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Supramolecular Design For Biological Applications - 1st Edition Instant Access

The book 'Supramolecular Design for Biological Applications' focuses on hydrophilic polyurethanes, detailing their chemistry, applications, and product development. It covers various case studies, product and process development, economic considerations, and quality systems regulations related to hydrophilic polyurethanes. The text aims to provide a comprehensive understanding of the use of these materials in biological applications, highlighting their unique properties and versatility.

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297 views15 pages

Supramolecular Design For Biological Applications - 1st Edition Instant Access

The book 'Supramolecular Design for Biological Applications' focuses on hydrophilic polyurethanes, detailing their chemistry, applications, and product development. It covers various case studies, product and process development, economic considerations, and quality systems regulations related to hydrophilic polyurethanes. The text aims to provide a comprehensive understanding of the use of these materials in biological applications, highlighting their unique properties and versatility.

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ghuynhghoan.groongn.am
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© © All Rights Reserved
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Supramolecular Design for Biological Applications 1st Edition

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©2000 by CRC Press LLC
©2000 by CRC Press LLC
Completing this work required the love and patience of a partner.
For this I thank my wife, Marguerite, who makes it all worthwhile.

©2000
©2004 by CRCby
©2000 CRC Press LLC
Press LLC
TABLE OF CONTENTS

Preface
Acknowledgments

Chapter 1. The Chemistry of Hydrophilic Polyurethanes


1.1 The Isocyanate
1.2 The Polyol
1.3 Crosslinking
1.4 Summary of the Components
1.5 Conclusion

Chapter 2. Case Studies


2.1 Case Study: Wound Care
2.2 Case Study: Specialized Postsurgical Dressings
2.3 Case Study: Agricultural Foams
2.4 Case Studies: Controlled Release Devices
2.5 Case Study: Adsorption and Entrapment of Biologicals
in a Hydrophilic Polyurethane Foam
2.6 Appendix: Examples of Immobilization Research

Chapter 3. Product Development


3.1 Absorption
3.2 Strength
3.3 Adsorption of Protein
3.4 Cell Growth
3.5 Permeability/Diffusivity/Controlled Release

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3.6 Compression
3.7 MVTR
3.8 Resilience
3.9 Density
3.10 Biodegradability

Chapter 4. Process Development


4.1 Introduction
4.2 The Chemistry
4.3 Critical Processing Steps

Chapter 5. Economics
5.1 Introduction
5.2 Cost of Prepolymer Manufacture
5.3 Aqueous
5.4 Foam Production
5.5 Effect of Density on Cost
5.6 Scrap
5.7 Sensitivities

Chapter 6. Analysis of Hydrophilic Polyurethane Foams


6.1 Pre-Hydrating a Hydrophilic Foam for
Subsequent Analysis
6.2 Foam Density
6.3 Indentation Force Deflection at a Specified Deflection
6.4 Indentation Force Deflection
6.5 Compression Force Deflection
6.6 Tensile Test
6.7 Tear Resistance
6.8 Air Flow-Through
6.9 Water Capacity and Draining
6.10 Wicking
6.11 Color
6.12 Linear Swell

Chapter 7. Quality Systems Regulations


7.1 Introduction
7.2 Design Control
7.3 Process Control
7.4 Identification and Traceability

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7.5 Inspection and Testing
7.6 Storage and Handling
7.7 Nonconforming Product
7.8 Conversion

References

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©2000 CRC Press LLC
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PREFACE

Polyurethanes in various forms have taken a permanent position in the


inventory of functional materials. From automobile bumpers to foam in-
sulation, this simple chemistry has won a dominant position due to its
durability, physical strength, cost, versatility and availability. It can be
made into elastomers, which are strong enough to withstand an automo-
bile collision and yet with only minor changes in chemistry and process-
ing can be used to make cushions for furniture.
Figure 1 shows the various forms polyurethanes can take. In 1992, 5
billion pounds were produced.
For the most part, the variations mentioned in Figure 1 were developed
to serve a physical purpose. For instance, low-density, rigid foams are used
as insulation. Low-density, closed-cell foams are used as flotation devices.
High-density elastomers are made into automobile bumpers or similar ap-
plications where high physical strength and flexibility are critical.
Figure 2 shows typical applications, differentiated by two of their most
important parameters: density and durability.
The overwhelming volume of polyurethane is used because of its phys-
ical properties. As mentioned, these materials were developed to fill some
physical purpose. Their density and/or their hardness essentially describes
their function. We will use a quality system analysis to describe or design
a new product. In the case of conventional polyurethanes, that design will
focus on physical properties.
The subject of this book, however, is an alternative class of poly-
urethanes. Foams and elastomers made from hydrophilic prepolymers are
used because of their chemistry, specifically, their ability to absorb or oth-
erwise manage water. In this sense, these materials are used to some de-
gree for the chemistry of polyurethanes.

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©2000 CRC Press LLC
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FIGURE 1. Distribution of the forms of polyurethanes (adapted from Reference [1]).

The most visible segment of this category is in hydrophilic poly-


urethanes. Re-invented in the middle 1970s by W. R. Grace & Co., its
function depends on its compatibility with water-based systems (it is
hydrophilic as opposed to the bulk of the polyurethane world, which is
hydrophobic). Applications range from cosmetics and personal care prod-
ucts to agricultural growing media to medical devices (absorbent dress-
ings). The commonality in all these applications is that in each case there
is a compelling reason for the material to be hydrophilic.
In the early 1980s, researchers began to notice that polyurethanes (both
hydrophilic and hydrophobic) served well as a scaffold or entrapment of

FIGURE 2. Uses of conventional polyurethanes differentiated by physical properties


(adapted from Reference [2]).

©2000
©2004 by CRCby
©2000 CRC Press LLC
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biologicals. By these processes, living cells, yeasts, molds, algae and en-
zymes could be attached (immobilized) on the surface of, or imbedded in
the matrix of polyurethane foams or films to create efficient means to pro-
duce enzymes or to degrade wastewater.
In this work we will describe the breadth of the work conducted in the
area of hydrophilic polyurethanes over the past 20 years. Much of the work
has been done with foams, but some references are made to elastomers.
We begin with a review of polyurethane chemistry with an emphasis on
the differences between conventional polyurethanes and hydrophilics. We
will then present some notable examples of how this property has been
used in commercial products. The final chapters of the book describe an
infrastructure for the development of new devices. Topics include prod-
uct development, processes, economics, quality systems, and analytical
methods.

©2000
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©2000 CRC Press LLC
Press LLC
ACKNOWLEDGMENTS

My work in this area has been in three specific phases. The first was as
the technical manager of the Hypol group with W. R. Grace & Co. My
introduction to this technology was guided by Cliff Kehr and much of my
education in the development of medical devices came as a result of col-
laborations with Hypol users.
The Hypol environment focused on research and development. It was
my experience at Rynel Ltd., Inc., that taught me how to turn those bench-
level developments into production volumes, with the requisite economic
and quality considerations taken into account. During this period, I prof-
ited greatly from the counsel of Henry Jalbert.
Lastly, and in case I don’t write another technical book, I want to ex-
press my thanks to Dr. L. Liefer, Professor of Chemistry, Michigan Tech-
nological University, for converting an immature, ignorant kid into
something resembling a scientist. Apart from the knowledge that he forced
into me, he taught me the discipline and life-style of the scientist. It was
this foundation that gave me the skills to be able to take the information
from Cliff and Henry and build it into the, hopefully, consistent story that
follows.

©2000
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©2000 CRC Press LLC
Press LLC
CHAPTER 1

The Chemistry of Hydrophilic


Polyurethanes

Polyurethanes are the result of the exothermal reaction between a poly-


isocyanate and a molecule containing two or more alcohol groups (OH).
Isocyanates contain a reactive group that can be made to react with OH
groups. Thus, if we react a diisocyanate with a molecule with an OH
group at each end, we create a basic building block of polyurethane; a
prepolymer.

SCHEME 1. Prepolymer reaction.

Notice that the ends of the prepolymer molecules are isocyanate groups.
These are subsequently reacted to produce the solid foams and elastomers.
As such, the material is usually a high-viscosity liquid. There are other
ways to make polyurethanes, as we will discuss, but as we will show hydro-
philic polyurethanes are made with the above prepolymer as an isolated
intermediate.
All polyurethanes go through this reaction, but this step might be im-
mediately followed by the reaction that produces the foam or other fin-
ished product. In the so-called one-shot process, the isocyanate and polyol,
as well as catalysts, crosslinkers, surfactants and blowing agents are
blended together in one step and deposited into a mold or other recepta-
cle for the reaction. We will discuss this process later and compare it to

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2 THE CHEMISTRY OF HYDROPHILIC POLYURETHANES

the most common method for the production of hydrophilic polyurethanes,


which is to produce the prepolymer and subsequently react it to make the
final product.
Regardless of this processing variance, the chemistry of a polyurethane
is sufficiently described by the contributions of each of the components.
The isocyanate and the polyol are illustrated above but an additional com-
ponent is necessary for the construction of a useful product, crosslinking.
This component gives the product its durability.
Thus to understand the chemistry, we must deal with the effect of the
following three components:

• the isocyanate
• the polyol
• the crosslinking

In as much as we will be describing a device that must provide an ad-


sorbing surface (the biochemist’s concern) as well as possess a durability
to permit the construction of industrial equipment (a chemical engineer’s
concern), each of these factors must be understood and considered.

1.1 THE ISOCYANATE

The world of polyurethanes is predominantly split between two iso-


cyanates, toluene diisocyanate and diphenylmethane diisocyanate.

SCHEME 2. Aromatic diisocyanates.

Their relative importance depends on a number of factors. While TDI


was the first successful isocyanate, and still remains important, it has been
shown to cause cancer in laboratory animals, as have many isocyanates.
Thus it is more difficult to handle from an industrial hygiene point of view.
Nevertheless, it is the preferred isocyanate for hydrophilics because it
tends to make softer, more hydrophilic foam.
As seen from the following graph, the bulk of the polyurethane busi-
ness has shifted toward MDI as the isocyanate of choice (see Figure 3).

©2000 by CRC
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FIGURE 3. Growth of MDI versus TDI (adapted from Reference [3]).

Some hydrophilics are based on MDI but they tend to make more boardy
foams. This is due, in part, to its increased mole percent in the urethane
molecule. For a given polyol, an MDI-capped polyol has a higher per-
centage of hard segments and, therefore, is not as soft as a TDI-based
polyurethane.
Another reason for the shift toward MDI is its faster reaction rate, which
makes it more appropriate for the one-shot process mentioned earlier.
For a researcher involved in immobilization, the relative lengths of the
isocyanate and the polyol are important. If the adsorption site were the
polyol, one would want to minimize the weight percent isocyanate and
focus on the proper polyol. As you will see there is a wide variety of poly-
ols available.
While aromatic represent the dominant isocyanates in the conventional
and hydrophilic polyurethane businesses, they present problems with re-
spect to weathering, specifically yellowing on exposure to light and heat.
While this may seem insignificant, the aesthetics of a product made from
these materials are typically important. Whether the device is a cosmetic
applicator or a wound dressing, yellowing is typically viewed as a degra-
dation of the usefulness of the product. Thus, even if there is no evidence
that the physical or hydrodynamic properties are affected by normal yel-
lowing, it is almost always an issue.
Three processes cause the yellowing. Exposure to UV light causes the
production of color bodies in aromatic isocyanates (TDI, MDI, etc.). This
can be inhibited by the use of UV-absorbing compounds. Most commonly,
however, packaging that is opaque to the ultraviolet is used to prevent
yellowing.

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4 THE CHEMISTRY OF HYDROPHILIC POLYURETHANES

Another major cause of yellowing is heat. Temperatures above 105°C


can noticeably yellow foam in a few minutes.
Lastly, exposure to hydrocarbon emissions causes yellowing. For this
reason, hydrophilic polyurethane foam manufacturers typically use elec-
tric forklift trucks. The effect seems to be related to the ability of the foams
to strongly adsorb hydrocarbons on their surface.
When the yellowing has to be eliminated (as opposed to inhibited), other
isocyanates are available. The most common are the aliphatics shown here.

SCHEME 3. Aliphatic isocyanates.

While each of these has its own peculiar characteristics, both are aliphatic
and therefore less subject to the yellowing that characterizes aromatic iso-
cyanates. For instance, hydrogels made from isopherone diisocyanates are
thought to have remarkably low protein adsorption characteristics.

1.2 THE POLYOL

For the most part, the polyol gives the polyurethane its chemical nature.
Especially when TDI is the isocyanate, the polyol is the major constituent.
Hence the secret to making soft foams is to change the length of the polyol
chain.
Two types of polyols are typically used, polyesters and polyethers. The
polyesters are usually based on adipic acid, but others are available. The
polyethers are derivatives of ethylene and propylene oxides.
To follow are typical polyesters:

©2000 by CRC
Technomic
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Publishing Company, Inc.

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