3,937,052

United States Patent Office Patented May 29, 1962

1 2
reaction of ole?ns and aliphatic acids is set forth in the
3,937,052 prior art. While their use as a replacement for other
CATALYZING REACTIONS WITH CATIGN catalysts, such as sulfuric acid, does offer advantages such
EXCHANGE RE§IN as ease of removal of catalyst from the product, etc.,
Newman M. Eortnick, Oreland, Pa, assignor to Rollin & 5 they do have serious shortcomings. Their catalytic ac
Haas Company, Philadelphia, Pa‘, a corporation of tivity is'lower than many of the commonly used homo
Delaware geneous catalysts and they frequently require prolonged
No Drawing. Filed Apr. 29, 1959, Ser. No. 869,606
26 Claims. (Cl. 269-485) reaction times at elevated temperatures. This is particu
larly disadvantageous in the preparation of tertiary alkyl
This invention concerns the preparation of esters by esters where the reaction between the ole?n and the acid
the reaction of organic acids with ole?ns. More particu to form the corresponding esters tends to reverse at ele
larly, it concerns the preparation of esters by the addi vated temperatures. As shown in the prior art, the yields
tion to ole?ns of saturated as well as monoethylenically of esters vary from 17% to 40% when employing ali
unsaturated‘ acids. More speci?cally, it concerns the di phatic monocarboxylic acids with the prior art cation
rect production of esters by reacting ole?ns, with organic 15 exchange resins as catalysts.
acids at low temperatures in the presence of a particular It is also true that some of the reactions which are cat
type of cation exchange resin. This particular type of alyzed by homogeneous acidic catalysts are not catalyzed
cation exchange resin is a nuclear sulfonic polymer pre- _ by the 'sulfonic type cation exchangers of the prior art.
pared by a new process. It has been surprisingly found that the reaction of ole
The direct esteri?cation of ole?ns, with organic acids 20 ?ns with carboxylic acids in the presence of a cation ex
can be resolved into two major problems: (1) the esteri? change resin catalyst containing sulfonic acid groups can
cation reaction of the ole?n with the acid; and (2) sep be effected at low temperatures to produce high yields of
arating the resulting organic ester from the catalyst and/ esters if the cation exchange resins used as catalysts are
or the rest of the reaction mixture. When the usual prepared by a process which results in cation exchange
type ‘acidic catalyst, such as sulfuric acid or benzenesul 25 resins containing sulfonic acid groups which possess a
fonic acid, is used, for instance, in the esteri?cation of macro-reticular structure.
isobutylene with acetic acid, the sulfuric acid catalyst may The term. “macro-recticular” structure as used herein
be washed out of the organic reaction products with after in the speci?cation, examples, ‘and in the claims re
water. It is uneconomical to recover the sulfuric acid by fers to a unique porous structure. It has been found
30 that this structure is developed when monoethylenically
concentration. It is likewise uneconomical to discard
the sulfuric acid since it contains acetic acid. While the unsaturated monomers are copolymerized with polyvinyl
‘sulfuric acid can be separated from the acetic, acetic acid idene monomers in the presence of certain compounds.
is then so dilute that it is uneonomical to conentrate it. Characteristic of these compounds is the fact that each
These difficulties are discussed in some detail in Ind. Eng. 35 is ‘a solvent for the monomer mixture being copolymer
Chem. 30, 55-8 (1938), and a number of attempts have ized rand exerts essentially no solvent action on said co
been made to overcome these difficulties. None of the polymer. For ease of reference hereinafter, such a com
suggestions for removing the ester from the soluble acidic pound will be termed “precipitan .”
catalysts are satisfactory. The ion exchange resins containing'sulfonic acid groups
This invention is for a novel process of preparing or prepared using said copolymers as intermediates also ex
40 hibit unusual and unexpected properties.
ganic esters by the direct esteri?cation of ole?ns.‘ It has
been discovered that a number of marked advantages It is necessary that precipitants form 1a homogeneous
are obtained when, in esteri?cation reactions employing solution with the monomer. Further requirements are
ole?ns and organic acids, an acid ion exchange resin is that the precipitants must be incapable of exerting solvent
used rather than the conventional soluble strong acid cat 4.5 action on or being: imbibed by the copolymer to any ap—
alysts. The advantages which are obtained by the ap preciable extent or the aforesaid unique properties will
plication of this new process include the ease of reaction, not ‘be obtained in the copolymers produced. An addi
the convenience with which the catalyst can be removed tional requirement is that the precipitants must be chem
from the reaction products, the lack of color bodies pro ically inert under the polymerization conditions, that is
duced in the ester products by the presence of the resin 50 to say they must not react chemically with any of the
catalyst, the economical features of recycling the recov reactants or the suspending medium if one be used. A
ered solid resin catalyst for re-use in further esteri?cation, preferred class of precipitants are those which are liquid
and the lack of corrosion of metal equipment. Further under the poymerization conditions. ,
more, since the acid ion exchange resin can be readily The determination of the most effective precipitant
separated from the unconverted acetic acid without dilu— and the amounts required for the formation of a par
tion of said acid, the acid can be recycled without any ticular copolymer with macro-reticular structure may
‘additional treatment. This ion exchange resin process, vary from case to case because of the numerous factors
particularly in the case of the tertiary alkyl esters, has involved. However, although there is no “universal” or
the added advantage of permitting complete removal of single class of precipitants applicable to ‘all cases, it is not
strong acids from the esters prior to puri?cation of the 60 too dif?cult to determine which precipitants will be effec—
esters by conventional methods, such as distillation. tive in a given situation. The requirmements 0f solu
These tertiary alkyl esters are unstable in the presence of bility with the monomer mixture and low or non-solu
even traces of strong acid, particularly at elevated tem bility in the copolymer can be tested empirically and the
peratures. If a homogeneous catalyst, such as sulfuric ‘solubilities of many monomers and copolymers are well
acid, is used, it is practically impossible to remove all 65 known from publications and textbooks.
traces of strong ‘acid without neutralization, and the ter Cross-linked copolymers are generally insoluble, but
tiary alkyl ester generally undergoes extensive decomposi they will absorb or imbibe liquids Which might be con
tion on distillation. With sulfuric acid as catalyst, the sidered as being good “solvents.” By immersing the cross
unreacted aliphatic acid cannot be recycled Without inter linked copolymer in ‘liquids and determining the degree
mediate puri?cation, and, therefore, high yields cannot of swelling, a suitable precipitant can be chosen. Any
be obtained. liquids which are solvents for the monomer mixture,
The use of cation exchange resins as catalysts for the which give negligible swelling of the copolymer, which
 3,037,052
3 4
are chemically inert under polymerization conditions, and Precipitants suitable for the styrene-divinylbenzene co
which are substantially insoluble in the suspending me polymers which are preferred as intermediates for the
dium, if one be used, will function as precipitants. sulfonic acid cation exchange resin catalysts of the pres
As a further guide in the selection of a suitable pre ent invention include alkanols with a carbon content of
cipitant, reference may be made to scienti?c literature, from 4 to 10, such as n~butanol, sec-butanol, tert-amyl
for instance as discussed in Hildebrand and Scott, Solu alcohol, n-hexanol, and decanol. Higher saturated ali
bility of Non-Electrolytes, 3d Ed, New York, 1950. In phatic hydrocarbons, such as heptane, iso-octane, and the
general, it may be stated that sufficiently wide differences like can also function as precipitants in these systems.
in the solubility parameters of polymer and solvent, re For use as the catalyst in the process of the present
spectively, must exist for the precipitant to be effec 10 invention, the preferred cation exchange resin is the
tive; and that, once an effective precipitant has been lo nuclear sulfonic acid type. These resins can be prepared,
cated, the behavior of many other liquids may be pre for example, by sulfonating a copolymer of styrene and
dicted from the relative position of the reference polymer a polyvinylidene monomer, such as divinylbenzene, tri
and precipitant in published tables, within the accuracy vinylbenzene, as well as polyvinyl ethers of polyhydric
of such published information. Furthermore, if the solu 15 alcohols, such as divinoxyethane and trivinoxypropane
bility parameter of a given polymer occupies an inter which have been prepared by the process set forth here
mediate position in these tables, solvents with both high inbefore. The sulfonating agent may be concentrated
er or lower parameters may become effective. sulfuric acid, oleum, sulfur trioxide or chlorosulfonic
A minimum concentration of any particular precipi acid. A typical preparation is as follows:
tant is required to effect'phase separation. This is com A mixture of styrene (121.6 grams) technical divinyl
parable to the observation that many liquid systems con benzene (38.4 grams containing 50% active ingredient),
taining two or more components are homogeneous when 87 grams of tertiary amyl alcohol and 1 gram of benzoyl
some components are present in only minor amounts; but peroxide was charged to a solution of 6.5 grams of so
if the critical concentration is exceeded, separation into dium chloride and 0.5 gram of the ammonium salt of a
more than one liquid phase will occur. The minimum commercial styrene-maleic anhydride copolymer in 174
concentration of the precipitant in the polymerizing mix grams of water. The mixture was agitated until the
ture will have to be in excess of the critical concentra organic components were dispersed as ?ne droplets and
tion. The amounts in excess of such critical concentra then heated to 86° to 88° C. for six hours.
tion can be varied and they will in?uence to some extent The resultant polymer pearls were ?ltered and washed
the properties of the product so formed. with water and freed from excess water and amyl alcohol
Too high a concentration of the precipitant may be by drying at elevated temperature. The product was ob
undesirable for practical reasons since the rate of co tained in the form of white opaque spherical or spher
polymerization may decrease and the space-time yields oidal particles amounting to 145 grams. When the dried
become low. In many cases, the amount of precipitant product was dropped into a ?uid such as hexane, ?ne
employed may be between 30% and 60% of the total bubbles were seen to rise from the immersed particles
weight of the monomer mixture and the precipitant. due to displacement of air held within the void spaces
Introduction of the precipitant leads to two effects, of the resin by the organic ?uid.
the second effect undoubtedly depending on the ?rst. By This copolymer was converted to the sulfonic acid
adding the precipitant to the monomer phase, the solu~ derivative by heatirn7 with agitation 75 grams of the
bility in the monomer phase of any copolymer formed is copolymer with 750 grams of 99% sulfuric acid at 118°
decreased and the copolymer separates from the mono C. to 122° C. for six hours. The mixture was then
mer phase as it is formed. This phenomenon is known cooled to about 20° C. and diluted with water. The di
as “phase separation.” As the concentration of monomer luted acid was removed by ?ltration and the resin washed
in the polymerizing mass decreases due to polymeriza with deionized water until free of acid.
tion, and as the concentration of resulting copolymer The deionized water used had a quality of 106 ohm
increases, the precipitant is more strongly repelled by cm. and the washing was continued until the effluent
the copolymer mass and is actually squeezed out of the from the wash had a value of 106 ohm-cm.
copolymer phase leaving a series of microscopic channels. As has been set forth hereinbefore, the ratios of styrene
These microscopic channels are separate and distinct to divinylbenzene can be varied widely, and other poly
from the micropores which are present in all cross 50 vinylidene cross-linking agents can be employed. The
linked copolymers as is well-known to those skilled in amount of precipitant can also be varied over the range
the art (cf. Kunin, “Ion Exchange Resins,” page 45 et hereinbefore set forth, and other precipitants of the type
seq., John Wiley & Sons, Inc., 1958). While said chan set forth hereinbefore can be successfully employed.
nels are relatively small in the commonly thought of For use as catalysts in the processes of the present in
sense, they are large when compared with the micropores 55 vention, the sulfonic acid cation exchange resins of the
hereinbefore referred to. Thus, as set forth hereinafter, type set forth hereinbefore must be dehydrated prior
the use of a precipitant results in the formation of an to use. One method of dehydration is drying at elevated
unusual and desirable macro-reticular structure. It is temperatures under reduced pressure until a constant
postulated that this “liquid expulsion” phenomenon and Weight is obtained. Thus, drying at 105° C. to about
the resulting macro-reticular structure is responsible for 125° C. at a pressure of 5 to 10 mm. will effect dehy
the unusual and unexpected properties of the resultant dration. The resin may also be dehydrated by azeo
copolymer. Since the rigidity of the polymer mass at tropic distillation with an organic liquid, such as an aro
the time of precipitant expulsion is important, it is not matic or aliphatic hydrocarbon until no water is obtained
surprising that the desirable properties obtained increase in the distillate. Typical hydrocarbons include heptane,
with increasing polyvinylidene content, i.e. increasing de 65 iso-octane, toluene, xylene or mixtures thereof. The
grees of cross-linking. As a speci?c example, using a precise Water content of the dehydrated resin produced
sulfonated styrene-divinylbenzene copolymer, the proc by either of these dehydration processes is very difficult
ess of the present invention is appreciably less effective to determine, but either process will produce catalysts
below about 4% to 6% divinylbenzene content in the which are eminently satisfactory. The presence of water
copolymer than it is at higher divinylbenzene levels. 70 not only decreases the catalytic activity of the resin but
With this speci?c system, a range of divinylbenzene con frequently tends to reverse the equilibrium of the reac
tent from about 6% to about 55% will give the desired tion. For similar reasons, it is important that the rc~
effect, and preferred effects are obtained With a divinyl actants be dried prior to the reaction. Well-known
benzene content of from about 10% to about 25%, based conventional methods of drying the reactants can be
on the weight of the monomer mixture. 75 employed.
 91,037,052
6
Acid anhydrides may also be employed to eifect re acetic, propionic, butyric, isobutyric, valeric, caprylic,
moval of water from the resin and/ or the reaction mix pelargonic, lauric, myristic, palmitic, stearic, pivalic,
ture. The amount of anhydride used should be equiva triethylacetic, dipropylacetic, neopentylacetic, neopentyl
lent to the water content of the reaction mixture, includ— dimethylacetic, oxalic, malonic, succinic, glutaric, adipic,
ing the resin. pimelic, sebacic, acrylic, methacrylic, crotonic, angelic,
In addition to styrene, other monovinyl aromatic hy tiglic, undecylenic, oleic, cyclohexanecarboxylic, pinonic,
drocarbons can be used in conjunction with polyvinyl cyclopropanecarboxylic, benzoic, toluic, mesitylic, durylic,
compounds to produce cross-linked copolymers possess a-naphthoic, ?-naphthoic, phenylacetic, p~tolylpropionic,
ing macro-reticular structures by the process hereinbefore ?-naphthylacetic, p-chlorobenzoic, rn-methoxyphenylace
set forth. Such monovinyl aromatic hydrocarbons in 10 tic, piperonylic, veratric, phthalic, isophthalic, terephtha
clude ot-methylstyrene, mono- and polychlorostyrenes, lic, naphthaiic, m-bromobenzoic, homoveratric, cinnamic,
vinyltoluene, vinylanisole, and vinylnaphthalene. The dihydrocinnamic, octa'nydrocinnamic, tetrahydrobenzoic,
copolymers so formed can be sulfonated as hereinbefore endomethylenetetrahydrobenzoic, methoxyacetic, ethoxy
set forth, dehydrated, and employed as catalysts in the propionic, butoxybutyric, phenoxyacetic, 2,4-dichloro
processes of the present invention. phenoxyacetic, 2,4,S-trichlorophenoxyacetic, cyanoacetic,
The ratio of moles of resin (a “mole” of resin is de chloroacetic, a,m-dichloropropionic, a,?,B-trichloroacrylic,
?ned as the weight in grams of dehydrated resin per trichlorocrotonic, dichloroacetic, etabromopropionic, tri
sulfonic acid group) per mole of mixed reactants, i.e. mesic, fumaric, maleic, itaconic, citraconic, aconitic,
ole?n and acid, Will vary widely depending on Whether a muconic, and acetylenedicarboxylic acids.
batch or a continuous process is employed. Thus, in a 20 The ratios of the ole?ns to the acids can be varied
batch process, the ratios of moles resin to moles reactant over Wide ranges and still be within the scope of the
mixture may vary from 0.001:1 to 0.25:1. A preferred present invention. Since it is postulated that one double
ratio is from I0.02:1 to 0.10:1. In the continuous proc bond reacts with one carboxyl group, the ratios of re
ess, it is dif?cult to state the ratios because one charge actants should be expressed as the ratios of double
of resin can be used for prolonged periods to produce bonds in the ole?n to carboxyl groups in the acid. If it
large quantities of esters. In any given section of the is desired to e?iect as complete reaction of the acid as
packed reactor, however, the ratio of the volume of the possible, then an excess of ole?n should be used. Ratios
resin to the volume of the reactant mixture is substan of moles double bond to moles carboxylic group as high
tially 1:1, since the resin as used has approximately as 10:1 can be employed. It should be noted, however,
50% void volume. 30 that such high excesses of ole?n may result in undesirable
The ole?ns which will react with carboxylic acids at polymerization of the excess ole?n. If it is desired to
low temperatures in the presence of the speci?c cation effect as complete reaction of the ole?n as possible, then
exchange resin of the present invention are limited in as high as 10 moles of carboxylic group per mole of
number and are all characterized by having the structure double bond may be employed. ‘In general, ratios of
35 moles double bond to moles carboxylic group from about
1.521 to 1:15 are suitable, with a 1:1 molar ratio con
stituting the preferred embodiment.
The reaction temperature required for satisfactory con
in which R1 and R2 taken singly are selected from the versions will depend on the speci?c ole?ns and acids
group consisting of methyl and ethyl, and R3 individual 40 employed. It will also depend to some extent on the reac
ly is selected from the group consisting of H, CH3, tion time permitted as in the case of batch or continuous
C2H5, R1 and R2 taken collectively represent a four- to processes. A reaction temperature of from about —20°
?ve-membered aliphatic chain and R1 and R3 taken to about 50° C. is satisfactory with the preferred range
collectively represent a three- to four-membered aliphatic being from 0° to 20° 1C. In many cases, the reaction
chain, and the total carbon atom content of the ole?n 45 is highly exothermic, and the desired temperature can be
is not greater than 8. maintained only by external cooling.
It has been noted that the equilibrium constant of The reaction time required is a variable value depend
the reaction in favor of ester formation ing on the speci?c reactants employed and the tempera
ture used, with the temperature having the greatest effect
in determining the reaction time. Thus, in the case of
continuous processes, a contact time of as little as ?ve
seconds will give satisfactory conversion. The upper limit
decreases rapidly as the size of the substituents R1, R2 on the reaction time is determined by the relative rates
and R3 increase, and the ester formation under the re of the esteri?cation reaction and the rates of reaction of
action conditions of the present invention is low if the 55 unwanted reactions, such as those which cause poly
total carbon content of the ole?n exceeds 6. Typical merization of one or both of the reactants, or breakdown
examples of the ole?ns which can be employed include or polymerization of the desired products.
isobutylene, trimethylethylene, Z-methyl-l-butene, 2 As set forth in the examples hereinafter, the process
methyl-l-pentene, Z-methyl-l-hexene, 2-methyl-1-heptene, can be conducted as a batch process in which the ole?n
Z-ethyl-l-butene, methylenecyclopropane, methylenecy 60 is slowly added to an agitated mixture of the acid and the
clobutane, methylenecyclopentane, methylenecyclohexane, sulfonic cation exchange resin in the dehydrated acid
methylenecycioheptane, 1 - methylcyclohexene, 1,4 - di form. At the completion of the reaction, the cation ex
methylcyclohexene, and ,B-pinene. change resin is removed from the reaction mixture by
Saturated or unsaturated carboxylic acids may be used ?ltration, centrifugation, etc., the unreacted acid and
and With the exception of oxalic acid, which is operable, 65 ole?n removed from the ester and recycled to the reac
are of the general formula tion vessel. If necessary, the ester can be further puri?ed‘
by distillation, but the purities of the esters produced by
R4(COOH)Z the process of the present invention are frequently so
in which R,, is selected from the group consisting of high that no further puri?cation is necessary.
hydrogen, carboxyl, a hydrocarbon group, and 70 A continuous process can be employed by passing a
CHg=C~
mixture of the ole?n and the acid through a ?xed bed
reactor which is packed with the sulfonic cation exchange
1103112)‘. resin in the dehydrated acid form. The reactor is main
in which n is an integer from 0 to 2 and Z is an integer tained at the desired temperature by cooling. It is pos~
from 1 to 2; typical examples of the acids include formic, 75 sible to make such a process completely continuous by
 3,037,052
8
employing a continuous distillation unit in which the un I, “TAA” is tert-amyl alcohol, “10” is iso-octane, and
reacted ole?n and acid are removed from the product and “SB” is sec-butyl alcohol.
continuously recycled with the necessary additions of TABLE I
fresh acid and ole?n. The ester is also continuously re
moved from the distillation unit.
Concentration
In some cases, due to the very high exotherm, it is not Catalyst Divinylben Preeipltant
possible to design a practical ?xed bed unit which can be zene, Percent
maintained at the temperature required. In these cases,
it is frequently advantageous to employ a combination 35% TAA.
stirred reactor and ?xed bed process in which the major
part of the exotherm is dissipated in the stirred reactor,
which can be readily maintained at the required tempera
ture by external and/or internal cooling, completing the
55 50% .
reaction in the ?xed bed reactor. Other process embodi 35% 'I‘AA.
ments will be apparent to those skilled in the art.
Since the reaction is an equilibrium process, the extent As set forth hereinbefore, other monovinyl aromatic
of reaction or conversion to the desired ester is a function hydrocarbons can be substituted for styrene without de
of the concentration of the reactants. Therefore, it is tracting from the catalytic ef?ciency of the cation ex
desired to use the highest possible concentration of re change resins so prepared. Typical of such monovinyl
actants, and, as a result of this, solvents are employed 20 aromatic hydrocarbons include u-methylstyrene, mono
only when necessary. Solvents may be required if the and polychlorostyrenes, vinyltoluene, vinylanisole, and
acid is a solid and/or insoluble in the ole?n. If the acid vinylnaphthalene.
has only a low degree of solubility in the ole?n, excess In addition to divinylbenzene, other cross-linking co
ole?n may be employed as solvent and recycled after monomers can be employed to produce satisfactory cata
separation from the reaction mixture. If the acid does lysts. Typical cross-linkers include trivinylbenzene, di
not have sufficient solubility in the ole?n, solvents which vinylnaphthalene, divinoxyethane and trivinoxypropane.
are chemically inert under the reaction conditions may The following examples set forth certain well-known
be employed. Typical solvents include dioxane, halogen de?ned embodiments of the application of this invention.
ated hydrocarbons, such as methylene chloride, chloro~ They are not, however, to be considered as limitations
form, carbon tetrachloride, and dichloroethane. Aro 30 thereof, since many modi?cations may be made without
matic hydrocarbons such as benzene and toluene may departing from the spirit and scope of this invention.
also be employed as can diethyl ether and substituted Unless otherwise speci?ed, all parts are parts by weight.
aliphatic ethers. Unless otherwise noted, all temperatures are centigrade.
The pressure employed is not critical, but it is pre
ferred to use a pressure which will maintain the reactants 35 Example I
in a liquid condition. Atmospheric pressure is generally A mixture of methacrylic acid (86 parts) and Catalyst
satisfactory, but when employing low boiling ole?ns, such A (10 parts) are charged to a reactor and allowed to
as isobutylene, increased pressure up to ?ve atmospheres stand at room temperature overnight. The reactor is
may be employed. There is no objection to the use of cooled and isobutylene (56 parts) is added to the stirred
pressures as high as 1000 atmospheres. However, super 40 mixture as a liquid. During the 10-minute period re
atmospheric pressure is used primarily to maintain the quired for this addition, the reactor and its contents are
reactants in the liquid phase and only secondarily to in-v cooled to —~5°. Thereafter, the temperature is main
crease the rate of the reaction. tained at 0°-1° ‘by cooling the reactor in an ice-bath;
The esters prepared by the process of the present in samples are removed from time to time so that the prog
vention are, in general, well-known compounds of com ' ress of the reaction can be followed throughout its course.
merce with well-established uses. Thus, the lower fatty Unreacted isobutylene is allowed to evaporate from these
acid esters are of value as solvents for lacquers and for samples and the residue is assayed (1) by titration with
the preparation of solutions of other resins, which solu N/10 sodium hydroxide solution to determine unreacted
tions can be used as impregnants, adhesives, coatings, etc. methacrylic acid, and (2) by means of gas chromatog
The acrylate, methacrylate and ethacrylate esters are 50 raphy.
well-known polymerizable monomers which can be poly
TYPICAL REACTION CHART
merized, alone or in admixture with other polymerizable
ethylenically unsaturated monomers to produce a variety
Percent Percent Percent
of plastics. Thus, poly(tert-butyl acrylate) is a very hard Reaction Time (Hours) Methaerylie Crude Con
polymer and minor amounts can be used in conjunction 55 Aeid Ester version
with softer acrylates to harden the ?lm and thus increase
the softening point. These acrylic monomers, either 52. 5
38. 3
alone or in conjunction with other monoethylenically 31. 8
unsaturated monomers, may be copolymerized with poly 25. 3
23. 2
vinylidene compounds to give cross-linked copolymers 23. 5
which can be hydrolyzed to carboxylic acid type cation
exchangers or subjected to aminolysis to produce anion
exchangers as set forth in the prior art. Quantitative gas chromatography of the crude product
The catalysts employed in the following examples are shows that in addition to methacrylic acid and tertiary
prepared as set forth hereinbefore in this application. The 65 butyl methacrylate which are obtained, small amounts of
other products are also observed. Among these are di
catalysts set forth in Table I are styrene-divinylbenzene
copolymers prepared in the presence of precipitants. The
isobutylene (4.2%), triisobutylene (1.9%), and tertiary
butyl alcohol (0.6%).
concentration of cross-linking agent, divinylbenzene, is When a sample of the reaction mixture is allowed to
varied over wide ranges, and the concentration is ex stand in contact with the catalyst at room temperature
pressed as percentage of the weight of the total monomer 70
overnight, little or no tertiary butyl methacrylate can be
mixture. The amount and nature of the precipitant is isolated because complete reversion of any ester formed
also varied and the concentration is expressed as per has occurred because of the prolonged contact with the
centage of the weight of the total organic phase, i.e. catalyst at room temperature. Quantitative recovery of
weight of monomer mixture plus precipitant. In Table methacrylic acid is observed and all of the isobutylene
 3,037,052‘
9 '10
initially fed can be accounted for as a mixture of di, tri, This chromatogram will show as little as 0.1% conver‘-‘
and tetraisobutylenes. It may be seen from the data that sion. Excess isobutylene is allowed to evaporate from a.
the addition of methacrylic acid to isobutylene is very sample of the reaction mixture and the residue is titrated
rapid in the presence of this catalyst and that equilibrium with dilute sodium hydroxide solution. The residue con
is reached at 0° about ?ve hours after the reactants are tains 98.3% pure methacrylic acid. The reaction mixture
initially combined. is transferred to a pressure vessel and allowed to stand
Example 11 for 23 hours at 25° to 30°. Under these conditions, a
The procedure of Example I is repeated with the ex 5.3% conversion to tertiary butyl methacrylate occurs.
ception that Catalyst B (10 parts) is substituted for Cata Example VI
lyst A of that example. Samples are taken as set forth 10 A conventional ion exchange resin is prepared as fol
in Example I and the data are as follows: lows: '
A styrene-divinylbenzene copolymer, prepared using
Percent Percent Percent 1% divinylbenzene instead of the customary 8% to 10%
Reaction Time (Hours) Methacrylic Crude Con
Acid Ester version 15 divinylbenzene, is sulfonated according to the usual proc
ess (concentrated sulfuric acid, 120° C., 6 hours). This
72. 6 27. 4 17.4 material is thoroughly washed with water, dried, and
52. 5 47. 5 32. 2 powdered to pass 100 mesh. \Finally, the powdered resin
41. 6 58. 4 41. 8
29. 8 70. 2 52. 9 is dried at 110° to 115° ‘(2 mm.) for 16 hours. This de
27. 3 72. 7 57. 2
26. 2 73. 8 59. 1 20 hydrated sulfonic acid cation exchange resin is used as a
catalyst in the reaction set forth as follows:
A mixture of methacrylic acid (86 parts) and the dried
Example III catalyst (10 parts) is allowed to stand overnight at room
In a similar fashion, Catalyst C is substituted for Cata temperature. The mixture is then cooled to 0° and iso—.
lyst B in an otherwise identical preparation. The data 25 butylene is added during 10 minutes at a temperature be
for this run are as follows: tween —5° and 0°. The reaction mixture is stirred and
cooled at 0° for the next 7 hours. After 7 hours at 0°, no
Percent Percent Percent more than a trace of tertiary butyl methacrylate can be de
Reaction Time (Hours) Methacrylie Crude Con tected in the gas chromatogram. After 7 hours, the iso
Acid Ester version
butylene is allowed to evaporate from an aliquot sample.
The residue is 97.4% pure methacrylic acid. The re
61. 8
48. 3 action mixture is transferred to a pressure vessel and is
41. 5 allowed to stand for 23 hours at 25° to 30°. At that
38. 4
34. 2 point, a conversion to 16.2% tertiary butyl methacrylate
30. 1 -35 has been attained.
27. 4
Example VII
Gas chromatography shows percent diisobutylene, 4.0; A mixture of acetic acid (60 parts) and Catalyst D ( 10
percent triisobutylene, 2.3; and percent tertiary butyl parts) is charged to a reactor at room temperature. To
alcohol, 0.9. the stirred mixture is added liquid isobutylene (56 parts)
40 which is pro-cooled to —40° C. In the course of the addi
Example IV
tion, the temperature of the reaction mixture drops to 5°.
The following experiments are carried out in which the External cooling is then applied. The reaction mixture is
procedures of Example I are repeated exactly, but Cata held at 0° and samples are taken every hour to test their
lysts D, E, F, G, H, and I are used in place of A in the conversion to tertiary butyl ester in the usual fashion.
respective runs. The next table shows data obtained in After one hour, conversion to tertiary butyl acetate is
terms of percent conversion after 2 hours and 7 hours 74%; after two hours the conversion reaches an equilib
as related to the nature of the catalyst. The data for these rium value of 80.6%.
runs are as follows: \In a similar fashion, trimethylethylene gives tertiary
amyl acetate in good yield and 1,1-diethylethylene is con
Percent Percent verted to 1—methyl—1-ethylpropylacetate in excellent yield
Catalyst Conversion, Conversion, 50
Two Hours Seven Hours but with low conversion.
Exam'ple VIII
40. 7 62. 3
19. 6
9. 5
47. 4
23. 0
A section of 1/4” inside diameter tubing is packed with
35. 2 59. 2 55 24.8 parts of Catalyst A. The tube is coiled to ?t into a
16. 0 37. 7 cooling bath, the entrance of the tube is attached to a pres
18. 2 42. 0
surized feeder and pump assembly and the exit of the tube
is connected to a reservoir and let-down valve. An equi
Example V molar mixture of acrylic acid and isobutylene are placed in
A mixture of methaerylic acid (86 parts) and a con 60 the pressurized feeder and slowly pumped through the cat
ventional sulfonated cation exchange resin (10 parts) alyst bed. The tube is cooled to 0° and maintained at 0° to
are mixed and allowed to stand at room temperature 1° C. during the entire course of the run. The mixture is
overnight. The catalyst is prepared from a sample of pumped through the tube at a rate such that one tube
a commercially available sulfonic acid cation exchange volume passes through the tube every 14 minutes. A .
resin (such as Amberlite IR-120, available from Rohm & 65 steady state is reached shortly after the ?rst hour of opera
Haas Company, Philadelphia, Pennsylvania) which is tion. The tube e?luent contains acrylic acid (28%),
converted to the hydrogen form and then dried ‘at 110° tertiary butyl acrylate (65.6%), isobutylene (2.5%), di-'
to 115° (2 mm.) for 16 hours. This particular resin is isobutylene (3.4%), and tertiary butyl alcohol (0.4%).
a sulfonated styrene divinylbenzene copolymer containing The conversion is, therefore, 66.7%, and the yield is in
8.5% divinylbenzene. Isobutylene is added in the fashion 70 excess of 95%, based on the acrylic acid which is con
described for Example I and samples are removed as in sumed. ‘No apparent loss in catalyst activity appears to‘
Example I. At two hours and at four and one-half hours, have occurred in the course of the passage of 5,000 parts
not a trace of the desired ester can be found nor after of reaction mixture through the system.
seven hours at 0° is any tertiary butyl methacrylate ‘In an entirely similar fashion, a conversion of 58.4%
observable in the chromatogram of the reaction mixture. is realized when the contact ‘time is shortened to one min
 3,037,052
11 12
ute and the temperature is raised to 20°. Slightly more of hours at room temperature, the conversion to the tertiary
the isobutylene is converted to diisobutylene, triisobutyl butyl ester has reached 49%.
ene, and tetraisobutylene under these conditions than is
observed at 0°. Example XIV
Example IX A mixture of benzoic acid (18.3 parts), Catalyst A
The conditions of Example VIII can be adapted for (3 parts), ether (40 parts per volume), and isobutylene
the preparation of tertiary butyl methacrylate. An equi (16.8 parts) are shaken in a pressure vessel at room
molar mixture of methacrylic acid and isobutylene is temperature for 21/2 hours. The reactor is cooled and
metered to a thermostated reaction coil. A total of 5,680 vented and the reaction mixture is ?ltered to remove the
parts of reaction mixture is passed through 40 parts of 10 catalyst. The ?ltrate is washed with water and then with
the catalyst. At a contact time of six minutes at 15°, a small amount of 10% sodium hydroxide solution. The
48.6% of the methacrylic acid in the feed is converted to mixture is dried over anhydrous magnesium sulfate and
tertiary butyl methacrylate. _ distilled under reduced pressure in the presence of a trace
In a similar experiment run at 20° and two and one-half of potassium carbonate. The product, tertiary butyl
minutes’ contact time, 51% conversion to tertiary butyl benzoate, 14.6 parts, 55% yield, has a B.P. of 80° to 85°
methacrylate is obtained. Similar results are observed (5 mm).
when 50 minute contact time at 0° is employed. In a similar fashion, 2-methyl‘1~butene and benzoic
Somewhat more isobutylene dimer, trimer, and tetramer acid gives tertiary amyl benzoate, isobutylene, and 2
accompany preparation of tertiary butyl methacrylate than naphthoic acid gives tertiary butyl Z-naphthoate, tri
is observed in the preparation of tertiary butyl acrylate. 20 methylethylene and phenylacetic acid gives tertiary amyl
Only traces of material which boiled higher than tetra phenylacetate, and cyclohexanecarboxylic acid and iso
isobutylene are observed. butylene gives tertiary butyl cyclohexanecarboxylate.
In a similar fashion, trimethylethylene and acetic acid Example XV
are converted to tertiary amyl acetate; the yield, based A ‘mixture of methylenecyclohexane (9.6 parts), acetic
on acetic acid consumed, is in excess of 95% of the theo
retical. acid (10 parts), and Catalyst B (1 part) are mixed and
Example X warmed at 60° C. for 8 hours. The reaction mixture is
washed with water and with 5% sodium bicarbonate solu
Undecylenic acid (73.7 parts), Catalyst C (4 parts), tion and is dried over anhydrous magnesium sulfate.
and isobutylene (22.4 parts) are placed in a pressure bot 30 The mixture is distilled in the presence of a trace of
tle and allowed to stand at room temperature for 16 hours. potassium carbonate to give l-methylcyclohexyl acetate.
Thirty-six and one-half percent of the undecylenic acid is The product has a BI’. 93° to 98° (50 mm.), 72° to
converted to tertiary butyl undecylenate under these con 75° (10 mm.), and nD25=1.44-l. In a similar fashion,
ditions, and small amounts of isobutylene, diisobutylene, methylenecyclobutane and acetic acid gives l-methyl
triisobutylene, tetraisobutylene, and tertiary butyl alcohol DO U! cyclobutyl acetate, rnethylenecyclopentane and propionic
are likewise formed. acid gives 1-methylcyclopentylpropionate, methylene
Example XI cycloheptane and benzoic acid gives l-methylcycloheptyl
Oxalic acid (13.5 parts), Catalyst A (3 parts), and di benzoate, and l-methylcyclohexene and phenylacetic acid
ethyl ether (40 parts by volume) are placed in a pressure gives l-rnethyleyclohexyl phenylacetate.
vessel and cooled to —-20°. isobutylene (33.6 parts) is 40 Example XVI
added to the mixture. The pressure vessel is sealed and A mixture of Z-methyI-I-hexene (9.8 parts), chloro
the reaction mixture is allowed to warm to room tempera
ture with shaking during a two and one-half hour period.
acetic acid (14 parts), Catalyst A (2 parts), and chloro
form (10 parts) is mixed and heated at 50° for 5 hours.
All of the oxalic acid dissolves and the reaction mixture be
The mixture is ?ltered, washed with water, and dried over
comes warm. It then cools to room temperature. The 45
magnesium sulfate. Distillation under reduced pressure
pressure vessel is cooled in an ice bath and is opened. The in the presence of a small amount of potassium carbonate
catalyst is removed by ?ltration and the precipitate is gives 1,1-dimethylpentyl chloroacetate. In a similar fash
washed with ether. The combined organic ?ltrates are ion, tertiary butyl ?-methoxypropionate is prepared from
washed with water and then with 10% sodium carbonate isobutylene and ?-methoxypropionic acid, tertiary butyl
solution. The combined ether extracts are stripped of phenoxyacetate from isobutylene and phenoxyacetic acid,
solvent and the product, tertiary butyl oxalate, MP. 68° and tertiary butyl cyanoacetate from isobutylene and
to 70°, is obtained in a yield of 44.5% of the theoretical. cyanoacetic acid.
Gne-third of the oxalic acid charged is recovered in the Example XVII
aqueous washings so that the yield, corrected for recov
ered oxalic acid, is 68%. Under the conditions set forth in Example I, an equiva
lent weight of itaconic acid is substituted for the meth
Example XII acrylic acid employed in Example 1. Excellent yields of
A mixture of malonic acid (15.6 parts), Catalyst A (3 tertiary butyl itaconate are obtained.
parts), and diethyl ether (40 parts) is cooled to ——20° in a Example XVIII
pressure vessel and liquid isobutylene (33.6 parts) is 60 Isobutylene is bubbled into a stirred mixture of formic
added. The pressure vessel is sealed and shaken at room acid (208 parts) and Catalyst A (2 parts). The gas is
temperature for 21/2 hours at which point the solid malonic introduced by means of a gas dispersion tube at a rate of
acid has entirely dissolved. The reaction mixture is 1 mole per hour. Virtually no isobutylene appears in a
cooled and ?ltered, the ?ltrate is washed with water and Dry Ice trap which is attached to the condenser vent. All
then with 10% sodium carbonate ‘solution. The ?ltrate is 65
of the gas is absorbed quantitatively on introduction until
dried over anhydrous magnesium sulfate and the solvent the reaction is nearly complete. Intermittent cooling is
is removed under reduced pressure. The residual oil is required to keep the temperature below 50° C. Break
distilled under reduced pressure to give tertiary butyl mal through of isobutylene gas occurs when about 75% of
onate, B.P. 102° to 103° (15 mm.), 36% yield, the theoretical amount of isobutylene has been absorbed.
70
nD25=1.4059. When 90% of the theoretical isobutylene has been passed
Example XIII through the mixture, 92% of that charged is absorbed at
A mixture of pivalic acid (15.3 parts), Catalyst A (3 42° and above. The temperature is lowered to 20° and
parts), ether (40 parts by volume), and isobutylene (16.8 the system is saturated with isobutylene and stirred at
parts) is treated exactly as in Example XII. After 21/2 75 that temperature for 30 minutes. The catalyst is sepa
 3,037,052
13 14
rated by ?ltration and the ?ltrate is washed ?rst with ice formic acid, swells the sulfonic cation exchange resins
cold water, then with cold saturated sodium bicarbonate of the prior art appreciably, and this solvation makes a
solution. The organic layer is separated and distilled higher percentage of the sulfonic acid groups in the
to give tertiary butyl formate in 80% yield. This result resin available for catalytic activity. While the sulfonic
is to be compared with the 43% yield reported in the acid cation exchange resin with macro-reticular structure
prior art, using conventional exchange catalysis. still exhibits a markedly superior catalytic effect, the dif
Example XIX ferences in catalytic efficiencies are much more in favor
of the macro-reticular structured sulfonic cation exchange
In order to investigate further how signi?cant an ad resins when the higher members of the homologous series,
vantage the macro-reticular catalysts have over the con 10 which effect little solvation of the prior art resins, are em
ventional ion exchange catalysts, the following pair of ployed.
experiments are carried out: A mixture of formic acid The differences in catalytic efficiencies between the
(46 parts), tertiary butyl formate (30.6 parts) and iso sulfonic acid type cation exchange resins of the prior
butylene (56 parts) is placed in a stirred reaction vessel art and the sulfonic acid type cation exchange resins
which carries a Dry Ice-cooled re?ux condenser. The 15 which exhibit macro-reticular structures are not as
?ask is immersed in an ice bath, and the re?uxing mix marked in aqueous media as they are in substantially non
ture is found to stabilize at a pot temperature of —-2.5°. aqueous media. However, the differences in resistance to
In one of the units, Catalyst A (0.92 part) is added, in physical and chemical degration which exist in non
the other, the same weight of the dehydrated acid form aqueous media also obtain in aqueous media. This re
of the conventional ion exchange catalyst Amberlite sults in an important economic advantage for the resins
IR-120 (hereinbefore described). The mixtures are with macro-reticular structure from the standpoint of
stirred and observed. The temperature rises from —2.5 repeated re-use. '
to +1.0° in the course of three hours in the macro The reactions set forth hereinafter are typical of the
reticular exchange resin experiment. In the conventional wide variety of reactions effectively catalyzed by the sul
resin-catalyzed experiment, the temperature rises from 25 fonic acid type cation exchange resins which possess
—2.5° to r-—1.8° after four hours. Triethylamine (0.47 macro-reticular structure.
part) is added to each of the reaction mixtures, and iso ADDITION OF CARBOXYLIC ACIDS TO OLEFINS WHICH
butylene is allowed to evaporate slowly as the Dry Ice YIELD SECONDARY ALKYL ESTERS
in the condenser gradually evaporates. The remaining
mixture of formic acid and tertiary butyl for-mate is 30 The conditions which are required to catalyze the ad
titrated with n/ 10 sodium hydroxide solution to a phenol dition of carboxylic acids to ole?ns which yield secondary
phthalein end point. If no conversion of formic acid alkyl esters are considerably more stringent than those
to tertiary butyl formate occurs, the mixture would con which are needed to give addition of carboxylic acids to
tain 60.1% formic acid. The run in which Catalyst A ole?ns which yield tertiary alkyl esters. The use of
is used analyzes for 28.3% formic acid; this corresponds 35 macro-reticular cation exchange resins in the acid form
to 40% conversion of the acid to the ester. The run in has permited addition‘ of carboxylic acids to these less
which the conventional resin is used analyzes for 58.4% reactive ole?ns to give signi?cantly higher yields ‘and
formic acid; this corresponds to 1.5% conversion of the shorter reaction times under milder conditions than can
acid to the ester. These ?gures show that the macro be obtained with the prior art ion exchange resins. The
reticular resin is about 25 times as e?iective as the con 40 following preparations illustrate the scope of the process
ventional resin catalyst. and in some instances show direct comparisons of the
The sulfonic acid type cation exchange resins which relative activities of macro-reticular and conventional
exhibit macro-reticular structures are very superior cat ion exchange catalysts:
alysts for a wide variety of hydrogen ion~catalyzed reac A mixture of methacrylic acid (86 parts), hydro
tions which occur in substantially non-aqueous media. quinone (05 part), benzoquinone (0.5 part), and Cata
Compared to the sulfonic acid cation exchange resins of 45 lyst A (110 parts) is charged to 1a pressure Vessel. The
the prior art, the resins exhibiting macro-reticular struc pressure vessel is pressurized with ethylene at 2000 lbs.
ture will catalyze reactions effectively at much lower tem per square inch, sealed and heated to 160° C. with agita
peratures and with much shorter reaction times to give tion. In the course of two hours at 150° to 160° C.,
higher yields of high purity products. There are some reaction occurs. The vessel is cooled and unreacted
of the reactions Iwhich are conducted in substantially 50 ethylene is vented. The residue is ?ltered to separate
non-aqueous media and catalyzed by hydrogen ion which the catalyst, and the ?ltrate is distilled under reduced
are effectively catalyzed by the macro-reticular structured pressure. The product, ethyl methacrylate, B.P. 117.5°
sulfonic acid cation exchangers which are not catalyzed to 119.5o (760 mm.), 11925 1.4115, is obtained in a yield
at all by the sulfonic cation exchange resins of the prior of 80% based on methacrylic ‘acid which is consumed in
55 the process.
art.
Furthermore, since it is possible to employ much Similarly, a mixture of methacrylic acid (86 parts),
higher concentrations of polyvinylidene compounds which hydroquinone (0.5 part), benzoquinone (0.5 part), and
function as cross-linkers, it is possible to obtain much Catalyst A (10 parts) is charged to a pressure'vessel and
higher chemical and physical resistance in the macro propylene (80 parts) is added. The vessel is sealed,‘
reticular structured sulfonic cation exchange resins with 60 agitated and heated. At a temperature of about 60“, an
out any sacri?ce of the very efficient catalytic properties exothermic reaction becomes evident and the temperature
which they exhibit. 'Ilhis substantially higher resistance rises to 114° before natural cooling occurs. In the
to degradation, either physical or chemical, permits pro course of the reaction, the pressure reaches a maximum
longed use with negligible loss of catalytic or operating pressure of 475 p.s.i. at 92° and drops to 175 p.s.i. at
characteristics. 65 105°. A total reaction period of one hour is employed.
The differences in the catalytic ef?ciencies between The reaction mixture is cooled and vented, and the prod
the sulfonic acid type cation exchange resins of the prior uct is separated from the catalyst by filtration. The
art and the sulfonic acid type cation exchange resins which ?ltrate is distilled under reduced pressure to give iso
exhibit macro-reticular structures will depend to some propyl methacrylate, B.P. 54° (50 mm.), nD25 1.4087.
The yield of ester is 85% based on acid charged.
extent at least on the particular reactancts being employed In another experiment, Catalyst A_ (40 parts) is
in the non-aqueous system. These differences in catalytic charged to a 1A" inside diameter stainless steel tube which
efficiencies are well-illustrated in the esteri?cation by ole is bent around a mandrel to form a helical coil 8" in
?ns of the homologous series of saturated monocar outside diameter. The coil is connected to an inlet and
boxylic acids. Thus, the lowest member of the series, 75 outlet system as follows: ‘
 3,037,052
15 16
The inlet system comprises separate reservoirs and change resin in the dehydrated acid form (Amberlite
pumps for feeding liquid propylene and anhydrous meth IR—120, hereinbefore described), only 24% conversion to
acrylic acid to a mixing chamber. This in turn is con secondary ‘butyl methacrylate is obtained at 80° C. with a
nected by means of a valve to the coil reactor. The out contact time of 40 minutes. Thus, when the prior art
let system consists of a product reservoir and let-down catalyst is used, 20 times the time is required to attain
valve. Liquid propylene (470 parts) under nitrogen at only % of the conversion observed when the macro-reticu
300 lbs. per square inch and methacrylic acid (900 parts) lar catalyst is employed under the same conditions.
containing hydroquinone (1.5 parts) are simultaneously In a similar fashion are prepared secondary butyl ace~
pumped into the coil reactor. The product reservoir is tate from acetic acid and butene-2, secondary butyl
prepressurized with nitrogen to 2000 lbs. per square inch. 10 pivalate from butene-2 and pivalic acid, and secondary
The coil is placed in a bath which may be heated to any butyl pelargonate from butene-2 and pelargonic acid.
suitable temperature. The extent of conversion of meth The reaction tube employed in the two preceding experi
acrylic acid to isopropyl methacrylate may be ascertained ments is packed with Catalyst C (40 parts), and a mixture
by titration of an aliquot of the product dropped from of butene-l (346 parts), acrylic acid (432 parts), and
the receiver from time to time. The conversion is a func 15 hydroquinone (1 part) are placed in the inlet system.
tion of the temperature which is employed and of the In this system, the equilibrium conversion value corre
?ow rate (hence, the contact time) at which the reactants sponds to approximately 73% conversion to secondary
are pumped through the reactor. Conversion to isopropyl butyl acrylate at 80° C. and a 1:1 mole ratio of reactants.
methacrylate occurs at temperatures as low as room Use of a contact time of ten minutes at 80° gives 71%
temperature. As the temperature is raised, at a given conversion to the desired product; doubling the contact
contact time, the conversion approaches the equilibrium time to twenty minutes produces virtually no change in
value. At equilibrium for the system, methacrylic acid conversion, a rise to 72% being observed. The yield
propylene there is 16% to 17% methacrylic acid present based on acrylic acid which is consumed is quantitative.
in the effluent at 80° C. Equilibrium is achieved at a The yield based on butene-l consumed is about 80%.
feed rate of 5 parts by volume per minute at 80° C. At Mechanical losses account for most of this loss and dimeri
60° under the same conditions, a conversion of approxi zation of the butene to branched chain octenes accounts
mately 70% of the equilibrium value is obtained. The for most of the remainder. For the most part, the butenes
mixture of unreacted propylene, unconverted methacrylic which are not converted are found to be isomerized to a
acid, and isopropyl methacrylate together with trace mixture of cis- and trans-butene-Z.
All three possible
amounts of propylene dimer, trimer, and tetramer are 30 straight-chain butenes are evident in a gas chromatogram
collected continuously during the course of the run. of the recovered ole?n. The chromatogram of the ole?n
Methacrylic acid is quantitatively accounted for as either recovered in this experiment resembles very closely that
unreacted starting material or isopropyl methacrylate; of the recovered butenes when the mixture of cis- and
the yield of isopropyl methacrylate based on methacrylic trans-butenes-2 are used as in the preceding experiment.
acid consumed is 100%. At equilibrium at 80° C., ap In a similar fashion, formic acid and butene-l give sec
proximately 75% of the methacrylic acid fed is con ondary butyl formate, chloroacetic acid and butene-l gives
verted to isopropyl methacrylate. The yield based on secondary butyl chloroacetate, and 2,2,4,4-tetramethyl
propylene consumed is in excess of 80% of the theoreti pentanoic acid and butene-l give secondary butyl 2,2,11,4
cal. tetramethylpentanoate.
In an entirely similar fashion are prepared isopropyl In another experiment, a mixture of octene-l (22.4
acrylate from propylene and acrylic acid, isopropyl ace parts), acetic acid (12 parts), and Catalyst A (2 parts)
tate from propylene and acetic acid, and isopropyl 2 are stirred and heated at 100° C. From time to time,
ethylhexoate from propylene and Z-ethylhexoic acid. samples of the reaction mixture are removed and titrated
When solid carboxylic acids are employed, it is entirely for unchanged acetic acid. The drop in acid concentration
feasible to feed a preformed mixture of propylene and the per gram of reaction mixture is a function of the rate at
carboxylic acid or, alternatively, to use the isopropyl ester which secondary octyl acetate is being formed in this
as part of the feed in order to be able to pump the feed as reaction. A similar experiment in which a conventional
a liquid. It is also possible to pump the acid in the molten
ion exchange resin (Amberlite IR~112, a sulfonated
form into the reactor. In this fashion, isopropyl benzoate styrene-divinylbenzene copolymer, 4.5% divinylbenzene
may be prepared from propylene and benzoic acid; iso available from Rohm & Haas Company, Philadelphia,
propyl adipate may be obtained from propylene and adipic Pennsylvania) in the dehydrated hydrogen ion form is
acid; and isopropyl itaconate may be obtained vfrom pro used as catalyst is carried out at the same time. A plot
pylene and itaconic acid. of the data which are obtained shows that rough second
The apparatus described in the preceding experiment is order rate constants can be calculated for the ?rst portion
employed for the preparation of secondary butyl meth 55 of the reaction. The rate constant for the macro-reticular
acrylate from a mixture of cis- and trans-butene-2 and catalyst system is three times that of the conventional
methacrylic acid. Thus, a mixture of the butenes (256 resin. Furthermore, when the prior art resin is employed,
parts), methacrylic acid (516 parts), and hydroquinone the reaction practically ceases when the conversion has
(1 part) is charged to the inlet system. The reaction is proceeded to only 39% of theoretical value. The corre
carried out at 80°. At this temperature the equilibrium 60 sponding level-off point in the case of the macro-reticular
conversion of the reactants to the ester is approximately catalyst is at 73.5% conversion, the latter ?gure very
66% at 1:1 mole ratio. At a pumping rate of 25 parts by probably representing the true equilibrium concentration.
volume per minute, which corresponds to a contact time When dodecene-l is used in a similar reaction, the ratio
of approximately 2 minutes, 95% of the theoretical equi of the rate constants is also ‘found to be approximately 3.
librium value is “attained. When the contact time is dou Again, a cut-oif point is observed in the case of the prepa
bled to 4 minutes, conversion of the acid to the ester ration of secondary dodecyl acetate which is much lower
reaches 65% or approximately 98% of the equilibrium for the prior art resin than for the macro-reticular species.
value. When the temperature is lowered to 60° and a When methacrylic acid is used instead of acetic acid in
contact time of 40 minutes is employed, the conversion these experiments, the ratio of the rate constants rises from
drops to 47% which is 72% of the equilibrium value. 70 3 to more than 30. This shows that higher molecular
At 40° under the same conditions, 10% conversion is weight carboxylic acids are much more sensitive to the
realized. Ester is formed even at temperatures of 20° C. structural features of the catalysts involved than are the
and below, but the rate of formation becomes impracti ?rst members of the series.
cally low. A mixture of octadecene-l, acrylic acid, and Catalyst A
When the reactor is packed with a conventional ion ex~ * in a 1:l:0.05 molar ratio are heated at 110° for six hours.
 3,037,052
17 18
The reaction mixture is cooled and washed with dilute scanned as ?lms in the infrared region of the spectrum.
sodium carbonate solution. The organic layer is distilled As heating proceeds, a peak at 1770 cm.-1 appears in the
under reduced pressure to give secondary octadecyl ‘acry spectrum; and this peak becomes larger and larger with
late in the high yield based on acrylic acid consumed, but time. After 8 hours at 140°, the magnitude of the peak
in low conversion based on ‘acrylic acid charged. corresponds to a 25% conversion of undecylenic acid to
In a similar fashion, ll-tricosene reacts acrylic 'y-n-heptyl-y-butyrolactone. The lactone may be isolated
acid at 110° for 8 hours to give secondary tricosanyl by extractively removing the carboxylic acid with cold
acrylate, as is shown by the infrared spectrum of the dilute sodium hydroxide solution and distilling the alkali
resulting reaction mixture after removal of unchanged insolu-ble material.
car-boxylic acid ‘by extraction with dilute sodium hydroxide 10 Oleic acid ‘(28.2 parts) and Catalyst A (4 parts) are
solution. heated at 150° for 24 hours. At this point, a 30% con
In a similar fashion, cyclopentene reacts with acetic acid version to 'y-n~tetradecyl-v-butyrolactone is indicated by
in the presence of Catalyst C at a 1:1:0.05 molar ratio of the magnitude of the peak of 1770 cm.-1.
reactants to give a high yield of cyclopentyl acetate. The A mixture of methyl undecylenate (19.8 parts), acetic
reaction is carried out under re?ux and is essentially com 15 acid (6 parts), and Catalyst A (1 part) is heated at 115°
plete in two hours. Similarly, cyclohexene ‘gives cyclo for 8 hours. Methyl acetate is formed and the presence
hexyl propionate when a mixture of cyclohexene and of 'y-n-heptyl-'y~butyrolactone is evident by inspection of
propionic acid are contacted in a similar fashion with the infrared absorption spectrum. ’
Catalyst D, and norbornene reacts with acrylic acid to ALKYLATION OF AROMATICS
give norhornyl acrylate in a similar fashion. 20
Typical of such reactions are the following:
LACTONE FORMATION A mixture of toluene (92 parts) and Catalyst A (7.5
parts) is charged to a stainless steel rocking autoclave.
Open chain carboxylic acids in Which a double bond is The autoclave is sealed and propylene (41 parts) is intro
present in the ,B,~/- or 'y,6—position with respect to the duced into the reaction mixture. Heat is then applied and
carboxyl group, or compounds which may be converted a maximum pressure of 300 pounds per square inch at
to such intermediates, are easily cyclized to the corre 100° is observed. At this point, heating is discontinued
sponding ly-lactones when heated in the presence of a and the temperature is observed to rise slowly to 120°.
macro-reticular structured sulfonic cation exchange resin The pressure drops to 250 pounds per square inch at 112°,
in the dehydrated acid form. Thus, 4-pentenoic acid gives and within 11 minutes reaches 100 pounds per square inch
'y-vaierolactone, 3-butenoic acid gives 'y-butyrolactone, 4“ at 120°. The reactor is then cooled and vented. The re
methyl-4-pentenoic acid gives v-methyl-v-valerolactone; 4. action mixture is separated from the catalyst by ?ltra
methyl-4-hexenoic acid gives y-ethyl-y-Valerolactone; 4 tion, and the ?ltrate is distilled under reduced pressure.
pl1enyl—3-butenoic acid gives '~,/—phenyl-y-butyrolactone; The product (38 parts) has a boiling point of 176°—l77°
and 5 -phenyl - 4 - pentenoic acid gives y-be1izyl-'y~butyro (760 mm.), nD25 1.4907. High-boiling products are ob
lactone. Furthermore, methyl-4-pentenoate when heated tained which boil at 130°~135° (50 mm.) (11 parts),
with acetic acid in the presence of macro-reticular struc 11325 1.4919 and 13.1’. 15'6°—159° (50 mm.) (5.5 parts),
tured sulfonic cation exchange resins in the dehydrated 711325 1.4912. The infrared absorption spectra of all three
acid form gives methyl acetate and 'y-valerolactone. Like of these cuts are carefully examined. The main product
wise, ethyl 4-pentenoate ‘gives ethyl propionate and 'y 40 cut contains major amounts of ortho-isopropyltoluene
valerolactone when it is heated with the resin catalyst and (ortho-cymene) and lesser amounts of meta- and para
propionic acid. IO-undecenoic acid (undecylenic acid) isopropyl-toulenes. The product in the intermediate boil
upon prolonged heating with macro-reticular cation ex ing range is largely 2,4-diisopropyltoluene; the highest
change resins in the acid form, undergoes double bond boliing product is largely 2,4,6-triisopropyltoluene.
migration from the terminal position. Finally, when the Toluene (36.8 parts), tetrapropylene (33.6 parts),
double bond has reached the 'y,5-position, cyclization can Catalyst A (2 parts), and glacial acetic acid (0.6 part)
occur and 'y-n-heptyl-ry-butyrolactone results. are heated for 6‘ hours under re?ux at 123 °. The catalyst
In a similar fashion, oleic acid yields y-tetradecyl-y is removed by ?ltration and the ?ltrate is freed of unre
butyrolactone. acted starting materials by heating to a distillation pot
Illustrative of such reactions are the following: temperature of 205° at atmospheric pressure. The resi
A mixture of acetic acid (66 parts), methyl 4-pentenoate due is distilled under reduced pressure to give the product,
(114 parts), and Catalyst A (5 parts) is placed in the pot B.P. 160° to 176° (25 mm.). The product is equivalent Q
of a distillation column and is heated to total re?ux. At to that obtained in the conventional manner by alkylation
a pot temperature of about 90°, methyl acetate (15.1’. of toluene with tetropropylene in the presence of concen
54°) distills as rapidly as it forms. The pot temperature ~ trated sulfuric acid as shown by examination of the infra
is held below 130° during the entire course of the run. red absorption spectrum. The product obtained in this
When 95% of the theoretical amount of methyl acetate way by means of the use of macro-reticular exchange resin
has been collected in the receiver, the residue is ?ltered catalysis has a rather narrower boiling range than is usual
and the ?ltrate is distilled under reduced pressure to give
ly obtained when sulfuric acid is employed.
'y-valerolactone in 88% of the theoretical yield (B.P. 60 These results should be contrasted with the experience
205° (760 mm.), D. 1.074). In a similar fashion, methyl of Loev and Massengale (J. Org. Chem. 22, 988 (1957)),
4-methylpentenoate gives 'y-methyL'y-valerolactone and who reported their inability to alkylate aromatic hydro
methyl acetate in 93% yield. carbons when employing the prior art sulfonic acid type
Similarly: 4-pentenoic acid (100 parts) and Catalyst A cation exchange resins as catalysts.
(3 parts) are heated at 100° C. for 4 hours. The reac 65
ALKYLATION OF PHENOLS
tion may be followed either by determination of the re
fractive index at intervals or by titration of an aliquot for A direct comparison of the reactivity of a macro
unreacted carboxylic acid. When conversion of the reticular sulfonic cation exchange resin in the dehy
carboxylic acid is nearly complete, the product is decanted drated acid form with the dehydrated acid form of a sul
from the catalyst and distilled under reduced pressure to 70 fonic cation exchange resin in the alkylation of phenol
give 'y-valerolactone in nearly quantitative yield, when with diisobutylene has been carried out according to the
corrected for that material which remains in contact with methods described by Loev and Massengale (J. Org.
the catalyst. Chem. 22, (1957)). Parallel experiments were carried,
Undecylenic acid (18.4 parts) and Catalyst C (2 parts) out as follows:
are heated at 140°. At intervals, samples of material are 75 Phenol (94 parts), diisobutylene (124 parts), and the
 3,037,052
19 20
dehydrated acid form of the sulfonic cation exchange ratios using Catalyst A, propylene trimer and phenol:
resin catalyst (0.75 part) were placed in a dry SOO-ml.
3-necked ?ask and heated at 70° to 75° under an atmos Mole Ratio Temp. Time Cut C Cut E
phere of dry nitrogen. The catalyst was removed by ?lter Range (Hours) (Parts) (Parts)
ing the hot reaction mixture and the p-tert-octylphenol
(B.P. 140° to 180°/20 mm.) was distilled from the re 70-75 2 71 55
110-115 2 70 50
action mixture under reduced pressure. The results of 110-115 2 71 78
these comparative tests are set forth in Table II. 110~115 4 57 97
60-05 10 04 14
minutes
521 _________________________ __ 70-75 2. 5 42. 5 111
TABLE H 10
An experiment was conducted under the same reaction
Reaction Percent conditions except that a prior art sulfonic cation exchange
Catalyst 'l‘ime Yield 3
(Hours) resin was substituted for Catalyst A. Using a nonene to
15 phenol ratio of 5:1, and after heating at 70°-75° for 2
Resin B I- 1 7. 3 hours, the Cut C fraction of the reaction mixture was
Resin 15.- __________ __ 8 59
Resin B 4.-. ___ 8 53 80 parts and the Cut E fraction only 2.6 parts. A com
Catalyst A 2 _________________________________ __ 1 57 parison of these data with the preceding data for Cata—
lyst A clearly shows the unusually high catalytic effective
1 Resin B is the dehydrated acid form of a cation exchangercsin pre 20 ness of the sulfonic cation exchange resin which has a
pared by sulfonating a styrenedivinylbenzene copolymcr containing 4.5% macro-reticular structure.
divinylbenzene (Amberlite IR-1l2, Rohm & Haas Company, Philadel
phlu, Pennsylvania). Similarly: A mixture of phenol (18.8 parts), ether (20
1‘ Catalyst A-See Table I. parts by volume), and Catalyst A (2 parts) are mixed in
3 “Yield” as used herein is de?ned as
a pressure vessel. The pressure vessel is cooled to --10°
moles of p-tert-oetylphenol
moles of phenol originally charged X 100 25 C. and isobutylene (22.4 parts) is added as a liquid. The
pressure vessel is closed and is agitated for 3 hours. Con
4 These data are the data reported by Loev and Massengale.
siderable heat is evolved as the mixture warms and the re
action is essentially complete after 3 hours. The pres
The data set forth in Table II clearly show the marked sure vessel is cooled and vented, and the reaction mixture
superiority of the macro-reticular structured sulfonic ca 30 is ?ltered. The ?ltrate is stripped of solvent and distilled
tion exchanger over a typical sulfonic cation exchanger under reduced pressure to get p-tert-butylphenol (18.9
of the prior art. It is ‘at least eight times as active as a parts, 63% conversion, B.P. 160°—167° (75 mm.)) and
catalyst for the addition of diisobutylene to phenol. These recovered phenol, 5.8 parts, 31%. Thus, the yield of p
data (since they are single runs) do not show the superior tert-butylphenol based on phenol consumed was 93% of
resistance of the macro-reticular structured resin to physi 35 the theoretical.
cal and chemical degradation. Catalyst A contains 20%
divinylbenzene and thus is a very highly cross~linked resin. POLYMERIZATION OF OLEFINS
Such highly cross-linked macro-reticular structured resins The sulfonic acid cation exchange resins described here
exhibit excellent resistance to physical and chemical degra inbefore also function very elfectively as catalysts for
dation, which, as hereinbefore set fourth, is a very real 40 the polymerization of ole?ns. The following experiment
economic advantage lbecause of the much longer life of sets forth the details of such a reaction:
the catalyst on repeated re-use. A mixture of isobutylene (11.2 parts) and Catalyst A
Another property of the macro-reticular structured sul (2 parts) are weighed into a pressure lbottle at —20°.
fonic cation exchange resins is the high selectivity ex The pressure vessel is closed and allowed to warm to
hibited when used as catalysts for the alkylation of phenols 45 room temperature slowly. After 15 minutes at room tem
with octenes and nonenes. At about a 1:1 ratio of ole?n perature, the reaction vessel becomes warm and after 25
to phenol, only a negligible amount of the di-substituted minutes is hot. The reaction is complete and the mixture
phenol is obtained. Surprisingly, however, if a large ex returns to room temperature within 45 minutes. The
cess of ole?n is used (from about 2 to about 5 moles reactor is opened and vented. A loss of only 0.5 part by
ole?n per mole of phenol), excellent yields of the di 50 weight shows that more than 95% of the isobutylene
substituted phenol are obtained. A typical experiment which has been charged has been converted to polymers.
employing a 5:1 molar ratio of nonene to phenol in The products are di-, tri-, and tetraisobutylenes in weight
which the di-substituted phenol constitute more than 75% ratios of 1:2:1. No product boiling higher than tetra
of the phenolic product is as follows: isobutylene is present. The presence of small amounts of
Phenol (47 parts) and Catalyst A (17.3 parts) are 55 acetic acid or of tertiary butyl acetate increases the rate
charged to a reactor and warmed to 40°. Propylene of polymerization beyond that shown here.
trimer (292 parts) is added slowly whereupon the reac Similarly, a mixture of nonenes (tripropylene, B.P.
tion temperature rises to 60°, then falls to 53° as the 134°-137° (760 mm.) and Catalyst A (5 parts) is heated
addition is completed. In the course of 30 minutes, the at 130° for 8 hours. The refractive index rises from 111325
reaction mixture temperature is raised to 70° and then 60 1.4200 to HD25 1.4400 at the end of this period; three
the mixture is heated for 2 hours at 70° to 75°. The re quarters of this change occurs during the ?rst two hours.
action mixture is ?ltered while hot and the ?ltrate is dis The mixture is cooled and ?ltered, and the ?ltrate is dis
tilled at 15 mm. to give Cut A to 50° (131 parts); Cut tilled to give recovered nonenes (37.5 parts), an inter
B to 145° (7 parts); Cut C to 195° (42.5 parts); Cut D mediate cut, B.P. 7l°—145° (20 mm.), 7.5 parts, the
to 195°-210° (14 parts); Cut E to 210°—225° (11 parts); 65 product cut, B.P. 145°~l76° (20 mm), 53 parts, nD25
residue 7 parts. Cut C is a mixture of mono-nonylphenol 1.4523, and residue (6 parts).
(22 parts) and nonene dimer (20.5 parts). Cut D and When this run is repeated using a 16-hour reaction
Cut E together contain 120 parts of dinonylphenol and period and acetic acid (5 parts) as an adjuvant, the prod
5 parts of mono-nonylphenol. Thus, 98% of the phenol uct, B.P. 140°~180° (20 mm.), 57 parts is obtained.
charged is accounted for as either nonyl- or dinonylphenol 70 When the reaction is repeated with a l2-hour reaction
period and with sulfolane (5 parts) as an adjuvant, 51
and the ratio of di- to monoalkylphenol is approximately parts of product, B.P. 145°—l77° (20 mm.), is obtained.
4:1. When Catalyst A was replaced by an equal weight of a
The following table shows the data on experiments dehydrated sulfonic acid cation exchanger of the prior
conducted at different temperatures and di?erent mole 75 art, prepared by the sulfonation of a divinylbenzene
 3,037,052
21 22
(4.5 %)-cross-linked polystyrene, no change whatsoever period. After 1 hour, water (8 parts) is separated, and
occurred in the initial refractive index, nD25 1.4200, after the pot temperature has risen from 74° to 95° during this
boiling at 135° for 72 hours. After this time, the reaction period. 2-ethylhex-2~enal, B.P. 175 ° to 180° (760 mm.),
mixture was ?ltered and the ?ltrate was distilled to give nDZ6 1.4485 is obtained in 63% conversion and 85% yield.
recovered starting material, B.P. 134°~137°, nD25 1.4200, The ratio of product to residue is 5.9.
117 parts, and a residue, 3 parts, 111325 1.4200. Thus, not When the dehydrated acid form of a conventional prior
a trace of dinonene was obtained under these conditions. art sulfonic acid resin prepared by sulfonating a cross~
A mixture of diisobutylene (112 parts) and Catalyst A linked copolymer of styrene and divinylbenzene (4.5%
(5 parts) is stirred together. A mildly exothermic reac divinylbenzene) was substituted for Catalyst A, the time
tion occurs. Heat is then applied and the mixture begins required rose to 2.3 hours. The conversion dropped to
to boil at a pot temperature of 103°. Within several 35%, and the yield dropped to 60%. The product to
minutes, the pot temperature rises to 130°, which con residue ratio» dropped to 1.9. Thus, not only does the
dition is maintained for 3 hours. The index of refraction use of the conventional catalyst require more than double
rises from an initial value of nD25 1.4081 to a value of the time which was required by the macro-reticular ion
H1325 1.4563 after 1.5 hours. After an additional 1.5 15 exchange resin catalyzed process, but also the convention
hours, the index of refraction advances only to n1325 al catalyst gave a much less ‘favorable product to residue
1.4372. The mixture is cooled and ?ltered and the filtrate ratio. Thus, it appears that the primary product of con
is distilled. Triisobutylene (40 parts), tetraisobutylene densation ?nds it difficult to diffuse away from the sul
(50 parts) and unchanged diisobutylene are isolated. The fonic acid reaction site in the conventional resin catalyst; ,
‘formation of triisobutylene in large quantities demon 20 hence, further self-condensation occurs with consequent
strates that reversion of these polymers to the monomer, destruction of the product. When the macro-reticular
catalysts are employed, diffusion of the product of the
isobutylene, must occur; it is possible that part of the loss
in weight (7 parts) which is observed is due to the failurecondensation from the reaction site can easily occur and
to collect any gaseous products which are not condensed relatively little destruction of the product occurs due to
by the cold water condenser. 25 self-condensation.
This experiment is repeated using only 1 part of ACYLATION OF‘ OLEFINS
Catalyst A. Heating is discontinued as soon as the tem— A mixture of diisobutylene (224 parts), acetic anhy
perature in the pot reaches 130°. This requires three dride (224 parts), and Catalyst A (10 parts) is stirred
hours. Upon distillation, the products are ‘found to be at room temperature for ‘5 hours, then allowed to stand
triisobutylene (27 parts) and tetraisobutylene (42 parts) 30 overnight. Within twenty minutes, the initial two-phase
as well as unchanged diisobutylene (37 parts). A loss of liquid mixture consolidates to a single phase. At this
6 parts may in part be due to monomer escape. The point, the refractive index is nD25 1.3983 and an 0.4 ml.
alteration of tri- to tetraisobutylene ratio from 1.5 to 1.25 aliquot requires 30.8 ml. of 0.1 N sodium hydroxide solu
on heating for an additional period suggests that, in part, tion vfor neutralization to a phenolphthalein end-point.
tri- is formed at the expense of tetraisobutylene. 35 After remaining overnight at room temperature, the re
A mixture of propylene tetramer (168 parts) and fractive index has risen to nDZ5 1.4038 and an 0.4 ml.
Catalyst A (5 parts) are heated at 130° with stirring. aliquot requires 29.1 ml. of 0.1 N sodium hydroxide solu
After 8 hours of heating, the refractive index of the mix tion for neutralization. The mixture is then warmed to
ture rises from nD25 1.4348 to nD25 1.4400. The mixture 50° for 1 hour and to 60° ‘for 21 hours. At this point,
_is ?ltered and distilled under reduced pressure to give out the refractive index is 111325 1.4091 and the titration value
1, B.P. 80° to 100° (25 mm.), 85 parts, cut 2, B.P. 100° is 27.5 ml. The resin is separated by ?ltration and the
to 180° (20 mm.), 26 parts, and cut 3, didodecene, B.P. ?ltrate is distilled at atmospheric pressure to remove un
180° to 216° (20 mm.), 42 parts, 25% conversion. changed diisobutylene, acetic acid, and acetic anhydride.
KETONE CONDENSATION That material which boils above 145° (760 mm.) is dis
A mixture of methyl hexyl ketone (256 parts) and 45 tilled at 50 mm. to give the product, B.P. 110° to 112°
Catalyst A (10 parts) is boiled under re?ux in an ap (50 mm.), 85 parts. The product is 3,5,5-trimethylhept
paratus ?tted with a Dean-Stark water separator. The 3-en-2-one, a compound which has been prepared previ
pot temperature rises from 145° to 163° in 50 minutes, ously by homogeneous catalysis but never before been
at which point water, 9 parts, has separated. This cor formed using ion exchange catalysis.
responds to 50% of the theoretical amount. The mixture 50 ACYLATION OF AROMATICS
is ?ltered and distilled to give 7-methylpentadec-7-en-9 A mixture of anisole (54 parts), acetic anhydride (51
one, B.P. 120° to 130° (2.0 mm.), and is obtained in parts), ‘and Catalyst A (5 parts) is heated for 8 hours at
yield of 76% based on methyl hexyl ketone consumed. 130° to 140°. The mixture ‘re?uxes at 140°. The cata
The ratio of product to residue is 3.2. The residue is al lyst is separated by ?ltration, and the ?ltrate is distilled
most entirely a C24 isophorone mixture, B.P. 200° 55 to give p-methoxyacetophenone, B.P. 142° to 146° (20
(1 mm.). mm.), 111325 1.5519, 27.5 parts, which crystallized on cool
When this reaction was repeated, but using a con ing. The analytical data and infrared spectrum are in
ventional cation exchange resin of the prior art in the accordance with the structure of p-methoxyacetophenone
acid form (30 parts) in place of Catalyst A, water (6.9 for this reaction product. The yield was 37% based on
parts) was separated during 20.5 hours under re?ux (pot 60 the anisole charged. Examination of the infrared spec
temperature 172° to 182.5°). Thus, the rate of the reac trum of the residue showed that the primary side reaction
tion using a macro-reticular ion exchange resin catalyst is in this process leads to formation of tris-(p-methoxy
at least 50 times that of the conventional resin. phenyl)benzene. ‘It has been shown to be primarily the
A mixture of cyclohexanone (100 parts) and Catalyst
A (1 part) is boiled under reflux for 20 minutes. Dur 65 1,3,5-trisubstituted derivative contaminated with some of
ing this time the pot temperature rises from 130° to 158° the 1,2,4-product.
and water (4.2 parts) separates. The reaction mixture When acetic anhydride (51 parts) is refluxed with
is cooled and ?ltered, and the ?ltrate is distilled under xylene (53 parts) for 12 hours at 127°, the product, B.P.
reduced pressure to give 2-cyclohexenylcyclohexanone, 125° to 130° (10 mm.) 11,325 1.5210 is dimethylaceto
B.P. 100° to 105° (1.4 mm.), 33 parts, 111325 1.5035. The 70 phenone. The infrared spectrum is fully consistent with
product to residue ratio is 4.7 which corresponds to 82% this formula for the reaction product. Again, a high
yield based on ketone utilized. -
boiling residue remained which was shown to contain tris
A mixture of n-butyraldehyde (100 parts) and Catalyst (dimethylphenyl)benzene.
A (1 part) are boiled under re?ux using a Dean-Stark trap To phenol (47 parts) and Catalyst A (5 parts) heated
to enable water to be separated in the course of the re?ux 75 at 110° is added acetic anhydride (51 parts) dropwise.
 3,037,052
24.
Addition is completed in 35 minutes and no exotherrn is from about —20° C. to about 50° C. (1) an ole?n con
noted during the entire addition. Five minutes after the taining four to eight carbon atoms of the structure
addition of anhydride is complete, all trace of anhydride R
has disappeared from the infrared spectrum of the re
action mixture. The reaction mixture is held at 130°
for 8 hours and is then boiled under re?ux for an addi
tional 8 hours; the temperature drops in the interim from in which R1 and R2 are alkyl groups of 1 to 2 carbon
145° to 136°. The catalyst is removed by ?ltration, and atoms and R3 is ——Cn_1H2n_1 in which n is an integer
the ?ltrate is distilled under reduced pressure. The major from 1 to 3 and (2) HCOOH in the presence of a dehy
product recovered is phenyl acetate, B.P. 92° to 98° (19 10 drated sulfonic acid cation exchange resin which pos
mm.), 34 parts, 111,26 1.5178. From the residue is ob sesses a macro-reticular structure, removing the cation
tained a fraction, B.P. 135° to 153° (1.5 mm.), 4.5 parts, exchange resin from the reaction mixture, and recovering
111326 1.5553. This cut solidi?es and the crystalline solid is the ester so formed.
separated by ?ltration. The solid has a M.P. 104° to 2. A process for the preparation of esters in non
105 ° and on recrystallization is shown to be identical with 15 aqueous media which comprises reacting at a temperature
p-hydroxyacetophenone both by infrared spectrum and from about —20° C. to about 50° C. (1) an ole?n con
melting point. Some ortho—hydroxyacetophenone is pres taining four to eight carbon atoms of the structure
ent in the phenyl acetate cut. R1
DECOMPOSITION OF CUMENE HYDROPEROXIDE TO 20
PHENOL AND ACETONE
R2
A mixture of acetone (25 parts) and Catalyst A (2 in which R1 and R2 are alkyl groups of 1 to 2 carbon
parts) are heated to re?ux and a 70% cumene hydro atoms and R3 is ——-Cn_1H2n_1 in which n is an integer
peroxide solution in cumene (44 pans) is added dropwise from 1 to 3 and (2) HOOC-COOH in the presence of a
under re?ux. The addition requires 3.5 hours. Scans 25 dehydrated sulfonic acid cation exchange resin which
of the infrared spectrum from time to time in the course possesses a macro-reticular structure, removing the cation
of the addition show that the hydroperoxide peak at 12.0 exchange resin from the reaction mixture, and recovering
microns is absent. This implies that the conversion of the ester so formed.
the hydroperoxide to phenol and acetone takes place as 3. A process for the preparation of esters in non
rapidly as the addition is carried out. The catalyst is 30 aqueous media which comprises reacting at a temperature
separated by ?ltration and the reaction mixture is distilled of from about —20° C. to about 50° C. (1) an ole?n
to give acetone, cumene, 11.5 parts, and phenol, ‘13.5 containing four to eight carbon atoms of the structure
parts, B.P. 180° to 184°. The yield of phenol was 17.6 R1
parts, 93% based on cumene hydroperoxide initially
present.
This simple acetone rellux procedure to give a 93% R2
yield of phenol based on cumene hydroperoxide is to be in which R1 and R2 are alkyl groups of 1 to 2 carbon
compared with the prior art. In the ?rst of the two atoms and R3 is —Cn_1H2n_1 in which n is an integer
examples of the prior art, a 200 ml. sample of cumene 40 from 1 to 3 and (2) carboxylic acid of the formula
solution containing 30 grams of cumene hydroperoxide R4(COOH)Z where R; is a hydrocarbon radical and Z
was heated with 20 parts of Zeo-Karb-H (a sulfonic acid is an integer from 1 to 2 in the presence of a dehydrated
type cation exchanger prepared by the sulfonation of sulfonic acid cation exchange resin which possesses a
coal) at 90° for one hour. A 56.8% yield of phenol was macro-reticular structure, removing the cation exchange
obtained. In the second example of the prior art, 200 resin from the reaction mixture, and recovering the ester
ml. of the solution containing 31 grams of cumene hydro so formed.
peroxide in cumene was passed through a column charged 4. A process for the preparation of esters in non
with sulfonated coal. The column was heated externally aqueous media which comprises reacting at a tempera
at 95° to 100°, and the residence time of the mixture ture of from about —20° C. to about 50° C. (1) an ole?n
of the column was 2 hours. Fifty-one percent of the 50 containing four to eight carbon atoms of the structure
peroxide in the solution was converted into phenol. It
is apparent that the process in hand is very much superior
to that of the prior art.
VON PE‘CHMANN REACTION 55 in which R1 and R2 are alltyl groups of 1 to 2 carbon
atoms and R3 is —Cn_1H2n_1 in which n is an integer
Resorcinol (11 parts), ethyl acetoacetate (13 parts), from 1 to 3 and (2) carboxylic acid of the formula
Catalyst A (2 parts), and iso-octane (20 parts by volume) CHFC~—COOH
are boiled in a reactor ?tted with a fractionating column.
Ethanol and water are removed by distillation during 60 H( H2)n—l
the course of a 7-hour reaction period. The pot tempera in which n is an integer from 1 to 3 in the presence of a
ture rises from 74° to 115° during this period. A total dehydrated sulfonic acid cation exchange resin which
of 6 parts by volume is removed. The product crystal possesses a macro-reticular structure, removing the cation
lizes and is recrystallized from boiling alcohol. There is exchange resin from the reaction mixture, and recovering
65 the ester so formed.
formed 4—methyl—7-hydroxycoumarin, 12 parts, M.P. 179°
5. A process for the preparation of esters in non
to 180°. The prior art describes the use of 50 mole per aqueous media which comprises reacting at a tempera
cent of catalyst, powdere/d Amberlite IR-12OH, a conven ture of from about -20° C. to about 50° C. (1) an
tional prior art sulfonic acid cation exchange resin con ole?n containing four to eight carbon atoms of the
taining 8.5% divinylbenzene (available from Rohm & 70 structure
Haas Company, Philadelphia, Pa.) to carry out the same
and analogous reactions.
I claim:
1. A process for the preparation of esters in non
aqueous media which comprises reacting at a temperature 75 in which R5 and R6 taken collectively represent a four
 3,037,052
25 . 26 v

to ?ve-membered aliphatic ‘chain and R3 is -—Cn_1H2n_1
in which n is an integer from 1 to 3 and (2) HCOOH in
the presence of a dehydrated sulfonic acid cation ex
change resin which possesses a macro-reticular structure,
removing the cation exchange resin from the reaction
mixture, and recovering the ester so formed.
6. A process for the preparation of esters in non
aqueous media which comprises reacting at a temperature
of from about —20° C. to about 50° C. (1) an ole?n
containing four to eight carbon atoms of the structure 10
R
a dehydrated sulfonic acid cation exchange resin which
possesses a macro-reticular structure, removing the cation
exchange resin from the reaction mixture, and recovering
the ester so formed.
10. A process for the preparation of esters in non
aqueous media which comprises reacting at a tempera
ture of from about —20° C. to about 50° C. (1) an
ole?n containing four to eight carbon atoms of the struc
ture
R1

in which R»; and R8 taken collectively represent a three

in which R5 and R6 taken collectively represent a four 15 to four-membered aliphatic chain and R2 is an alkyl of
to ?ve-membered aliphatic chain and R3 is —Cn_1H2n_1 l to 2 carbon atoms and (2) HOOC——COOH in the pres
in which n is an integer from 1 to 3 and (2) HOOC- ence of a dehydrated sulfonic acid cation exchange resin
COOH in the presence of a dehydrated sulfonic acid cat which possesses a macro-reticular structure, removing the
ion exchange resin which possesses a macro-reticular cation exchange resin from the reaction mixture, and re
structure, removing the cation exchange resin from the covering the ester so formed.
reaction mixture, and recovering the ester so formed. 11. A process for the preparation of esters in non
7. A process for the preparation of esters in non aqueous media which comprises reacting at a temperature
aqueous media which comprises reacting at a tempera of from about —20° ‘C. to about 50° C. (1) an ole?n
ture of from about —20° C. to about 50° C. (1) an containing tour to eight carbon atoms of the structure
ole?n containing four to eight carbon atoms of the struc 25
ture
R1
C=CHR3 in which R7 and R8 taken collectively represent a three
R2 30 to four-membered aliphatic chain and R2 is an alkyl of
in which R5 and R6 taken collectively represent a four l to 2 carbon atoms and (2) vcarboxylic acid of the for
to ?ve-membered aliphatic chain and R3 is —Cn_1H2n_1 mula ‘

in which n is an integer from 1 to 3 and (2) carboxylic ngcoorr)Z

acid of the formula where R4, is a hydrocarbon radical and Z is an integer
from 1 to 2 in the presence of a dehydrated sulfonic acid
cation exchange resin which possesses a macro-reticular
where R4 is a hydrocarbon radical and Z is an integer structure, removing the cation exchange resin from the
from 1 to 2 in the presence of a dehydrated sulfonic acid reaction mixture, and recovering the ester so formed.
'cation exchange resin which possesses a macro-reticular 12. A process for the preparation of esters in non
structure, removing the cation exchange resin from the »aqueous media which comprises reacting at a temperature
reaction mixture, and recovering the ester so formed. of from about —20° C. to about 50° C. ( 1) an ole?n con
8. A process for the peparation of esters in non taining four to eight carbon atoms of the structure
aqueous media which comprises reacting at a tempera
ture of from about —20° C. to about 50° C. (1) an 45
ole?n containing four to eight carbon atoms of the struc
ture
R in which R; and R8 taken collectively represent a three
to fouremembered aliphatic chain and R2 is an alkyl of 1
to 2 carbon atoms and (2) carboxylic acid of the formula
0112:0-0 0 OH
in which R5 and R6 taken collectively represent a four
to ?ve-membered aliphatic chain and R3 is -Cn_1H2n_1 mom»,
in which n is an integer from 1 to 3 and (2) 'carboxylic in which n is an integer from 1 to 3 in the presence of a
acid of the formula 55 dehydrated sulfonic acid cation exchange resin which
CHFC-OOOH possesses a macro-reticular structure, removing the cation
exchange resin from the reaction mixture, and recovering
HJZ‘HZ) u-l the ester so formed.
in which n is an integer from 1 to 3 in the presence of a 13. A process for the preparation of tertiary butyl
dehydrated sulfonic acid cation exchange resin which pos acetate in non-aqueous media which comprises reacting
sesses a macro-reticular structure, removing the cation at a temperature of from about —20° C. to about 50° C.
exchange resin from the reaction mixture, and recovering (1) isobutylene and (2) acetic acid in the presence of a
the ester so formed. dehydrated sulfonic acid cation exchange resin which
9. A process for the preparation of esters in non possesses a macro-reticular structure, removing the cation
aqueous media which comprises reacting at a tempera 65 exchange resin from the reaction mixture, and recovering
ture of from about —20° C. to about 50° C. (1) an the tertiary butyl acetate so formed.
ole?n containing four to eight carbon atoms of the struc 14. A process for the preparation of tertiary butyl
ture acrylate in non~aqueous media which comprises reacting
at a temperature of from about —20° C. to about 50° C.
R’\ 0:01am 70 (1) isobutylene and (2) acrylic acid in the presence of a
dehydrated sulfonic acid cation exchange resin which
R2 possesses a macro-reticular structure, removing the cation
in which R, and R8 taken collectively represent a three exchange resin from the reaction mixture, and recovering
to four-membered aliphatic chain and R2 is an alkyl of the tertiary butyl Xacrylate so formed.
1 to 2 carbon atoms and (2) HCOOH in the presence of 75 15. A process for the preparation of tertiary butyl meth
 3,037,052
27
acrylate in non-aqueous media which comprises reacting
at a temperature of from about —20° C. to about 50° C.
(1) isobutylene and (2) methacrylic acid in the presence
of a dehydrated sulfonic ‘acid cation exchange resin which
possesses a macro-reticular structure, removing the cation
exchange resin from the reaction mixture, and recovering
the tertiary butyl methacrylate so formed.
16. A process for the preparation of tertiary butyl
itaconate in non-aqueous media which comprises reacting
at ya temperature of from about —20° C. to about 50° C.
(1) isobutylene and (2) itaconic acid in the presence of
a dehydrated sulfonic acid cation exchange resin which
possesses a macro-reticular structure, removing the cation
exchange resin from the reaction mixture, and recovering
the tertiary butyl itaconate so formed.
17. A process for the preparation of —alkyl phenols in
non-aqueous media which comprising reacting (1) an
ole?n ‘and (2) a phenol in the presence of ‘a dehydrated
sulfonic 'acid type cation exchange resin which possesses
a macro-reticular structure, removing the cation exchange
resin from the reaction mixture, ‘and recovering the alkyl
phenol so formed.
18. A method for catalyzing reactions which are con
ducted in non-aqueous media and which ‘are catalyzed by
‘acids which comprises contacting a mixture of the reac 25 fonic acid type cation exchange resin which possesses a
tants with the dehydrated acid form of a sulfonic acid
cation exchange ‘resin which possesses a macro-reticular
structure.
19. A method for catalyzing reactions which are con
ducted in non-aqueous media and which are catalyzed by 30
acids which comprises contacting a mixture of the reac
tants with the dehydrated acid form of a sulfonic acid
cation exchange resin which possesses a macro-reticular
structure, separating the cation exchange resin from the
reaction mixture, and recovering the product so formed. 35
20. A process for the preparation of esters of car
boxylic acids in non-aqueous media which comprises re
acting ;an ole?n having ‘a carbon content of from 2 to 25
carbon atoms with a carboxylic acid in the presence of
the ‘acid form of ‘a dehydrated sulfonic acid cation ex 40
change resin which possesses a macro-reticular structure.
21. A process for the preparation of secondary esters
in non-aqueous media which comprises reacting an ole?n
having a carbon atom content of from 3 to 25 carbon
atoms with a carboxylic acid in the presence of the acid 45
form of a dehydrated sulfonic acid cation exchange resin
which possesses a macro-reticular structure, removing said
cation exchange resin from the reaction mixture and re'
covering the ester so ‘formed.
28
22. A process as set forth in claim 21 in which the
ole?n is an a-ole?n.
23. A process for the preparation of primary esters
in non-aqueous media which comprises reacting a car
tboxylic acid with ethylene in the presence of the acid
form of a dehydrated sulfonic acid cation exchange resin
which possesses a ‘macro-reticular structure, removing
said cation exchange resin from the reaction mixture and
recovering the ester so formed.
10 24. A process for the polymerization of ole?ns in non
aqueous media which comprises reacting ole?ns and mix
tures of ole?ns in the presence ,of the acid form of a de
hydrated sulfonic acid type cation exchange resin which
possesses a macro-reticular structure.
15 25. A process for the alkylation of aromatic hydrocar
bons in non-aqueous media which comprises reacting an
aromatic hydrocarbon with an ole?n in the presence of
the acid form of a dehydrated sulfonic acid type cation
exchange resin which possesses a macro-reticular struc
ture.
26. A process for the decomposition of cumene hydro
peroxide in non-aqueous media to produce phenol and
acetone which comprises heating cumene hydroperoxide
in the presence of the acid form of a dehydrated sul
macro-reticular structure.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,018,065 Ipatie? ______________ __ Oct. 22, 1935
2,366,007 D’Alelio ____________ __ Dec. 26, 1944
2,415,000 Bearse et al ___________ __ Jan. 28, 1947
2,500,149 Boyer ______________ __ Mar. 14, 1950
2,527,522 Bond et al. __________ __ Oct. 31, 1950
2,534,304 Serniuk et a1. ________ __ Dec. 19, 1950
2,678,332 Cottle ______________ __ May 11, 1954
2,694,095 Medcalf et a1. ________ __ Nov, 9, 1954
2,761,877 Mosnier _____________ __ Sept. 4, 1956
2,789,143 Arnold et a1 ___________ __ Apr. 16, 1957
2,836,627 Neuworth et a1. ______ __ May 27, 1958
OTHER REFERENCES
Bodamer et 211.: “Industrial and Engineering Chem
istry,” vol. 43, pages 1082 to 1085, May 1951.
Calmon et al.: “Ion Exchangers in Organic and Bio
chemistry,” 1957, pages 658-687.