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POLYMERS

Polymers - long chain molecules of high molecular weight


-(CH2)nn

State

Use

1-4

gas

burned for energy

5-11

liquid

gasoline

9-16

med. visc.
liquid

kerosene

16-25

hi visc. liq.

oil, grease

25-50

solid

paraffin wax

10003000

tough plastic PE bottles, containers

Common Polymer Biomaterials

Polymers In Specific Applications


application

propertiesanddesignrequirements

polymersused

dental

stabilityandcorrosionresistance,plasticity
strengthandfatigueresistance,coatingactivity
goodadhesion/integrationwithtissue
lowallergenicity

PMMAbasedresinsfor
fillings/prosthesis
polyamides
poly(Znacrylates)

ophthalmic

gelorfilmformingability,hydrophilicity
oxygenpermeability

polyacrylamidegels
PHEMAandcopolymers

orthopedic

strengthandresistancetomechanicalrestraintsand
fatigue
goodintegrationwithbonesandmuscles

PE,PMMA
PL,PG,PLG

cardiovascular

fatigueresistance,lubricity,sterilizability
lackofthrombus,emboliformation
lackofchronicinflammatoryresponse

silicones,Teflon,
poly(urethanes),PEO

drugdelivery

appropriatedrugreleaseprofile
compatibilitywithdrug,biodegradability

PLG,EVA,silicones,
HEMA,PCPPSA

sutures

goodtensilestrength,strengthretention
flexibility,knotretention,lowtissuedrag

silk,catgut,PLG,PTMCG
PP,nylon,PBTE

The Bulk State : Solid


Polymers can be either amorphous or semi-crystalline, or can exist
in a glassy state.
amorphous glassy state

hard, brittle
no melting point
semi-crystalline glassy state

hard, brittle
crystal formation when cooled
exhibit a melting point

Glass
transition
temperature, Tg
related to chain
mobility
increased flexibility, lower Tg
factors :
flexible links in backbone

size of pendent groups

interaction between chains

plasticizers interfere with bonding, increase chain


movement, decrease Tg
5

Effect of Temperature
semi-crystalline

Rubber
Liquid

Viscous
Liquid

Tm
tough plastic

Tg

semi-crystalline plastic
crystalline solid
10

1000

100000

1000000

molecular weight (g/mol)


6

Crosslinked Networks
crosslinks
covalent; H-bonding; entanglements
crosslinking
increased molecular weight
swell in solvents
organogel
hydrogel

Thermal Properties
Polymer

Tg(C)

Tm(C)

Nylon6,6

45

267

UHMWPE

125

140

Silicone

123

29

poly(urethane)

090

125225

poly(methylmethacrylate)

105

160

poly(D,Llactide)

50

amorphous

poly(caprolactone)

60

57

poly(glycolicacid)

35

210

Mechanical Properties

Diffusion in Polymers
Polymers can also act as solvents for low molecular weight
compounds. The diffusion of small molecular weight components
in polymers is important in a number of fields :

purification of gases by membrane separation


dialysis
prevention of moisture loss in food and drugs (packaging)
controlled drug delivery (transdermal patches, Ocusert)
polymer degradation

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Leaching - Undesirable
polymers often contain contaminants as a result of their
synthesis/manufacturing procedure/equipment

may also contain plasticizers, antioxidants and so on


these contaminants are a frequent cause of a polymers
observed incompatibility

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Drug Delivery
Ocusert

TD - Scopolamine

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In Vivo Degradation of Polymers


no polymer is impervious to chemical and physical actions of
the body

Mechanisms causing degradation


Physical

Chemical

sorption/swelling hydrolysis
softening

oxidation

dissolution

enzymatic

stress cracking
fatigue cracking

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Hydrolytic Degradation
hydrolysis
the scission of chemical functional groups by reaction with
water
there are a variety of hydrolyzable polymeric materials:
esters
amides
anhydrides
carbonates
urethanes
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Hydrolytic Degradation
degradation rate dependent on
hydrophobicity
crystallinity
Tg

impurities
initial molecular weight, polydispersity
degree of crosslinking
manufacturing procedure
geometry
site of implantation

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Hydrolytic Degradation
bulk erosion (homogeneous)
uniform degradation throughout polymer
process
random hydrolytic cleavage (auto-catalytic)

diffusion of oligomers and fragmentation of device


surface erosion (heterogeneous)
polymer degrades only at polymer-water interface

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Polyesters

Oxidative Degradation
usually involves the abstraction of an H to yield an ion or a radical
direct oxidation by host and/or device
release of superoxide anion and hydrogen peroxide by
neutrophils and macrophages
catalyzed by presence of metal ions from corrosion

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% weight loss

Enzymatic Degradation
Natural polymers degrade primarily via enzyme action
collagen by collagenases, lysozyme
glycosaminoglycans by hyaluronidase, lysozyme
There is also evidence that degradation of synthetic polymers is
due to or enhanced by enzymes.
80.0

in vitro
60.0

in vivo

40.0

20.0

0.0

-20.0

-5

10

15

time (weeks)

C.G. Pitt et al.,


J. Control. Rel. 1(1984) 3-14

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25

Z Gan et al., Polymer 40 (1999) 2859

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