3,773,856

United States Patent Office Patented Nov. 20, 1973

2
foregoing drawbacks can possibly become the cause for
3,773,856 hindering the development of the epoxy resins. Hence,
PROCESS FOR THE PREPARATION OF UNSATU the correction of these shortcomings is a desirable thing
RATED EPOXY ESTER COMPOSITIONS for the development of the epoxy resins.
Eiichiro Takiyama, 17-7-201, 2-chome, Minami Kamata, On the other hand, while the unsaturated polyester
Ota-ku, Tokyo, Japan, and Sadakazw Hokamura, 125 resins have more shortcomings than the epoxy resins, their
11 Aza Kaminohara, Kamiwada, Yamato-shi, Kana
gawa-ken, Japan far greater excellence over the latter in respect of their
No Drawing. Continuation-in-part of abandoned applica curing properties and workability is recognized. That is to
tion Ser. No. 70,543, Sept. 8, 1970. This application say, the unsaturated polyester resins can be cured under
Nov. 11, 1971, Ser. No. 197,935 0 practically unrestricted conditions at either room tempera
Int. C. C08g 45/04 ture or under application of heat by the use of a small
U.S. C. 260-836 8 Claims amount of an organic peroxide and, if necessary, a small
amount of a polymerization accelerator.
ABSTRACT OF THE DISCLOSURE In view of the hereinbefore given reasons, the com
5 bining of the curability and workability of the unsaturated
A process for preparing an unsaturated epoxy ester resin polyester resins with the properties of the epoxy resins
composition which can be cured by the addition of an is conceivable as an ideal.
organic peroxide and an accelerator even at room tem When an epoxy compound and a polymerizable un
perature, said process comprising heat reacting an epoxy saturated monobasic acid are reacted, an ester compound
component Selected from the epoxy compounds having at 20 is formed, for example, in accordance with the follow
least one glycidyl ether type epoxy group in their molecu ing equation
lar structure, with a first acid component from the group O Rs R4 O R8 O R R5
consisting of the polymerizable unsaturated monobasic
acids of 2-8 carbon atoms and a second acid component –04 Sc-R+R-(-)-coon r) d- -o-c-d--R,
selected from the group consisting of the saturated mono 25 k l, k, l,
basic acids, Saturated polybasic acids, saturated polybasic (epoxy compound) Seyssible (ester compound)
acid anhydrides, polymerizable unsaturated polybasic acids monobasic acid)
and polymerizable unsaturated polybasic acid anhydrides,
in the presence of a polymerization inhibitor and an esteri wherein R, R2, R3, R4, R5 and Rs are each hydrogen or
fication catalyst in an atmosphere of air or molecular 30
alkyl. When the resulting ester compound is dissolved in
OXygen. a polymerizable monomer copolymerizable with the afore
said polymerizable unsaturated monobasic acid (herein
This is a continuation-in-part of applicants' copending after may, at times, be referred to as merely monomer),
application, Ser. No. 70,543, filed Sept. 8, 1970 now a so-called unsaturated epoxy ester resin composition is
abandoned. 35 obtained. However, when a resinous composition contain
This invention relates to a process for preparing un ing a polymerizable substance in its system, such as in this
Saturated epoxy ester compositions which can be cured case, is heated for a prolonged period of time, gelation
even at room temperature. of the system frequently occurs, which is very dangerous.
In view of their possession of various good points, It is therefore an object of the present invention to pro
the epoxy resins are widely used for such purposes as 40 vide an unsaturated epoxy ester resin composition which
coating material, adhesive, material for casting, reinforced measures up to the hereinbefore indicated ideal without
plastics, etc. The epoxy resins form insoluble and infusible, possession of the foregoing defect.
three-dimensional cured products by the addition thereto Other objects and advantages of the invention will be
of an acid substance such as organic acids or their anhy come apparent from the following description.
drides or a basic substance such as an amine. Numerous 45 As a result of extensive researches, we found that an
classes of hardeners are provided for the cure of epoxy unsaturated epoxy ester resin composition which can be
resins, and hence it is well known that cured products of cured by the addition of an organic peroxide and an
exceeding excellence can be obtained, if the hardener accelerator even at room temperature could be obtained
is decided in accordance with the properties required in and that the foregoing objects of the invention be achieved
the product. On the other hand, an error in the choice of 50 by heat reacting an epoxy component selected from the
the hardener results in the degradation of the properties of epoxy compounds having at least one glycidyl ether type
the cured product. Hence, great care must be exercised epoxy group in their molecular structure, with a first acid
in the choice of the hardener. component selected from the group consisting of the
Further, not only the choice of the hardener to use but polymerizable unsaturated monobasic acids of 2-8 carbon
the amount of its use must be right; or otherwise a deg 55 atoms and a second acid component selected from the
radation of the properties of the product will take place group consisting of the saturated monobasic acids, satu
in most cases. In addition, the majority of the hardeners rated polybasic acids, saturated polybasic acid anhydrides,
commonly in use require a prolonged period of time for polymerizable unsaturated polybasic acids and polymeriz
curing the resin. Furthermore, since the hardener must able unsaturated polybasic acid anhydrides, in the presence
generally be used in a prescribed amount, it is not possible 60 of a polymerization inhibitor and an esterification catalyst
to control the curing time indiscriminately by increasing and, if necessary, a solvent or polymerizable monomer,
or decreasing the amount of its use. Consequently, the in an atmosphere of air or molecular oxygen.
curing temperature has been relied on for the control of For obtaining resinous cured products possessing vary
the curing time. Further, if the cure is attempted at room ing properties it was the usual practice in the prior art to
temperature during those periods when the temperature 65 vary the choice of the starting materials, i.e. the class of
falls below 10° C., as in winter, the cure cannot be ac the epoxy compounds and/or polymerizable unsaturated
complished adequately and in most cases the resulting monobasic acids used, or vary the reaction ratio of the
cured product cannot demonstrate the properties that are two starting materials. On the other hand, according to
intrinsically possessed by the epoxy resins. Furthermore, the present invention described above, it is not only pos
the amines are used as the hardener when curing at room 70 sible to vary the properties by varying the class of the
temperature, but there is an aversion on the part of the epoxy compound, one of the starting materials, but also
users to such products on account of their toxicity. The since the class of organic acids, the other starting ma
 3
8,778,856
4
terail, useable is multifarious, a still greater variation in In this case, the monomer added at the beginning and
the properties of the product can be expected by a suit that added later may be the same or different.
able choice of the organic acid. Further, in conducting the esterification reaction of the
Further, in the past the adjustment of the degree of epoxy component and the acid component on a comme
cross-linkage of the unsaturated epoxy ester resin de cial scale, a method wherein one of the components is
pended on the amount used of the polymerizable unsatu first dissolved or mixed in the monomer and then the
rated monobasic acid. Hence, when, for example, a low other component is added dropwise is convenient.
degree of cross-linkage was desired, i.e., when the amount Monomers which can be used for practicing the inven.
used of the polymerizable unsaturated monobasic acid tion include such as acrylic esters, methacrylic esters, vinyl
was small, the result was an excess of the epoxy group in 0 benzene, vinyl toluene, acrylonitrile, vinyl acetate, diallyl
the resinous composition. The cured product of a resinous phthalate and glycidyl methacrylate. These monomerS
composition containing a functional group such as this can be used either singly or in combinations of two or
is inferior in its resistance to boiling as well as resistance Ot.
to attack by chemicals. Now, in accordance with the pres On the other hand, the epoxy compounds useable in
ent invention, an improvement of these drawbacks is also 5 the invention include those of the glycidyl ether type
possible. When a saturated acid such as a saturated mono which have usually been synthesized from epichlorohydrin
basic acid, a saturated polybasic acid or a saturated poly or methyl epichlorohydrin and a compound having a hy
basic acid anhydride is used as an acid component along droxyl group. For example, mention can be made of such
with a polymerizable unsaturated monobasic acid in ac as the diglycidyl ether of 2,2-bis(4-hydroxyphenyl) pro
cordance with a mode of operating the present invention 20 pane, the polyglycidyl ethers obtained by reacting either
in preparing the unsaturated epoxy ester resin composi epichlorohydrin or methyl epichlorohydrin with the so
tion by reacting an epoxy component with an acid com called novolak obtained by the reaction of phenol and
ponent, the degree of cross-linkage can be optionally formaldehyde, triglycidyl ether of glycerine and tetragly
varied in accordance with the amount used of the fore cidyl ether of tetraphenylene ethane.
going saturated acid and thus, with the amount used of 25 The polymerizable unsaturated monobasic acids used
the polymerizable unsaturated monobasic acid being de in the invention include such, for example, as acrylic
creased, the foregoing drawbacks are eliminated. acid, methacrylic acid and crotonic acid.
In the esterification reaction of an epoxy component The polymerizable unsaturated polybasic acids and their
with an acid component, a rise generally takes place in anhydrides, which are useable in the invention, are exem
the viscosity of the system as the reaction proceeds to 30 plified by such as maleic acid, maleic anhydride, fumaric
make stirring impossible and invite the danger of gelation acid and itaconic acid.
of the system. As a result, there are times when the re On the other hand, the saturated polybasic acids and
action cannot be carried to completion. To solve this their anhydrides, which are useable in the invention, in
problem a procedure consisting of the use of an organic clude such as phthalic anhydride, tetrahydrophthalic an
solvent as a viscosity reducing agent may be adopted, 35 hydride, hexahydrophthalic anhydride, succinic acid,
the addition of the organic solvent being made at an adipic acid, trimellitic anhydride, pyromellitic anhydride,
optional stage of the progress of the reaction thereby 1,4,5,6,7,7-hexachlorobicyclo - (2,2,11-5-heptene-2,3-di
preventing a rise in the viscosity and make it possible to carboxylic acid (Het Acid) and endomethylene tetrahy
bring the reaction to completion without encountering drophthalic anhydride. And as the saturated monobasic
any difficulty in carrying out the stirring of the system. 40
acids, mention can be made of such as benzoic acid and
However, if the reaction is carried out using a solvent, p-tert-butylbenzoic acid.
there is the trouble involved in removal of the solvent
from the resin after completion of the reaction. Further, The reaction ratios of the first acid component and the
even though the solvent is removed, the possibility that second acid component to the epoxy component are such
some might remain behind in the resin to cause a decline 45
that the first acid component is present in a ratio of 1.10
of the properties of the resin is not absolutely nil. Again, 2.05 moles, per mole of the epoxy component and the
when the reaction is to be carried out commercially, the second acid component is present in a ratio of 0.05-0.45
additional step required for solvent removal is eco moles per mole of the epoxy component. The reaction
nomically a disadvantage. ratios are determined within the aforesaid limits depend
As hereinabove noted, the use of a solvent does make it 50 ing upon the properties required of the cured resin prod
possible to complete the esterification reaction, but for ucts. When the amount of the acid components are less
preventing the decline in the properties of the resulting than the above ratios, it tends to give rise to insufficient
resin and also for making the commercial production of room temperature curing. On the other hand, if the acid
the resin profitable, it is preferred to avoid the use of a component ratios exceed the aforementioned limits, un
solvent, if at all possible. 55 reacted carboxyl groups are present in the final product,
We also investigated into this matter also and, as a which tends to decrease the chemical resistance of the final
result, found that by carrying out the reaction in the products.
presence of air or molecular oxygen and, if necessary, in When the use of either a solvent or monomer is re
the presence of a solvent or a polymerizable monomer it quired, the amount used will vary depending upon the
was possible to obtain by a safe operations resins possess 60 reactants, but at least one part per 100 parts of the esteri
ing good properties. This was a truly surprising result fied product is required.
when considered in view of generally accepted idea, as The polymerzation inhibitors, which are usually used for
hereinbefore indicated, that there was the danger of gela promoting the safety of a reaction, such, for example, as
tion upon heating in the case of the presence of a polym hydroquinone, p-tert-butylcatechol, methoxyhydroqui
erizable monomer. 65
none, copper salts and hydrazine salts may be convenient
According to the invention process, there is no necessity ly used in the invention process. Again, the use in the in
for removal of the solvent after the reaction, since the vention process, as catalyst for the esterification reaction,
monomer becomes a component making up the resulting of such compounds as boron trifluoride, chlorides of tin,
resin. The monomer may be added wholly at once or in 70 lithium halides, paratoluenesulfonic acid, the amines such
increments either at the start of the reaction or optional as tertiary amines, is of great advantage in carrying out
stages during the progress of the reaction. When only the reaction.
a part of the monomer has been added at the start of For further illustration of the invention, the following
the reaction or during the intermediate stages, the re non-limitative examples are given. The parts in the ex
mainder can be added after completion of the reaction. 75 ample are on a weight basis.
 3,773,856 6
5
EXAMPLE I 0.1 part of dimethylaniline were added to 100 parts of the
A mixture consisting of 98 parts of maleic anhydride, so obtained resin, it gelled in about 9 minutes and the
2000 parts of Epikote 828 (trade name of an epoxy resin maximum temperature of heat generated then was 146 C.
produced by Shell Oil Company, U.S.A.), 687 parts of EXAMPLE IV
methacrylic acid, 11.3 parts of benzyldimethylamine and 5
A mixture consisting of 350 parts of DEN 438 (trade
0.01 part of hydroquinone was reacted by heating on an name of epoxidized novolak produced by Dow Chemical
oil bath for 2 hours at 120° C. The acid value became Company, U.S.A.), 130 parts of methacrylic acid, 72 parts
practically zero. The resulting unsaturated ester resin was of p-tert-butylbenzoic acid and 2 parts of benzyldimethyl
designated sample C. Thirty-five parts of styrene were O amine was heated for 3 hours at 110-120° C. The acid
added to 100 parts of sample C to yield a product having value declined to below 10. 250 parts of styrene and 0.15
a viscosity at 25 C. of 7.8 poises and a color of Gardener part of hydroquinone were added to the reaction mixture
3-4. This latter product was designated sample A. in the latter stages of the reaction, after which the reac
Separately, a mixture consisting of 860 parts of meth tion mixture was held at 100° C. for 20-30 minutes and
acrylic acid, 2000 parts of Epikote 828 and 11.4 parts of 5 then cooled. The color of the product becomes a value of
benzyldimethylamine was heated on an oil bath for 2 hours Gardener 5. When 100 parts of the so obtained resin were
at 120° C. To 100 parts of the so obtained unsaturated heated at 82° C. after addition thereto of one part of
ester resin were added 30 parts of styrene and 0.01 part benzoyl peroxide, gelation took place in 4 minutes and 40
of hydroquinone. The so obtained product was designated seconds. The maximum temperature of heat generated
sample B. 20 then was 212° C. The Rockwell hardness of the so ob
Samples A, B and C were cured by adding to each 0.5 tained cured product was 114-115 or the M scale.
part of benzoyl peroxide and 0.1 part of dimethylaniline. We claim:
The results obtained are shown in the following table. 1. A process for preparing an unsaturated epoxy ester
Maximum Heat distor
resin composition which can be cured by the addition of
Gelation temperature tion tempera 25 an organic peroxide and an accelerator even at room tem
Sample
time of heatgen ture of cure
(min.) erated (C.) resin ( C.)
perature, said process comprising heat reacting one mol
of an epoxy component selected from epoxy compounds
8
12
160
149
145
128
having at least two glycidyl ether type epoxy groups in
11 155 144 their molecular structure, with 1.10 to 2.05 mols of a first
30 acid component selected from the group consisting of
EXAMPLE II polymerizable unsaturated monobasic acids of 2-8 carbon
atoms and 0.05 to 0.45 mol of a second acid component
A mixture consisting of 148 parts of phthalic anhydride, selected from the group consisting of saturated monobasic
1200 parts of Epikote 828, 290 parts of acrylic acid and 7 acids, saturated polybasic acids, saturated polybasic acid
parts of benzyldimethylamine was heated for 1 hour and 35 anhydrides, polymerizable unsaturated polybasic acids and
40 minutes at 110-120° C. Since stirring became difficult polymerizable unsaturated polybasic acid anhydrides, in
in the latter stages of the reaction on account of a rise in the presence of a polymerization inhibitor, an esterifica
the viscosity of the mixture, 200 parts of styrene and 0.4 tion catalyst and at least one part of an ethylenically un
part of hydroquinone were added and heating was con saturated polymerizable monomer per 100 parts of the
tinued for a further 40 minutes at 100° C. with stirring. 40 esterified product, in an atmosphere of air or molecular
The acid value declined to below 5. After completion of OXygen.
the reaction, 400 parts of styrene monomer were further 2. The process according to claim 1 wherein said first
added. The resulting resin had a color whose value was acid component is acrylic acid.
Gardener 3-4, and its viscosity at 25 C. was 15.3 poises. 3. The process according to claim 1 wherein said first
When 100 parts of this resin was cost after incorpora 45 acid component is methacrylic acid.
tion of 1 part of benzoyl peroxide and 0.2 part of dimeth 4. The process according to claim 1 wherein said sec
ylaniline, gelation took place in about 30 minutes and the ond acid component is p-tert-butyl benzoic acid.
cure was practically completed in 2 hours. The resulting 5. The process according to claim 1 wherein said second
cast product was not only hard but had elasticity as well. acid component is phthalic anhydride.
Its Rockwell hardness (M) was 114, Charpy impact value 50 6. The process according to claim 1 wherein said second
was 3-4 kg/cm., and flexural strength was 11-13 kg/ acid component is 1,4,5,6,7,7-hexachlorobicyclo-2,2,1)-5-
mm...?. heptene-2,3-dicarboxylic acid.
EXAMPLE III 7. The process according to claim 1 wherein said second
A mixture consisting of 2000 parts of Epikote 827 (trade acid component is maleic anhydride.
name of an epoxy resin produced by Shell Oil Company, 55 8. The process according to claim 1 wherein said
U.S.A.), 602 parts of methacrylic acid, 0.01 part of hy polymerizable monomer is styrene.
droquinone, 555 parts of Het Acid (trade name of 1,4,5,6,
7,7-hexachlorobicyclo-2,2,1-5-heptene-2,3-dicarboxylic References Cited
acid produced by Hooker Chemical Company, U.S.A.) UNITED STATES PATENTS
and 12.7 parts of benzyldimethylamine was heated for 2/2 60
3,256,226 6/1966. Fekete ------------- 260-837
hours at 110-120° C. The acid value became practically 2,824,851 2/1958 Hall --------------- 260-837
zero. A considerable rise in the viscosity took place in the 2,970,983 2/1961 Newey ---------...-- 260-78.4
latter stages of the reaction. Hence, it would have been 3,066,112 11/1962 Bowen -------------- 260-41.
convenient to add a monomer or solvent in this case, but
it was possible to carry out the operation without such 65
PAUL LIEBERMAN, Primary Examiner
an addition. After completion of the reaction, 1040 parts
of styrene were added to the reaction product. The vis U.S. C. X.R.
cosity was 25 poises at 25 C. and the color was a value 260-47 EC, 78.4 Ep, 837 R
of Gardener 2-3. When 0.5 part of benzoyl peroxide and