2,931,819

United States Patent EQQ Patented Apr. 5, .1960

1 2
preferably in the ratio of at least three-and-a-half moles
2,931,819 of the ester to one mole of the carboxylic acid.
MANUFACTURE OF VINYL ESTERS We have discovered that while the reaction may he
carried out at temperatures ranging from normal room
John Edwin Oakley Mayne, Henry Warson, and Robert 6 temperature or even below, to the normal boiling point
John Parsons, Carshalton, England, assignors to Vinyl of the lowest boiling constituent in the mixture, which
Products Limited, Carshalton, England, a British com will usually be vinyl acetate or other starting ester, the
Pally
rate of conversion increasing with rise in temperature, it
No Drawing. Application January 30, 1956 is preferable to conduct the conversion at room tempera?
Serial No. 561,984 10 ture or just above in order to obtain the most e?icient
conversion without the formation of ethylidene diester
Claims priority, application Great Britain type by-products in quantities su?iciently large to require
February 3, 1955 elaborate separation from the desired vinyl ester product,
11 Claims. C(Cl. 260-4109) The reactions forming these by-products, at rates in
15 creasing with rise in temperature, may be represented in
This invention is for improvements in or relating to the case of the vinyl esters of higher fatty acids, as
the manufacture of vinyl esters and has for an object to follows: 1
provide an economical process for the manufacture of
those vinyl esters of higher acids not ordinarily easily
synthesised or not heretofore economically available. 20
One apparently simple way of obtaining such vinyl
esters would be by means of an ester interchange reac
tion between a readily available vinyl ester of a lower
fatty acid, such as acetic acid, and the higher molecular
weight acid Whose vinyl ester is required. However, 25
Adelman, in the Journal of Organic Chemistry, volume
14 (1949), at page 1057, has concluded that the inter
change of the vinyl group between a vinyl ester and an
acidv is different from the interchange reaction which oc
curs with other esters. The normal ester-ester or ester 30 in which R'COO and R"COO represent the radicals of
acid interchange reactions occur readily in the presence the lower and higher aliphatic acids respectively. When
of mineral acids or bases except when starting ester is a R"COO is the aromatic radical, the reactions are similar,
vinyl ester, in which case the reaction is catalysed by involving addition across the -CH=CH2 double bond,
neither acids nor bases. It has been proposed to use the hydrogen being attached to the =CH2 group carbon
various salts such as mercuric sulphate or phosphate but 35 atom.
we have found that the use of mercury salts of aromatic Further, we have discovered that the conversion to the
sulphonic acids as catalysts for this reaction has the sur required vinyl ester sometimes reaches an optimum value
prising result that ester interchange can be effected at before the whole of the original vinyl ester has reacted,
temperatures as low as room temperature with yields as after which the formation of the undesirable diesters be
high as the theoretically possible yield. 1 40 comes increasingly important. The optimum conversion
According to the present invention, therefore, we pr - value varies from one acid to another and also from one
vide a process for the manufacture of a vinyl ester which catalyst to another but the optimum point can be deter
comprises effecting an ester interchange between a vinyl mined by testing the yield from time to time during the
ester, particularly a readily available and comparatively course of the reaction, conveniently by estimating the
cheap ester such as vinyl acetate, and an organic car 45 acetic acid produced from the original vinyl acetate for
boxylic acidcontaining from three to twenty-six carbon instance. Since the production of the by-products ap
atoms by reacting the ester and acid together in the pres ' pears to be exothermic it may often be necessary to cool
ence of a mercury salt (preferably a mercuric salt) of an the reaction mixture to obtain the best yields. >
aromatic sulphonic acid. The ester interchange reaction The reaction is thus preferably stopped, for example by
is preferably carried out in the presence of a polymerisa 50 the addition of sodium acetate, at this optimum conver
tion inhibitor, such as copper acetate, particularly when sion value and the reaction mixture cooled down.
the reaction is carried out at elevated temperatures. We have also discovered that the most satisfactory and
The carboxylic acids which may be employed in the economical method of separating the products of the re
practice of this invention may be either aliphatic or aro action is by distilling off the excess starting vinyl ester of
matic and may contain more than one carboxyl group 55 a lower fatty acid together with the fatty acid formed in
and, if desired, an hydroxyl group or other substituent; the reaction from this starting ester, for example vinylv
the invention is more readily applicable to the manufac acetate and acetic acid, at atmospheric pressure, remov
ture of those acids containing less than twenty-two car ing the last traces by distillation under slightly reduced
bon atoms since it is di?icult to effect a separation of the pressure, ?nally distilling the desired vinyl ester from the
higher molecular Weight esters from the acids due to their 60 residual material. This last distillation may be the nor;_
low volatility and consequently their high boiling points mal vacuum distillation though we have discovered steam
even under high vacua. distillation to be quite as effective.
We have found that the most effective catalysts are the The following examples are illustrative of the inven
mercuric salts of aromatic sulphonic acids, especially tion, indicating certain embodiments of the procedure,
p-toluene sulphonic acid, benzene sulphonic acid and 65 the parts and percentages quoted being by weight and the
naphthalene-Z-sulphonic acid, prepared in situ from mer yields given being calculated kinetically from the amount
curic acetate and a slight excess over the equivalent of acetic acid produced.
amount of aromatic sulphonic acid. Only small amounts
of these catalysts need be used, as little as 2% or less EXAMPLE I
being desirable and effective. - 70 Vinyl acetate (225 parts), capric acid (130 parts) and
An excess of the vinyl ester over the acid is desirable copper acetate (0.075 part) are heated with slow :stirring
for the e?icient interchange, vinyl acetate being used under a re?ux condenser to obtain a homogeneous
 2,931,819 .
3 4
ture. The temperature is raised to the boiling point of homogeneous mix and then maintained at 60 C. through
vinyl acetate and a slight re?ux is maintained in the re?ux out the reaction. Mercuric acetate (3.39 parts) is added
condenser. Mercury p-toluene sulphonate (4.5 parts) is followed by p-toluence sulphonic acid (3.68 parts). A
then added and the conversion followed by removing conversion of 77% in one-and-a-half hours was observed.
samples periodically and estimating the acetic .acid EXAMPLE X
formed _in the reaction. A conversion of "76.5%, based
on .thecapric acid, was observedin two hours .from .the Vinyl acetate '(300'parts), adipicacid (73'parts), cop
addition of .the catalyst. per acetate (0.1 part) are heated to 60 C. and then
maintainedat this temperature throughout the vreaction.
EXAMPLE "II
10 Mercuric acetate (1.50 parts) .is added, followed hype
Vinyl acetate (225 parts), capric acid (130 parts) and toluene sulphonic acid (1.62 parts). The melting :point
copper acetate (0.075-part) are heated with stirring under of adipic acid being above the reaction temperature, the
.a reflux condenser as in Example 'I. Mercuric acetate reaction mixture'wasinitially nonlhomogeneoussince the
(2.625 parts) is added at the re?ux .temperature followed acid does not dissolve in the vinyl acetate but during the
a few minutes later by ,p-toluene sulphonic acid (2.85 15 course of the reaction the adipic acid goes "into solution
parts). A conversion of 69.4%, based on ,capric acid, and the reaction mixture becomeshomogeneous. A con
was observed in half an hour from the time of addition. of version of 92% in ?ve-and-a-half hours was observed.
thegp-to'luene sulphonic acid.
EXAMPLE XI
EXAMPLE III
20 Vinyl acetate ( 516 parts), sebacicacid v(202ilzrarts') and
Vinyl acetate (225 parts), capric acid (130 parts) and copper acetate (0.2.part) are heated to 60 C. and .then
copper acetate (0.075 part) are heated to obtain 'a maintained at this temperature throughout _the reaction.
homogeneous mix, as in Example I, and cooled down to Mercuric acetate (4.00 parts) is added, .followed .by,_p
30 C. Mercuric acetate (2.625 parts) is added, followed toluene sulphonic acid (4.35 parts). 'lntthis example,~as
a few minutes later by p-toluene sulphonic acid (2.85 25 in Example X, the reaction mixture is initially .non
parts) and the mixture kept at 30 C. thermostatically. homogeneous but becomes homogeneous .during the
A conversion of 100% was observed in four-and-a-half course of the reaction. .A conversionof 63.4% indive
hours from the addition of the p-toluene sulphonic acid. hours was observed.
EXAMPLE IV EXAMPLE XII
30
Vinyl acetate (225 parts), Capric acid .(130parts) and Vinyl acetate (I602 , parts), distilled .linseed .OII .fatty
copper acetate (0.075 part) are heated with stirring to acids (290 parts) .andcopper acetate ;(.0..1,part) are heated
obtain a homogeneous mix, as in Example I, and then to obtain a homogeneous mix and thereafter maintained
heatedzto-obtaina slight re?ux. Mercuric acetate (2.625 at 35 C. throughout the reaction. ,Mercuric acetate
parts) is added followed by naphthalene-2-sulphonic acid 35 (23.2 parts.) is added followedbyp-toluene sulphonicacid
(3.725 parts) and the mixture kept at a constant tem (25.1 parts). .A conversion vof .87'% .in .3 hours
:perature- throughout the reaction. A conversion of 72.6% observed. '
was observedin one 'hour from the time of additionof the EXAMPLE XIII
second catalyst.
TEXAMPLE ~V 40
:Vinyl acetate (600 parts), ~distilled dehydrated castor
oil fatty acids (280 parts) and'copper acetate (0515 'part)
Vinyl acetate (225 parts),~caprylic acid (109 parts) and are heated to obtain a homogeneous mix and then "main
copper acetate (0.075 .part) are .heated ;to .obtain a tained at 50 C. throughout the reaction. '-Mercuric ace
homogeneousmix and then _cooled to 30 C. The tem tate (11.5 parts) is added followed by p-toluenesulp'honic
peraturejsmaintained:at_30 .C. throughout ,thereaction.
Mercuric acetate (2.18 _parts) .is added, ;followed .by p 45 acid (l2.4'parts'). A conversion of 92'%'in"\31/'fz"hour$
was observed.
toluenegsulphonic acid (2.36 parts). A conversion ;.of EXAMPLE XIV
65.6% iniivehours was observed.
'Vinyl acetate (300 parts) behenic acid (340-parts') sand
EXAMPLE VI copper acetate (0.1 part) are heated to obtaina homoge
"Vinyl acetate (225 parts), benzoic acid (91.5 parts) 60 neous mix and thereafter maintained at 60 C. through
and copper acetate (0.075 part) are heated to obtain a out the reaction. Mercuric acetate (6.87parts) is added
homogeneous mix. The mix was .then maintained at 60 followed .by _p-toluene sulphonic acid (736 parts). A
vC. throughout the reaction and mercuric acetate (1.83 conversion of 80.5% in 11/: hours wasobserved.
parts) added, followed by p-toluene sulphonic .acid (1.985 EXAMPLE XV
'parts). A conversion of 70.4% ,in two vhours was 55
observed. Vinyl acetate (300 parts), stearic acid (282.5,parts) and
EXAMPLE VII copper acetate (0.1 part) were heated to obtain a 'homogm
Vinyl acetate (225 parts),'lauricacid (>1'52-parts') and vneous mix and thereafter maintainedat 50 10. through
copper acetate (0.075 part) are heated to obtain a the reaction period. .Mercuricacetate (5.6 parts) iisz'addeii
homogeneous mix and cooled to 30 C. Mercuric acetate 60 followed by _p-toluene sulphonic acid (6.06 parts). A
(3.05-parts) is added followed byp-toluene'sulphonic acid conversion of 74.5% in 3 hours was observed. Onrre
'(3i30parts). A conversion of 37.5% in ?ve hourswas .catalysing with a further :amount ofmercuric acetate (2:8
observed. parts) and p-toluene sulphonic acid (5.03 parts) , .a TBDD'
EXAMPLE VHI version rat-"96% in -a :total .time of 6 hours was observed.
65
Vinyl taeetate _(225 _parts), lauric acid (.152 parts) and EXAMPLE vXVI .Tetra vinyl vpyrome'llita'te
copper acetate (0.075 part) are heated to obtain a Vinylacetate .(602aparts), pyromelliticacid (127parts)
homogeneous _mix and then maintained at 60 _C. Mer and copper acetate (0.2 part) are .heated together ".to ob
curic acetate (3.05 parts) is added followed by p-toluene tain _a homogeneous mix and thereafterrmaintained'at 160
sulphonic acid (3.30 parts). A conversion of 100% in 70 C. throughoutjthe reaction period. Mercuric acetate (2554
one-and-a-half hours was observed. parts) is added followed by p-toluene :sulphonic acid
.EXAMPLE .IX monoehydrate (3.03 parts). A conversion :of 95.5% in
3% hours was observed.
Vinyl acetate (225 parts), myristicacid ('170parts)1and In the foregoing .examples, .-all :except Example
copper acetate (0.075 part) are heated to obtain :a 75 employ the anhydrous .form :of the aromatic sulphonic
 2,981,819.
6
acid but it is to be understood that the hydrated form of 5. A process according to claim 2 wherein said vinyl
the acids can be used as in Example XVI. acetate is employed in excess of said carboxylic acid in
It may be further observed that it has been found ad the ratio of at least three-and-a-half moles to one.
vantageous to add the catalyst in stages during the course 6. A process according to claim 2 wherein said ester
of the reaction. The most advantageous procedure ap interchange reaction is carried out at a temperature be
pears to be to re-catalyse the reaction when it reaches the low the normal boiling point of the lowest boiling constit
stage of optimum conversion and it is found that more uent of the reaction mixture.
than one further addition of catalyst may be desirable to 7. A process according to claim 6 wherein the tempera
obtain the maximum yields with the mimimum formation ture is maintained below 60 C.
of by-products. The re-catalysing of the reaction is il 10 8. A process according to claim 2 wherein the ester
lustrated in Example XV in which a 96% yield is to be interchange reaction is stopped at the point of optimum
noted. .
conversion to avoid undue production of by-products.
This procedure of re-catalysing the reaction may in 9. A process according to claim 2 wherein the re
some instances, at least, render it unnecessary to adopt action mixture is recatalysed' during the course of the
the alternative procedure, referred to earlier herein, of 15 ester interchange reaction.
stopping the reaction when the optimum conversion has 10. A process for the manufacture of a vinyl ester
been obtained. ' which comprises effecting ester interchange between an
The higher vinyl esters which are produced by the organic carboxylic acid containing from three to twenty
process of the present invention may be used, in addi six carbon atoms and an excess of vinyl acetate in the
tion to being converted to simple polymers, in the manu 20 presence of a mercuric catalyst produced in situ by inter
facture of copolymers, especially with vinyl acetate and action between mercuric acetate and a slight excess there
with vinyl acetate together with other monomers such over of an aromatic sulphonic acid, maintaining the re
as maleate esters. V >
action temperature at a value not exceeding 60 C. and
We have found such copolymers, in emulsion form, to adding further quantities of mercuric acetate and sul
be exceptionallyuseful in the manufacture of emulsion 25 phonic acid during the course of the reaction.
paints, owing to the high tensile strength, elongation, 11. The improvement in the manufacture of vinyl
?exibility, gloss and clarity of the emulsion ?lms, to esters by the ester interchange reaction between a vinyl
gether with the highly important internal plasticisation ester and an organic carboxylic acid in the presence of a
properties of the higher vinyl esters eliminating the mercuric salt as catalyst which comprises the use of a
need for addition of external plasticisers and the asso 30 mercuric salt of an aromatic sulphonic acid as the cata
ciated disadvantage of plasticiser migration. lyst.
We claim: '
1. A process for the manufacture of a vinyl ester References Cited in the ?le of this patent
which comprises e?ecting an ester interchange between UNITED STATES PATENTS
vinyl acetate and an organic carboxylic acid containing 35 2,249,768 Kropa ______________ __ July 22, 1941
from three to twenty-six carbon atoms by reacting the 2,299,862 Toussaint et al ________ .._ Oct. 27, 1942
ester and acid together in the presence of a mercury salt 2,646,437 Dickey et al ___________ __ July 21, 1953
of an aromatic sulphonic acid.
2. A process according to claim 1 wherein said FOREIGN PATENTS
mercury salt is a mercuric salt. _ 40 686,050 Great Britain _________ .._ Jan. 14, 1953
3. A process according to claim 1 wherein said organic OTHER REFERENCES
carboxylic acid is an aliphatic acid.
4. A process according to claim 2 wherein said mer Markley: Fatty Acids, 1947, page 292.
curic salt is formed in situ by interaction between Groggings: Unit Processes in Organic Synthesis, 1952,
mercuric acetate and an aromatic sulphonic acid. 45 pp. 597, 607, 608, 620.