CYCLOALIPHATIC EPOXY RESINS

Robert Kultzow* and Stephanie Foxhill

Huntsman Advanced Materials

Advanced Technology Center
8600 Gosling Road
The Woodlands, Texas

Presented at a meeting of the Thermoset Resin Formulators

Association at the Hyatt Regency Savannah in Savannah,
Georgia, September 10 through 11, 2007

This paper is presented by invitation of TRFA. It is publicly distributed upon

request by the TRFA to assist in the communication of information and
viewpoints relevant to the thermoset industry. The paper and its contents have
not been reviewed or evaluated by the TRFA and should not be construed as
having been adopted or endorsed by the TRFA
Abstract: Cycloaliphatic epoxy resins
are a class of materials of choice for a
wide variety of electrical, electronic and
structural applications. Having fully
saturated molecular structures, they are
ideally suited for use in applications
requiring resistance to ultraviolet
degradation and electrical arc-tracking.
This paper describes the commercially
available types of cycloaliphatic epoxy
resins, presenting their features and
applications. Physical property data for
a number of systems containing these
resins is provided. This paper also
explores alternative epoxy resins in
formulations where cycloaliphatic
epoxies are typically used.
INTRODUCTION
Cycloaliphatic epoxy resins are a unique
class of materials that are characterized by
non-aromatic saturated rings in their
molecular structures. There are two
commercial types of cycloaliphatic epoxy
resins in widespread use. Among their
most notable features are inherently low
viscosity, coupled with excellent weathering
and electrical performance. Both
commercial cycloaliphatic resins are ideally
suited for applications in severe
environments such as near seacoasts and
in areas of high industrial pollution.
APPLICATIONS
An important application for cycloaliphatic
epoxy resins is for the fabrication of non-
ceramic outdoor electrical insulating
components. This would include electrical
insulators, bushings and switchgear parts
used for the transmission and distribution of
electrical power. Compared to porcelain,
components made with epoxy formulations
are lighter in weight, show greater impact
resistance, excellent electrical properties,
reduced maintenance and can be
fabricated economically into complex
shapes with embedded inserts2,4. The
outstanding resistance to both ultraviolet
degradation and carbon tracking provided
by these resins are noteworthy1. They are
among the primary requirements for
electrical components used in severe
outdoor environments. The inherent low
viscosity of these resins enables them to be
formulated with higher levels of inorganic
fillers. This enhances mechanical and
electrical track resistance for such
components.
Encapsulation of transformers, coils and
various electronic devices is another
important area of application for
cycloaliphatic epoxy resins. Their
characteristics of low dielectric loss and
high electrical resistivity, up to or above
their glass transition temperatures provide
high performance and reliability in both AC
and DC circuitry. In such applications, low
viscosity enables facile penetration into
tightly-wound electrical coils. Void-free
encapsulation is a pre-requisite in high
voltage electrical coils. It prevents failure
due to internal arcing and partial discharge.
The inherent low color characteristics
coupled with high resistance to yellowing
from ultra-violet light absorption makes the
cycloaliphatic epoxies useful in formulations
for such applications as light emitting
diodes.
Cycloaliphatic epoxy resin formulations are
used to fabricate many fiber-reinforced
structural components. Their low viscosity
allows for rapid fiber wet-out in commonly
used processes that include filament
winding, pultrusion and resin transfer
molding. Formulations incorporating these
resins can exhibit high glass transition
temperatures in the range of 200C. These
are used to fabricate structural components
requiring high temperature service.
Cycloaliphatic epoxies show distinct
advantages over the glycidyl ether epoxy
materials in their ability to produce high
bond strengths on poorly cleaned and oily
surfaces. A number of commercially
available adhesive formulations include
these materials for this benefit.
recent supply issues has the chemical
name of 3,4 epoxycyclohexylmethyl -3,4
epoxy-cyclohexane carboxylate. This resin
is referred to as Epoxy B throughout this
paper. Its chemical structure is illustrated in
Figure 2.

COMMERCIAL CYCLOALIPHATIC
EPOXIDES
Figure 2.
An important and widely used cycloaliphatic Epoxy B structure
epoxy resin is the diglycidyl ester of
hexahydrophthalic acid. This resin is Typical properties of this material are
referred to Epoxy A throughout this paper. shown in Table 2.
Its structure is shown in Figure 1.
Table 2

O O Typical Properties
C O CH 2CH CH 2 Color Gardner 1
EEW 131 - 143
Specific Gravity 1.14 1.18
C O CH 2CH CH 2 Viscosity, 25C 350 450 cps.
Flash Point > 200F
O O Vapor Pressure, 20C <0.1 mbar

Figure 1 Some cured physical properties of these

Epoxy A structure cycloaliphatic epoxy resins, as neat
systems (without filler) are given in Table 3.
Typical properties of this resin are given in
Table 1. Table 3
Table 1 [Neat systems cured with HHPA + BDMA]
Property @ 25C Epoxy A Epoxy B
Typical Properties Tensile strength (psi) 8,000 9,900
Color Gardner 3 max. Tensile modulus (psi) 472,000 480,000
Elongation (%) 1.9 1.2
EEW 164 - 172 Flexural strength (psi) 19,300 12,900
Specific Gravity 1.20 1.25 Flexural modulus (psi) 490,000 440,000
Viscosity@ 25C, cps. 700 - 900 Comp. strength (psi) 22,300 21,200
Flash Point 374F Tg (C) 110 - 125 150 - 160
Vapor Pressure, 20C <0.1 mbar Dielec. constant, 60 3.3 3.3
Hz,
Diss. Factor, 60 Hz 0.005 0.005
Another widely used cycloaliphatic epoxy Volume resist. (/cm) 5 E16 5 E16
resin that has been readily available until Dielectric Strength
@ 1/8 (V/mil) 476 433 Table 4
The most common curing agents for the Epoxy A / HHPA System
diglycidyl ester cycloaliphatic epoxy resin Containing 62% by weight silanized silica filler
include the carboxylic acid anhydrides and
acid catalytic types. For outdoor Property @ 25C Typical
applications it is recommended to use fully Values
Tensile strength, psi 12,000
saturated curing agents in order to retain
Tensile modulus, psi 1,500,000
both optimum uv light resistance and Flexural strength, psi 18,000
electrical arc-tracking resistance. The most Flexural modulus, psi 1,450,000
common acid anhydrides of this type Tg , C 110 - 120
include both hexahydrophthalic anhydride Dielectric constant, @ 60 Hz 3.5
and methylhexahydrophthalic anhydride. At Dissipation factor @ 60 Hz 0.005
room ambient temperature, HHPA is a solid Dielectric strength, 1/8, v/mil 450
but melts to a low very viscosity liquid at Time-to-track @ 2.5 kv
(ASTM-D 2303), minutes >2000
35-37C. The MHHPA is a very low
viscosity liquid at room temperature having
Thermal endurance testing is used to
a melting point of less than -15C. Lewis
predict the long term stability of an
acid catalysts including both BF3 and BCl3
insulating material. Property changes such
amine complexes are used to formulate
as tensile or flexural strength are measured
single component systems with this epoxy
after exposure to heat. The test times may
resin. Such formulations exhibit excellent
vary between 5,000 and 20,000 hours. A
latency at room temperatures with rapid
thermal endurance profile, in the form of an
cure at elevated temperatures.
Arrhenius plot, is shown in Figure 3 for
anon-filled formulation utilizing the Epoxy A
Two-component casting formulations
type cycloaliphatic resin6. These tests were
utilizing this epoxy resin that employ
performed in accordance with the IEC 216
saturated acid anhydride curatives
Standard.
commonly contain inorganic mineral fillers.
These fillers are used to increase thermal
100000
conductivity and modulus while reducing
thermal expansion, reaction exotherm
Time at 50% Initial Strength (hours)

during gelation and cost. The

recommended fillers for outdoor electrical 10000

applications are silica and hydrated

alumina. Silane pre-treatment of these
fillers has been shown to significantly 1000
improve retention of mechanical and
electrical properties on long term exposure
in outdoor conditions and in hostile
environments. Such silane coupling agents 100 280 260 240 220 200 180 160 140 120
Temperature (C)
provide a stronger bond between the resin
matrix and filler surfaces3,5. Some typical
properties of a pre-filled cycloaliphatic Figure 3
epoxy system based on the Epoxy A Thermal Endurance Profile:
cycloaliphatic type containing 62% by Epoxy A / HHPA System Non-Filled
weight silanized silica filler are given in
Table 4.
The 3,4 epoxycyclohexylmethyl-3,4 epoxy-
cyclohexane carboxylate resin has
exceptionally low viscosity as well as very
low color. Similar to the diglycidyl ester
cycloaliphatic type, the most common
curing agents used with this epoxy are the
acid anhydrides and certain acid catalytic
types. This epoxy type is manufactured by
epoxidizing a diolefin with peracetic acid.
Since chlorine is not present in these raw
materials they are free of hydrolysable
chlorine. This characteristic is of great
importance in formulating high purity
electronic encapsulants. Nadic-methyl
anhydride is frequently used in systems
demanding the highest glass transition
temperatures that can exceed 180C, and
with certain high temperature cure
conditions, they can exceed 200C.
However, NMA is generally less reactive
that other anhydrides and usually requires
longer cure cycles to develop full
properties. For such high Tg applications
this resin can either be used alone or in
combination with other epoxy resins for the
best balance of physical properties. Certain
Lewis acid type catalysts such as BF3-
amine complex types can be used with this
epoxy yielding systems with moderate
latency at room temperature coupled with a
very rapid elevated temperature cure.
would effectively reduce the Tg to the
desired range. Where outdoor electrical
performance is not a primary requirement
but low viscosity coupled with high Tg are of
paramount importance, the Epoxy B type
resin would be a material of choice. As an
alternative, this resin can be substituted for
blends of the Epoxy A with low viscosity
multi-functional epoxy resins such as 4-
glycidyloxy-N,N-diglycidyl aniline. This
particular tri-functional epoxy is referred to
Epoxy C in this paper. Its chemical
structure is illustrated in Figure 3. The Tg
values of several blends of Epoxy A and
Epoxy C, cured with two different
carboxcylic acid anhydrides are shown in
Table 5.
Figure 4
Epoxy C structure

In applications that require superior

electrical properties in outdoor Table 5
environments, either of the cycloaliphatic
epoxy resins discussed in this paper can be Cure: 2 h / 90C + 1 h / 150C + 1 h / 200C
used if cured with fully saturated acid System Formulations
anhydrides. In most of these applications, Component (pbw)
Epoxy B 100 100 - - - -
glass transition temperatures in excess of
Epoxy A - - 75 50 75 50
125C are not required and generally not Epoxy C - - 25 50 25 50
desired. For such cases the Epoxy A resin MTHPA 110 - 105 120 - -
can be used without modification. However NMA - 115 - - 110 130
if the type B resin is used for such 1-m. imidazole 0.5 0.5 0.5 0.5 0.5 0.5
applications, it would commonly be modified Tg by DSC, C 183 206 135 158 156 181
with flexibilizing additives, such as polyether
or polyester polyols. This modification
 CONCLUSIONS Over a Decade, Georgia Power Company,
1996.
Cycloaliphatic epoxy resins continue to be
used in a wide variety of electrical, 5. O. Margreve, B. Mistiaen, Silica-Filled
electronic and structural applications. Their Cycloaliphatic Epoxy Resin Insulation,
fully saturated molecular structures make Laboratory Research and Field Experience,
them ideal for use in applications where CIGRE 12 WG Instrument Transformers,
protection in outdoor and severe Chapter 2, Manufacture and Quality Tests,
environments is needed In such cases they GEC AlthomT&D Balteau S.A.
are an attractive alternative to porcelain4.
There are two structurally different 6. E. Hubler, B. Hanisch, Long Term
commercially available cycloaliphatic epoxy Experience with Cycloaliphatic Epoxy
resins today. For many systems intended Systems, SEE Conference, Paris, 1994
for use in outdoor high voltage electrical
insulating components, either of these
epoxy resins can be used if properly
formulated. Each of these cycloaliphatic
epoxy resins has a number of unique
characteristics favoring them for use in
certain specialized applications.
Formulations that utilize these versatile
epoxy resins can be tailored to meet the
requirements of many of these specialized
applications.

REFERENCES

1. U. Massen, C. Beisele, Cycloaliphatic

Epoxy Insulators Experiences oner 30
Years, EFG-Fachtagung, Bad Nauheim,
Germany, (1999).

2. P. Mahonen, Outdoor Endurance of

Cycloaliphatic Epoxy Insulation,
International Symposium on Modern
Insulator Technologies, Coral Gables,
Florida, (1997).

3. U. Massen, Worldwide Outdoor

Experiences with Cycloaliphatic Epoxy
Insulators over 30 Years, Symposium on
Non-Ceramic Insulator Technology,
Singapore, (June 1996).

4. P.M. Vagle, Cycloaliphatic Epoxy

Outdoor Bushings / Insulators In a Heavily
Polluted Industrial Area A Ultilitys View