SYNTHETIC ORGANIC POLYMERS

Convenor: Dr. Fawaz Aldabbagh

Polymers are large molecules made up of repeating units called Monomers The synthetic process is Polymerization. E.g.
Polymerization

H2C CH2 Monomer O Monomer

Polymerization

CH2 CH2 Polymer

CH2 CH2 O Polymer

Note define repeating unit in terms of monomer structure Degree of Polymerization is the number of monomer units in a Polymer However, for synthetic polymers it is more accurate to state average degree of polymerization (DP)

A polymer prepared from a single monomer is a homopolymer If two or more monomers are employed, the product is a copolymer

Linear polymer has no branching

Graft copolymer is an example of a branched network

Two main classifications of Polymerization Addition reaction or Chain growth

Molecular weight increases by successively adding monomers to a reactive polymer chain end resulting in high molecular weights at low conversions.

STEP reaction or growth

Polymers are formed by linking monomer molecules to form dimers, trimers and higher species in a step-wise fashion. The most abundant species react, and thus high molecular weight formed only beyond 99% conversion.

Polymerization Conversion (p)

P =

M0 - Mt M0

M0 = initial number of monomer molecules Mt = Number of monomer molecules at time t

Ionic Chain (addition)-Growth Polymerization

The choice of ionic procedure depends greatly on the electronic nature of the monomers to be polymerized

Vinyl monomers with electron-withdrawing groups

CN CO2R CO2R CN CO2R

Anionic Polymerization Vinyl monomers with electron-donating groups

N OR SR

Cationic Polymerization Monomers and reagents should be scrupulously purified; water and oxygen should be removed. Polymerizations carried out at very low temperatures

Anionic Polymerizations
Initiators include alkyl lithiums and sodium amide

Cationic Polymerization

-- the formed carbocation must be quite stable

+ H+
Stable tertiary carbocation

OR H+

+ OR
stable oxonium ion

E.g. proton initiates polymerization of isobutane (2-methylpropene)

BF3/H2O n
Adhesive, sealant, insulating oil, lubricating oil

Reactions of water with reactive carbanions and carbocations

H
_

O acid

H CN +
_

CN

CN

CN

CN OH

CN

Note viable substrates for anionic polymerizations do not have E-protons H H H + OMe OMe OMe OMe n OMe OMe n H base

H3O+

Chain Reaction: Free Radical Polymerization Initiation

RO RO OR 2 RO RO Ph

+
RO

Propagation

Ph

RO Ph Ph

n
Ph

n Ph

Random Termination

Dead chains

Conventional Radical Polymerization Advantages 1/wide range of vinyl monomers polymerizable 2/can be carried out in bulk, water, organic solvents and other solvents 3/no rigorous purification or drying of reagents required Conditions: Usually heat required for initiation Initiator decomposition time should be considered - Amount of initiator, reaction temperature and initiator half-life (slow decomposition) Initiation Rate = Termination Rate - steady state kinetics apply Overall, [radical concentration] = low
Since termination (disproportionation and coupling mechanism) is random, a broad MWD results. This polymer is dead (cannot initiate new monomer additions).

Examples of Polymers Prepared by Radical Polymerization Monomer

H H H CH2CH

Polymer
n

Poly(styrene)

H H H H

H CN H O MeO

CH2CH CN

Poly(acrylonitrile)

n
CH2CH C OMe
n

Poly(methylacrylate)

H H Me

n
O O

CH2CH O C Me

Poly(vinylacetate)

Advantages of Radical Polymerization

1. Wide variety of vinyl monomers can be polymerized (electron rich and deficient DBs) 2. Can be carried out in bulk and in a wide variety of solvents, which include water and organic solvents 3. No rigorous purification of reagents or drying of solvents required 4. Rapid formation of high molecular weight polymer after small conversions of monomer to polymer ( chain (addition) polymerization) 5. Living/controlled polymerizations enable easy formation of block copolymers and sophisticated architectures

75% of commercial polymers are made by radical polymerizations

Some monomers can only be polymerized by radical means, e.g. acrylic acid (AA) H C H O C C OH H AIBN C H C n COOH H H

Ion-exchange resins, smart polymers

Radical Polarity
Polar Effects are important in radical polymerizations, and can give alternating copolymers

CN R
H

H

R Ph CN

Ph

Ph

R Ph CN Ph CN
n

Chain Reaction initiation, propagation, termination Chain polymerization with termination

e.g. conventional radical polymerization
Life time of polymer radical chain is about 1 second Initiator added so to slowly decompose throughout polymerization time Typically, rate of initiation = rate of termination Therefore, [propagating radical] remains constant Steady State
100 50 conversion DP

Chain polymerization without termination

e.g. nitroxide-mediated radical polymerization (NMP)

DP

Living

DP =

[monomer] [Initiator]
100 50 conversion

Initiator decomposes quickly, and polymer chains have long life times

Nitroxide-mediated Controlled/living Radical Polymerization (NMP)

P T P

T = Nitroxide P = Propagating radical

propagation T is sterically congested

Features: 1. Molecular weight increases linearly with conversion 2. Narrow molecular weight distributions obtained 3. Polymer chains contain living ends enabling chain extension or block copolymer synthesis Block copolymer synthesis
AAAA n A T AAAA n A

propagation

Bn
AAAA
n

BBBB

B n

Conventional Radical Polymerization Broad MWD

Dead Polymer

Controlled Radical Polymerization

T T T T T T

Narrow MWD
Living Polymer

Life time of radicals extended from 1 second to hours, as the radicals do not get involved in irreversible bimolecular termination reactions, since radicals are trapped by nitroxide reversibly Initiator must decompose quickly to insure narrow MWD

Example of Block Copolymer Formation

m O OMe
Ph n AIBN, heat SG1 n = 60 Ph n-1 Ph heat N O P OEt

n-1 Ph Ph

D : n = 60 : m = 20

O OEt

Please correct block copolymer structure in questions

Reversible trapping added to propagation to prevent irreversible termination

n-1 Ph Ph

N O SG1

OEt P OEt O

First living poly(styrene) block heated in the presence of methyl acrylate to give diblock D

OMe O m

propagation m = 20

n-1 Ph Ph O

O N m OMe

O P O O

D : n = 60 : m = 20

H C H MeO C

Me C O

n AIBN

Me CH2 C C
n

OMe

Poly(methyl methacrylate) perspex

MMA Nitroxides cannot control MMA Polymerizations

H C H CH3 C + CO2Me PMMA disproportionation N O SG1 H C H

OEt P OEt O

CH2 C + CO2Me OEt N P OEt OH O SG1-H

PMMA=

McHale, Aldabbagh, Zetterlund, J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 2194-2203

Alternating, Block and Graft Copolymers are made by radical copolymerization

AIBN, heat excess small monomer

macromonomer

Graft Copolymer

Graft Copolymer Formation

Recent Example of a Graft Copolymer Synthesis

Copolymerization

macromonomer

monomer

Poly(AA)

NIPAM
H H H CH2 C O C OH O CH C n 2 C C H

Graft copolymer

H 2C

CH C O

Br

CH2 C O C OH

+
OCH2CH3

H3C CH N H3C

Poly(acrylic acid) macromonomer

N-Isopropylacrylamide NIPAM monomer (excess)

Insoluble in water above the lower critical solution temperature (LCST)

McHale, Aldabbagh, Carroll, Yamada, J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 4394-4400

Copolymerization of Poly(AA) Macromonomer with NIPAM in ethanol at 60 C

0.6 0.5
macromonomer
W (log M )

0.4 0.3 0.2 0.1 0.0 2

4%

63% 40%

19%

5
log M

Shift to higher MW

Dual-Responsive Smart Graft Copolymer

Copolymerization

macromonomer

Monomer NIPAM

Poly(AA)

Graft copolymer

Insoluble in water Soluble in NaOH (aq)

Poly(NIPAM) in water (40C)

Graft copolymer in NaOH solution (40C)

Graft copolymer in NaOH (50C)

McHale, Aldabbagh, Carroll, Yamada, J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 4394-4400 Gibbons, Carroll, Aldabbagh, Yamada, J. Polym. Sci. Part A: Polym. Chem. 2006, 44, 6410-6418

Ziegler-Natta Chain (Addition) Polymerization

H C H C H H TiCl4/AlEt3 1-4 atm, rt n

Milder conditions than radical polymerization HDPE (high density poly(ethylene) is 3-10 times stronger than LDPE Less cross-linking, as terminal DBs less reactive than substituted DBs of radical polymerization Termination reaction
H Cl3 Ti H

Cl H Ti Cl Cl

Few monomers polymerized by Z/N

Ziegler-Natta Addition Polymerization

Isotactic polymerization
TiCl4 / AlR3 1-4 atm, rt R n

R TiCl4 + AlR3 Cl3Ti Cl AlR2 Cl3Ti R + Cl AlR2

Wcomplex

R Cl3Ti R Cl3Ti Cl3Ti

Tcomplex

Cl3Ti

Cl3Ti Cl3Ti R

Cl3Ti n

Stereochemistry and Polymers

M an y usef ul pol ym er s, such as pol y(s t yr ene), poly(acrylonitrile) and poly(vinyl chloride) are atactic as normally prepared. Customized catalysts that effect stereoregular polymerization of poly(propylene) and some other monomers have been developed, and the improved properties associated with the increased crystallinity of these products has made this an important field of investigation.

Amorphous polymer melts to a hard rubbery, glassy state

The properties of a given polymer will vary considerably with its tacticity. Atactic poly(propylene) is useless as a solid construction material, and is employed mainly as a component of adhesives or as a soft matrix for composite materials. In contrast, isotactic polypropylene is a high-melting solid (ca. 170 C) which can be molded or machined into structural components.
Because poly(propylene) rope is so light, it is the only rope that floats. For this reason, it is very popular among ropes for pool makers and water sports. Also when wet it is flexible and does not shrink.

Step-growth Polymerization
Step-polymers are made by allowing difunctional monomers with c om pl e me n ta r y fu nc ti ona l gr o u ps t o r e a c t w i th one a n o the r Condensation between two molecules
HO

+
MeO OMe OH

C OCH2CH2O
n

terephthalic acid

ethylene glycol

Poly(ethylene terephthalate) PET

Recyclable plastic bottles and textile fabrics

This is an example of a poly(ester) The reaction is a transesterification

Using a condensation reaction

Step-growth Polymerization

These are poly(amides) bristles of toothbrishes, stockings, rope, tires, carpet fibre

Molten nylon spun into fibres

- H2O
260-280 C 250 psi

First patented by Dupont

MW = 10,000, m.pt. 250 C, fibres stretched (to increase strength) to 4 times their length

Self-Condensation or Ring-Opening Polymerization

Also opened by cations & anions

First patented by BASF

High temp. to drive off water

Nylon 6 is made by heating caprolactam to about 250 C with about 5-10% water

Step-growth Polymerization 1. Polymers retain their functionality as end groups at the end of the polymerization 2. Only a single reaction is responsible for polymer formation 3. Molecular weight increases slowly even at high conversion. This is given by the Carothers equation, where conversion is (p)

DP =

1 1-p

At 98% conversion, the degree of polymerization is only 50%

Larger chains react only at very high conversion

4. Exact stoichiometric balance and very pure monomers are required to achieve high molecular weights

5. Equilibrium reactions necessary to remove by-product

Step-growth Polymerization

Step-addition no by-products

Insulation foam, HP adhesives, sealants, carpet underlay

N O

HO OH O

Bayer-patented

180 C

N H
Lower Temp. than condensation reactions O
CH2 +
6

N H
Poly(urethane)

O O n
O

rt
O

CH2
6

bisdiene

n
O
Cyclic diene held cis is very reactive e.g. dicyclopentadiene

benzoquinone Chain-growth condensation CH2N2

BF3

[ CH2 ]n

N2
Impurity found in diazomethane

Time for litter to biodegrade

Product Paper Wool socks Plastic coated paper milk cartons Plastic bags Nylon fabric Aluminum cans Plastic 6-pack holder rings Glass bottles Plastic bottles Time to biodegrade 2-5 months 1 to 5 years 5 years 10 to 20 years 30 to 40 years 80 to 100 years 450 years 1 million years Forever

Plastic resin identification codes (1)

Codes Descriptions
Polyethylene terephthalate (PET, PETE) is clear, tough, and has good gas and moisture barrier properties. Commonly used in soft drink bottles and many injection molded. Other applications include strapping and both food and non-food containers. Cleaned recycled PET flakes and pellets are in great demand for spinning fiber for carpet yarns, producing fiberfill and geo-textiles. High Density Polyethylene (HDPE) is used to make bottles for milk, juice, water and laundry products. Unpigmented bottles are translucent, have good barrier properties and stiffness, and are well suited to packaging products with a short shelf life such as milk. Because HDPE has good chemical resistance, it is used for packaging many household and industrial chemicals. Polyvinyl Chloride or PVC has excellent chemical resistance, good weatherability, flow characteristics and stable electrical properties. The vinyl products can be broadly divided into rigid and flexible materials. Bottles and packaging sheet are major rigid markets, but it is also widely used as pipes and fittings, siding, carpet backing and windows. Flexible vinyl is used in wire and cable insulation, film and sheet, floor coverings synthetic leather products, coatings, blood bags, medical tubing and many others.

Recycled products
Fiber, tote bags, clothing, film and sheet, food and beverage containers, carpet, strapping, fleece wear, luggage and bottles.

Bottles; pipe, buckets, crates, flower pots, garden edging, film and sheet, recycling bins, benches, dog houses, plastic lumber, floor tiles, picnic tables, fencing. Packaging, binders, decking, paneling, gutters, mud flaps, film and sheet, floor tiles and resilient flooring, cables, mats, cassette trays, electrical traffic cones, boxes, garden hose, mobile.

Plastic resin identification codes (2)

Codes Descriptions
Low Density Polyethylene (LDPE) used predominately in film applications due to its toughness, flexibility and relative transparency, making it popular for use in applications where heat sealing is necessary. LDPE is also used to manufacture some flexible lids and bottles and it is used in wire and cable applications. Polypropylene (PP) has good chemical resistance, is strong, and has a high melting point making it good for hot-fill liquids. PP is found in flexible and rigid packaging to fibers and large molded parts for automotive and consumer products.

Recycled products
Shipping envelopes, garbage can liners, film and sheet, furniture, compost bins, paneling, trash cans, landscape timber, lumber Automobile battery cases, signal lights, battery cables, brooms, brushes, oil bins, funnels, bicycle racks, trays pallets, sheeting. Light switch plates, vents, thermal insulation, desk trays, rulers, license plate frames, foam packing, foam plates, utensils Bottles, plastic lumber

Polystyrene (PS) is a versatile plastic that can be rigid or foamed. General purpose polystyrene is clear, hard and brittle. It has a relatively low melting point. Typical applications include protective packaging, containers, lids, cups, bottles and trays. Other. Use of this code indicates that the package in question is made with a resin other than the six listed above, or is made of more than one resin listed above, and used in a multi-layer combination.

Recycling of plastic containers and wrapping

Chemical Recycling by Eastman Kodak methanolysis

O O

C OCH2CH2O
n

CH3OH

O C MeO C

HO

H+

+
OMe OH

PET
These monomers are purified by distillation or recrystallization and used as feedstocks for further PET film manufacture.

Representative Exam Questions

1. Using one appropriate monomer for each polymerization classification, discuss the mechanism and kinetics; (a) Step-growth, b) conventional (non-living) chain (addition), c) living chain (addition) polymerizations. In your answer give details of reaction conditions and reagents required. 2. (a) Discuss the stability of nitroxide radicals, and there use in living radical polymerizations. (b) Why is it not possible to control the radical polymerization of methyl methacrylate with nitroxides? 3. How would you prepare the following polymers? Give reaction conditions, reagents and detailed mechanisms for each polymerization. Name polymers A-D.
n B C

n-1 Ph Ph O

m OMe

A
CO2Me MeO2C

D : n = 60 : m = 20

4. Draw structures of the polymers obtained from the following reactions;

H+

+
O

HO

OH

KOH

5. Give one example of an isotatic polymer and block and alternating copolymer. Provide reactions (with conditions) and mechanisms for their synthesis.