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Патент USA US3098069

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United States Patent 0 ice
2
1
3,098,059
RESINOUS COMPOSITIONS FROM TRIMELLITIC
ANHYDRIDE AND VIC-EPOXIDES
Richard E. Van Strien, Gri?ith, Ind., and William Hodes,
Stamford, Conn., assignors to Standard Oil Company,
Chicago, 111., a corporation of Indiana
No Drawing. Filed Sept. 17, 1958, Ser. No. 761,479
13 Claims. (Cl. 260-785)
3,098,059
Patented July 16, 1963
positions of our invention can ‘be prepared directly by ef
fecting reaction of the epoxide compound and tn'mel
litic anhydride at more elevated temperatures.
We have found that by proper selection of reaction
conditions and the molar ratio of trimellitic anhydride to
epoxy compound employed, partially polymerized resins
can vbe obtained having high acid number and low hy
droxyl number, low acid number and high hydroxyl num~
ber or, and this comprises the preferred embodiment of
This invention relates to resinous products or compo 10 our invention, approximately equivalent acid number and
hydroxyl number. The latter partially polymerized resins
sitions and to the process of making same and relates
are soluble in ‘acetone or other ordinary solvents and are
especially to resinous compositions comprising the prod
eminently suited for they preparation of baked ?nishes
net of reaction of trimellitic anhydride with a mono-epoxy
since they may be heated at baking temperatures to give
compound containing a 1,2-epoxy group.
The reaction of polycarboxylic acids with polyhydric 15 essentially non-acidic, insoluble, hard and ?exible surface
coatings.
alcohols to produce resinous products is well known. In
The epoxy compounds which are employed as compo
particular the preparation of resins by the reaction of
nents of our invention are mono-epoxide compounds hav
phthalic anhydride with glycerol has been widely investi
ing a 1,2-epoxy group. Such compounds have the gen
gated and forms the basis for the alkyd resin industry
which employs such resins variously modi?ed by reaction 20 eral formula
with drying oils, together with polymerizable unsaturated
monomers such as styrene and with other known reac
tants for the production of polymeric products of value in
the surface coating ?eld.
wherein R may be hydrogen, an aliphatic radical or an
The preparation of alkyd resins, for example by the 25 aromatic radical. Typical epoxy compounds which can
reaction of phthalic anhydride with glycerol, is essen
be employed in our process include ethylene oxide, pro
tially a polyesteri?cation reaction wherein the reactants
pylene oxide, styrene oxide, glycidyl ethers, glycidyl esters
combine with the elimination of water to yield a three
of aliphatic carboxylic ‘acids, epichlorohydrin and the like.
dimensional polymer network characterized by high hard
We have found that particularly valuable protective coat
ness and brittleness. In the course of prepartion of these 30 ings are obtained by reaction of trimellitic anhydride ‘and
resins it has been found that the esteri?cation reaction
an ‘unsatured 1,2~epoxy compound for example glycidyl
proceeds rapidly until the reaction is 60 to 70% com
methacrylate, glycidyl allyl ether and the like. Suchun
plete, the rate of reaction then falling off markedly. In
saturated epoxy compounds provide the advantage of ex
tremely rapid cure at elevated temperatures thus reducing
order to obtain resins of desirably low acid number, it
has been found necessary to subject such reactants to 35 the baking time required to produce a protective coating
extensive heating at elevated temperatures which often
of high ?exibility and high impact resistance. Mixtures
results in uncontrolled gelation of the product and the
production of an infusible, insoluble material. The form
ation of such gelled reaction mixtures not only makes
of epoxy compounds can be employed, especially mixtures
of ethylene oxide or propylene oxide together vw'th
difficult the further elimination of water and thus the
cidyl methacrylate.
obtention of a product having desirably low acid number
but also yields a product having low solubility in ordinary
tion, we have found that the properties of the resin can be
solvents and hence incapable of being applied as a thin
readily controlled by varying the ratios of trimellitic an
10—90% of an unsaturated epoxy compound such as gly
In the preparation of the resinous products of our inven
?lm for use as a protective coating.
hydride to 1,2-epoxy compound employed as reactants.
An object of our invention is to provide a resinous 45 Resinous reaction products of our invention can be pre~
product capable of use in baked ?nishes. Another object
pared by reacting from about 0.5 mole to about 10.0
is to provide an alkyd type resin for baked ?nishes ‘from
moles, or even more, of epoxy compound per mole of tri
mellitic anhydride. Where the lesser amounts of mono
epoxide compound within the indicated range are em
relatively inexpensive components. A {further object is
to provide resinous reaction products capable of being
further reacted to provide compositions of diverse use in 50 ployed, for example from about 0.5 to about 1.5 moles of
resins and protective coatings. These and other objects
epoxy compound per mole of trimellitic anhydride, resin
will become apparent in the course of the detailed descrip
ous products are obtained having relatively high acid num
tion of the invention.
.
ber (mg. KOH required to neutralize one gram of sample)
and extremely low hydroxyl number (mg. KOH required
The novel compositions of our invention, consisting es
sentially of the reaction product of trimellitic anhydride 55 to neutralize the acetic acid liberated from one gram of
and mono-epoxy compounds having a 1,2-epoxy group,
acetylated sample), it any. These resinous products can
are valuable resinous products suitable as surface coatings
not be cured by baking, but can be further reacted with
and as intermediates for the preparation of high boiling
solvents and plasticizers. By proper selection of reaction
monohydric alcohols, for example, lower alkanols having
conditions, partially polymerized, resinous compositions
60 duce viscous high molecular weight polyesters suitable as
from 1 to about 8 carbon atoms in the molecule, to pro
of our invention can be prepared which can be dissolved
solvents, plasticizers for synthetic and natural resins, and
in ordinary solvents for application as surface coatings
and ‘subsequently baked to hard infusible and solvent
resistant ?lms. Alternatively, infusible and insoluble com
the like.
-In a preferred embodiment of our invention, we pre
pare resins by reacting from about 1.5 to about 5 moles
3,098,059
3
4
of mono-epoxide compound per mole of trimellitic an
in acetone, followed by addition of the acetone solution
to cold water. The precipitated resin was then powdered
hydride. We have found that this ratio of reactants re
sults in the formation of soluble resinous reaction prod
and dried under vacuum.
The resinous products obtained in Examples 1(a)-1 (d)
ucts having approximately equal acid number and hy
droxyl number, that is, acid number/hydroxyl number 5 were analyzed and the results obtained are given in
ratios of about 2:1 to 1:2, which are eminently suitable
Table I.
Table I
for further heat treatment, as by baking to produce hard,
?exible and solvent-resistant ?nishes.
Where a large excess of 1,2-epoxy compound is re
acted with trimellitic anhydride, for example more than 10
about 5 moles per mole of trimellitic anhydride, resinous
products are obtained having high hydroxyl content and
relatively little carboxyl content. Such resins can be
further reacted with lower aliphatic monocarboxylic acids
for the preparation of high boiling polyesters suitable
as plasticizers, solvents and the like.
The resinous products of our invention are prepared by
reacting trirnellitic anhydride and a 1,2-epoxy compound
in desired proportions in the presence of an alkaline
catalyst at a temperature between about 20° C. and about
200° C. In the preparation of resinous products suitable
for baked ?nishes, we prefer to employ a reaction tem
perature below about 120° C. in order to avoid cross
linking and gelling of the resinous reaction product with
resultant insolubility of the resin in ordinary solvents
such as acetone, methylethyl ketone and the like.
As
catalysts there may be employed inorganic or organic
Example
Mole Ratio,
Trimellitie
Anhydride/
Propylene
Acid Hydroxyl
No. Number
Ester
No.1
M ol_ecular
Weight I
Oxide
1/5
1/2. 5
1/2
1/1
60
158
417
2, 700
94
73
416
__________ _ _
138
309
85
0
394
317
1, 480
726
l Ester No.=Saponi?eation Number-Acid Number.
1! Ebullioscopic in acetone.
As will be apparent from Table I, the reaction of tri
mellitic anhydride with propylene oxide in a 1/ 1 molar
ratios results in a product having substantially no free
hydroxyl groups. While such products, or analogously
those having only hydroxyl groups and no free carboxyl
groups, are useful resins for various purposes described
hereinafter, the resinous products having both residual
hydroxyl and carboxyl groups are particularly valuable
bases such as alkali hydroxide, calcium oxide, sodium
since they can be baked to hard, ?exible, and solvent
in an amount of about 0.1% to about 5% based on the
ture of 40 g. (0.208 mole) trimellitic anhydride, 12.1 g.
weight of trimellitic anhydride employed. Suitably, the
(0.21 mole) propylene oxide, 29.6 g. (0.21 mole) glycidyl
resistant ?lms.
amide, secondary amines such as di-ethylamine, dibutyl
EXAMPLE 2
amine, piperidine and the like and tertiary amines such 3O
This example illustrates the preparation of a resinous
as trimethylamine, tri-ethanolamine, pyridine and the
product from an unsaturated epoxy compound. A mix
like. We prefer to employ tertiary organic amines usually
reaction is etfected during a period of 2-24 hours, pref 35 methacrylate and 0.2 g. pyridine was stirred at room
erably 2-8 hours.
temperature for 24 hours, then allowed to stand over
night. The reaction product which had the appearance
The present invention is further illustrated with respect
of a ‘brittle glass was ground to a ?ne powder and stripped
to certain speci?c embodiments in the ‘following examples
and although said examples specify particular reactions,
conversion conditions, etc., they are not intended thereby
to limit the generally broad scope of the invention.
EXAMPLE 1
A series of compositions was prepared by reacting tri
mellitic anhydride with varying amounts of propylene 45
oxide as follows:
of volatile materials in a vacuum dessicator. The resin
so obtained had an acid ‘number of 49, a hydroxyl num
ber of 66 and an ester number of 492. It was soluble in
acetone.
EXAMPLE 3
Similarly, 2.0 g. (0.01 mole) trimellitic anhydride, 4.06
g. (0.044 mole) epichlorohydrin and 0.02 g. pyridine was
stirred at 100° C. in an atomsphere of nitrogen. To avoid
gelling, the temperature was maintained below 120° C.
(a) A mixture of 50 g. (0.260 mole) of trimellitic
anhydride, 75.6 ‘g. (1.3 mole) propylene oxide and 0.26
ml. of pyridine was agitated without external heating for
After 4 hours, the solution was treated with 1.0 g. of
3 hours. A mildly exothermic reaction occurred, the 50 activated carbon and ?ltered. The clear pale, yellow solu
tion was freed of volatiles by heating at 70° under a vacu
temperature being maintained below the boiling point of
um of 1 mm. Hg. A pale yellow, soft resin was obtained
propylene oxide (37° C.). The mixture was allowed to
having a softening point of 70-75° C. and soluble in
stand at ambient temperature to complete the reaction,
chloroform. After 2 hours in an oven at 150° 0., this
and the viscous liquid product then added with vigorous
resin was converted to a hard, tough sheet which was in
agitation to 5 00 ml. cold water. The tacky resinous prod
not which precipitated was dried in a vacuum dessicator
fusible and insoluble in ordinary solvents such as acetone,
and then ‘ground to a ?ne white powder.
alcohol and benzene.
(b) Similarly 5.0 g. (0.026 mole) trimellitic anhydride,
5.2 ‘g. (0.09 mole) propylene oxide and 0.05 g. triethyl
amine was stirred at 25° C. ‘for 8 hours. The excess
liquid was then removed under vacuum and the resinous
EXAMPLE 4
A resinous product was prepared by re?uxing a mixture
of 50 g. (0.26 mole) trimellitic anhydride, 214 g. (4.65
mole) ethylene oxide and 0.25 ml. pyridine for 20 hours
product ground to a white powder having a melting point
of 63-65“ C.
at 12-13° C. The viscous product of reaction was dis
(c) A mixture of 50 ‘g. (0.26 mole) trimellitic an
solved in acetone and reprecipitated by addition of the ace
hydride, 37.8 g. (0.652 mole) propylene oxide ‘and 0.23 65 tone solution to cold water. The product melting at 60°
ml. pyridine was agitated for 3 hours the temperature
C. was a somewhat tacky solid.
being maintained below 37° C. The resinous reaction
In order to demonstrate the utility of the resinous prod
product was recovered by treating the mixture as in (a)
ucts of our invention as surface coatings, particularly in
above.
the form of baked ?nishes, the resinous products obtained
(d) A mixture of 146.4 g. (0.762 mole) trimellitic 70 as described above were dissolved in acetone and the ace
anhydride, 44.2 g. (0.762 mole) propylene oxide and
tone solutions spread on glass and metal panels for
0.73 ml. pyridine was stirred without cooling for 2 hours.
standard tests. The product of Example 1(b) was tested
The reaction temperature rose spontaneously to 60° C.,
and the mixture became extremely viscous. After two
alone, and in admixture with a commercial melamine
formaldehyde resin of the type widely employed for in
hours the product solidi?ed. ‘It was puri?ed by solution 75 corporation in alkyd resins for the production of baked
3,098,059
5
6
?nishes. For this purpose 8 grams of the resin obtained
in Example 1(b) was mixed with 4 grams of Cymel 245-8
for preparation of heat-curing ?nishes. Other uncured
polymers that can be modi?ed by the product of our in
(American Cyanamid Company melamine resin contain
vention includes the melamine resins, phenol-formalde
ing 50% solids in a 1:1 butanolzxylene solvent) and the
mixture stirred with an additional 8 grams of 1:1
butanol:xylene solvent until solution was complete. The
hyde resins, polyurethanes, polyacrylic acid, polyvinyl al
F.
cohol and the like.
We claim:
1. A resinous composition consisting essentially of the
results of these tests are tabulated in Table II.
Table II
_
Resin of Example N0.
1(a)
1(b)+25%
1(b)
Melamine
1(c)
3
Resin
(Solids)
Baking Schedule, "C ______________ .. 150° for 16
150° for 4
150° for %
150° for 16
hours.
hour.
hours.
hours.
150° for %
hour.
Hardness:
Sward
Pencil
Flexibility 1 (Conical Mandrel) ____ ._
52
‘4H’
Pass ______ -.
5';
RH’
22, a
335,
Pass ______ ..
Pass ______ __
Pass.
Impact Strength 2 (Inch-pounds).___ 160
12
48
160
160.
Resistance 3 To Alkali (3% N e011),
6
F
rs.
Pass ........ _.
4%
411
............ --
v
Washability 4 ______________________ .- No e?ect ____ .- No effect...
No effect...
Ink Stain __________________________ .-
None ____________________ __
Very Slight...
None._..____
No eltect____ No eirect.
IASTM D-522-4l.
2 Gardner Variable Impact Tester.
a ASTM D-154-53.
4 Federal Speci?cation TT-P-lltlb.
While the advantages of the products obtained by the
product obtained by reacting trimellitic anhydride with
process of the present invention are apparent from‘ the
a mono-epoxide compound having a 1,2-epoxy group
selected from the class consisting of lower-alkyl mono
data provided, the extreme hardness and ?exibility of the
baked ?nishes should be noted. These ?nishes were addi 30 epoxides, aryl lower-alkyl mono-epoxides, glycidyl esters
of lower alkenoic acids and glycidyl ethers of lower
(ASTM test D-154-5 3) and retained their gloss even after
alkenols in the presence of an alkaline catalyst at a tem
long treatment with Water. In particular, the rapid cure
perature between about 20° C. and about 200° C.
of the product of Example 3, which contains glycidyl
2. A soluble resinous material having an acid num
methacrylate, should be noted.
35 ber/hydroxyl number ratio in the range of about 2:1 to
1:2 and capable of being converted to the infusible in
EXAMPLE 5
soluble state by heating at a temperature of about 150° C.
tionally highly resistant to water, gasoline and alcohol
Resinous compositions of our invention having high acid
number and low hydroxyl number, or conversely high
hydroxyl and low acid number are valuable intermediates
for the preparation of high boiling polyesters as illustrated
by this example.
consisting essentially of the product obtained by reacting
trimellitic anhydride with a mono-epoxide compound hav
ing a 1,2-epoxy group selected from the class consisting
of lower-alkyl mono-epoxides, aryl lower-alkyl mono
epoxides, glycidyl esters of lower alkenoic acids and
A solution containing 5 grams trimellitic anhydride ‘and
glycidyl ethers of lower alkenols in a mole ratio of from
10.4 grams propylene oxide was stirred with .05 gram
about 1:15 to about 1:5 said reaction being e?ected at
triethylamine for 8 hours at 30° C. The excess volatile 45 a temperature between about 20° C. and about 120° C.
material was removed by evaporation and the resin vacu
in the presence of an alkaline catalyst.
um‘ dried at 60° C. The product had an acid number of
3. The product of claim 2 wherein the 1,2-epoxy com
181, a molecular weight of 685, and a ratio of free car
pound is propylene oxide.
boxyl to ester groups of 1 to 2.
4. The product of claim 2 wherein the 1,2-epoxy com-v
A portion of this product (5.8 grams) was esteri?ed
pound is ethylene oxide.
with 11.1 grams of n-butanol in the presence of 0.15 gram
5. The product of claim 2 wherein the 1,2-epoxy com
methane-sulfonic acid by re?uxing at 110° to 120° C.
pound is epichlorohydrin.
for 31/2 hours. The unreacted butanol was stripped o? by
6. The product of claim 2 wherein the 1,2-epoxy com
heating ‘to 150° C. at 100 milliliters pressure. The prod
pound
comprises from about 10% to about 90% of an
not was a clear, colorless viscous liquid having an acid 55
epoxy
compound
having an ole?nic linkage.
number of 20.8. This polyester is compatible with poly
7. A resinous composition consisting essentially of the
vinyl chloride and is suitable as a non-migratory, non
product obtained by reacting trimellitic anhydride and
volatile plasticizer alone or in combination with other
propylene oxide in a mole ratio of about 1:2 at a tem
plasticizers for polyvinyl chloride such as dioctylphthalate
perature of about 20 to about 50° C. in the presence
and the like.
Similarly, desirable products of our invention having, 60 of a catalytic amount of a tertiary amine, said composi
residual unreacted hydroxyl groups, can be reacted with
a Wide variety of carboxylic acids to produce high
boiling neutral liquids or to produce products capable
of further reaction to form resinous or plastic materials.
For example, they may be reacted with lower aliphatic
monocarboxylic acids, with aliphatic dicarboxylic acids
tion having an acid number/hydroxyl number ratio of
about 1.5 and capable of being converted to an infusible
insoluble resin by heating at ‘a temperature of about
150° C. for a period of from 4 to 16 hours.
8. A resinous composition consisting essentially of the
product obtained by reacting trimellitic anhydride with
such as adipic acid, sebacic acid and the like to produce
an equimolar mixture of propylene oxide and glycidyl
?exible resins suitable as protective coatings. Addition
methacrylate,
the molar ratio of trimellitic anhydride to
ally, they may be reacted with other polyfunctional mate
total
epoxide
compound
being about 1:2, at a temperature
70
rials such as diisocyanates, polyepoxides, epoxidized acids
of about 20° to about 50° C. in the presence of a catalytic
and esters and the like to produce thermosetting resinous
amount of a tertiary amine, said composition having an
compositions.
acid number/hydroxyl number ratio of about 1.0 and an
The products of our invention may be blended or react
ester number of ‘about 492 and capable of being con
ed with other resins including polyesters, polyamides ‘and
the like, or fused with uncured urea-formaldehyde resins 75 verted to an infusible, insoluble resin by heating at a tem
3,098,059
7
8
perature of about 150° C. for a period of from about 0.5
to 4 hours.
about 120° C. in the presence of an alkaline catalyst,
the mole ratio of trimellitic anhydride to epoxide com
9. A composition of matter prepared by esterifying
a lower monohydric alkanol having from 1 to 8 carbon
atoms in the molecule with the product of reaction of
pound being between about 1:15 and about 1:5.
12. The process of claim 11 wherein the epoxy com
pound contains an ole?nic linkage.
13. The process of claim 12 wherein the epoxy com
propylene oxide with trimellitic anhydride in a molar
pound comprises from about 10 to about 90% glycidyl
ratio between about 05:1 and about 1.5:1, said reaction
methacrylate.
being e?fected at a temperature between about 20° and
200° C. in the presence of an alkaline catalyst.
References Cited in the ?le of this patent
10. The composition of claim 9 wherein said alkanol 10
UNITED STATES PATENTS
is n-butanol.
11. A process for the preparation of a resinous mate
rial capable of being converted to the infusible insoluble
state which comprises reacting trimellitic anhydride with
a mono-epoxide compound having a 1,2-epoxy group
selected from the class consisting of lower-alkyl mono
epoxides, aryl lower-alkyl mono-epoxides, glycidyl esters
of lower alkenoic acids and glycidyl ethers of lower
alkenols at a temperature between about 20° C. and
2,847,395
2,947,712
Wear ________________ __ Aug. 12, 1958
Belanger et a1. ________ __ Aug. 2, 1960
OTHER REFERENCES
“Trirnellitic Anhydride” by Amoco Chemicals Corpora—
tion, Development Department, 910 South Michigan Ave.,
Chicago, Ill. (1958), 32 pages in publication, only pages
8, 9, 27, 28 and 29 relied on.
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