J . POLYMER SCI.: PART C NO. 24, PP.

1-5 (1968)

Critical Factors Affecting Chemical Reactions on Polymers

NORMAN G. GAYLORD, Gaylord Associates, Inc.,
Newark, New Jersey 07104

Synopsis

Chemical reactions on polymers are influenced not only by the reac-

tivity of a funtional group but also by its accessibility. Although in-
trachain steric factors that result in neighboring-group effects are well
recognized, the interchain interactions that determine the availability
of a potential reaction site have not been adequately considered. The
factors that influence polymer reactions include amorphous or crystal-
line content, orientation, solubility, and compatibility. The interchain
interactions involved are not only those between chains of the initial
polymer but, more significantly, those between polymer chains that have
reacted or partially reacted and polymer chains that have not. Chemical
react,ion may change solvent-polymer interactions so that either chain
extension or coiling occurs with resultant changes in the accessibility
of reaction sites. Incompatibility between polymer that has partially re-
acted and polymer that has not may result in phase separation. Increased
compatibility may result from the generation of block copolymers, due to
localized or segmental reaction, which then act a s compatibilizing agents
and make the separation of reaction products, such as by extraction of
unreacted material, extremely difficult.

INTRODUCTION

The major factors influencing chemical reactions on polymers are the

reactivity of the functional group or site on the polymeric substrate and
its accessibility.
The reactivity of a functional group on a high molecular weight sub-
strate is generally considered to be essentially the same a s that of the
same group on a low molecular weight homologue. However, the validity
of this concept is dependent upon the proper choice of homologue. There
are a sufficient number of deviations from this generalization to show
the significance of neighboring-group effects resulting both from the ac-
tual location of potentially interacting groups and from the population of
neighbors resulting from chain flexibility or chain folding. Although the
enhanced reactivity resulting from group interactions is highly signifi-
cant. reduced reactivity due to steric factors is of even greater impor-
tance in attempted alterations of polymer structure through chemical re-

1
2 N. G .GAYLORD

action.
To consider a polymer chain a s a sequence of pendant functional
groups strung from an extended backbone chain is to oversimplify.
Chemical reactions are not carried out on an isolated polymer chain but
on one or more chains in an environment consisting of similar chains
that have not reacted, have partially reacted, and have completely re-
acted, any or all of which are in the solid state or the liquid state, i.e.
melt or solution, and not all in the same state at the same time. Thus, one
of the most critical factors in reactions on polymers, even when the
chemical reagent involved is a simple molecule, is that of polymer-poly-
mer interaction in a reacting and changing system, with its influence on
the accessibility of sites on the polymeric backbone in addition to the
influence of intrachain steric factors.
The following factors influence interchain interactions and the ac-
cessibility of reactive sites: amorphous or crystalline content, orienta-
tion, solubility, and compatibility.
A reacting system is in flux, and properties change as the reaction
proceeds. The initial system, which is homogeneous in polymer struc-
ture and properties, becomes heterogeneous, and both interchain and in-
trachain relationships change.

CRYSTALLINITY AND ORIENTATION

In the solid state polymer chains may be in one of the following

forms: amorphous and unoriented, amorphous and oriented, crystalline
and unoriented, and crystalline and oriented. Obviously, the polymer
does not exist in any of these forms exclusively, and the degree of
crystallinity and orientation may vary, not only from one sample to an-
other, but also from one bundle of chains to another.
It has been amply demonstrated that the attack of a chemical reagent
on an amorphous structure occurs more readily than on a crystalline
structure: hydrolysis of poly(ethy1ene terephthalate), chlorination of
polyethylene, and oxidation of polyethylene and polyformaldehyde. How-
ever, the degree of penetration of the reagent and the extent of reaction
are dependent upon the degree of orientation of the chains, the number
and complexity of chain entanglements, and the temperature of the reac-
tion in relation to the glass-transition temperature of the polymer,
In the case of a crystalline polymer the oriented chains act as a unit
and make available a lower surface area for chemical reaction. In addi-
tion, the penetration of the reagent is restricted to the periphery of the
oriented areas.
In the molten state the persistence of crystalline or ordered areas is
temperature dependent and influences the homogeneity of the reaction.
Chain entanglements that may not exist in the crystalline state are gen-
erated when the polymer is melted and may increase the localized in-
CRITICAL FACTORS AFFECTING REACTIONS 3

ternal melt viscosity as well as decrease the accessibility of sites on

the chains.

SOLUBILITY

Although reactions carried out on polymers in solution would appear

to hold the most promise for the greatest extent and uniformity, polymers
in solution are not necessarily in the ideal, extended form. A solvent
that is inert from the point of view of the particular chemical reaction
under investigation may be a poor solvent for the polymer undergoing re-
action. A s a result the polymer chains may be present as tight coils,
and the reactive sites may be inaccessible. The coiled polymer chains
in a solvent are therefore not necessarily more available or reactive
than the chains in the molten or solid polymer.
The choice of solvent is not only dictated by inertness to the chem-
ical reagent but also by solvent-reagent interactions, which determine
the course of the reaction, e.g., the chlorination of ethylene-propylene
copolymers. The most desirable solvent for achieving a specific inter-
action may be a poor solvent for the polymer: consequently the reaction
may result in a heterogeneous product.
A factor inadequately considered in solution reactions is the solubil-
ity of the reaction product. Thus, although the environmental factors,
such as the solubility of the starting polymer and the reagent, may be
ideal for a uniform reaction, the insolubility of the product at low levels
of reaction will result in a precipitation and termination of the reaction
or in a nonuniform reaction. This effect has been noted in chelate-
forming reactions.
Conversely, chemical reaction may result in increased solubility, so
that an attempt to carry out homogeneously a partial, limited reaction is
not possible, owing to the greater accessibility of sites on the reaction
product. This is clearly noted in the preparation of cellulose deriva-
tives, in which the hydrogen bonding and crystallinity in the cellulose
initially limit reaction to the surface. Subsequent reaction occurs to a
greater extent in the areas that have already reacted, while reaction
slowly progresses inward.
An interesting problem in solubility exists in the preparation of vari-
ous types of thermosetting acrylic resins. The initial reaction involves
the copolymerization of an acrylic ester with acrylamide, often with
styrene as a comonomer. For end-use purposes it is desirable to have
the finished resin in a hydrocarbon solvent. However, the insolubility
of acrylamide monomer in xylene or other hydrocarbon solvents dictates
the presence of an alcohol such as butanol. When the copolymerization
is completed, the solubility of the copolymer is the important factor,
since the copolymer next reacts with formaldehyde to produce an N-me-
thylolated acrylamide copolymer. The solubility of the N-methylolacryl-
4 N. G. GAYLORD

amide copolymer in a hydrocarbon solvent is less than that of the acryl-

amide copolymer. The reaction with formaldehyde is carried out with
butyl formal, which yields an N-butoxymethylolated acrylamide copoly-
mer, which is more soluble in hydrocarbon solvents. At this point a
large amount of the excess butanol may be distilled from the system to
yield an N-butoxymethyl acrylamide copolymer in a hydrocarbon-rich
mixed solvent system, and the butanol-rich distillate may be reused in
subsequent reactions to provide a suitable solvent system for the acryl-
amide monomer.

COMPATIBILITY

The significance of polymer incompatibilities has only recently been

recognized. A s a general rule most polymers are incompatible: e.g., not
only do mixtures of different polymers form heterogeneous masses in the
solid or molten state, but also, when solutions of different polymers in
the same solvent are mixed, two phases are formed. Even polymers that
appear to be similar in structure such as polystyrene and poly-tert-butyl-
styrene, are generally incompatible. Copolymers that differ in monomer
composition by as little a s 5% may be incompatible and produce hetero-
geneous mixtures.
Not only is incompatibility manifested in visible stratification or opac-
ity but, as in the poor solvent-polymer interaction, coiling of the chains
occurs.
Compatibility becomes a significant factor when chemical reactions
are carried out on polymers, a s a result of the difference in structure be-
tween the starting polymer and the reaction product. When the polymer
has undergone a low degree of reaction it tends to coil and become less
accessible for further reaction. This effect is noted not only for a given
percentage of the total polymer concentration but also within an individ-
ual polymer chain. A s a result the reaction product is heterogeneous,
considering both the individual chains and the chains within the mass.
The tendency of two incompatible polymers i n the same solvent to
form a two-phase system may be manifested in polymer reactions by the
separation of the reaction mixture into two phases, even before the reac-
tion has been carried out to the desired extent.
In the absence of separation the effect of chain coiling is a reduced
solution or melt viscosity. A s a result, the reaction may become local-
ized on the surface of the coils or diffusion-controlled, or both.
Another aspect of polymer compatibility relationships involves the
generation of block or graft copolymers not only in monomer reactions
with polymers but also a s a result of localized reactions, for example, in
amorphous areas or on surfaces. These segmented polymeric structures
may act as compatibilizing agents for chains that have reacted and that
have not reacted, and separation of the reaction products may be extremely
CRITICAL FACTORS AFFECTING REACTIONS 5

difficult.
It is apparent that environmental factors, including the reaction condi-
tions and the physical state of the starting polymer and the final prod-
uct, play as critical a role in polymer reactions as the reactivity of the
functional groups and the nature of the reagents.