Siloxane-Modified Epoxy Resins

E. M. Yorkgitis, N. S. Eiss, Jr., C. Tran, G. L. Wilkes, and J. E. McGrath

Departments of Chemical Engineering, Mechanical Engineering, and Chemistry and
Polymer Materials and Interfaces Laboratory Virginia Polytechnic Institute and
State University Blacksburg, VA 24061/USA

Epoxy resins chemically modified with functionally terminated poly(dimethyl siloxane), poly(dime-
thyl-co-methyltrifluoropropyl siloxane), and poly(dimethyl-co-diphenyl siloxane) oligomers are de-
scribed in terms of their synthesis, morphology, solid-state properties, and friction and wear properties.
The compatibility between the epoxy resin and the siloxane modifiers can be enhanced by increasing the
percentage of methyltrifluoropropyl (TFP) siloxane or diphenyl (DP) siloxane relative to dimethyl
siloxane. The compatibility, of the siloxane modifier with the epoxy resin subsequently controls the size
and make-up of the phase-separated elastomeric domains. Fracture toughness of the epoxy resin can be
improved by modification with siloxanes containing 40°//0 or higher TFP content or 20 and 40% DP
content. Both fracture toughness and modulus changes are given a morphological basis. Friction and wear
properties in both fatigue and abrasive wear tests have been found to be related to changes in modulus,
fracture toughness, and morphology in ways dependent on the particular modifier. The properties and
morphology of epoxy resin modified with amine-terminated and carboxyl-terminated butadiene acrylo-
nitrile elastomers prepared under similar curing conditions have been determined and compared to
those of the sitoxane-modified resins.

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.2 Sample Designation . . . . . . . . . . . . . . . . . . . . . . . 84
2.3 Static Mechanical Properties . . . . . . . . . . . . . . . . . . . 84
2.4 Dynamic Mechanical Properties . . . . . . . . . . . . . . . . . . 85
2.5 Scanning Electron Microscopy . . . . . . . . . . . . . . . . . . 85
2.6 Friction and Wear . . . . . . . . . . . . . . . . . . . . . . . . 85

3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . 86

3.1 Characteristics of the Siloxane-Modified Epoxy Networks . . . . . . . 86
3.2 Morphology and Solid-State Properties . . . . . . . . . . . . . . . 91
3.3 Friction and Wear Properties . . . . . . . . . . . . . . . . . . . 102

4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . 107

5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
80 E.M. Yorkgitiset al.

I Introduction
Since the first epoxy resin patents were granted in the 1930's and 40's, the properties
of epoxy resins, for example, excellent chemical resistance, very good adhesion, and
good electrical insulation, have been utilized in many applications 1,2.3~. These include
surface coatings, adhesives, castings, and laminates. The versatility of these cross-
linked systems stems in large part from the fact that one can choose from a wide
variety of resins, curing agents, and preparatory conditions and often tailor a resin
to suit a particular need.
Current demands for so-called high performance materials has heightened interest
in epoxy resins as structural adhesives and as matrix resins for high-strength compos-
ites. Both of these applications take advantage of the resin's outstanding strength
and modulus and generally good adhesion. However, such uses also require good
fracture resistance and impact strength, properties which epoxy resins do not generally
exhibit.
The most common route to toughening epoxy resins has involved the incorporation
of elastomeric modifiers into the final glassy matrix. A reactive liquid elastomer is
mixed with the resin and curing agent at relatively low temperatures to form a homo-
geneous mixture. As cure proceeds (generally at elevated temperatures), the increasing
molecular weight of the epoxy matrix forces the elastomeric component to separate
within the crosslinked resin and form a second dispersed phase. Unlike thermoplastics
modified with rubbers through blending, the ideal rubber-modified thermoset links
the resin and the elastomer through covalent bonds such that, in the final state, the
rubber, resin, and curing agent form a multi-phase three-dimensional glassy network.
As will be discussed, the dispersed elastomeric domains act to alleviate crack prop-
agation through various proposed mechanisms.
The principal objective of rubber modification is the improvement of fracture
properties with the smallest possible decrease in modulus and strength. The CTBN
and ATBN (carboxyl- and amine-terminated butadiene acrylonitrile) copolymers
have done much towards reaching this end. The first publications by McGarry 4, 5j as
well as B. F. Goodrich co-workers Rowe, Siebert, and Drake 6.v) reported strong
improvements in fracture surface work and fracture energy, respectively, with the
addition of 5 to 15~o CTBN. Particle sizes in the best of these systems range from
0.1 to 1.0 micron. Riew, Rowe, and Siebert 8~ have reported 30- to 40-fold increases
in fracture energy. Although they are successful as general purpose toughening agents
for epoxies, CTBN and ATBN elastomers possess two drawbacks. First, their glass
transition temperatures are high relative to most elastomers 9~, which limits their
application far below room temperature 1°'~1). Second, their highly unsaturated
structure provides possible sites for reaction in oxidative and high temperature envi-
ronments 12)
Siloxane elastomers present an attractive alternative to the butadiene acrylonitrile
elastomers most often used for epoxy modification. Poly(dimethyl siloxanes) exhibit
glass transition temperatures well below those of butadiene acrylonitrile modifiers
(minimum -- 123 °C vs. about - 4 0 °C) and also display very good thermal stability 13,
14). Other favorable and potentially useful attributes include good weatherability,
oxidative stability, and moisture resistance. Finally, the non-polar nature and low
surface energy of poly(dimethyl siloxanes) constitute a thermodynamic driving force