Specialty Monomers and Polymers. Synthesis, Properties, and Applications

244 Pages·2000·27.176 MB·English

by  Kathleen O. Havelka and Charles L. McCormick (Eds.)

ACS SYMPOSIUM SERIES 755
Specialty Monomers and
Polymers
Synthesis, Properties, and Applications
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American Chemical Society, Washington, DC
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Library of Congress Cataloging-in-Publication Data
Specialty monomers and polymers: synthesis, properties, and applications / Kathleen O. Havelka, editor,
Charles L McCormick, editor.
p. cm — (ACS symposium series, ISSN 0097-6156; 755)
Includes bibliographical references and index.
ISBN 0-8412-3637-2
1. Polymers—Congresses. 2. Monomers—Congresses.
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w I. Havelka, Kathleen O., 1964- . II. McCormick, Charles L., 1946- . III. Series.
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Sept Pu The citation of trade names and/or names of manufacturers in this publication is not to be construed as
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PRINTED IN THE UNITED STATES OF AMERICA
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Foreword
1HE ACS SYMPOSIUM SERIES was first published in 1974 to provide
a mechanism for publishing symposia quickly in book form. The pur
pose of the series is to publish timely, comprehensive books devel
oped from ACS sponsored symposia based on current scientific re
search. Occasionally, books are developed from symposia sponsored
by other organizations when the topic is of keen interest to the chem
istry audience.
1 Before agreeing to publish a book, the proposed table of contents
0
w0 is reviewed for appropriate and comprehensive coverage and for in
5.f terest to the audience. Some papers may be excluded in order to better
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7
0 focus the book; others may be added to provide comprehensiveness.
0-
00 When appropriate, overview or introductory chapters are added.
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k- Drafts of chapters are peer-reviewed prior to final acceptance or re
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21/ jection, and manuscripts are prepared in camera-ready format.
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0.1 As a rule, only original research papers and original review pa
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acs.org 000 | doi: poeurssl ya preu bilnischluedd epda piner sth aer ev noolut macecse. pVteedr.b atim reproductions of previ
http://pubs.March 27, 2 ACS BOOKS DEPARTMENT
2012 | Date:
ember 7, blication
Sept Pu

In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Preface
This book is a compendium of refereed papers based on invited talks presented at the
American Chemical Society (ACS) Symposium on Specialty Monomers and Their Polymers.
Specialty monomers are inherently different from commodity monomers, and it is these
differences that result in new and important polymer properties. The most versatile feature of
specialty monomers and polymers is their built-in functionality. This functionality offers
significant opportunity to customize the design of polymers to meet specific performance,
physical, and chemical properties. These properties are needed for many of today's hi-tech
applications and cannot be easily obtained with more common commodity monomers and
polymers.
Specialty polymers have emerged as an important class of materials because they offer
flexibility, both at the molecular and bulk levels, to optimize physical and chemical properties
1 for medical and industrial applications. Because the structure of synthetic specialty polymers
0
0 can be easily controlled and measured, they are frequently used to model the more complex
pr
5. natural polymers. Using well defined model compounds facilitates significant advancements
5
7 in our understanding of fundamental properties. Increased understanding of materials issues
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0- will expedite the development of "smart polymers" that have unique, tunable, and responsive
0
0
2 properties. Developing "smart polymers" requires a highly multidisciplinary approach, the
k-
b progress of which depends on active collaboration from diverse groups, including chemists,
1/
2 biologists, physicians, physicists, material scientists, and engineers.
0
1
0. Considering that interest in specialty polymers and "smart polymers" is growing
1
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2 | e: We acknowledge the overwhelmingly positive response from the specialty polymers
201Dat community. The breadth of participation in the symposium is due in part to the support from a
September 7, Publication n IAnucCm.S;b tehfroe Wr o Ltfehu eobiarrrgri efzai onntliar znuCacltoyiioar plni nossd.ru aeptbIipotnoen rdpt; . aa trnotid c tuhlea r,n uwmee rthoaunsk atuhteh oArsC Sf oDr itvhiesiiro nt imofe lPyo leyfmfoertr Canhde mtois ttrhye,
referees for their critical evaluation of the manuscripts.
KATHLEEN O. HAVELKA
The Lubrizol Corporation
29400 Lakeland Boulevard
Wickliffe, OH 44092-2298
CHARLES L. MCCORMICK
Department of Polymer Science
University of Southern Mississippi
Hattiesburg, MS 39046-0076
vii
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
Chapter 1
Specialty Polymers: Diverse Properties
and Applications
Kathleen O. Havelka
The Lubrizol Corporation, Research and Development,
29400 Lakeland Boulevard, Wickliffe, OH 44092-2298
Many of the most accessible commodity polymers have been studied in
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00 detail and their applications have been developed extensively. Interest is
h
5.c now focused on the synthesis and study of specialty polymers to meet
5
7 today's critical applications. Specialty polymers are primarily water
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0- -soluble polymers with functional groups that are pendent to or on the
0
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2 backbone; their global market value currently exceeds 9 billion dollars
k-
b and continues to grow (1). They are used extensively for their unique
1/
02 solution properties in various fields of industry, agriculture, medicine,
1
0. biotechnology, and electronics. Applications of specialty polymers are
1
g doi: diverse, including: water treatment, paper processing, mineral
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2 | e: properties depends on the type of polymer, the amount used, and
201Dat interactions with other chemistries in the formulation.
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present and future hi-tech and biological applications. Of particular interest is the
ability to tailor a polymer to deliver a specified property in response to an external
stimuli. This is highly desirable as it enables one to minimize both the amounts of
material used and competitive reactions, which is critical in control-release functions,
particularly in drug delivery applications. Effective delivery of drugs to a target cell or
tissue largely diminishes adverse side effects and increases the pharmacological
activity. It is the potential to tailor macromolecules to provide specified properties in
an environmentally benign manner that motivates much of the current applied and
fundamental research in the field of specialty polymers. These properties are critically
needed for many of today's demanding applications.
2 © 2000 American Chemical Society
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
3
Material Considerations of Specialty Polymers
There are numerous considerations in determining the appropriate polymer for a given
application. In general, for a polymer to be commercially viable it must meet stringent
environmental regulations, high performance standards, and be cost effective. The
properties of specialty polymers depend on their basic chemical and structural
properties, as summarized below.
• Molecular Weight - The molecular weight and molecular weight distribution
strongly affect the solution properties of specialty polymers and their applications.
• Hydrophile to Lipophile Balance (HLB) ~ the type and content of hydrophiles and
lipophiles significantly impacts specialty polymers inter- and intra-molecular
associations.
01 • Sequence distribution of monomers — block, alternating, or random distribution
0
ch impacts interaction of monomer groups within the polymer.
5.
5 • Degree of Branching - a branched polymer frequently has different properties than
7
0
0- its linear analog, such as, lower tendency to crystallize, different solution
0
20 properties and light scattering behavior.
bk- • Hyperbranched materials and dendrimers - offer the synthetic ability to chemically
1/
2 tailor the branches in a step-wise fashion.
0
1
0. • Degree of crosslinking ~ a crosslinked polymer has chemical linkages between
1
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2 | e: • Polyelectrolytes ~ macromolecules bearing a net charge
201Dat • anionic ~ macromolecules bearing a negative charge.
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units, or have a net charge of one sign.
• Polybetaines ~ macromolecules containing both cationic and anionic
charges on the same pendent group.
• Degree of Chemical Modification - Synthetic macromolecules and many natural
polymers (e.g., polysaccharides) can be chemically modified to adapt their
properties to the needs of a particular application. For example, the ionic character
of cellulose may be chemically modified from nonionic to anionic through
nitration.
Origins of Specialty Polymers
Specialty polymers are typically water-soluble polymers that come from three origins,
natural, semisynthetic, and synthetic macromolecules. Natural polymers are plant or
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
4
animal based materials such as cellulose and proteins. Semisynthetic polymers are
modified natural polymers manufactured by chemical derivatization of natural organic
macromolecules, generally based on polysaccharides. Synthetic polymers are obtained
by the polymerization of monomers synthesized from petroleum or natural gas
precursors.
Natural and Semisynthetic Polymers
A significant number of water-soluble polymers are derived from biological sources,
biopolymers (2). Biopolymers are an abundant and diverse class of polymers that
includes polysaccharides (3), polynucleotides (4), and proteins (5). Since these
polymers perform unique biological functions, they have specific microstructures and
are often monodisperse.
01 Polysaccharides are a diverse class of biological macromolecules with a wide range
0
ch of structural and behavioral characteristics (3). They are biodegradable, cyclolinear,
5.
5 polyhydroxyl compounds that are widely used in industry. Industrial polysaccharides
7
0
0- have traditionally been extracted from renewable resources like starch and gums from
0
0 plant seeds.
2
bk- Solution properties, such as solubility, viscosity, and phase behavior, are highly
21/ dependent on the macrostructure of the chain and the chemical microstructure of the
0
0.1 repeat units. The presence of acidic or basic functionality causes pH, electrolyte, and
1
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2 | e:
201Dat Polynucleotides are biopolymers that carry genetic information involved in the
ember 7, blication pocfor ompcrbeoistnseaeintsis oo ncfs ar enap nbldiec asmteiqaodunee an bncyde aplsersnoegtmethinbsl .is nyTgnh tethh ee2s 0i2s 0a(m 4a)im.n oiAn oan c aeidcssisde cns otiinnatl alvyian ri infoofuiunsr i tmme iacnjruoomrs tbtryeurpc,et usr aolf
Sept Pu side chains, i.e., hydrophobic, hydrophilic, basic and acidic. Most polypeptides and
proteins are water-soluble or water-swellable. The solubility of proteins varies
considerably based on composition and condition of ionic strength, pH, and
concentration. Those with the highest density of polar groups or electrolyte character
are the most soluble. Therefore, solubility in water is lowest at the isoelectric point
and increases with increasing basicity or acidity.
Polynucleotides are utilized extensively in medical, industrial, and agricultural
applications. The development of recombinant DNA techniques has led to the ability
to clone genes and has facilitated the production of a large numbers of proteins with
significant commercial potential (6). Among the first genetically engineered proteins
are insulin, the pituitary growth hormone, and interferon. Other water-soluble proteins
are isolated from biological sources in a more traditional manner for a number of
commercial applications. Enzymes are used as detergent additives to hydrolyze
polysaccharides and proteins, to isomerize various glucose and sucrose precursors, and
for mineral recovery. Supported enzymes are becoming commercially significant for
large-scale substrate conversion of macromolecules(7).
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
5
Commercial Advantages of Natural and Semisynthetic Polymers
Natural and semisynthetic polymers have some commercial advantages over many
synthetics, particularly in food applications.
• FDA Status — Many have been assigned "generally recognized as safe" (GRAS)
status by the US Food and Drug Administration (FDA).
• Ease of Production -
• The processes for producing natural polymers are frequently simpler, involving
harvest and refinement through chemical and mechanical operations.
• Semisynthetics involve chemically derivatizing natural macromolecules instead
of complex polymerization of monomers.
• The facilities for producing them, therefore, are less capital-intensive, and the
equipment can be more flexible.
1
0
0
h
5.c Synthetic Polymers
5
7 Synthetic specialty polymers are obtained by the polymerization of monomers
0
0- synthesized from petroleum or natural gas precursors. Linear or branched
0
0
2 macromolecules may be formed from one or many monomers. Distribution of
k-
b monomers, along the backbone or side chain, can be controlled in a number of ways,
1/
2 including: controlling monomer reactivity, concentration, addition order, and reaction
0
1
0. conditions.
1
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2 | e: in the research laboratory. However, only a few are of commercial interest. Of
201Dat particular commercial interest is synthesis of specialty polymers in solutions,
ember 7, blication Cdiospmemrseiorncisa, ls uAsdpevnasniotangse, so ro fe mSyunlstihoentsi.c Polymers
Sept Pu Synthetic, semisynthetic, and natural polymers frequently can perform similar

functions. However, synthetic polymers have a number of inherent advantages and are
preferred in many applications for a number of reasons, including:
• Greater Flexibility - Synthetic polymers can be designed at the molecular level and
are frequently used as model compounds to develop structure-property
relationships for the more complex natural polymers.
• Greater Versatility - Synthetic polymers can be tailored to provide a specific
property or properties for a given application. The naturals and semisynthetics are
limited in the types of chemical modification because of the fragile polysaccharide
backbone.
• Greater Efficacy - Since synthetic polymers can be tailored for a specific property,
significantly less synthetic polymers are needed to facilitate the same performance
as natural polymers.
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
6
• Lower Biological Oxygen Demand (BOD) - Since synthetic polymers have lower
BOD, the effluents containing synthetic polymers are easier to treat than the other
types.
• Greater Product Consistency - Since the raw materials and the reaction conditions
can be well defined and controlled, synthetic polymers can be manufactured with
more consistent quality than natural or semisynthetic polymers.
• Greater Price Control - Synthetics are less subject to variations in price than
natural polymers due to availability.
Functionality of Specialty Polymers
Specialty polymers are best known for their built in functionality and water-solubility.
This functionality is present in natural and synthetic polymers and can be broken down
01 into two broad categories nonionic and ionic polymers. These two categories will be
0
ch discussed in greater detail.
5.
5
7
0
0- Nonionic Polymers
0
0 Nonionic specialty polymers contain diverse functional groups that do not bear a
2
bk- charge, such as, vinyl esters, acrylates, acrylamides, imines, and ethers. Most of these
21/ commercially important polymers are soluble in water. Their water solubility is the
0
0.1 result of a high number of polar or hydrogen-bonding functional groups per repeat
1
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2 | e: soluble in water in all proportions. Since polyacrylamide can be polymerized to very
201Dat high molecular weight, it is a highly efficient viscosifier. Applications of
ember 7, blication pmwoaoltyleearc cutrrlyealara tmmwieedniegts.h ti Anccpolpuprodolexy mifmloeacrstce uloylfa nsaetcsvr,e yrrlahalem ohiludonegd yar ercedo ntmhtierlo llim oanog spet onwutsni,d dase nloydf upasdoehldye aspcivoryelysla.m meirHd eifg oihrs
Sept Pu used annually in water treatment, with a market value of approximately one billion
dollars (9).
Poly(ethylene oxide) is prepared by ring-opening polymerization of ethylene
oxide. It is a white free-flowing powder with commercial grades ranging from
100,000 to 5,000,000 molecular weight (10). Polyethylene oxide)s are completely
soluble in water at room temperature, but show a lower critical solution temperature
(LCST) near the boiling point of water. The solution properties of poly(ethylene
oxide)s have been extensively used in commercial applications for rheology control.
The unique phase transition properties are being explored for control-release in
thermally-responsive applications.
Ionic Polymers
Polymers possessing ionic groups pendent to the backbone are perhaps the most
important class of macromolecules, ranging from biopolymers such as polynucleotides
and proteins to technologically important rheology control agents and polysoaps.
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
7
These ion-containing polymers may be divided into two groups, polyelectrolytes and
polyampholytes. Polyelectrolytes have either anionic or cationic groups along the
chain while the polyampholytes have both anionic and cationic groups present. Both
have high charge densities and typically are water-soluble.
Water-soluble ionic polymers share a number of common properties with
water-soluble nonionics, e.g., they both can act as viscosifiers. However, differences
arise from the presence of charge on the macromolecular backbone and from the
electrostatic interactions of mobile counterions. These differences have a significant
impact on the structure of ionic polymers in solution and will be discussed further.
Polyelectrolytes
Polyelectrolytes are macromolecules bearing a net charge. Interest in these
unique materials spans numerous and diverse areas. They have been investigated
1
0 because of their essential participation in biological systems, such as, conformation
0
h
c transition of DNA (11). In ion-exchange membranes, they have been used for ion
5.
5 selectivity, such as recovery and separation of precious and heavy metals. Also they
7
0
0- have been explored in polyion gels for controlled release and phase transitions, such
0
20 as, drug delivery (12). Their molecular structure can be tailored to allow large
bk- conformational changes with pH, temperature, or added electrolytes. Molecular
1/
2 parameters that significantly influence behavior include: hydrophobic/hydrophilic
0
0.1 balance, molecular weight, number, type and distribution of charge on the
1
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2 | e: attain large hydrodynamic volumes in deionized water at low concentrations (14).
201Dat This effect is caused by coulombic repulsion between charged groups along the
ember 7, blication prsaaonlltdy, omcmoeur, lcohmeanbitnrico t phrieacptau lfllosyri coenfssa vtahoreere dcshh iaeiclnod neindfot,o ram lala ortwioodinn- lgik wteh iect hop nofloay rmmseaurt ibcoshnea.q iunIe ntno tt haesd supecmrereseae asn ecm e ooirnfe
Sept Pu hydrodynamic volume. Electrostatic repulsions not only cause an increase in
hydrodynamic volume but also increase shear sensitivity or non-Newtonian behavior.
The extent of ionization of polyelectrolytes depends on the relative base or acid
strength, degree of solvation, and dielectric constant of the solvent. The structure and
properties of acidic (anionic) and basic (cationic) polyelectrolytes, are discussed
further.
Polyelectrolytes (Anionic) are macromolecules bearing a negative charge.
Depending on the strength of the acid, they can strongly interact with positive charges.
Anionic polyelectrolytes that have been studied extensively have primarily carboxylic
or sulfonic acid functionality, including: poly(acrylic acid), poly(vinylsulfonic acid),
poly(styrenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid),
poly(methacrylic acid), and their salts. Applications of anionic polyelectrolytes are
diverse ranging from gels for medical applications to latex stabilizers and dye
receptors in synthetic fibers.
Polyelectrolytes (Cationic) are macromolecules bearing a positive charge.
Cationic functional groups can strongly interact with suspended, negatively charged
In Specialty Monomers and Polymers; Havelka, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.