POLYMERS

What is a polymer?

plastic videos: http://www.tvo.org/iqm/plastic/video.html#

http://www.cem.msu.edu/~reusch/OrgPage/VirtualText/polymers.htm#polmr2b

Introduction
While we take them for granted, prior to the early 1920's, chemists doubted the existence of molecules with molecular weights greater than a few hundred. This limiting view was challenged by Hermann Staudinger, a German chemist with experience in studying natural compounds such as rubber and cellulose. In contrast to the prevailing rationalization of these substances as aggregates of small molecules, he proposed that they were macromolecules of 10,000 or more atoms. He formulated a polymeric structure for rubber, based on a repeating isoprene unit (referred to as a monomer). For his contributions to chemistry, Staudinger received the 1953 Nobel Prize. Recognition that polymeric macromolecules make up many important natural materials was followed by the creation of synthetic analogs having a variety of properties. The terms polymer and monomer were derived from the Greek roots poly (many), mono (one) and meros (part). Applications of these materials as fibers, flexible films, adhesives, paints and tough but light solids have transformed modern society.

Writing Formulas for Polymeric Macromolecules

The repeating structural unit of simple polymers reflects the monomer(s) structure. However, most polymers are not composed of identical molecules. For linear high-density polyethylene (HDPE), ethylene is the monomer. The polymer is called polyethylene rather than polymethylene, (-CH2-)n, because ethylene was the actual monomer. This polymer is composed of macromolecules in which n (degree of polymerization, DP) ranges from 10,000 to 100,000 (molecular weight 2*105 to 3*106 ).

How about in DNA?

Polyethylene molecules are all long carbon chains, but their lengths (DPs) may differ by thousands of monomer units. Because of this, polymer molecular weights are usually given as averages. Two experimentally determined values (by gel permeation chromatography, a process similar to column chromatography) are: Mn, the number average molecular weight, calculated from the mole fraction distribution of different sized molecules. Mw, the weight average molecular weight, calculated from the weight fraction distribution of different sized molecules. Since larger molecules weigh more than smaller molecules, Mw is skewed to higher values, and Mw > Mn. The Mw / Mn ratio is called polydispersity. If all polymer molecules have identical weights (monodisperse sample), the ratio Mw / Mn = 1 (DNA). Typically Mw/Mn > 2.

Polymerizations occurs via either chain growth or step growth mechanism. In chain growth (addition) an active chain propagates via continuous monomer addition (like a zipper).

http://www.youtube.com/watch?v=i3QTlsh VSXo&feature=related

Radical Polymerization of Vinyl Chloride

Polymerization occurs via either chain growth or step growth mechanism. In step growth (polycondensation) oligomers of various sizes grow simultaneously. They all have the same reactivity and propagate via elimination of a small molecule (H2O, HCl, etc)

Synthesis of Addition (chain growth) Polymers

Most addition polymers are derived from substituted alkenes. The most common and thermodynamically favored chemical transformations of alkenes are addition reactions and proceed via reactive intermediates. Since a p-bond in the monomer is converted to a s-bond in the polymer, the polymerization reaction is usually exothermic by 8 to 20 kcal/mol. Explosively, uncontrolled polymerizations can happen. http://www.youtube.com/watch?v=w9uFymAPIu4

There are four chain growth polymerization mechanisms: Radical. The initiator is a radical, and the propagating site is a carbon radical. Cationic. The initiator is an acid, and the propagating site is a carbocation. Anionic. The initiator is a nucleophile, and the propagating site is a carbanion. Coordination. The initiator is a transition metal complex, and the propagating site of is also attached to a metal complex (remember Grignard?).

Radical Chain-Growth Polymerization Most vinyl monomers are subject to radical polymerization. Since this can be initiated by traces of oxygen or other minor impurities, monomers are often stabilized by small amounts of radical inhibitors to avoid unwanted reaction. A radical polymerization is started by using a radical initiator, such as a peroxide or certain azo compounds.

For example, the radical polymerization of styrene to polystyrene (lab): The first two equations illustrate the initiation, and the last two, the chain propagation. Each monomer unit adds to the growing chain in a manner that generates the most stable radical. Since carbon radicals are stabilized by most substituents, there is a preference for head-to-tail regioselectivity.

In principle, a radical polymerization could produce just a few very long chains. In practice, a large number of medium size chains are formed, because of chaintransfer and termination reactions. The most common termination processes are recombination and disproportionation. In both, two reactive radical sites are removed simultaneously. Since the concentration of radicals is small, the rate of termination is also very small. Therefore, most growing chains achieve moderate length before termination. The relative importance of the termination depends on the monomer. For acrylonitrile and styrene recombination is dominant while methyl methacrylate and vinyl acetate are terminated by disproportionation.

Another side reaction is the chain transfer of a radical from one location to another by an intermolecular or intramolecular hydrogen atom transfer.

Chain transfer reactions are especially prevalent in the high pressure radical polymerization of ethylene, the method used to make LDPE (low density polyethylene). The 1-radical at the end of a growing chain is converted to a more stable 2-radical by H atom transfer. Further polymerization at the new radical site generates a side-chain radical, and this may in turn lead to creation of other side chains by chain transfer reactions. As a result, the morphology of LDPE is an amorphous network of highly branched macromolecules.

Ring opening polymerization is another example of chain-growth

what is the mechanism?

Many polymeric materials with chain-like structures similar to polyethylene are known. Polymers formed by linking together monomer units, with no loss of material, are called addition or chain-growth polymers.

Name(s)
Polyethylene-branched low density (LDPE) Polyethylene-linear high density (HDPE) Polypropylene (PP) different grades Poly(vinyl chloride) (PVC) Poly(vinylidene chloride) (Saran A) Polystyrene (PS) Polyacrylonitrile (PAN, Orlon, Acrilan) Polytetrafluoroethylene (PTFE, Teflon) Poly(methyl methacrylate) (PMMA, Lucite, Plexiglas) Poly(vinyl acetate) (PVAc) cis-Polyisoprene natural rubber

Formula
- (CH2-CH2)n- (CH2-CH2)n-[C -H2-CH(CH3)]n- (CH2-CHCl)n-

Monomer
ethylene CH2=CH2 ethylene CH2=CH2 propylene CH2=CHCH3 vinyl chloride CH2=CHCl vinylidene chloride CH2=CCl2 styrene CH2=CHC6H5 acrylonitrile CH2=CHCN tetrafluoroethylene CF2=CF2 methyl methacrylate CH2=C(CH3)CO2CH3 vinyl acetate CH2=CHOCOCH3 isoprene CH2=CH-C(CH3)=CH2

Properties
soft,waxy solid rigid, translucent solid
atactic: soft,elastic solid isotactic: hard, strong solid
http://www.youtube.com/watch?v=m3X3BRes__8&feature =related

Uses

film wrap, plastic bags candles electrical insulation bottles, toys similar to LDPE carpet, upholstery pipes, siding, flooring

strong rigid solid dense, high-melting solid hard, rigid, clear solid soluble in organic solvents high-melting solid soluble in organic solvents

- (CH2-CCl2)n-

seat covers, films

toys, cabinets packaging (foamed) rugs, blankets clothing non-stick surfaces electrical insulation lighting covers, signs skylights

- [CH2-CH(C6H5)]n-

- (CH2-CHCN)n-

- (CF2-CF2)n- [CH2-C(CH3)CO2CH3]n- (CH2-CHOCOCH3)n- [CH2-CH=C(CH3)-CH2]n- [CH2-CH=CCl-CH2]n-

resistant, smooth solid

hard, transparent solid soft,sticky solid soft,sticky solid tough, rubbery solid

latex paints, adhesives requires vulcanization for practical use

Polychloroprene (cis/trans) (Neoprene)

chloroprene CH2=CH-CCl=CH2

synthetic rubber oil resistant

 Step-growth (condensation) polymerizations proceed by functional group transformations. They often occur with loss of a small byproduct, such as water, and frequently combine two different components in an alternating structure. In contrast to chain-growth polymers, most of which grow by C-C bond formation, step-growth polymers generally grow by C-heteroatom bond formation (C-O & C-N in Dacron & Nylon below).

protein

Examples of naturally occurring condensation polymers include cellulose, polypeptide (proteins), and DNA.

 Condensation polymers form slower than addition polymers, often requiring heat, and are generally of lower Mn. The 2 terminal functional groups on a chain remain active, and groups of shorter chains combine into longer chains in the late stages of polymerization. Polar functional groups on the chains often enhance chainchain attractions, and thus crystallinity and tensile strength. For commercial synthesis, the carboxylic acid components may be employed in the form of derivatives such as esters.

Formula ~[CO(CH2)4COOCH2CH2O]n~

Type Polyester Polyester Dacron Mylar Polyester

Components
HO2C-(CH2)4-CO2H HO-CH2CH2-OH para HO2C-C6H4CO2H HO-CH2CH2-OH meta HO2C-C6H4CO2H HO-CH2CH2-OH (HO-C6H4-)2C(CH3)2 (Bisphenol A) X2C=O (X = OCH3 or Cl) HO2C-(CH2)4-CO2H H2N-(CH2)6-NH2

Tg C <0 70

Tm C 50 265

50

240

Polycarbonate Lexan (CDs)

150

267

~[CO(CH2)4CONH(CH2)6NH]n~ ~[CO(CH2)5NH]n~

Polyamide Nylon 66 Polyamide Nylon 6 Perlon Polyamide Kevlar Polyamide Nomex

45 53

265 223

para HO2C-C6H4CO2H para H2N-C6H4-NH2 meta HO2C-C6H4CO2H meta H2N-C6H4-NH2 HOCH2CH2OH

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500

For polyurethanes, the polymerization does not eliminate a small molecule.

Nylon 6 is also made by ring opening (chain growth).

273

390

Polyurethane Spandex

52

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The Nylon Rope Trick

Note that the same polymer can be synthesized by both chain (ring opening) and step polymerizations.

http://www.youtube.com/ watch?v=7nCfbZwG http://www.youtube.com/ watch?feature=endscree n&v=yFEHKRdXb9Y&N R=1 WK8

Thermosetting vs. Thermoplastic Polymers Most linear polymers are thermo-plastic. Above their glass/softening transition (Tg) (which is a type of melting) they may be shaped or pressed into molds, spun or cast from melts or dissolved in solvents for later fashioning. Other polymers which are crosslinked resist deformation and are insoluble. They are usually prepared directly in molds that yield the desired object. Since they cannot be reshaped by heating, they are called thermo-sets. Bakelite is one of the first completely synthetic plastics to see commercial use (~1910).

http://www.youtube.com/watch?v=NpO2DA vMWi4&feature=related

In the lab: radical polymerization of styrene with benzoyl peroxide book, page 753, experiment 69.4.4 4th edition 67.4 5th ed., p 770-772 6th ed.

To Read Chapter 69 Pages 757-779 6th; 813-836 5th 739-761 (4th) Homework: Questions 2 and 4

Final
FINAL Thursday 05/01/14 5-5:50pm Will concentrate primarily on the second semester, but will assume you already know the techniques discussed in the first semester

If anybody is interested in doing research in polymers, please come and see me! ;-)