Polymerization Mechanisms PDF

Polymerization Mechanisms
Essentials of Polymer Science and

Engineering
ChE 297
What we have covered so far…
• Introduction; How we classify polymers
• Polymerization mechanisms
– Chain-reaction polymerization
– Ionic and coordination polymerization
– Step-growth polymerization
– Ring-opening polymerization
Polymerization Mechanism
• new and most general classification scheme
for classifying polymers - based on the
polymerization mechanism involved during
polymer synthesis
• chain-reaction (addition) and step-reaction
(condensation)
Chain-Reaction Polymerization
• involves addition of unsaturated molecules to a rapidly
growing chain
• most common unsaturated compounds are olefins (vinyl
monomers)
• chain-reaction is induced by free-radical-forming reagents or
by ionic initiators
• initiation, propagation, termination, chain transfer maybe
involved
Initiation
• involves acquisition of an active site by the monomer
• may occur spontaneously by absorption of heat, UV
light, or high-energy irradiation
• done by addition of small amounts of initiators
• common initiators peroxides (ROOR), azo
compounds (highly colored, used in dyes, G-Ar-N=N-
Ar; G – electron-releasing groups –OH, -NH2, etc),
Lewis acids, and organometallic reagents
Initiation
• initiators initiate free-radical polymerization
and accelerate polymerization; however, they
are not catalysts
• usually a weak organic compound that
decomposes thermally or by irradiation to
produce free radicals (molecules containing
atoms with unpaired electrons)
Free radical forming reagents
thermal decomposition of benzoyl

peroxide
homolytic cleavage of O-O bond to
yield benzyol free radicals
may react to give phenyl free radicals
and CO2 (60-90oC)
decomposition of AIBN is by short-

wavelength visible light or
near UV radiation at temperatures as
low as 0oC
Ionic initiators
• if free-radical polymerization is carried out in
aq. medium (e.g. emulsion polymerization),
peroxide/persulfate decomposition is
accelerated by reducing agent (redox
initiation)
• low temperature advantage (peroxides above
are at room temp or higher)
Ionic initiators
persulfate ion initiator (e.g.
K2S2O8) reacts w/ reducing agent
bisulfate (e.g. NaHSO3) to produce
radicals for redox initiation
ferric ion is also used as

reducing agent
alkyl hydroxide (initiator) and

ferrous ion (reducing)
Initiation
• when choosing initiator, consider temperature range and reactivity of free
radicals formed
• nature of monomer and presence of accelerators/initiators affect
decomposition rate of initiators
• e.g. decomposition of benzoyl peroxide can be accelerated at room temp
by presence of ternary/quarternary amines; oxygen deactivates free
radicals by formation of peroxides/hydrogen peroxides (need of O2-free
atmosphere); handling of organic peroxides (shock or high temp =>
detonation)
• process is two-step (initiator decomposition to form radicals and addition
of initiator radical to monomer)
Propagation
• initiated monomer adds to other monomers
(in thousands of monomer molecules) in rapid
succession
• addition of a free radical to the double bond
of the monomer generates another radical
Three possible ways to propagate
Head-To-Tail
Head-To-Head
Tail-To-Tail
Termination
• growth activity of a polymer chain radical is destroyed w/
reaction to another free radical
• can occur with initiator radicals (unproductive)
• termination by combination/coupling (2 growing polymer

chains react with destruction of growth activity; predominates
at low temperature; creates a single polymer)
Termination
• termination by disproportionation (a labile atom, usually
hydrogen, is transferred from polymer radical to another;
results to two polymers; more pronounced at high
temperature since energy to break bonds is high)
Chain Transfer
• usual steps are initiation, propagation, and
termination
• a growing polymer is deactivated/terminated
by transferring its growth activity to a previous
inactive species
Chain Transfer
• TA monomer, polymer, solvent molecule; new radical A*
may or may not initiate the growth of another polymer chain
• if reactivity of A* is comparable to that of propagating chain
radical new chain maybe initiated
• if reactivity to monomer is less than that of propagating chain
radical overall reaction rate is retarded
• if unreactive toward monomer entire reaction could be
inhibited
• no creation/destruction of radicals; at any instant, overall
number of growing radicals remains unchanged
• may result to branching
Diene Polymerization
• sample conjugated dienes (butadiene,
chloroprene, isoprene); double bonds in 1,2
and 3,4
Diene Polymerization – Possible
Product Structures
- for butadiene, 1,2 and 3,4 are identical
- 1,4 may occur in cis or trans
- relative abundance of each possible
structure depends on the nature of
initiator, experimental conditions, and
diene structure; proportion affects
thermal and physical properties
How to control proportion of these
structures?
- e.g. polymerization of butadiene at low
temp => almost entirely trans-1,4 and 20%
1,2 units
- e.g. as T increases 1,2 units fairly
constant but cis-1,4 increases
- e.g. using lithium/organolithium initiators
in nonpolar solvent (pentane/hexane)
high cis-1,4 content
- e.g. w/ alkali metal initiators or polar
solvents cis-1,4 units decrease
All chain-reaction polymerizations involve essentially same number of steps;
difference in initiation (free radical, ionic, or coordination)
Explain the following observation:

α – methyl styrene polymerizes much less
readily than styrene.
Reactivity of vinyl monomer depends on

the nature of substituents on the monomer
double bond
Activation of the double bond by the
phenyl group is compensated by the presence
of methyl (electron-donating)
Steric hindrance at the reactive site
Cationic Polymerization
• monomers w/ electron-donating groups (e.g. isobutylene)
form stable cations converted to polymers by cationic
catalysts
• a growing chain end w/ a positive charge
(carbonium/carbenium) ion
• strong Lewis acid (like BF3) or Friedel-Craft catalysts (like AlCl3)
initiate cationic polymerization in the presence of co-catalyst
like water serves as Lewis base or source of protons
• proton is added to the monomer to form carbonium ion
forms an association w/ a counterion
Cationic Polymerization
propagation: consecutive addition of monomer molecules to the carbonium ion at

the growing chain end
termination: rearrangement to produce w/ an unsaturated terminal unit and the
original complex or chain-transfer to a monomer, another polymer molecule, or
solvent
termination by combination of two cationic polymer growing chains doesn’t occur
usually conducted in solutions; low temperature (-80 to -100oC); fast rates
increase the dielectric strength of solution (max electric field the solution can
withstand) so that intimate association between the ion pair is not too strong to
prevent monomer insertion during propagation
Anionic Polymerization
• growing chain end carries a negative charge or carbanion
• monomers generally contain electron-withdrawing
substituent groups (to stabilize formation of anion) e.g.
styrene, acrylonitrile (vinyl monomer w/ R = CN), butadiene,
methacrylates, acrylates, ethylene oxide, lactones
• initiator maybe any compound providing a strong nucleophile
(e.g. Grignard reagents -aryl- or alkyl magnesium halides),
organometallic compounds); addition of the initiator to the
double bond of monomer
• carbanion at the head end is associated to the
positively charged lithium counterion
• propagation: successive insertion of monomer
molecules by anionic attack of carbonion
• no chain transfer or branching esp. at low
temperature
• termination: deliberate/accidental introduction of
O2, CO2, MetOH, H2O, or other molecules capable of
reaction w/ the active chain ends
• in free-radical initiation & anionic polymerization initiator or part of it
becomes part of the resulting polymer product molecule; in cationic
polymerization catalyst is needed in initiation and propagation, but is
regenerated at the termination step
• termination can be avoided by using pure starting reagents should
remove oxygen and water in the reactor
• polymer molecules can remain active even all monomers are exhausted;
polymerization resumes after addition of fresh monomer “living
polymers” because of absence of termination
• since chain ends grow at the same rate:
• characterized by very narrow MW distribution (Poisson pdf)
Q = MW/MN = 1 + 1/DP
the absence of termination step permits the synthesis of unusual/unique

block copolymers; control the architecture of the polymer; introduce a
variety of desired functional groups
Coordination Polymerization
• formation of coordination compound between the
catalyst, monomer, and growing chain
• use of Ziegler-Natta catalysts; complex catalyst
systems derived from groups IVB to VIIIB of the
periodic table and an organometallic compound
usually from a group IA or IIIA metal. Example of
catalyst system used (trialkyl aluminum and titanium
trichloride)
Coordination Polymerization
• usual monomers: monoolefins (propylenes/dienes
like butadiene and isoprene)
• use of catalyst: form transient π complexes bet.
monomer and transition metal species;
• initiating species is metal-alkyl complex;
• propagation: consecutive insertion of monomer
molecules into a polarized titanium-carbon bond;
• termination: introduction of water, hydrogen,
aromatic alcohols, or metals like zinc
Step-Growth Polymerization
• a series of reactions in w/c any 2 species (monomers,
dimmers, trimers, etc) can react at any time, leading
to a larger molecule
• usually involves a classical condensation reaction
(esterification, ester interchange, amidization, etc)
• occurs between pairs of chemically reactive or
functional groups on the reacting chemical molecules
• accompanied by elimination of a small molecule such
as water as a by-product
• e.g. formation of prepolymer polyester from
glycol and dicarboxylic acid
• involve either one or more types of
monomers; each monomer has at least two or
more reactive functional groups
• when only one type of monomer is involved:
A-B step-growth polymerization
- e.g. formation of aliphatic polyester
through self-condensation of ω-
hydroxycaproic acid to
polycaprolactone; monomer
contains two different functional
groups (-OH and –COOH)
- shaded area is series of ester
linkages
• when more than one type of monomer is
involved, functional groups on each type of
monomer are the same, but capable of
intermolecular reaction with the other type of
monomer
• known as A-A/B-B step-growth polymerization
- for PET, combine terephthalic acid

(dicarboxylic acid) and ethylene glycol (diol)
Polycondensation and Polyaddition
• w/ and w/o elimination of small molecule by-
product
Polyaddition examples
 Preparation of polyurethane by
the ionic addition of diol (1,4 butane
diol) to a diisocyanate (1,6 hexane
diisocyanate) using base catalyst
Reaction of diisocyanate and diamine

to produce polyurea; see table for
characteristic linkages
Table of Characteristic Linkages
Example
• Unsaturated polyester resins, which are used as the
matrix of component of glass fiber composites, may
be obtained by the copolymerization of maleic
anhydride and diethylene glycol. The low-molecular-
weight product is soluble in styrene. Describe, w/ the
aid of equations, the possible structures of the
prepolymer and that of the polymer resulting from
benzoyl peroxide-initiated polymerization of a
solution of the prepolymer in styrene.
Typical Step-Growth Polymers:
1. Polyesters
• synthetic fiber, film, bottle applications
• traditional route for the production of commercial PETP/PET is
through two successive ester interchange reactions:
– on 1st step, a 1:2 molar ratio of dimethyl terephthalate to
ethylene glycol is heated at 200oC in presence of calcium
acetate catalyst; MetOH and oligomeric product (x=1-4) is
obtained
– on 2nd step, temperature increase to 300oC; formation of
high polymer and ethylene glycol
1. Polyesters
1. Polyesters
• PETP (or PET) is a linear polyester
• to get branched/network polymer, use polyol
(trifuncitonal/polyfunctional) monomers;
glycerol for glyptal (saturated polyester) and
unsaturated dicarboxylic acids (e.g. maleic
anhydride) for unsaturated polyester
1. Polyesters (Glyptal Preparation)
• how to prepare glyptal: glycerol + phthalic
acid to form a viscous liquid; further reaction
will lead to network formation
• glyptal is used as adhesive; alkyd resin
(coatings industry) is modified glyptal w/
natural/synthetic oil (fatty acid from
drying/nondrying oils)
2. Polycarbonate
• special class of polyesters derived from
carbonic acid (HO-CO-OH)
• preparation involves linking together of
aromatic dihydroxy compounds (2,2-bis(4-
hydroxy-phenyl propane) or bisphenol A, by
reacting then w/ a derivative of carbonic acid
such as phosgene or diphenyl carbonate
2. Polycarbonate
For phosgene route: bubbling the
phosgene into a solution of bisphenol A
in pyridine at 20oC – 35oC and isolation
of the resulting polymer by
precipitation in water or methanol
For diphenyl carbonate: mixture is

heated at 180oC – 200oC in vacuum to
form prepolymer. Temperature is slowly
raised to 280-300oC at reduced pressure
to ensure the removal of the final traces
of phenol
3. Polyamides (Nylons)
• amide linkages (-CONH-)
• 4 main synthetic routes
– condensation bet. dicarboxylic acid and diamine
– reaction bet. diacid chloride and diamine
– dehydration-condensation reactions of amino acids
– ring-opening polymerization of lactams
• first two routes are synthetic
• commercial products nylon 6,6 and nylon 6
3. Polyamides – Classical Route for Nylon 6,6
- dicarboxylic acid (adipic acid) and

diamine (hexamethylene diamine)
- to achieve exact stoichiometric

equivalence between functional
groups, 1:1 salt of the two reactants
is prepared initially and subsequently
heated at a high temperature to form
the polyamide
- intermediate hexamethylene
diammonium adipate salt
3. Polyamides – Classical Route for Nylon 6,6
- a slurry of 60-80% of the
recrystallized salt is heated rapidly
- released steam is purged by air
- temperature is raised to 220oC and
finally to 270-280oC when monomer
conversion is about 80-90% while
maintaining the steam pressure
generated during polymerization at
200-250 psi
- pressure subsequently reduced to
atmospheric pressure, and heating is
continued until completion of
polymerization
- under melt polymerization
(polymerization occurs above the
melting points of reactants and
polymer)
- Analogs of polyamides (nylon 11; 12; 6,10; and 6;12);

- In A-A/B-B nylons, 1st number is # of carbons in diamine;
- 2nd number is # of carbons in acid;
- E.g. is nylon 6,10 or poly(hexamethylene sebacamide)
development of aromatic polyamides to

- Kevlar: linear aromatic polyamide:
improve flammability and heat resistance of
decomposes only above 500oC
nylons; example is poly(m-
- Kevlar aramid’s high thermo-oxidative
phenyleneisophthalamide) or Nomex;
stability is due to absence of aliphatic units in
obtained from solution or interfacial
main chain; highly crystalline; higher fiber
polymerization of a metasubstituted diacid
strength and modulus than steel
chloride and a diamine
4. Polyimides
• from reaction of aromatic dianhydrides and
aliphatic/aromatic diamines
• 2-stage process; condensation of aromatic
dianhydrides and aromatic diamines in a suitable
solvent (e.g. dimethylacetamide) to form a soluble
precursor such as poly(amic acid); then dehydration
of the intermediate at elevated temperatures
4. Polyimides condensation of aromatic dianhydrides and
aromatic diamines in a suitable solvent (e.g.
dimethylacetamide) to form a soluble
precursor such as poly(amic acid); then
dehydration of the intermediate at elevated
temperatures
imide group is two acyl groups (RC=O)

bound to nitrogen
- cured or fully imidized polyimide is insoluble
and infusible w/ high thermo-oxidative stability
and good electrical-insulation properties
- can be melt-processed at high temperatures
or cast in solution
- phenyl/alkyl pendant groups or main-chain
aromatic polyether linkages can be introduced
by using appropriate aromatic diamine
- resulting polyimides are soluble in nonpolar
solvents
4. Improvement of Polyimides
- to improve processing and melting of
polyimides, combine basic imide
structure w/ more flexible aromatic
groups
- diamines can introduce flexible linkages
like aromatic ethers and amides into the
backbone
- e.g. polyamide-imides are obtained by
condensing trimellitic anhydrides and
Polyamide-imide aromatic diamines
- polyether-imides are produced by nitro

displacement reaction involving
bisphenol A, 4,4’-methylene dianiline,
and 3-nitrophthalic anhydride
Polyether-imide
5. Polybenzimidazoles and Polybenzoxazoles
• aromatic rings/groups in the main chain could improve
mechanical/thermal properties of polymers
• in aromatic polyamides, they are formed by repetitive
reaction of aromatic amino group and carboxyl group in a
molar ratio of 1:1
• in aromatic polyamides and aromatic polyesters, the aromatic
groups are usually separated by 3 consecutive single bonds;
the two tetrahedral angles associated with the bonds permit
some degree of chain flexibility
• To reduce flexibility, reduce the number of
consecutive single bonds in the main chain
• Polyether, polysulfide, and polysulfone
reduces the number of consecutive single
bonds to two
• Polyimides, polybenzimidazoles, and polybenzoxazoles number of
consecutive single bonds is reduced to one; ladder polymers have zero
consecutive single bonds
• Aromatic polyimides two of the three consecutive single bonds
between aromatic groups in polyamides are eliminated by the formation
of new ring (could be done by employing 2:1 molar ratio of aromatic
carboxyl and amino groups)
• When molar ratio of carboxyl groups (e.g. terephthalic acid) to amino
groups (3,3’-diaminobenzidine) is 1:2, we got polybenzimidazole; if molar
ratio of carboxyl, amino, and hydroxyl groups is 1:1:1, polybenzoxazoles
are formed
6. Aromatic Ladder Polymers
• zero consecutive single bonds to increase the
rigidity of the polymer
• composed of only condensed cyclic units
• individual cyclic units are aromatic, cycloaliphatic,

homocyclic, or heterocyclic
preparation of longer
segments in ladder of
polyimidazopyrrolones:
aromatic dianhydrides/aromatic
tetracarboxylic acids w/ ortho-
aromatic tetraamines
polyquinoxalines are
identified by the presence of
fused-six-membered cyclic
diimide structure (reaction of
1,4,5,8-naphthalene
tetracarboxylic acid w/ aromatic
tetraamines in polyphosphoric
acid at temps up to 220oC
• double chain, double strand polymers
(backbone consists of 2 chains)
• two bonds have to be broken to reduce
molecular weight and deteriorate its
properties (very unlikely though); exceptional
thermal, mechanical, and electrical properties
Example
• Polyimides have been prepared from aromatic
anhydrides and aliphatic diamines by melt fusion of
salt from the diamine and tetracid (dianhydride).
Aliphatic polypyromellitimide derived from straight-
chain aliphatic diamines containing more than nine
carbon atoms gave thin, flexible films, whereas those
from shorter chain aliphatic diamines allowed the
preparation of only thick, brittle moldings. Explain
this observation.
Explanation…
general structure of aliphatic
polypyromellitimide; R is alkylene
group
- flexibility can be introduced by
introducing flexible diamines
- longer the alkylene group, the
more flexible is the diamine
- straight-chain alkylenes w/ nine
or more carbons introduce
sufficient flexibility
- when R is less than 9 carbon
atoms, resulting polymer is rigid
and brittle
7. Formaldehyde Resins
• thermosets; two classes
• aminoplasts (condensation reaction between
urea (urea-formaldehyde/UF resins) or
melamine (melamine-formaldehyde/MF
resins) with formaldehyde (formula is H2C=O) )
• phenoplasts/phenolic/phenolic-
formaldehyde/PF resins are condensation
products of phenol/resorcinol and
formaldehyde
7. Urea-Formaldehyde Resins
2nd step is condensation of methylol

1st step is production of methylol groups under acidic conditions to form
derivatives of urea under slightly alkaline network structure
conditions
7. Melamine-Formaldehyde Resins
initial production of methylol derivatives of

melamine; subsequent condensation to form
methylene bridges between melamine groups
to form a rigid network
7. Phenol-Formaldehyde Resins
base-catalyzed (resoles) or acid-
catalyzed (novolacs) addition of
formaldehyde to phenol
in preparation of RESOLES, phenol and

excess formaldehyde react to produce a
mixture of methylol phenols; they
condense on heating to produce soluble,
low-molecular weight prepolymers or
resoles; on heating of resoles at elevated
temperature under basic, neutral, or
slightly acidic conditions, a high-molecular-
weight network structure or phenolic rings
linked with methylene bridges is produced
formaldehyde to phenol ratio of

greater than one
7. Phenol-Formaldehyde Resins
novolacs are low-molecular-weight,
fusible but insoluble prepolymers from
reaction of formaldehyde and molar
excess of phenol
do not contain residual methylol

groups; network is produced by heating
novolac with additional formaldehyde,
paraformaldehyde, or hexamethylene
tetramine
8. Polyethers
• introduction of aromatic units into the main chain
results in polymers w/ better thermal stability
• PPO (poly(phenylene oxide)): high impact strength,
resistance to mineral/organic acids, low water
absorption
• usually blended w/ high-impact polystyrene (HIPS) to
ease processability in manufacture of machined
parts and business machine enclosures
8. Polyethers
PPO is from free-radical, step-growth oxidative coupling of 2,6-

dimethyl phenol (2,6-xylenol)
Passing oxygen into a reaction mixture of 2,6-xylenol, cuprous
chloride, and pyridine
9. Polysulfides
Aromatic polythioethers; e.g. poly(phenylene sulfide) or PPS for electrical

insulators and structural parts in the building of engines and vehicles;
condensation reaction between p-dichlorobenzene and sodium sulfide
10. Polysulfones
linear aromatic polymer; tough, high-temperature-resistant engineering

thermoplastic; nucleophilic substitution of alkali salts of biphenates w/
activated aromatic dihalides
Preparation of bisphenol A polysulfone from the reaction of disodium salt of
bisphenol A w/ dichlorodiphenyl sulfone; initial preparation of the disodium
salt of bisphenol A by the addition of aq. NaOH to bisphenol A in dimethyl
sulfoxide (DMSO); solution of dichlorodiphenyl sulfone is added, and
polymerization is carried out at 160oC
Ring-Opening Polymerization
• no small molecule is split off in ring-opening polymerization
(contrast to condensation)
• driving force for ring-opening polymerization is not derived
from the loss of unsaturation (unlike olefin polymerization)
• X may be a heteroatom (O or S); can be a group (NH, O-CO-,
NH-CO, -C=C-)
• not all cyclic compounds can undergo ring-opening
polymerization
• X provides a mechanism for catalyst or initiator to form the
initiating coordination intermediate with the cyclic ring
Ring-Opening Polymerization:
1. Poly(propylene oxide)
• attack of the least sterically hindered carbon by the hydroxyl
anion to produce the alkoxide
• poly(propylene oxide) or polypropylene glycol (PPG) are
utilized extensively as soft segments in urethane foams; used
as automobile seats
• modify the growing species in propylene oxide polymerization
by ethylene oxide in order to produce a polymer with
acceptable reactivity with isocyanates and urethane product
with desirable properties
2. Epoxy Resins
• base-catalyzed reaction between an epoxide such as
epichlorohydrin and polyhydroxy compound such as
bisphenol A
• molar ratio of bisphenol A to epichlorohydrin can range from
10:1 to 1.2:1 (liquid to semisolid to solid)
• pendant hydroxyl groups and terminal epoxy groups
• can be cross-linked or cured by primary/secondary amines
3. Polycaprolactam (Nylon 6)
• industrial manufacturing is water-initiated (hydrolytic) or
strong base-initiated (anionic) polymerization
• in hydrolytic polymerization, water opens the caprolactam
ring to produce aminocaproic acid (zwitterion; ionized form of
an amino acid that has a net zero charge); zwitterion interacts
with and initiates step polymerization; initial ring-opening of
the monomer followed by the step polymerization
Hydrolytic Polymerization of
Caprolactam
- can be continuous or batch

- heating caprolactam in oxygen-free atmosphere in presence of
water at 250oC -270oC from 12h – 24h
- at 80-90% conversion, most of the water is removed; not
complete conversion due to various equilibria
- residual monomer is usually 8-10%; 3% predominantly cyclic
low-molecular-weight oligomers; purification by hot-water
extraction or vacuum evaporation
Anionic Polymerization of
Caprolactam
• base-initiated anionic polymerization of caprolactam
is characterized by high conversion rates
• high temperature (e.g. 220oC, above MP of nylon)
and low temperature (e.g. 140-180oC, above MP of
caprolactam but below nylon) polymerization
• bases are sodium hydride or Grignard reagent
(RMgX, R – alkyl/aryl, X – halide)
• Co-initiator: N-acyl caprolactam or acyl urea (for low
temperature polymerization)
Caprolactam
1st stream is catalyst dissolved 2nd stream is initiator dissolved in monomer

in monomer
- sodium or magnesium caprolactam salt is produced

from reaction to sodium hydride or Grignard reagent
- rapid polymerization during mixing of acylated lactam,
catalyst, and monomer at 140oC or higher
- 2-stream reactor
Caprolactam
- in high temp polymerization, 8-10% cyclics are

generated; in low temp polymerization, can be less
than 2% (no additional purification of polymer
product);
- high degree of crystallinity; nylon 6 objects of any
desired shape is obtainable in a single step
polymerization; cast nylon 6 or reaction injection
molded (RIM) nylon 6
Example
• Ethylene oxide polymerizes readily to high
conversions under either anionic or cationic
conditions. Tetrahydrofuran can be induced to
polymerize in the presence of phosphorus or
antimony pentafluorides as catalysts.
Tetrahydropyran is unreactive under
polymerization conditions. Explain these
observations.
Solution
ethylene oxide tetrahydrofuran

tetrahydropyran
- ease of polymerization high degree of strain

- EO is a highly-strained three-membered ring
- need to release the strain driving force for
polymerization

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Polymerization Mechanisms

Essentials of Polymer Science and

thermal decomposition of benzoyl

decomposition of AIBN is by short-

ferric ion is also used as

alkyl hydroxide (initiator) and

• termination by combination/coupling (2 growing polymer

Explain the following observation:

Reactivity of vinyl monomer depends on

propagation: consecutive addition of monomer molecules to the carbonium ion at

the absence of termination step permits the synthesis of unusual/unique

- for PET, combine terephthalic acid

Reaction of diisocyanate and diamine

For diphenyl carbonate: mixture is

- dicarboxylic acid (adipic acid) and

- to achieve exact stoichiometric

- Analogs of polyamides (nylon 11; 12; 6,10; and 6;12);

development of aromatic polyamides to

imide group is two acyl groups (RC=O)

- polyether-imides are produced by nitro

• individual cyclic units are aromatic, cycloaliphatic,

2nd step is condensation of methylol

initial production of methylol derivatives of

in preparation of RESOLES, phenol and

formaldehyde to phenol ratio of

do not contain residual methylol

PPO is from free-radical, step-growth oxidative coupling of 2,6-

Aromatic polythioethers; e.g. poly(phenylene sulfide) or PPS for electrical

linear aromatic polymer; tough, high-temperature-resistant engineering

- can be continuous or batch

1st stream is catalyst dissolved 2nd stream is initiator dissolved in monomer

- sodium or magnesium caprolactam salt is produced

- in high temp polymerization, 8-10% cyclics are

ethylene oxide tetrahydrofuran

- ease of polymerization high degree of strain

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