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Chapter 16: Polymers
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Reading All of Ch. 16 except Sec. 16-10 and 16-11.
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Homework No. 12 Problems 16-8, 16-10
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Polymers Natural polymers Synthetic polymers
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Examples of natural polymers Cellulose (e.g., wood, wool, cotton) Starches Proteins Natural rubber
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Examples of synthetic polymers Polyethylene Polyvinyl chloride Synthetic rubbers
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(PVC)
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Copyright © 2006 by Nelson, a division of Thomson Canada Limited
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Addition polymerization.OH is the initiator.
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Degree of polymerization = No. of mers in a molecule = Molecular mass / mer mass
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Molecular mass is M i for size interval i.
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Population described as Number fraction of molecules in size interval i = X i = No. of molecules in size interval i divided by No. of molecules in polymer Number-average molecular mass = Σ i (X i M i )
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Population described as Mass fraction of molecules in size interval i = W i = Mass of molecules in size interval i divided by mass of molecules in polymer Mass-average molecular mass = Σ i (W i M i )
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Number-average molecular mass < Mass-average molecular mass
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Example problem 18 g sugar (C 6 H 12 O 6, M = 180 g/mole) 18 g water (H 2 O, M = 18 g/mole) No. of molecules of sugar = 18/180 = 0.1 mole No. of molecules of water = 18/18 = 1.0 mole Mass-average molecular mass = (0.50) (180 g/mole) + (0.50) (18 g/mole) = 99 g/mole Number-average molecular mass = (0.1/1.1) (180 g/mole) + (1.0/1.1) (18 g/mole) = 32.7 g/mole
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Polymer blend (a solid solution)
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Homopolymer: 1 type of mer Copolymer: >1 type of mer
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Copolymer
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license. Styrene-butadiene block copolymer
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license. Polyamide Condensation polymerization
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Polyester Polyamide
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.
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Functionality No. of reaction sites in a monomer for polymerization = 2 for linear polymers >2 for network (3D) polymers
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Due to stereohindrance, functionality = 3, i.e., each phenol ring is at most linked to 3 other phenol rings. One water molecule is formed per bridge.
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Network polymer
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Kinked conformation
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.
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Isomers
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Isotactic Syndiotactic Atactic No side group
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license. Isotactic Syndiotactic Atactic
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Tacticity Fractions that are atactic, syndiotactic and isotactic
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Branching
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Types of polymer Thermoplastic (softens upon heating) Thermoset (does not soften upon heating)
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Compression molding
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Necessary but not sufficient conditions for elastomers Noncrystalline at room temperature Glass transition temperature well below room temperature Macromolecular chains - very long with many bends - in constant motion at room temperature - cross-linked every few hundred atoms
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Degree of crystallinity Degree of crystallinity = Fraction of the polymer that is crystalline For the same cooling rate, different polymers have different tendencies toward crystallinity
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Copyright © 2006 by Nelson, a division of Thomson Canada Limited Crystalline region
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Copyright © 2006 by Nelson, a division of Thomson Canada Limited Orthorhomic unit cell of polyethylene
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Copyright © 2006 by Nelson, a division of Thomson Canada Limited Network polymers Glassy usually, because rearrangement is difficult.
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Copyright © 2006 by Nelson, a division of Thomson Canada Limited Linear polymers Factors that affect the tendency toward crystallinity 1.Character of the side groups (a) Bulkiness of the side groups (b) Arrangement of the side groups 2.Amount of chain branching 3.Macromolecular chain length (long molecules tend to be kinked) 4.Homopolymers tends to be more crystalline than copolymers
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Effect of the degree of crystallinity
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.
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Copyright © 2006 by Nelson, a division of Thomson Canada Limited
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Description of a polymer Mer(s) Type of copolymer Molecular mass (degree of polymerization) Tacticity Degree of crystallinity
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