Improved Performance
Sugar-Based Chemistries for
Biomedical Applications
BPA Replacement
Water Uptake
High Use Temperature Polyesters
Low Molar Mass Designer Compounds
M. Jaffe, A. J. East, W. Hammond, X. Feng, P. Saini
New Jersey Institute of Technology
Biotech Forum
February 9, 2011
Overview
Tm=61°C, Tb=160°C, GRAS,
8 kilo soluble 1 liter water
Isosorbide was developed as a
polyester backbone modifier:
Raises Tg, lowers dX/dt in PET
for next generation package
(Hoechst, DuPont)
Coatings and
Adhesives
Medical Adhesives,
soluble drugs,
Performance biomaterials
Polyesters
Polycarbonates
Polyamides
Polyurethanes
Thermoplastics
Backbone
Modification
Thermosets
Isosorbide
isosorbide diglycidyl
ether for bis-A free
epoxies
Low molar mass
Cosmetic and Polymer
Additives
UV Stabilizers,
Plasticizers,
humectants, antioxidants
New Monomers
and polymers
New AB
Monomers with
controlled
stereochemistry
2
Isosorbide Chemistry
• Isosorbide reactivity and stereochemistry is complex but
can be exploited
 Unequal reactivity of pendent hydroxyls (endo-exo) allows
asymmetric substitution with stereochemical control
o New stereoregular AB monomers
– New stereoregular polyesters
Fast
Slow
o New approach to ester backbone modification
o Low molar mass multifunctional “designer” compounds
 Isosorbide thermodynamics allow
for epimerization reaction to isoidide (exo-exo)
Isosorbide is a precursor to isoidide stereochemistry
 Glucose  isosorbide, other sugars not investigated (yet)
 Strong IP position
Isosorbide
Isoidide
3
Isosorbide-based Epoxy
Replace BPA
O
O
O
H
H
O
O
O
O
O
H
H
O
O
OH
O
O
(S)
O
(R)
O
O
O
Water soluble before
crosslinking
•Dry mechanical properties similar to
Bis A epoxy
•Water uptake <1% to > 50%
4
Isosorbide Compounds Water Uptake
High Water Uptake
•
Observations

O
O
Isosorbide-based epoxy networks are
capable of significant water uptake
O
F3CCOOH
O
O
O
O
OH
O
O
H2O
O
o Current data ranges from < 1% to > 50%
–
o Reacting free OH with isocyanates to
produce polyoxazolidones significantly
lowers water uptake

Bisisosorbide diglycidyl ether
Target is application dependent but < 1%
is often desired
PEG Replacement
O
O
HO
Isosorbide based polyesters are not
noticeably hydroscopic
•
Cinnamic acid esters, fatty acid esters,
hydroxy acids are not noticeably
hydroscopic
Conclusion: Isosorbide water uptake
is a function of the local chemical
environment and is controllable
O
O
HO
OH
O
OH
OH
O
Bisisosorbide triglycerol
o Large PEIT database
o AB monomers
o Stereochemically controlled PisosT.
PisoiT

O
O
Low Water Uptake
Medical Adhesive
O
O
O
O
O
N
O
H
H
N
O
O
O
O
H
O
O
H
O
R
O
R
R
NH
5
Isosorbide - Thermoplastics
Polycarbonates
 Replace bis-phenol A
 Improve thermal performance
• Polyesters
 Improved performance for commodity polyesters, Raise
Tg
 New stereoregular polymers
 New LCPs with renewable disrupters, mesogens
• Polyurethanes
6
Controlled Stereochemistry Isosorbide/Isoidide Monomers and Polymers
•
Advantages
 Controlled stoichiometry,
stereochemistry
 New group of high performance
semicrystalline polyesters
o Tg>150 °C, Tm>300 °C
o Low water uptake
 Will works with all condensation
polymers tp increase Tg
o Reduced sublimation, reduced color
Poly(isoidide phenyl ether)
 Biocompatible, Resorbable
compositions
 New patent platform
O
O
O
HO
OH
R
O
O
O
HO
OH
R
O
O
O
7
Commercial Polymer Backbone Modification with Isosorbide: Next
generation
•
New High Use Temperature Homopolymers, Tg > 150 C, Tm ~ 300C+


•
Modify PET To Increase Tg




•
Controlled stereochemistry based on AB monomers
Esters or ether ester backbones
TA + EG + AB
Transesterify PET + AB
Poly(AB) + PET
Control modifier Stereochemistry
Modify PLLA To Increase Tg



Isosorbide based AB monomer
Decouple backbone relaxations to increase Tg
Raise IV to increase toughness
Tg as f[(Poly(isoTA)]
160
140
PLLA
120
100
80
(calculated)
60
•
New LCPs


Disrupters
Mesogens
40
0
0.2
0.4
0.6
0.8
1
8
Low molar mass compounds
UV Absorbance of all synthesized sunscreens
60000
• Bis compounds
UVA, UVB absorbers
Plasticizers
Anti-oxidants
Thermoset monomers
• Asymmetric substituted
(“designer”) compounds





UVA-UVB
UVA-plasticizer
Plasticizer-Cl scavenger
Limited by utility
All new compositions of
matter
extinction coefficient




50000
40000
30000
20000
10000
0
250
300
350
400
450
500
-10000
wavelength(nm)
(1)
Series1
(12)
Series2
(6)
Series3
(10)
Series4
(11)
Series5
(3)
Series6
(7)
Series7
(9)
Series8
(14)
Series9
Not water soluble
Stable to 300 °C+
9
Support
• Companies






Food packaging
Surfactants and solvents for personal care
UV absorbers for cosmetics
High performance polyesters (in progress)
BPA free low water uptake epoxies (in progress)
Improved polyester fiber
• Agencies
 Sustainable liquid crystalline polymers
10
Conclusions
• Sugar derived compounds
possess unique, exploitable
stereochemistry
• Isosorbide provides a
ubiquitous platform of costeffective chemistries for
biomedical applications and
 Isosorbide isomers
• A proprietary technology
platform is being created
Isosorbide
Isoidide
11