Note: Descriptions are shown in the official language in which they were submitted.
2195468
TITLE OF TI~E INVENTION
A PROCESS FOR PRODUCING AN UNSYMMETRICAL DIESTER OF
a, ~ -UNSATURATED DICARBOXYLIC ACID
BACKCROUND OF TIIE INVENTION
Field of the Invention: ~
This invention relates to a process for producing a
colorless unsymmetrical diester of a, ~ -unsaturated dicarboxylic
acid, useful as a raw material of an emulsifier for emulsion
polymerization and as a modifier for a polymer.
Description of the Prior Art:
It is vell known to produce an unsymmetrical diester
by reacting a dicarboxylic acid anhydride ~ith a monohYdric
alcohol to obtain a monoester, and then reacting it with an
alkyl halogenide in the presence of a tertiary amine.
But, an unsymmetrical diester of an a, ~ -unsaturated
dicarboxylic acid Produced by above-mentioned process, is
remarkable of a color development. The diester is got color
through a reaction of the monoester with the alkyl halogenide.
SUMMARY OF THE INVENTION
It is an object of the present invention to Provide a
process capable of providing a colorless unsymmetrical diester of
an ~, ~ -unsaturated dicarboxylic acid ~ith high purity.
Briefly, the object of this invention as hereinafter
will become more readily apparent having been attained broadly by
2 ~ 4 5 4 6 %
providing a process for producing a colorless unsymmetrical
diester of an ~ unsaturated dicarboxylic acid, which
comprlses:
(1) reacting an ~ unsaturated dicarboxylic acid
anhydride (al) with a monohydric alcohol (a2), in the presence
of an inert organic solvent, in a molar ratio of (al):(a2) of
1:(1.0-1.2) to obtain an ~, ~-unsaturated dicarboxylic acid
mono ester(A), containing substantially no unreacted
unsaturated dicarboxylic acid anhydride, and
(2) reacting (A) with an alkenyl halide (B) in the
presence of a tertiary amine (C) and water in a molar ratio
of (A):water of 1:(0.01-0.20).
According to the present invention, there is also
provided a process for producing an unsymmetrical diester of
~, ~-unsaturated dicarboxylic acid, which comprises:
(1) reacting an ~ unsaturated dicarboxylic acid
anhydride (al) with a monohydric alcohol (a2), in the presence
of an inert organic solvent, in a molar ratio of (al):(a2) in
the range of 1:(1.0-1.2) to obtain an a, ~-unsaturated
20 dicarboxylic acid mono ester(A), containing substantially no
unreacted ~, ~-unsaturated dicarboxylic acid anhydride,
(2) reacting (A) with an alkenyl halide (B) in the
presence of a tertiary amine (C) and water in a molar ratio
of (A):water of 1:(0.01-0.20),
(3) removing the tertiary amine from the reaction
product; and
(4) treating the product with an adsorbent (D).
DETAILED D~SCRIPTION OF THE PREFERRED EMBODIMENTS
Suitable examples of an ~, ~-unsaturated
dicarboxylic acid anhydride (al) include maleic anhydride and
citraconic anhydride. Preferred is maleic anhydride.
Suitable examples of a monohydric alcohol (a2)
include C1_22) aliphatic alcohols, including saturated ones
(such as methanol, butanol, octanol, decyl alcohol, lauryl
~D
D
2 ~ 4 5 4 6 8
alcohol, tridecyl alcohol, tetradecyl alcohol and stearyl
alcohol), and C8_22 alkenyl alcohol (such as oleyl alcohol,
l-octene-3-ol and 7-decene-1-ol); C7_22 aromatic alcohols
(such as benzyl alcohol and l-phenyl ethyl alcohol); and mono
or polyoxyalkylene (for example oxyethylene and oxypropylene)
ether of Cl_22 aliphatic alcohol, C 7-22aromatic alcohol,
phenol and C7_22 alkyl phenol (such as nonyl phenol and
dodecyl phenol). Among these, preferre~
2a
7l~7~
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are C8 22 aliphatic alcohols.
A molar ratio nr (al):(a2) is generally 1:(1.0-1.2),
preferably 1:(1.0-1.10), more preferably 1:(1.0-1.05). (a2) less
than 1.0 results in color development.
During the process of reacting (al) with (a2) to obtain
(A), containing substantiallY no unreacted (al), an inert organic
solvent is used to minimize an unreacted (al) by bringing
sublimed (al) back to a reactor, by a vapor of said solvent. The
inert organic solvent means a solvent unreactive with (al) and
(a2). Said solvent has a boiling point generally in the range of
40-220~C at normal pressure.
Suitable examples of the inert organic solvent include
aromatic hYdrocarbons (such as benzene, toluene and xylene),
aliphatic hYdrocarbons (such as hexane and heptane), hYdrogenated
hydrocarbons (such as chloroform and l,2-dichloroethane), ethers
(such as tetrahYdrofuran and dioxane) and a mixture thereof.
Benzene, toluene, xYlene and hexane are preferred.
An amount of said solvent is generally in the range of
1-30X, preferably 5-20% by weight, based on a total amount of
(al) and (a2).
(A) contains unreacted (al) generally less than 0.6%,
preferably 0.3% by weight, based on (A).
A reaction temperature is generally in the range of
40-120~C, preferably 50-100~C.
- Suitable examples of an alkenyl halide (B) include
vinyl halides, allyl halides, methallyl halides and oleyl
halides. Allyl chloride or methallyl chloride is Preferred.
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Suitable examples of a tertiary amine (C) include
tri C, 22 alkyl (such as triethyl and tri-n-propyl), aryl (such
as triphenyl), aralkyl (such as tribenzyl) and alkenyl (such as
triallyl) amine. Among these, triethyl amine or tri-n-propyl
amine is preferred.
A molar ratio of (A):(B) is generally 1:(1.0-1.3),
preferably 1:(1.0-1.2), and (A):water is generally 1:(0.01-0.20),
preferably 1:(0.01-0.05). (B) less than 1.0 causes poor purit~,
(C) less than 0.7 results in poor yield, and water less than 0.01
causes remarkablY color developement, over 0.20 results in poor
yeiId Or said diester, because of carrying out a hydrolYsis of
(A).
A molar ratio of (A):(C) is generally 1:(0.7-1.5), preferablY
1:(O.9-1.3)
~ ater maY be one formed through neutralization of (A)
with small amount of an alkali (such as sodium hydroxide and
potassium hYdroxide).
The reaction of (A) with (B) in the presence of (C) and
water to obtain said diester, can be carried out with or without
an organic solvent. In case the reaction is carried out with the
organic solvent, illustrative examples of the organic solvent
include the same as used at producing (A).
A reaction temperature of (A) ~ith (B) is generally in
the range of ~0-130~, preferably in the range of 60-100~.
After the reaction of (A) with (B) in the presence of
(C), the product can be purified to isolate the diester, for
example, by rinsing it with water or an acidic aqueous solution
--4--
2l~5468
(such as 10% hydrochloric acid) to remove (C), mineral salt and
by-product, followed by distilling off the organic solvent.
It is better to provide a colorless said diester of high
purity, that isolated purified said diester is further treated
with an adsorbent (D).
Suitable examples of (D) include activated charcoal,
silica-alumina, activated alumina, synthetic zeolites, silica
gel, acid clay and activated clay. Illustrative examples of (D)
include activated charcoal powder (produced by WAKO JUNYAKU Ind.
Etd.), silica-alumina powder (produced bY SYOKUBAI KASEI Ind.
Ltd.) and KYOWARD #500 (produced by KYOWA CIIEMICAL Ind. Ltd.).
Among these, preferred are activated chacoal and silica-alumina.
An amount of (D) is generally in the range of 0.1-10.0%,
preferably 0.5-2.0% bY weight based on said diester.
Ilaving generallY described the invention, a more complete
understanding can be obtained bY reference to certain specific
examples, which are included for purpose of illustration onlY and
are not intended to be limiting unless otherwise specified.
In the following examples, part, parts and % mean part
by weight, parts by weight and % by weight, respectively.
Measuring methods an(l conditions are as follo~s:
(I) Color:
Cardner Color (ASTM D15~)
(2) Unreacted a , ~ -unsaturated dicarboxYlic acid content and
purity measurement with gel permeation chromatography:
Equipment: IILC-8020, produced by ToYo Soda Manuf.
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Columns : TSK gel G~OOOIIXL, G300011XL and GZOOOIIXL produced
by Toyo Soda Manuf.
Temperature : 40~C.
Sample solution : 0.5% tetrahYdrofuran solution.
Amount Or solution : 100 microlitters.
Detector : Refractometer.
Content and purity were estimated from areas of charts.
Example 1
Into an autoclave, were charged 295 parts of maleic
anhydride, 570 parts of lauryl alcohol and 85 parts of toluene.
The mixture was reacted at 60~C for 5 hours under sealed
condition, to obtain maleic acid monolauryl ester, containing
0.2% unreacted maleic anhydride. After adding to the mixture, 5
parts of sodium hydroxide, 275 parts of allyl chloride and 375
parts of triethyl amine, an atmosphere was substituted with
nitrogen. The mixture was reacted at 80~C for 8 hours, and cooled
to a room temperature. The mixture was rinsed ~ith 90 parts of
10% hydrochloric acid aqueous solution, followed by distillation
of toluene under vacuum, to obtain 965 parts of lauryl allyl
maleate of 98.6% purity and of Gardner Color 3. ~ molar ratio of
maleic anhydride:lauryl alcohol was 1:1.02, and maleic acid
monolauryl ester:allyl chloride:triethyl amine:formed water was
1:1.19:1.23:0.04.
Example 2
In the same manner as Example 1 except using 575 parts of
lauryl alcohol, 90 parts of xylene, 355 parts of methallyl
214~16~
chloride and 530 parts of tri-n-propyl amine, in place of 510
parts of lauryl alcohol, 90 parts of toluene, 275 parts of allyl
chloride and 375 parts of triethyl amine, was obtained 1,000
parts of lauryl methallYI maleate of 98.6% purity and of Gardner
Color 3. A molar ratio of maleic anhydride:lauryl alcohol was
1:1.03, and maleic acid monolaurYI ester:methal IYI chloride:
tri-n-propyl amine:formed water was 1:1.30:1.23:0.04.
Example 3
In the same manner as Example I except using 600 parts of
tridecyl alcohol, 2.2 parts of water, 240 parts of allyl chloride
and 335 parts of triethYI amine, in place of 570 parts of lauryl
alcohol, 5 parts of sodium hydroxide, 275 parts of allyl chloride
and 375 parts of triethyl amine, was obtained 960 parts of lauryl
allyl maleate of 97.1% puritY and of Gardner Color 3. A molar
ratio of maleic anhydride:lauryl alcohol was 1:1, and maleic acid
monolauryl ester:allYI chloride:triethyl amine:water was 1:1.05:
1.10:0.04.
Example 4
In the same manner as Example I except using 865 parts of
stearyl alcohol, 90 parts of hexane, 7 parts of sodium hydroxide,
250 I)arts of allyl chloride and 560 parts of tri-n-propyl amine,
in place of 570 parts of laurYI alcohol, 90 parts of toluene, 275
parts of allyl chloride and 375 parts of triethyl amine, was
obtained 1,200 parts of stearyl allyl maleate of 97.6% purity and
of Gardner Color 3. A molar ratio Or maleic anhydride:stearyl
alcohol vas 1:1.07, and maleic acid monostearyl ester:allYI
chloride:tri-n-propyl amine:formed water was 1:1.10:1.30:0.06.
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Example 5
In the same manner as Example 1 except using 610 parts of
tridecyl alcohol, 7 parts of sodium hydroxide and 325 parts of
methallyl chloride, in Place of 570 parts of lauryl alcohol,
5 parts of sodium hydruxide and 275 parts of allyl chloride, was
obtained 1,010 parts of tridecyl methallYl maleate of 98.6%
purity and of Cardner Color 3. A molar ratio of maleic anhydride:
tridecyl alcohol was 1:1.02, and maleic acid monotridecyl ester:
methallyl chloride:triethYl amine:formed water was
1:1.19:1.23:0.06.
Example 6
In the same manner as Example I except using 890 parts of
oleyl alcohol, 300 parts of allyl chloride and 455 parts of
triethyl amine, in place of 570 parts of lauryl alcohol, 275
parts of allyl chloride and 375 parts of triethyl amine, was
obtained 1,200 Parts of oleYl allyl maleate of 97.4% purity and
of Gardner Color 4. A molar ratio of maleic anhydride:oleyl
alcohol was 1:1.1, and maleic acid monooleyl ester:allyl
chloride:triethYl amine:formed water was 1:1.3:1.5:0.04.
Example 7
100 parts of lauryl allyl maleate produced in Example 1,
and I part of a silica-alumina powder (produced by SYOKUBAI KASEI
Ind.Ltd.) were mixed at 75~C for I hour, followed by filtering
off silica-alumina powder, to obtain 99 parts of lauryl allyl
maleate of Cardner Color 1.
Example 8
100 parts of tridecyl allyl maleate produced in Example
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3, and I part of a silica-alumina powder (produced by SYOKUBAI
KASEI Ind.Ltd.) were mixed at 75~C for l hour, follo~ed by
filtering of r the silica-alumina powder, to obtain 99 parts of
tridecyl allyl maleate of Cardner Color less than l.
Example 9
lOO parts of tridecyl methallyl maleate produced in
Example 5, and l part of an activated charcoal powder (produced
by ~AKO JUNYAKU Ind. Ltd.) were mixed at 75~C for I hour,
followed by filtering off the activated charcoal, to obtain 99
parts of tridecyl methallyl maleate of Gardner Color less than l.
Example lO
lOO parts of oleyl allyl maleate produced in Example 6,
and 2 parts of an activated charcoal powder (produced bY WAKO
JUNYAKU Ind. Ltd.) were mixed at 75~C for l hour, followed bY
filtering off the activated charcoal, to obtain 98 parts of oleYI
allyl maleate of Cardner Color less than l.
Comparative Example l
Into an autoclave, were charged 295 parts of maleic
anhydride and 560 parts of lauryl alcohol. The mixture was
reacted at 60~C for 5 hours under sealed condition, to obtain
maleic acid monolaurYI ester, containing 1.3% unreacted maleic
anhydride. After adding to the mixture, 275 parts of allyl
chloride and 375 parts of triethyl amine, an atmosphere was
substituted with nitrogen. The mixture was reacted at 80~C for
8 hours, and cooled to a room temperature. The mixture was rinsed
by 90 parts of 10% hydrochloric acid aqueous solution, to obtain
960 parts of laurYl allyl maleate of 92.7X purity and of Cardner
g
21~5468
Color more than 10. A molar ratio of maleic anhydride:lauryl
alcohol ~as 1:1, and maleic acid monolauryl ester:allyl chloride:
triethyl amine ~as 1:1.19:1.23.
Comparative Example 2
In the same manner as Comparative Example 1 except using
300 parts of maleic anhydride and 600 parts of tridecyl alcohol,
in place of 295 parts of maleic anhydride and 570 parts of
laurYI alcohol, respectively, was obtained 985 parts of tridecyl
allyl maleate of 93.0 % purity and of Gardner Color more than 10.
Maleic acid mono tridecyl ester contained 1.0% unreacted maleic
anhydride. A molar ratio of maleic anhydride:tridecyl alcohol
was 1:0.98, and maleic acid mono tridecyl ester:allyl chloride:
triethyl amine was 1:1.19:1.23.
Comparative Example 3
Into an autoclave, ~ere charged 295 parts of maleic
anhydride and 825 parts of stearYI alcohol. A mixture ~as reacted
at 60~ for 5 hours under sealed condition, to obtain maleic acid
monostearyl ester, containing 1.5% unreacted maleic anhydride.
Arter adding to the mixture, 11.2 parts of toluene, 275 parts of
allyl chloride and 530 parts of tri-n-Propyl amine, an atm~sphere
~as substituted with nitrogen. The mixture was reacted at 80~
for 8 hours, and cooled to a room temperature. The mixture was
rinsed by 90 parts of 10% hydrochloric acid aqueous solution,
followed by distillation Or toluene, to obtain 1,200 parts of
stearyl al IYI maleate of 9~.5% purity and Or Gardner Color 9.
A molar ratio of maleic anhydride:stearyl alcohol ~as 1:1.02, and
maleic acid monostearyl ester:allyl chloride:tri-n-propyl amine
-10-
2l~5l68
was 1:1.19:1.23.
Comparative Example 4
100 parts of lauryl allyl maleate produced by Comparative
Example 1, and 10 parts of silica-alumina powder (produced by
SYOKUBAI KASEI Ind.Ltd.) were mixed at 75~C for 1 hour, followed
by fiItering off silica-alumina powder, to obtain 90 parts of
lauryl al IYI maleate of Gardner Color 8.
As shown in Example 1-6, the unsymmetrical diesters of
a, ~ -unsaturated dicarboxylic acid produced by the Process of
the invention, were colorless, while those of Comparative
Examples 1-3 Yere severely colored, and therefore are useful as
a lav material of an emulsifier for emulsion PolYmerization and
as a modifier for a polymer. Moreover as shown in Example 7-10,
said diester treated with an adsorbent were perfectly colorless.
On the other side, as shown in Comparative Example 4, laurYl
allyl maleate, produced in Comperative ExamPle 3, treated with
adsorbent 10 times as ExamPles was still colored.
Obviously, numerous modifications and variations of the
present invention are possible in light of the above teachings.
It is therefore to be understood that within the scope of the
appended claims, the invention may be practiced otherwise than as
specifically described herein.
