “poly-” is added to the name of the monomer.
• E.g.: polystyrene, poly(vinyl chloride)
• If the monomer is one word with no locants, the parentheses can be eliminated.
• E.g.:- polystyrene
• Locants are numbers (or occasionally letters e.g. N-) that define the position of the
principal functional group and substituents.
[https://sciencing.com/how-to-name-a-polymer-12731376.html]
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2) In some condensation polymers made by reacting two types of monomers together.
• For example:- between ethylene glycol and terephthalic acid, the polymer is termed
as poly(ethylene terephthalate).
1. Thermoplastic polymers
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2. Thermosetting polymers
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Based on structure:-
2. Branched polymers:-
• with branches at irregular intervals along the polymer chain
• made up of main chain (linear chain) with smaller chains
• often soluble in one or more solvents because it is possible to separate the polymer
chains
• thermoplastic
• E.g.:- Low-density polythene, glycogen, and starch
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3. Crosslinked polymers:-
• formed when long polymer chains are cross-linked together to create a three
dimensional network
• contain branches that connect polymer chains
• insoluble in all solvents because the polymer chains are tied together by strong
covalent bonds
• thermoset
• E.g.:- Polyester fiberglass, polyurethanes
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Based on the number of types of monomer:-
Homopolymer
• Homopolymer that is formed by polymerizing a single monomer.
• A-A-A-A-A-A-A-A-A-A- -B-B-B-B-B-B-B-B-B-B-
• E.g.:- PVC, Polyethylene, Polypropylene
• Copolymers are formed by polymerizing more than one monomer.
• E.g.:- Polyvinyl acetate, Polyethylene oxide
Classification of copolymers
• Copolymers are classified on the basis of the way monomers are arranged along the polymer chain,
1) Random copolymer
• contain repeating units arranged in a purely random fashion
• A-B-A-B-B-B-A-B-A-A-B-A-B-B-B-A-B-A-A-B-A-B-B-A-
2) Alternating copolymer (Regular copolymers)
• contain a sequence of regularly alternating repeating units
• A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-
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3) Block copolymer
• The repeating units occur in blocks of different lengths
• -A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-A-A-A-A-A-A-A-A-
4) Graft copolymer
• have a chain of one repeating unit grafted onto the backbone of another
• -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-
B B
B B
B B
B B
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Goals for the Experiment
By doing this lab the student will:
• demonstrate the synthesis of nylon-6,10
• demonstrate the synthesis of polymer hydrogel
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I. Synthesis of Nylon 6,10
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• Currently, Nylon is used in many applications, including
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Interfacial polymerization
• reaction proceeds at the interface of two immiscible liquid phases.
• Each phase contains one monomer.
• involves the reaction of monomer A dissolved in an organic phase with a monomer B
dissolved in an inorganic phase at the interface between the two non-miscible (immiscible)
phases.
• In this experiment, acid chloride resides in the organic phase and diamine in the aqueous
phase.
• Polymerization rate is controlled by the rate of diffusion of reactants to the interface.
• In contrast to bulk condensation polymerization, high molecular weight polymers are
synthesized rapidly in the interfacial polymerization at room temperature without the strict
control of stoichiometry of reactants.
• But more controlled approach is to take advantage of the fast kinetics of the polymerization
of diamines and diacid chlorides at the interface between two immiscible phases.
NB:-
• Molecular weight is the sum of the atomic masses of all atoms in a molecule.
• Stoichiometry:-
05/24/2023 the determination of the proportions in which elements or compounds react with one another. 20
Two types of Interfacial polymerization:-
1. Stirred interfacial polymerization:-
• one phase is dispersed as tiny droplets in the other (continuous) phase by using high speed
stirring.
• used to produce tiny microcapsules and microspheres
2. Unstirred interfacial polymerization:-
• two separate macroscopic layers in contact with each other.
• used to produce membranes and to create polymer by continuous removal in a single rope.
• 1,6 diamino hexane (HMDA) with diacid chloride (sebacoyl dichloride-SC) to form Nylon 6,10
• Polymer will form at the interface between
• layer of diamino hexane dissolved in water (aqueous phase)
• layer of diacid chloride dissolved in dichloromethane-DCM (organic phase)
• Aqueous phase also contains sodium bicarbonate/sodium hydroxide as a getter for HCl.
• HCl can be neutralized by the presence of weak base in the reaction solvent.
• Denser organic phase forms the lower phase (chlorinated solvents are used, which are denser than
water)
• Aqueous phase will be carefully poured on top of the organic phase
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• NB:- water density=1 g/cm3 and dichloromethane density= 1.33 g/cm3
(a)
(b)
(a) Reaction chemistry for the synthesis of Nylon 610. (b) Figures for the synthesis of Nylon
610. 05/24/2023 22
Materials and Equipment Equipment:
Materials:
Reactor
3) Slowly add the solution in Step 2 to the solution in Step 1 by pouring down the side of
the beaker. Do not stir or mix.
4) A film (Nylon 6-10) will form at the interface of the two solutions. Carefully hook the
film with a glass rod and pull the film from the beaker in a long strand.
5) Rinse the Nylon several times with water until it is free of all traces of amine.
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Results & Discussion
1) Calculate the number of moles of Sebacoyl Chloride and Hexamethylenediamine.
2) Show the pictures of Nylon and explain the mechanism of nylon synthesis.
4) Explain the meaning of the number of 610 and draw the chemical structure of Nylon-10,
10.
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References
1. Kang, M.; Myung S. J.; Jin. H. Nylon 610 and Carbon Nanotube Composite by in situ
Interfacial Polymerization. Polymer (2006) 47, 3961-3966.
2. Wikipedia (key word: Nylon, Polymerization, molecular weight)
3. "Science of Plastics". Science History Institute. 2016-07-18. Retrieved 26 March
2018.
4. "Nylon, a Petroleum Polymer". American Oil and Gas Historical Society. Retrieved 21
June 2017.
5. Nicholson, Joseph L.; Leighton, George R. (August 1942). "Plastics Come of Age".
Harper's Magazine. pp. 300–307. Retrieved 5 July 2017.
6. Wolfe, Audra J. (2008). "Nylon: A Revolution in Textiles". Chemical Heritage
Magazine. 26 (3). Retrieved 20 March 2018.
7. [Rempp & Merrill, Polymer Synthesis, pp280-287]
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II. Synthesis of Polymer Hydrogel
Hydrogel:-
• 3D cross-linked networks of polymer chains
• a dispersion of liquid molecules within a solid
• due to its cross-linked network,
• Mostly liquid, yet behave like solids within liquid
• its structure (hardness)
• adhesive stick (tack)
• Water-insoluble/ don’t dissolve
• jelly-like material
• infinite polymer networks
• ranging from soft and weak to hard and tough
• Holding/retain/imbibe or ability to absorb large amount of water/ swell in aqueous solutions
• Monomers with greater than 2 functional group, branched copolymer formed and then branches
reacted together cross-linked copolymer formed.
• Branched polymers can form cross-links between the chains, which lead to progressively larger
polymers.
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• Infinite polymer networks called hydrogels are made and this process is called gelation.
• Gelation is the process of formation of a gel from a system with polymers.
• Hydrophilic hydrogels:-
• form an insoluble network when cross-linked and are capable of absorbing several times
their weight in water.
• synthesized using
1.Carbopol (-CH2-CH-COOH-)n
• Used as thickener in gels, viscosity control, emulsion stabilization
2.Triethanolamine (C6H15NO3)
• Neutralizer (neutralizing the carboxylic groups of the polymers), colorless viscous
liquid
3.Ethylenediaminetetraacetic acid disodium salt dihydrate-EDTA-2Na
(C10H14N2Na2O8.2H2O)
• gelling agent or solidifiers
• Solidifiers are a super absorbent polymer powder that can turn liquid into a gel-like
substance
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4. Glycerin (C3H8O3):- improved the water absorption rate and the swelling rate at
equilibrium of hydrogel beads.
5. Polyvinylpyrrolidone-PVP (C6H9NO)n:- biocompatible polymer with good chemical
stability and solubility in water.
EDTA-2Na
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Experiment
1) Dissolve 0.025 g of EDTA-2Na in 32 mL of water.
3) Stir for 1 h.
4) Remove the stirring bar and add 0.25 g of triethanolamine for neutralizing the solution.
5) Whip the solution with a glass bar until the solution turns to hydrogel.
6) Add PVP solution which was made by dissolving 2 g of PVP in 8 mL of water to the
hydrogel and mix it with a glass bar.
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Results & Discussion
1) Show the pictures of hair gel which you synthesized.
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References
1) Islam, M.; Hornedo, N.; Ciotti. S.; Ackermann. C. Rheological Characterization of
Topical Carbomer Gels Neutralized to Different pH. Pharma. Res. (2004) 21, 1192-
1199.
3) https://www.youtube.com/watch?v=o9twC_-MZ1w
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Polymer Characterization I – Measurement of Molecular
Weight
• Monomers polymerize into polymer, its structure and physical properties change such as
glass transition temperature, melting temperature, stiffness, tensile strength, toughness,
viscoelasticity, and viscosity.
• Measuring viscosity is a good and simple method to check the polymerization.
• Viscosity of a fluid is a measure of its resistance to deformation at a given rate.
• For liquids, viscosity corresponds to the concept of thickness.
• For example:- syrup has a higher viscosity than water.
• Before polymerization,
• styrene (monomer) as a small molecule shows low viscosity,
• thus flows the small-diameter tube or capillary fast.
• After polymerization,
• viscosity, resistance to flow, increases due to its increased chain length
• then flow is delayed.
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• Mark–Houwink equation gives a relation between intrinsic viscosity [η] and molecular
weight M.
[η]=KMa
• Intrinsic viscosity [η]:- reflects the capability of a polymer in solution to enhance the
viscosity of the solution.
• Molecular weight, M:- the sum of the atomic masses of all atoms in a molecule
• Molecular weight of a polymer can be determined by plotting data on the intrinsic viscosity
and vice versa.
• Mark–Houwink parameters values, ‘a’ and ‘K’, depend on the particular polymer-solvent
system.
• For solvents,
• a = 0.5 is indicative of a theta solvent
• a = 0.8 is typical for good solvents
• For most flexible polymers, 0.5 ≤ a ≤ 0.8
• For semi-flexible polymers, a ≥ 0.8
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(b)
(a)
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Materials and Equipment
Materials:
• Polystyrene,
• Tetrahydrofuran (THF)
Equipment:
• Rotary Viscometer
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Experiment
1) Prepare polystyrene solution sample (Average Mw = 192kDa). Dissolve 10 g of the
polymer in 200 ml of THF (viscosity of THF = 0.48 cP).
2) Measure the dynamic viscosity (ηd) of polystyrene by using automatic rotary viscometer
(Unit: cP, Sample measurement time: 20 s).
3) Calculate the intrinsic viscosity with this equation.
ηd = ([η]ρ+1) η0
where [η] (dL/g) is the intrinsic viscosity, η0 is the viscosity of the solvent and ρ (g/mL) is
the concentration of solution (100mL/g = 1dL/g).
4) Calculate the viscosity average molecular weight (Mv) by using Mark-Houwink-Sakurada
Relationship (K = 5.2 10-3 and a = 0.712 for polystyrene in THF).
[η] = K Mva
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Results & Discussion
1) Investigate viscosity units, their definitions and their relations (ex. Pascal-Second,
Poise).
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References
1) Herman L. Wagner. The Mark-Houwink-Sakurada Equation for the Viscosity of Atactic
Polystyrene. J. Phys. Chem. Ref. Data (1985) 14, 1101-1106.
3) https://my.che.utah.edu/~tony/chen4903/equipment/A_Viscometers/
ViscosityDefinitions.pdf
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