26
Epoxide
Resins
26.1
INTRODUCTIONThe epoxide resins (also widely known as epoxy resins and, occasionally, asethoxyline resins) are characterised by the possession of more than one
1,2-
epoxy group (I) per molecule. This group may lie within the body of the moleculebut is usually terminal.
/"\
-CH-CH-
(1)
The three-membered epoxy ring is highly strained and
is
reactive to manysubstances, particularly by with proton donors,
so
that reactions of the followingschematic form can occur:
OH
/"\
I
-CH-CH-
+
HX -CH-CH-
X
Such reactions allow chain extension andfor cross-linking to occur without theelimination of small molecules such as water, i.e. they react by a rearrangementpolymerisation type of reaction.
In
consequence these materials exhibit a lowercuring shrinkage than many other types of thermosetting plastics.There is, quite clearly,
scope
or a very wide range of epoxy resins. The non-epoxy part
of
the molecule may
be
aliphatic, cycloaliphatic or highly aromatichydrocarbon or it may
be
non-hydrocarbon and possibly polar. It may containunsaturation. Similar remarks also apply to the chain extension/cross-linkingagents,
so
that cross-linked products of great diversity may
be
obtained. Inpractice, however, the commercial scene is dominated by the reaction products ofbis-phenol
A
and epichlorohydrin, which have some
80-90%
of the marketshare.
744
Preparation
of
Resins from Bis-phenol
A
745The commercial interest in epoxide (epoxy) resins was first made apparent bythe publication of German Patent 676 117 by I G Farben' in 1939 whichdescribed liquid polyepoxides. In 1943 P. Castan* filed
US
Patent 2 324 483,covering the curing of the resins with dibasic acids. This important process wassubsequently exploited by the Ciba Company. A later patent of Castan3 coveredthe hardening of epoxide resins with alkaline catalysts used in the range
0.1-5%
This patent, however, became of somewhat restricted value as the importantamine hardeners are usually used in quantities higher than 5%.In the early stage of their development the epoxy resins were used almostentirely for surface coating and developments in this field
are
to a large extentdue to the works of
S.O.
Greenlee and described in a number of patents. Theseincluded work on the modification of epoxy resins with glycerol4, theesterifiction of the higher molecular weight materials with drying oil acidss andreactions with phenolic6 and amino
resin^.^
Before World War
I1
the cost of the intermediates for the these resins (in mostcases epichlorohydrin and bis-phenol
A)
would have prevented the polymersfrom becoming of commercial importance. Subsequent improvements in themethods of producing these intermediates and improved techniques of polymer-isation have, however, led to wide commercial acceptance.By the beginning of the 1980s world capacity for epoxide resins reached about
600
000
tonnes per annum but at this time plant utilisation was only about
50-60%.
Thus with a global consumption of about 10 million tonnes per annumfor thermosetting plastics, epoxide resins had a share of about 3%. WesternEurope and the USA each had about
40%
of the market and Japan a little over10%. This situation has not greatly changed since then; but by the late 1990s theworld market for epoxide resins had risen to about
750
000
t.p.a.About half of epoxide resin production is used for surface coating applications,with the rest divided approximately equally between electronic applications(particularly for printed circuit boards and encapsulation), the building sector andmiscellaneous uses. In tonnage terms consumption
of
epoxide-fibre laminates isonly about one-tenth that of polyester laminates, but in terms of value it is muchgreater.Whilst the properties of the cross-linked resins depend very greatly on thecuring system used and on the type of resin, the most characteristic properties
of
commercial materials are their toughness, low shrinkage on cure, highadhesion to many substrates, good alkali resistance and versatility informulation.26.2PREPARATION
OF
RESINS FROM BIS-PHENOL
A
The first, and still the most important, commercial epoxide resins are reactionproducts of bis-phenol A and epichlorhydrin. Other types
of
epoxide resins wereintroduced in the late 1950s and early
1960s,
prepared by epoxidisingunsaturated structures. These materials will be dealt with in Section 26.4. Thebis-phenol
A
is prepared by reaction of the acetone and phenol
(Figure
26.1).
Since both phenol and acetone
are
available and the bis-phenol
A
is easy tomanufacture, this intermediate is comparatively inexpensive. This is one of thereasons why it has been the preferred dihydric phenol employed in epoxide resinsmanufacture. Since most epoxide resins are of low molecular weight and because
746
Epoxide Resins
Em-@
+
c=o
+
@-OH
I
Figure 26.1
colour is not particularly critical the degree of purity of the bis-phenol
A
does nothave to be
so
great as when used in the polycarbonate resins. Bis-phenol
A
witha melting point
of
153°C is considered adequate for the most applications whilstless pure materials may often be employed.Epichlorohydrin, the more expensive compound is derived from propylene bythe sequence of reactions shown in
Figure
26.2.
CH,=CH
+
Cl*+ CH2=CH
+
HCl
I
I
I
CH,
Propylene
I
CH**Cl
Allyl
Chloride
CH
-
H
+
H20/C12
-----+
Cl-CCH~-CH(OH)-CH2-CCI
Dichlorohydrin
2-
I
CHZCl
Figure 26.2
It
will noticed that the initial steps correspond with those used in themanufactureofglycerol. The material is available commercially at
98%
purityand is a colourless mobile liquid.Many of the commercial liquid resins consist essentially of the low molecularweight diglycidyl ether of bis-phenol
A
together with small quantities
of
highermolecular weight polymers. The formation of the diglycidyl ether is believed tooccur in the manner shown in
Figure
26.3,
the hydrochloric acid releasedreacting with the caustic soda
to
form sodium chloride.Although it would appear, at first glance, that diglycidyl ether would beprepared by
a
molar ratio of
2:
1
epichlorohydrin-bis-phenol
A,
probabilityconsiderations indicate that some higher molecular weight species will beproduced. Experimentally it
is
in fact found that when a
2:
1
ratio is employed, theyield
of
the diglycidyl ether is less than
10%.
Therefore in practice two to three
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Epoxide Resins
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