Polymers

Polymers Polymerization ie. A large molecule consisting of repeating smaller structural units (called monmrt units) The sequence of repetitive reactions between a monomer unit and the growing macromolecule or polymer chain CH2=CH2 a monomer unit →→→→ polymerization [-CH2-CH2-]n polymer

Categories of polymers, by Structural Linking of Monomer Units Homopolymer Only one type of monomer molecule is used to make a polymer, with repeating units of this one monomer

Copolymer Polymer formed by the combination of 2 or more different monomer molecules; The sequence arrangement of these units can vary in four different ways. 1) Random copolymer random sequence of different monomer units (A and B) -A-A-B-B-B-A-B-B2) Alternating copolymer alternating sequence of monomer units -A-B-A-B-A-B-A-B3) Block copolymer a sequence where there are repeating blocks of identical monomer units. -A-A-A-A-B-B-B-B-A-A-A-A-B-B-B-B4) Graft copolymer a chain which have side-chains from which to create extensions to another polymer chain.
CH2 CH CH2 CH side-chain extension reaction n polystyrene chain O OCH3 O OCH3 n The ester could further be functionalized by nucleophilic additon to the carbonyl and expulsionof -OCH3 groups -perhaps by a polyamide chain CH2 CH CH2 CH

Polymers are commonly named according to the chemical structure of the monomer unit, and then the prefix poly is added.
Monomer ethylene CH2=CH2 vinyl chloride CH2=CH-Cl tetrafluoroethylene CF2=CF2 ethylene glycol HO-CH2CH2-OH Polymer -[-CH2CH2-]npolyethylene poly(vinyl chloride) (PVC) -[-CF2CF2-]npoly(tetrafluoroethylene) (Teflon) poly(ethyleneglycol) (PEG) (-CH2CH2-O)CN CH2 CH
Cl CH2 CH n

Commercial Use plastic bags, film nearly everything plastic fittings and valves tubing inert, non-stickcaoting used in carpets to make them stain resistant emulsifying and thickening agent (non edible) in shampoos, lubricant oils, antifreeze used to make a co-polymer with PMMA (polymethylmethacrylate) in acrylic fibres for clothing
n

acrylonitrile CH2=CH-C≡N

n

poly(acrylonitrile) Orlon, Acrilan
O C O C O CH2 CH2 O

terephthalic acid
O HO C O C OH

poly(ethylene terephthalate) (PET

plastic pop bottles clothing fibres

Physical properties
The structure of the monomer will confer unique structural and physical characteristics in the polymer at different temperatures. Some polymer chains can pack or arrange/order themselves in a highly organized manner, resulting in highly crystalline material. For example linear polyethylene Some polymer chains have branching on the chain and cannot order themselves in a crystalline lattice and often said to be amorphous solids. For example rubber (polyisoprene) Most polymers are semi-crystalline, where some regions are highly ordered and crystalline, while other regions are not and have amorphous properties. Intermolecular forces that increase the melting point of a polymer are: a) structural regularity in polymer chain b) bond rigidity c) close-packing ability d) strong inter-chain attractive forces (eg. H-bonding)

Examples

Polymer
O C O C O R O n

R-Goup
CH2 CH2

Physical Poperty solid Melting point 265°C

a terephthalate-based poyester
CH2 CH CH3 CH2 CH CH2 CH3 CH3 CH2 C CH2 CH3
H3C O C O C O R O CH3 O C O C O R O CH3
CH 2 CH

not crystalline not crystalline solid Melting point 140°C solid Melting point 170°C

n

CH2 CH2

n

CH2 CH2

solid Melting point 70°C soft and rubbery

n C O O CH 3

poly(methacrylate)
CH3 CH2 C n C O O CH3

hard plastic Melting point 200°C

poly(methyl methacrylate)
CH2 CH n C O OH

solid absorbs water used in diapers soft plastic used in making soft contact lenses

poly(acrylic acid)
CH2 CH n C O NH2

polyacrylamide

Polymers
Free radical Polymerization Initiation -usually by homolysis of an initiator molecule for example benzoyl peroxide.
Benzoyl peroxide O Ph O O O Ph heat homolysis O 2 Ph O β-bond cleavage Ph + CO2

Radical chain polymerization initiating species

phenyl -- Ph

Radical Polymerization of vinyl Monomers: For example styrene. Propagation steps:
In H2C styrene Where "In" is formed by homolysis of a suitable initiator molecule e.g. "In" = Ph from decomposition of benozyl peroxide Ph In H2C In Ph Ph

H2C

CH

Styrene
Ph In benzylic radical

Ph

Ph

etc.

H2C

Ph

Note: the polymer is not homogeneous with respect to molecular weight. i.e. a mixture of polymers with different number of units in each chain is formed

Ph n polystyrene

Chain termination:
Radical combination:
In Ph n Ph Ph n Ph In

In

Ph n

Ph

Ph n

Ph

In

H-atom transfer

Ph In n

Ph H H H

Ph Ph n In

Ph In

Ph H n H +

Ph H

Ph

In n

Chain transfer to polymer
R R In n R H H n

R In n

R H H +

R

n new radical site along a poly mer molecule chain R

terminated poly mer chain m

Branched chain poly mer f ormation

R

n R m R

Intramolecular H-Atom Transfer
new site f or poly mer chain extension H CH 2 C H2 C C H2 CH2=CH2 H CH 2 CH 2 CH 2 C H2 C C H2 H CH 3 CH 2

growing chain of poly ethy lene

CH 2

CH H2 C

CH 2

CH 2 n

4-carbon branch

CH 2 H2 C CH 3

This process occurs frequently during free radical polymerization of polyethylene Branching prevents close-packing of the polymer chains and lowers the density of the polymer (called low-density polyethylene) High density poly ethylene, formed by other methods, has little branching and has substantial regions of crystallinity resulting from close-packing of the polymer chains

High Density Polyethylene Low Density P What effect does branching have on the physical properties of a polymer (packing, density and melting point) Branching causes a decrease in melting point, decreases density and makes the material more amorphous. Branching causes a decrease in the intermolecular forces between the molecules. For example vegetable oils are unsaturated and contain cis double bonds. The double bonds do not allow the molecules to pack well together and thus the intermolecular forces between the molecules are weak. To make margarine vegetable oil is hydrogenated (hydrogen is added to the double bonds) to make saturated fatty acids. Since the molecules pack better together the oil becomes a solid. The oil is only partially hydrogenated because if the oil becomes completely saturated it becomes hard and brittle. One problem with partial hydrogenation, is that the catalyst isomerizes some of the unreacted cis double bonds to the unnatural trans arrangement, and there is accumulating evidence that “trans” fats are associated with an increased risk of cardiovascular disease. Frequent chain terminations by this mechanism decrease the average molecular weight of the polymer obtained in this way For some monomers (e.g. propylene) this process occurs so frequently that polymers of useful chain length cannot be made by free radical polymerization

Some vinyl polymers
H2C CF2 used in piezoelectric material audio speakers and microphones styrene ion exchange resins used in plastics, stryofoam and isolation

H2C CHCl vinyl chloride monomer

vinylidine fluoride

CH2 CH Cl n PVC polymer

N 4-vinylpyridine

O O methyl methacrylate photoresists for microelectronics

plastics, plexiglas

O HO acrylic acid

thickeners adhesives sporting goods

O O t-BOC styrene O O (CH2)6 O CN

O O CH2 CH2 OH soft contact lenses

cyano-biphenyl mesogenic monomer side chain liquid crystal polymer

hydroxy ethyl methacrylate (HEMA)

Interpenetrating polymer
There are many compounds that have been developed containing more than one polymerizable vinyl group. As you can expect with two reactive sites on one monomer at some point crosslinking will occur. Interpenetrating polymer networks or IPNs are combinations of two or more polymers in network form. At least one of the polymers is synthesized and/or crosslinked in the presence of another. As such, IPNs share some of the advantages of both polymer blends and network polymers. One of the earliest commercial IPNs used in the automotive industry consists of polypropylene and ethylene-propylene-diene terpolymer (EPDM). Potential applications include toughened plastics, ionexchange resins, pressure sensitive adhesives, soft contact lenses, preparation of novel membrane systems and sound- and vibration-damping material. Given below is an example of the formation of an IPN. First formed is the crosslinked poly(ethyl acrylate) (PEA) network by free radical polymerization. Then the monomers styrene and divinylbenzene are added (this is called swollen, i.e. the polymer is swollen with the monmers) and then polymerized to form a crosslinked interpenetrating polystyrene (PS) network.

CH C

CH2 O +

O(CH2CH2OCH2CH2O CH C

CH2 )2 O

AIBN heat

OCH2CH3 ethyl acrylate

OCH2CH3 tetraethylene glycol dimethacrylate PEA network

CH +

CH2 +

CH

CH2 AIBN heat

CH PEA network styrene

CH2 PEA-PS IPN

divinylbenzene

HC

CH2 In HC CH2 In HC CH2 CH CH2CH CH2 Ph Ph Ph
n

Cross linking:

CH

CH2

CH2 CH2 C CH2 CH CH2CH CH2 Ph Ph Ph CH CH2

n

CH CH2

n

CH CH2CH CH2 CH CH2 C CH2 CH CH2CH CH2 Ph Ph Ph Ph Ph

n

n

CH CH2CH CH2 CH CH2 HC CH2 CH CH2CH CH2 n Ph Ph Ph Ph Ph

Catalysts for Cationic Polymerization e.g. boron trifluoride
F F B F Lewis acid (electron deficient) + O H H F F F B O H H

Lewis base (electron rich)

this complex can now act as a protic acid (i.e. proton donor)

Initiation
F F F B O H H H2 C CH 3 CH 3 F F F B O H + H3 C CH 3 CH 3

Propagation
CH 3 H3 C CH 3 H2 C CH 3 CH 3 H3 C H3 C H3 C CH2 CH 3 CH 3 H2 C

CH 3

CH 3

etc.

Chain Termination

Proton transfer to catalyst
CH 3 CH2 CH 3 CH2 CH 3 CH 3 H F O B F F CH2 CH 3 CH 3 CH2 CH 3 CH 2

+

terminated chain +
H O H F B F F

Chain transfer to monomer
CH 3 CH2 CH 3 CH2 CH 3 CH 3 CH 3 CH 3 CH2 CH 3 CH 3 CH2 CH 3 CH 2

+

H2 C

terminated chain +
CH 3 H3 C CH 3

Chain transfer to monomer results in short polymer chains (approx. molecular weight = 2,000 -3000) when the polymerization is carried out at room temperature Such polymers find some use as additives to lubricating oils but are not useful as plastics or rubber Much longer chain polymers can be produced by using low temperature (-90o C). -the activation energy for chain transfer to monomer reactions is higher than that for chain propagation; therefore, lowering the temperature slows down the chain terminating step more so than the propagation step These longer chain polymers are still too soft and pliable for use as rubber because the polymer chains move fairly easily relative to one another The polymers can be made tougher and more rigid by decreasing the ability of polymer chains to move relative to one another by forming covalent bond between polymer chains The polymer chain crosslinking of rubber is called vulcanization. In order to create polymer crosslinks, potentially reactive sites for covalent bond formation have to be introduced along the polymer chain. This is done by adding a small amount (approx. 1- 5%) of a second monomer (often isoprene) when polymerization is carried out. The resultant co-polymer has vinyl (alkene) groups at some positions along the polymer chains

In older vulcanization processes, the co-polymer was simply heated with elemental sulfur to form sulfide or poly sulfide crosslinks, however this reaction is usually very slow. Current vulcanization processes use so-called vulcanization accelerators
N S SH

mercaptobenzothiazole (MBT)

The mechanism of the acceleration process is not well understood A reasonable speculation is that the accelerator may react with elemental sulfur faster than does the copolymer to form a reactive sulfur containing species which is soluble in the polymer and which then carries out the crosslinking Free radical addition of sulfur radicals the vinyl side chains of the copolymer is probably involved.

Vulcanization
CH 3 CH 3 C H2 CH 3 C H2 CH 3 H2 C CH 3 CH 3 C H2 CH 3 CH 3 C H2 CH 3 C H2 CH 3 CH 2 H2 C Sx H2 C CH 3 C H2 CH 3 CH 3 CH 3 CH 2 C H2 CH 3 CH 3 CH 3 C H2

CH 3

CH 3

n

n S heat
C H2 CH 3

CH 3

CH 3 C H2 CH 3 C H2

H2 C CH 3 C H2 CH 3 CH 3

CH 3

m

x = 1 (sulfide or thioether crosslink)
CH 3

m x > 1 (polysulfide crosslink)

N SH S

N S S Sx H

mercaptobenzothiazole (MBT)

a hypothetical intermediate acelerated vulcanization

Condensation Polymerization Involves the condensation of two different bifunctional monomers, resulting in the elimination of a small stable molecule (H2O, HCl, ROH). It essentially involves a nucleophilic acyl substitution by one nucleophilic monomer on the electrophilic monomer.
Examples: 1) Poly(amide) Synthesis, e.g. Nylon 6,6

O O n HO C (CH2)4 C OH + nH2N (CH2)6 NH2 hexanedioic acid (adipic acid) 1,6-hexanediamine

O O HN (CH2)6 NH C (CH2)4 C n Nylon 6,6 6 carbons in diamine 6 carbons in the acid

+ 2n H2O vaporized which drives the reaction

Mechanism
O HO C (CH2)4 O C OH H2N (CH2)6 NH2 HO O C (CH2)4 O C H2N + amide linkage O HO C (CH2)4 O C + H2O HN (CH2)6 NH2 HO O C (CH2)4 O C HN + H O H (CH2)6 NH2 OH (CH2)6 NH2

O H2N (CH2)6 NH2 HO C (CH2)4

O C OH

O HN (CH2)6 NH C (CH2)4

O C n

2)

Polyester Synthesis e.g. PEN – polyethylene Naphthalate
O C n HO C O OH High temp and pressure acid buffer pH 4-5 ethylene glycol O C O C O

+ n HO CH 2 CH 2 OH

Naphthalene dicarboxylate

O CH 2 CH 2 n

+ 2n H2O

Mechanism:
O HO C O R1 C OH

poly(ethylenenaphthalate)

O HO R2 OH HO C R1

O C OH

HO R2 OH +

ether linkage O H2O + HO C O R1 C O R2 OH HO O C O R1 C HO O HO R2 OH HO C R1 O C OH + H O H R2 OH

O O R2 O C R1

O C n

3)

Polycarbonate, or specifically polycarbonate of bisphenol A, is a clear plastic used to make shatterproof windows and lightweight eyeglass lenses. General Electric sells it as Lexan.
CH3 C CH3 Bisphenol A O or CH3 C CH3 O O C n + 2n HO O O C O diphenyl carbonate NaOH

n HO

OH + n

n HO

CH3 C CH3 Bisphenol A

OH + n

Cl

O C

NaOH Cl

O

CH3 C CH3

O O C n

+ 2n HCl

phosgene

O HO R O Cl Cl -HCl OH Cl C Cl O HO R O C Cl

H HO R O C
+

-HCl

HO R OH O O Cl C
etc

O H HO R O C O R OH Cl
+

Cl

HO R O C O R OH

Glyptal polyester which can be used as plasticizers create a network polymer, forming a cross-linked polyester.
O C O n O O + n HO OH OH O C O O heat O O O O C O O O n

O n

Addition reactions 1) Poly(urethane) Synthesis

Polyurethanes are the most well known polymers used to make foams like foam cushions. Polyurethanes can also be used as in paints, synthetic fibers, and they can also be used as adhesives. Notice that in the mechanism not only monomers react, but also dimers, trimers, and so on. This makes it a step growth polymerization. Also, because no small molecule by-products are produced, it is called an addition polymerization
n O C N CH2 a di-isocyanate N C O + n HO CH2 CH2 OH ethylene glycol H 3O + catlyst In this reaction there is not a loss of a small molecule

O C N H

CH2

O N C O CH2 CH2 O H urethane linkage

n

Mechanism
O C N R R N C O H
+

CH2

N C O + HO

OH R2 O H O R + H etc

R

N

C

catalyst

O H + HO + H O R2

R2

R

N

C

R

+ N H

O C

H O R2 R N H

O C +

-H+

O R N C O R2 H urethane linkage

Sometimes, instead of using a small diol like ethylene glycol, a polyglycol, one with a molecular weight of about 2000 can be used. This produces a polymer within a polymer and polyurethane that looks something like this:
O C N H O N C O CH2 CH2 O x H soft rubbery block

Spandex

CH2

n

hard rigid block

Polyurea If a diamine is used instead of a diol in this reaction a polyurea is made

n O C N

CH2 a di-isocyanate

N C O + n H2N CH2 CH2 NH2 ethylene diamine O C N H O N C N CH2 CH2 O H H urea linkage

CH2

n

O C N R R N C O

CH2

N C O + H2N

NH2 R2

H+ catalyst

O R N C O H + H2N + H N R2 -H+ R N R2 R N

H

C N R + H H etc

R

+

O N H C

H N H R2 R N H

O C +

O C N R2 H urea linkage

3)

Urea-Formaldehyde (a polyurea plastic)

n H2N

O C

NH 2

+ n

urea
Mechanism

H H formaldehyde

O C

pH 4-7 N H

O N H N H

O N H CH2 n

O C H H

H

+

H + O C H H

H O + H2N C NH2 O

O

C + C NH2 N H H H H O H2N C N H O C N H NH2 etc

H O C H2N NH2 + H C H

H O+ N H

O C NH2

-H2O

H C H

H2N n
Melamine - Formaldehyde resins

N N N NH2

NH2 + n

H H formaldehyde

O C

pH 4-7

n N H

N N N

H N H N N

H N N N N

N N N H N H

n

melamine

n cross-linked polyurea

Phenol-Formaldehyde Resins – Bakelite used for heat and electrical coatings
OH OH n + n O C pH 4-7 OH HO HO HO a crossed polyol OH H H formaldehyde

phenol

Mechanism
OH + H O H OH -H2O + H O H H+ HO HO H H HO H + H HO HO H H O + H H OH + H HO H H -H+ HO H H OH

O H H

H+

OH OH H + OH

H

+

OH

OH etc

Nucleophilic Substitution Reactions forming polyethers 5) Epoxy Resins Highly cross-linked polyethers made from epoxide monomers
O CH 3 + HO CH 3 epichlorohydrin NaOH 50 - 100
o

Cl

OH

bisphenol-A

C

Cl

O O

CH 3 O CH 3

O

Cl

O Cl H2C HC H2C O

CH3 O CH3

O CH2 CH CH2 Cl

O H2C HC

CH3 H2 C O CH 3 O CH2 CH

O CH2

R CH3 O CH3 O
O H2C HC

CH2 O

R

CH3 O CH3 O

O CH2 CH CH2 O R

etc

Epoxy glues often consist of two components which the user mixes just before the desired "gluing " process. One component is the polymer shown above. The other component is often ethylene diamine. Ethylene diamine reacts with the epoxide "end" groups of the epoxy resin shown above to effect ring opening to form amino alcohols. Each amino group can react with two epoxide groups so that the resultant system is a network of cross-linked polymers which have very strong adhesion properties. The process of forming this network of cross-links is called "curing ".

O O

CH3 O CH3

OH O

CH3 O CH3 n

O

NH2 H2N

OH O

CH3 O CH3

OH O

CH3 O CH3 n

OH

N

N N

N OH

HO O

O

H3C H3C CH3

CH3

O

O

OH HO

O

O

H3C H3C CH3

CH3

O O HO OH

Conducting Polymers
From the web site: Plastic polymers: http://www.rsc.org/lap/educatio/eic/2003/higgins_may03.htm Prior to the 1970’s all synthetic polymers were insulated Conjugated polyacetylene was one of the first conducting polymers But hard to work with – insoluble – unstable, sensitive to oxygen. Polythiophene and polyohenylevinylene – less sensitive to oxygen -- more stable – long chain backbones could be attached to the polymers to make them more soluble in non-polar solvents. Why are they conducting? Large number of delocalized π bonding electrons allows movement along skeletal structure.

Conducting polymers (ICPs) have attracted much attention because of their potential applications in organic light emitting diodes (OLEDs), printed circuits, chemical sensors, electronic switches, rechargeable batteries, electrolytic capacitors, smart windows, EMI shielding and electrostatic charge dissipation (ESD) coatings. In spite of the thousands of papers published and patents filed in this field, the number of commercial applications of ICPs is still small. Poor long term stability and lack of reasonable processing methods have been the major showstoppers to the commercialization of ICPs. TDA's research on ICPs has focussed on improving the solvent processability of conducting polymers with proven stability, including poly(3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole.

Organic-Processable PEDOT:
Materials that combine electronic conductivity with optical clarity are sought for the fabrication of flat panel displays and other electronic devices. PEDOT has excellent transparency in the visible region, good electrical conductivity, and environmental stability. Unfortunately PEDOT, like most conducting polymers, is infusible and insoluble and therefore difficult to process in a thin-film form or in other shapes. Lack of processability has been a major impediment to the commercial acceptance of this polymer. A water dispersion of PEDOT doped with poly(styrenesulfonate) (PSS) is available from H.C. Starck under the trade name of Baytron®

Potential use in medicine, computing and telecommunication – molecular switches
http://quark.physics.uwo.ca/~smittler/Silvia%20Mittler%20Surface%20Fu nctionalisation.htm

Langmuir Trough
Amphiphilic Molecules (Soap) connection between hydrophilic and hydrophobic liquids

Compression organizes monolayer

Monolayer can be transferred onto a solid support

hydrophilic hydrophobic hydrophilic

bilayers can also be made

Molecular Switch
One of the focuses of our research is the development of novel molecular electronic devices. That is, devices made from a hybridization of conventional semiconductor fabrication methods and self-assembling synthetic molecules which have unique and useful electronic characteristics. We presently utilize a break junction method for making two terminal electrical contact to single molecule. We also have a method for making electrical contact to both sides of a molecular SAM (self-Assembled Monolayer): the nanopore. Using these measurement tools we have identified molecules which work well as insulators, conductors, diodes, two-terminal switches and random access memory cells.

http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#overview

Molecular Switch
The conduction path in a conventional microelectronics transistor is turned on using an applied voltage at the gate electrode. Similarly, the conduction path through a molecular switch is turned on by an applied voltage. The applied voltage is believed to cause a conformational shift which, in concert with the charging of the molecule, opens the conduction pathway.
NH2 O S O2N C CH3

http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#overview

Electroactive Polymers as Artificial Muscles - A Primer (J. Y. Cohen) http://www.polysep.ucla.edu/Research%20Advances/EAP/electroactive_polymers_a
Electroactive polymers (EAPs) are touted as the basis for future artificial muscles. EAPs can be deformed repetitively by applying external voltage across the EAP, and they can quickly recover their original configuration upon reversing the polarity of the applied voltage. To explore the potential use of EAP’s as artificial muscles, a brief evaluation is presented of an ionic-based EAP composite as a candidate artificial muscle material. The electromechanical properties of the EAP under dry and moist conditions are presented along with the EAP’s performance under load conditions. AS shown through a series of simple tests, the EAP has a high load bearing capacity to mass ratio, short response time, and nearly linear deformation response with respect to applied voltage

Illustration of an EAP-powered forceps. (a) forceps open; (b) forceps closes upon polarity reversal; (c) and (d) lift action.

Upon the application of an electrical field across a moist EAP, which is held between metal electrodes attached across a partial section of an EAP strip, bending of the EAP is induced. Positive counter ions move towards the negative electrode (cathode), while negative ions that are fixed (or immobile) to the polymer (e.g. SO3) experience an attractive force from the positive electrode (anode). At the same time, water molecules in the EAP matrix diffuse towards the region of high positive ion concentration (near the negative electrode) to equalize the charge distribution. As a result, the region near the anode swells and the region near the cathode de-swells, leading to stresses which cause the EAP strip to bend towards the positive anode.

Sign up to vote on this title
UsefulNot useful