Essentials of Polymer Engineering

(Introduction to Polymers)
Polymer Modification
 What we have covered so far…
• Introduction; Classification of Polymers
• Polymerization mechanisms (chain-reaction,
ionic, coordination, step-growth, ring-
opening)
• Chemical bonding and polymer structure
(primary: monomer, secondary: polymer
molecule, and tertiary: aggregate)
• Thermal transition in polymers
• Polymer modification
It is usually cheaper to develop novel polymeric materials by
modification of existing ones than synthesis of new of new
homopolymers.

• Copolymerization of more than one monomer

• Control of molecular structure
• Functional/reactive groups deliberately
introduced into the polymer chain or side
groups (postpolymerization reactions)

Modification techniques related to chemical

phenomena during or after polymerization.
Polymer modification by copolymerization
example: styrene-butadiene copolymers
Polybutadiene Polystyrene
• Good elastic properties • Chemically inert
• Outstanding toughness and • Resistant to alkalis, halide
resilience acids, oxidizing/reducing
agents
- Poor resistance to oils and • Easy to process
solvents, oxidation, and
abrasion - Brittle
Styrene and butadiene can be - Low heat deflection
copolymerized to achieve a temperature
variation of polymer properties
(depends on composition and
structure)
Polymer modification by copolymerization
example: styrene-butadiene copolymers

Styrene Butadiene Rubber (SBR)

-Random copolymer
-Irregular structure
-Not crystallizable
-Butadiene can undergo 1,2 or 1,4 polymerization
Polymer modification by copolymerization
example: styrene-butadiene copolymers
• Styrene-butadiene block copolymers
(thermoplastic elestomers TPE)
• Rubberlike solid (like vulcanized rubber) ; can be
recycled
• S-B-S type; two phases (continuous
polybutadiene rubber phase + dispersed glassy
domains of polystyrene)
• Tg between PB and PS; at normal temperature,
retains thermoplasticity of styrene blocks and
toughness/resilience of elastomer units
Polymer modification by copolymerization
example: ethylene copolymers
Copolymerization between ethylene and polar α-olefins

Variety of materials ranging from rubbery to low

melting products (suitable for hot-melt adhesives) to
those with unusual toughness and flexibility
 Polymer modification by copolymerization
example: Acrylonitrile-Butadiene-Styrene (ABS)

Acrylonitrile – polymer chemical

resistance and heat aging stability

Butadiene – toughness, impact resistance,

property retention at low temperature

Styrene – rigidity, glossy surface apperance,

ease of processability
Polymer modification by copolymerization example:
Condensation polymers – Acetal Copolymer

- Copolymerization of trioxane with small amounts of comonomer, usually

cyclic ethers like ethylene oxide
- Results to random distribution of C-C bonds
- Depolymerization of ethylene oxide units is much more difficult than
oxymethylene units
- Copolymerization confers thermal stability on the acetal copolymer
 Polymer modification by copolymerization example:
Condensation polymers – Epoxies

- Epoxies have lower heat resistance than phenolics due to the lower
aromatic units in their structures
- What would happen if we modify epoxy resin with novolak phenolics?
 Polymer modification by copolymerization example:
Condensation polymers – Epoxies

Structure of novolak-modified epoxy resin

Three Araldite epoxy adhesives

Epoxy-phenolic copolymer
 Polymer modification by copolymerization example:
Condensation polymers – Urea-Formaldehyde (UF) Resins
UF resin based adhesive PF resin based adhesive

- Both for wood adhesive bonding

- Though UF is cheaper than PF adhesive, UF-bounded wood products have
poor stability

We can use copolymerization to incorporate urea derivatives of flexible di-and

trifunctional amines to UF resin

Structure of propylene
oxide-based triamine
modifier
 Polymer modification by copolymerization example:
Condensation polymers – Urea-Formaldehyde (UF) Resins

Enhanced soak–dry stress resistance of solid wood joints bonded with UF-resin
modified with the urea derivative of a flexible propylene oxide-based triamine
 Polymer modification by postpolymerization example:
Reactions of polysaccharides – Cellulose derivatives

- Cellulose is a natural polymer; structure is glucosidic rings linked through

oxygen bridges; repeating unit has 3 hydroxyl groups and an acetal linkage
- stiff molecules; highly crystalline; insoluble and infusible; burn rather than melt

Make cellulose processable by reducing its melting temperature below

decomposition temperature by derivatization
Polymer modification by postpolymerization example:
Reactions of polysaccharides – Cellulose derivatives

• Most important derivatives are cellulose esters and

ethers
• Preparation of cellulose esters – reaction of activated
cellulose with carboxylic acid, acid anhydride, or acid
halide. Once triesterification is complete, they are
hydrolyzed back to desired free hydroxyl content
• Control of viscosity and molecular weight during
reaction – high MW for plastics; low MW for
adhesives, lacquer, and hot melts
 Polymer modification by postpolymerization example:
Reactions of polysaccharides – Cellulose derivatives

• Sample inorganic cellulose ester – cellulose nitrate or

nitrocellulose; obtained from reaction of cellulose w/ nitric-
sulfuric acid mixture for 30 mins; can control nitrate content

• Preparation of cellulose ethers like methyl cellulose – reacting

sodium cellulose (aq. NaOH on cellulose) w/ alkyl halide:

• Can control ether content and viscosity of product

• Most important cellulose ether is ethyl cellulose – molding
material that is heat stable, low flammability, high impact
strength; flexibility and toughness at low T; high water abs.
 Polymer modification by postpolymerization example:
Reactions of polysaccharides – Starch and dextrins

- Starch is a mixture of linear amylose and branched amylopectin chains

- Granular starch has no adhesive use
- For most applications, granular starch must be dispersed and cooked in water so
the granules will swell and rupture
- Aqueous dispersion of starch is extremely viscous (we need to modify starch)
Polymer modification by postpolymerization example:
Reactions of polysaccharides – Starch and dextrins

• Granular starch modification is partial

depolymerization/rearrangement of molecules
• Acid-converted (thin boiling) starch – reaction with
warm mineral acids (HCl or H2SO4)
• Oxidized starch – reaction w/ sodium hypochlorite;
introduces carbonyl and carboxyl groups and cleaves
the glycosidic links
• Dextrins – heating w/ or w/o hydrolytic agents
Polymer modification by postpolymerization example:
Reactions of polysaccharides – Starch and dextrins

Hydrolysis and repolymerization during dextrination of starch

Polymer modification by postpolymerization example:
Cross-linking – Unsaturated polyesters

• Unsaturated polyester is unsaturated polyester

prepolymer mixed w/ cross-linking monomer and
catalysts
• UP is usually a viscous liquid that could be poured,
sprayed, or shaped; transformed into a thermoset
solid by cross-linking
• UP prepolymer – usually obtained from
condensation of polyhydric alcohols (glycol, glycerol,
etc) and dibasic acids (saturated and/or unsaturated
acids)
Polymer modification by postpolymerization example:
Cross-linking – Unsaturated polyesters

Condensation of polyhydric alcohols and dibasic acids to

obtain unsaturated polyester prepolymer
Polymer modification by postpolymerization example:
Cross-linking – Unsaturated polyesters

• Reactive monomer responsible for cross-linking

reaction – styrene, vinyl toluene, methyl
methacrylate, diallyl phthalate
• UP prepolymer (stable) + reactive monomer (stable)
= unstable blend
• Addition of inhibitors (e.g. hydroquinone) to avoid
premature gelation and cross-linking
• Cross-linking initiated by organic peroxide and heat
• Room temp curing – accelerators and activators like
cobalt salts
Polymer modification by postpolymerization example:
Cross-linking – Unsaturated polyesters

Cross-linking reaction of unsaturated

polyester prepolymer with reactive
monomer
 Polymer modification by postpolymerization example:
Cross-linking – Unsaturated polyesters

• Alkyd resins – surface coatings (organic paints) and sometimes

molding compounds
• Cross-linking monomer of alkyd is non-volatile allyl phthalate
• Usually modified with fatty acids from mineral and vegetable
oils
• Air-drying type – alkyd resin modified w/ oleic or linoleic acid;
cured through oxidation by atmospheric oxygen
• Varnish – alkyd surface coatings that dried through chemical
reactions
• Lacquers – alkyd surface coatings that dried through solvent
evaporation
Polymer modification by postpolymerization example:
Cross-linking – Vulcanization

• Introduction of network of cross-links to elastomers

(1,4-diene polymers such as polychloroprene,
polybutadiene, etc) and related copolymers
(butadiene-acrylonitrile and butadiene-styrene)
• Transforms an elastomer from a weak thermoplastic
mass w/o useful properties into a strong, elastic,
tough rubber
• Decreases the flow; increases its tensile strength and
modulus; preserves its extensibility
 Polymer modification by postpolymerization example:
Cross-linking – Vulcanization
• First vulcanization was achieved by Goodyear in 1939 by heating
elastomer w/ sulfur (slow and inefficient process)
• Accelerators speed up vulcanization; require activators/promoters (e.g.
ZnO) in presence of soap (metallic salt of stearic acid) for optimal function
Polymer modification by postpolymerization example:
Cross-linking – Vulcanization
- Double bond in diene elstomers provides the site for
vulcanization
- Residual double bonds susceptible to oxidative and
ozone attack
polybutadiene - Development of butyl rubber and EPR (not readily
vulcanized)
copolymerization of unsaturated
monomers
Polymer modification by postpolymerization example:
Cross-linking – Vulcanization

- Dicyclopentadiene used as comonomer for EPR

- EPDM is a branched polymer w/ slow cure rates
- EPR requires peroxide cure; EPDM requires sulfur
for vulcanization
Polymer modification by postpolymerization example:
Cross-linking – Vulcanization

Vulcanization reaction of polyisoprene w/ sulfur

Polymer modification by postpolymerization example:
Cross-linking – Polyolefins and Polysiloxanes

• Neither heat nor sulfur is imperative for

vulcanization
• Cross-link can be effected by non-sulfur
containing compounds (peroxides, nitro
compounds, etc)
• Polyethylene, ethylene-propylene copolymer,
and polysiloxanes can be cross-linked w/
peroxide and heat
Polymer modification by postpolymerization example:
Cross-linking – Polyolefins and Polysiloxanes

Cross-linking in polyolefins and polysiloxanes

- Efficiency is less than one cross-link per peroxide molecule decomposed

- Use copolymerization to increase cross-linking efficiency (EPR


EPDM)
- Enhancing cross-linkability in polysiloxanes using vinyl-methyl silanol
 Polymer modification by
postpolymerization example: Hydrolysis
• Poly(vinyl acetate) is used in production of water-based emulsion paints;
also production in poly(vinyl alcohol) and poly(vinyl acetal)
• Production of poly(vinyl alcohol) by hydrolysis/alcoholysis w/ MetOH or
EtOH; usually base catalyzed

- poly(vinyl alcohol) is used as thickening agent for various emulsion and

suspension systems; used as water-soluble adhesive w/ excellent binding
capacity to cellulostic materials (e.g. paper)
 Polymer modification by
postpolymerization example: Hydrolysis
• Partially hydrolyzed poly(vinyl acetate) – contains both hydroxyl and
acetate groups
• Condensation of OH groups w/ aldehydes results to acetal units

poly(vinyl acetals)

- OH groups of poly(vinyl
acetals) can condense w/
methylol groups of PF/MF/UF
resins (structural adhesive in
metals)
- Interlayer in laminated
automotive and aircraft
safety glass
Polymer modification by postpolymerization example:
Block and Graft Copolymer Formation

• Reaction of a previously formed homopolymer or

copolymer w/ fresh monomers
• 1st method: polymerization of a vinyl monomer in the
presence of a polymer by the initiation of growth
through chain transfer (graft copolymers)
• 2nd method: polymerization of a vinyl monomer in
the presence of a polymer w/ reactive sites (if
terminal sites, block copolymer; backbone/pendant
groupd, graft copolymer)
Polymer modification by postpolymerization example:
Block and Graft Copolymer Formation

• Resulting mixture during polymerization of monomer

in presence of a polymer: 1) initial homopolymer; 2)
homopolymer of fresh monomer; 3) cross-linked
parent homopolymer through graft or branched
block copolymer polymerization; 4) desired
copolymer
• Composition of product mixture depends on
polymer, monomer, and initiator
Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Block copolymerization)

Some techniques for block copolymerization:

1) Butyl acrylate-styrene and acrylonitrile-styrene – irradiation
of butyl acrylate or acrylonitrile w/ a photosensitive initiator
under intensive UV radiation. Radical-rich monomer is then
mixed with styrene
2) In situ formation – water-soluble and oil-soluble monomers;
e.g. dissolve acrylic acid in water followed by emulsification
of styrene. Use persulfate initiator to polymerize acid in
water until its growing chains diffuse to styrene micelle,
forming acrylic acid-styrene block copolymer.
Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Block copolymerization)
Some techniques for block copolymerization:
3) Mechanical rupture of polymer chains – terminal-free radicals can be generated
that may initiate copolymerization; cold milling or mastication of two different
polymers or a polymer in the presence of a monomer

Various block copolymers

prepared by mechanical rupture
of polymer chains in presence of
monomer
Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Block copolymerization)

Some techniques for block copolymerization:

4) When polymer chains are terminated by labile end groups,
block polymers can be produced by irradiation.

Irradiation of terminal-brominated styrene dissolved in methyl

methacrylate to yield block copolymer
Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Block copolymerization)

Some techniques for block

copolymerization:
5) Introduction of peroxide groups
into the polymer backbone or as
stable end groups. Modified
polymer is then mixed with fresh
monomer, and the peroxide groups
are decomposed at appropriate
conditions to yield block copolymers

1) Polymerization of
polymeric phthaloyl
peroxide with
styrene
2) Mix with MMA and
heat to form block
copolymer
Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Graft copolymerization)

• Three approaches for the preparation of graft

copolymers by free radical mechanism
1) Chain transfer to a saturated or unsaturated
polymer
2) Activation by photochemical or radiative
methods
3) Introduction and subsequent activation of
peroxide and hydroperoxide groups
 Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Graft copolymerization)

1) Chain transfer to a saturated or unsaturated polymer

- Requires polymerizable monomer, a polymer, and an
initiator
- Initiator create active sites in the backbone; polymer
itself must be capable of generating radicals
- Not all monomers can be grafted onto a polymer
backbone; not all polymers can react w/ a given
monomer
How to introduce sites that are susceptible for chain
transfer into the polymer structure?
-During synthesis
-As a postreaction
 Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Graft copolymerization)
Example: Introduction of sites susceptible for chain transfer in the polymer
structure by a postreaction:

introduction of a reactive mercaptan group by the reaction of thioglycolic acid or hydrogen sulfide
with a copolymer of methyl methacrylate and glycidyl methacrylate
Monomers such as styrene, acrylate, and methacrylate can now be grafted into the
resulting polymer (high yield of pure graft copolymer)

Another example under this mechanism: butadiene grafted to polystyrene

backbone to produce impact polystyrene
 Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Graft copolymerization)
2) Preparation of graft copolymers by activation by photochemical or
radiative methods

Mutual irradiation techniques:
-Simultaneous irradiation of polymer in contact w/ monomer
- Irradiation of polymer predipped in the monomer

Pre-irradiation techniques
-pre-irradiation of polymer in absence of O2 followed by monomer
exposure
-pre-irradiation of the polymer in air to form peroxide and
subsequent decomposition in the presence of the monomer

Mechanism of photolytic activation: some functional groups absorb and get

ativated by radiation (pendant halogen atoms, carbonyl groups)
when sufficient
energy is absorbed, bond scission occurs that results to generation of radicals
 Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Graft copolymerization)
Properties of graft copolymers produced by mutual irradiation of monomer

-Generation of active sites for radical graft copolymerization using

X-rays or γ-rays is less selective
- Hydrogen cleavage and carbon–carbon bond scission occur
resulting in homopolymerization of the vinyl monomer, cross-
linking in addition to the grafting reaction
 Polymer modification by postpolymerization example: Block and
Graft Copolymer Formation (Graft copolymerization)
We can also prepare copolymers (block type) via step growth mechanism
(condensation) by coupling low-molecular-weight homopolymers w/ appropriate
reactive end groups

Formation of block copolymers from condensation polymers:

(I) from two prepolymers with mutually reactive terminal end groups;
(II) by the use of a coupling agent.
Polymer modification by postpolymerization example:
Surface Modification

• Surface modification to improve the feel, washability,

dye retention, antistatic properties, abrasion
resistance of fibers
• Enhance printability, solvent resistance, adhesion,
and permeability to liquids and vapors of films
• How to modify a surface of a polymer:
interpolymerization (formation of block and graft
copolymers by energy irradiation or chemical means)
and conventional chemical reactions of polymers
Polymer modification by postpolymerization example:
Surface Modification

Surface oxidation
-use of corona discharge, ozone, hydrogen peroxide,
nitrous acid, alkaline hypochloride, UV irradiation,
oxidizing flame, and chromic acid
- sample application: increase the printability of PE and
PET and to improve the adhesion of PE and PP to polar
polymers and that of polytetrafluoroethylene to
pressure-sensitive tapes
Polymer modification by postpolymerization example:
Surface Modification

Alkali and acid treatment/halogenation of surface

-Permanently amber-colored PE containers suitable for
storing light-sensitive compounds have been produced
by treating fluorosulfonated PE with alkali
-PET dipped into trichloroacetic/chromic acid mixture
has improved adhesion to PE and nylons
-Surface halogenation of the diene polymers natural
rubber and polyisobutylene resulted in increased
adhesion to polar surfaces
Polymer modification by postpolymerization example:
Surface Modification

Modifying the surface of glass fibers to improve adhesion in glass fiber reinforced
polymer composites using γ-aminopropyltriethoxy silane, (C2H5O)3-Si-(CH2)3-NH2,
 Functional Polymers
• Efficiency and characteristics are based on a
functional group
• Specific functional group is carefully designed and
located (or dispersed) on the polymer chain
• The modified polymer gains special features
• Examples are polyurethanes, polymer-bound
stabilizers, and polymers in drug administration
 Polyurethanes elastomers for
biomedical applications
• Vascular prostheses, membranes, catheters,
plastic surgery, heart valves, artificial organs
• Biocompatibility and formulation versatility
• Thermoplastic copolymers of (AB)n;
alternating block of long, flexible, “soft
segment” and another block of highly polar,
stiff, “hard segment”
 Two-step synthesis of
polyurethane elastomer
diisocyanate

diol

chain extender

The unique physical and chemical properties of polyurethane elastomers can be

regulated by proper choice of R, R’, and R” functional groups during synthesis of
starting monomers.
 Sample biomedical application of
polyurethane: Cardiothane
• Polymers in reconstructive surgery of soft
tissue and cardiovascular surgery – resistance
to tear and fatigue
• Block copolymer used in intra-aortic balloons,
catheters, artificial hearts, and blood tubings
• Good mechanical properties of cardiothane
from polyurethane; surface properties from
silicone
Structure of Cardiothane
 Polymer-bound stabilizers
• Traditional stabilizers (antioxidants, UV stabilizers,
flame retardants) are low-molecular-weight
compounds
• Problems such as evaporation and leaching during
fabrication; incompatibility at higher levels of
incorporation; toxicity (e.g. chlorine, bromine,
phosphorus compounds as flame retardant are toxic)
• Therefore, use oligomeric or polymer-bound
stabilizers in fabrication of polymers
Example of polymer-bound
stabilizer (antioxidant)
vinyl monomer
Polymer
stabilized w/
antioxidant

AIBN –
2,6-ditertiarybutyl-1,4-vinyl phenol Azobisisobutyronitrile
(the “antioxidant functional group”) as radical initiator
 Polymers in Drug Administration
• Two distinct approaches to improve drug action through
its mode of delivery – controlled drug release and site-
directed drug delivery
• Aim of controlled drug release – eliminate/reduce the
danger of overdose by producing and maintaining an
optimal therapeutic concentration of the drug in the
body
• Aim of site-directed drug delivery – carrier will recognize
the disease-related target or biochemical site of action,
interact with it, and concentrate delivery of the drug at
the site
 Tablets with prolonged and
sustained drug release
Eudragit E-cationic polymer
- Basic; swells in the pH range of 5 – 8
but is soluble at pH = 2.5.
Eudragit anionic polymer
-Resistant to gastric juice; soluble in
the small intestine; insoluble and
impermeable to water below pH 6 to
7 range
-Full protection against gastric juices;
ensure drug release in small intestine