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Polymers are large molecules made up of repeating units called Monomers The synthetic process is Polymerization. E.g.
Polymerization
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
P =
M0 - Mt M0
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
+ H+
Stable tertiary carbocation
OR H+
+ OR
stable oxonium ion
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+
+
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).
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)
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
DP
Living
DP =
[monomer] [Initiator]
100 50 conversion
Initiator decomposes quickly, and polymer chains have long life times
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
Dead Polymer
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
n-1 Ph Ph
D : n = 60 : m = 20
O OEt
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
OEt P OEt O
PMMA=
McHale, Aldabbagh, Zetterlund, J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 2194-2203
macromonomer
Graft Copolymer
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
4%
63% 40%
19%
5
log M
Shift to higher MW
Copolymerization
macromonomer
Monomer NIPAM
Poly(AA)
Graft copolymer
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
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
Wcomplex
Tcomplex
Cl3Ti
Cl3Ti Cl3Ti R
Cl3Ti n
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.
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
Step-growth Polymerization
These are poly(amides) bristles of toothbrishes, stockings, rope, tires, carpet fibre
- H2O
260-280 C 250 psi
MW = 10,000, m.pt. 250 C, fibres stretched (to increase strength) to 4 times their length
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
4. Exact stoichiometric balance and very pure monomers are required to achieve high molecular weights
Step-growth Polymerization
Step-addition no by-products
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
[ CH2 ]n
N2
Impurity found in diazomethane
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.
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.
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.
n-1 Ph Ph O
m OMe
A
CO2Me MeO2C
D : n = 60 : m = 20
+
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.