Process for the epoxidation of olefins using a group V metal co-catalyst I and a phenolic hydrocarbon co-catalyst II

A process for epoxidizing olefins with hydrogen peroxide in the presence of a catalyst composition comprising a Group V element containing Co-catalyst I, such as diphenylarsinic acid, and a phenol containing compound having a pK.sub.a of from about 5 to about 13 as Co-catalyst II such as p-chlorophenol is disclosed.

BACKGROUND OF THE INVENTION 
This invention relates to a process and catalyst composition for the 
epoxidation of olefins by hydrogen peroxide. 
The epoxides constitute a class of compounds of which the industrial 
importance is measured by the tonnages produced and by the diversity of 
their applications in the field of urethanes, glycols, surface-active 
agents, plasticizers and numerous other derivatives. 
While many specific methods for epoxidizing olefins are known, the most 
prominent of these methods can generally be divided into four basic types. 
For example, the oldest industrial technique for the epoxidation of double 
bonds is the process known as the chlorohydrin process. In the 
chlorohydrin process an olefin is reacted with chlorine in an alkaline 
medium. The yields (based on the chlorine) are unsatisfactory. This 
process also gives rise to the simultaneous formation of considerable 
quantities of chlorinated by-products, both inorganic and organic, which 
products are unsuitable for any known purpose. The disposal of these 
by-products involves problems of such magnitude that this process may 
eventually be abandoned. 
The second type of epoxidation method is generally limited to the 
epoxidation of ethylene. In accordance with this method ethylene is 
epoxidized with good yields in the vapor phase by means of molecular 
oxygen over a catalyst on a silver base. However, this technique is not 
very useful for the higher carbon olefins because of its lack of 
selectivity. 
A third and more recent type of epoxidation process is characterized by the 
use of organic hydroperoxides. In accordance with processes of this type 
an olefin is epoxidized catalytically in an organic medium containing an 
organic hydroperoxide oxidant. In addition to employing a relatively 
expensive organic hydroperoxide as an oxidant, it is also a characteristic 
disadvantage of these processes that the epoxide formation is accompanied 
by the formation in an equivalent or even greater amount of an alcohol 
derived from the organic hydroperoxide employed in the process. 
Consequently, the commercial viability of these processes is always 
influenced by the ability to economically dispose of the alcohol 
by-product in addition to the epoxide. 
Accordingly, new methods of access to the olefin oxides have been sought 
which are more direct, more selective, and especially are free from the 
problem of byproducts. 
This has led to the development of the fourth type of epoxidation process 
which is characterized by the use of hydrogen peroxide as the oxidant. 
Hydrogen peroxide is in principle a desirable reagent, for the very reason 
of its oxidizing non-polluting nature. However its reactivity towards 
olefins is weak or non-existent in the absence of an activating agent 
which enables a more active peroxy compound to be formed in-situ. 
Different processes of epoxidation have therefore been proposed using, for 
example, organic per-acids such as performic, peracetic or perpropionic 
acids (see, for example, Belgium Pat. No. 535,068). Nevertheless, because 
of the instability of the epoxides in acid medium, such processes are 
particularly difficult to put into practice. 
It has been proposed to use oxides, oxyacids, or peroxyacids derived from 
metals such as arsenic, antimony, bismuth, and tungsten (see for example 
U.S. Pat. No. 3,993,673, European Patent Application Publication Nos. 0 
008 496 and 0 009 262; and British Pat. No. 754,359). However, when such 
metal catalysts are employed in conjunction with aqueous hydrogen 
peroxide, the hydrogen peroxide is either rapidly decomposed or the rate 
of epoxidation is uneconomical. Thus, in an aqueous medium the addition of 
a metallic catalyst can be self-defeating. Consequently, for optimum 
performance when using these catalysts an important requirement of the 
system is that the hydrogen peroxide be anhydrous. However economic mass 
production of hydrogen peroxide has become possible owing to developments 
in the oxidation of secondary alcohols or quinone compounds. These routes 
to hydrogen peroxide synthesis as practiced commercially ultimately 
produce dilute aqueous solutions of hydrogen peroxide. Consequently, the 
cheapest commercially available hydrogen peroxide is generally sold as a 
35-40% by weight, aqueous solution thereof. If one has to remove the water 
from these solutions for use in anhydrous sytems, the effective cost of 
the hydrogen peroxide is increased substantially, thereby increasing the 
cost of any system requiring the use of anhydrous hydrogen peroxide. It 
would therefore be economically beneficial to develop a catalytic system 
which can operate in a medium containing sufficient water such that 
commercially available aqueous solutions of hydrogen peroxide could be 
used directly without concentration and/or purification. 
U.S. Pat. No. 3,778,451 discloses the epoxidation of olefins in an organic 
solvent medium containing hydrogen peroxide, transition metal compounds, 
i.e., those of molybdenum, tungsten, vanadium, niobium, tantalum, uranium 
or rhenium, and a nitrogenous organic base. The organic solvent employed 
includes alcohols, glycols, esters, linear or cyclic ethers, and certain 
weak carboxylic acids. However the hydrogen peroxide is employed in 
substantially anhydrous and concentrated form e.g. contains less than 10%, 
preferably less than 1% water to limit the production of undesirable 
hydroxylated by-products. 
British Pat. No. 1,399,639 discloses the use of a fluorinated ketone, e.g., 
hexafluoroacetone, or hydrate thereof as a catalyst which can be used in 
excess quantities to function also as a solvent, or hexafluoroisopropanol 
(HFIP) as the solvent. However, this patent does not disclose the use of 
the phenolic Co-catalyst II of the present invention nor does it disclose 
the use of any catalyst in conjunction with the specific Group V element 
containing co-catalysts disclosed herein. Moreover, a majority of reaction 
times disclosed therein range from about 4 to as high as 270 hours, 
generally between 5 and 18 hours. 
Similarly, it has been reported that the reaction product of 
hexafluoroacetone with concentrated hydrogen peroxide, i.e., 
2-hydroperoxy-hexafluoro-2-propanol, in combination with 30% to 90% 
H.sub.2 O.sub.2 (latter gives best results) provides for the catalytic 
epoxidation of alkenes (see R. P. Heggs, JACS, 2484-2486, 1979). Later, 
the same Journal reported on arsenated polystyrenes as catalysts for the 
epoxidation of olefins by aqueous hydrogen peroxide (Jacobson et al, JACS 
6946-6950, 1979). 
U.S. Pat. No. 4,024,165 discloses that the olefin epoxidation process with 
hydrogen peroxide can be carried out in a fluorinated alcoholic solvent in 
which all the reactants and catalysts are soluble by using as the catalyst 
composition a soluble transition metal compound (the disclosed transition 
metals being limited to molybdenum, tungsten, vanadium, niobium, tantalum, 
uranium, or rhenium) and a soluble nitrogen-containing compound. In this 
patent the hydrogen peroxide is present as an aqueous solution, usually 
50% by weight (see column 3, lines 19-27). However, the reaction times 
reported in this reference associated with yields of any significance of 
olefin oxide range from about 5 to about 8 hours. At reaction times below 
about 5 hours, the yield of olefin oxide drops substantially and in some 
instances no reaction at all takes place. Moreover, when either the 
transition metal compound or the nitrogen containing compound is 
eliminated from the catalyst composition, yields of olefin oxide also drop 
significantly. (Compare Examples 1 and 2 wherein Example 2, elimination of 
the nitrogen containing compound results in the undesirable polymerization 
of the olefin oxide; compare also Examples 21 and 24 wherein elimination 
of the transition metal compound in Example 24 drops the yield from 70 to 
35%). 
U.S. Pat. No. 4,257,948 discloses a process for epoxidizing acyclic, 
cyclic, or polycyclic olefins using hydrogen peroxide and a 
hexachloroacetone catalyst. This patent does not disclose the use of any 
transition metal catalysts or any other catalyst. 
U.S. Pat. No. 3,993,673 discloses a process for epoxidizing olefins in the 
presence of an arsenic catalyst essentially free of tungsten, molybdenum, 
vanadium and chromium, a hydrogen peroxide oxidant, and an inert organic 
solvent. Suitable organic solvents include ethers, esters, alcohols, 
glycols, chlorinated solvents including chlorinated hydrocarbons, and 
chlorinated aromatics (e.g., chlorobenzene, o-dichlorobenzene, chloroform, 
and 1,1,2,2-tetra chloro ethane). Although the "hydrogen peroxide can be 
used in aqueous solutions . . . it is preferred to use less water than 
more" (column 3, lines 43-47). Such chlorinated solvents are not disclosed 
in this reference to possess any catalytic activity, nor do any of the 
disclosed chlorinated materials include the phenolic co-catalysts of the 
present invention. 
European patent application Publication No. 0 008 496 discloses a polymer 
supported arsenic heterogeneous catalyst and a process for using the same 
to oxidize ketones, esters, and olefins in the presence of hydrogen 
peroxide. When dilute aqueous solutions of hydrogen peroxide are employed 
as the oxidant, a water immiscible solvent must be employed to avoid 
contact and hydrolysis of the oxidation products with water. In this 
embodiment, the substrate to be oxidized as well as the oxidation product 
are dissolved in the water immiscible solvent creating a two phase 
organic/aqueous system wherein the hydrogen peroxide is present in the 
aqueous phase. The polymer supported arsenic catalyst, functioning as a 
phase transfer catalyst, concentrates at the phase boundary whereat the 
arsono groups in the polymer are converted by contact with the hydrogen 
peroxide to perarsono, and this group on contacting the compound to be 
oxidized in the organic phase oxidizes it with regeneration of the arsono 
group. Thus, while suitable water immiscible solvents are disclosed as 
including chlorinated hydrocarbons, such as chloroform, these solvents are 
employed solely for their water immiscible property and not for any 
promoting effect on the arsenic catalyst. 
Other phase transfer catalytic systems are disclosed in U.S. Pat. No. 
3,992,432 and British Pat. No. 1,324,763. 
European patent application Publication No. 0 009 262 discloses the in-situ 
production of hydrogen peroxide and use of the resulting hydrogen peroxide 
directly in arsenic catalyzed epoxidation reactions of olefins. The 
in-situ production of hydrogen peroxide as well as the epoxidation 
reaction can be conducted in the presence of aliphatic or cycloaliphatic 
ethers, aliphatic esters, chlorinated alkanes, chlorinated arenes or 
sulfolane. None of the solvents disclosed include the phenolic 
Co-catalysts II of the present invention. 
British Patent Specification No. 1,452,730 discloses a process for 
epoxidizing olefins using acetic acid as the catalyst in the presence of 
aqueous hydrogen peroxide and an inert, chlorinated aliphatic hydrocarbon 
solvent such as chloroform. The solvent limits the hydrolysis of 
epoxidized products by the aqueous H.sub.2 O.sub.2 /acetic acid solution. 
Although, the exact mechanism by which this is achieved is not disclosed, 
it is known that the chlorinated hydrocarbon solvents are water 
immiscible. Consequently, it is believed that these solvents shield, to 
varying degrees, the epoxidized product from contact with the aqueous 
phase by solubilizing the epoxidized product therein. The phenolic 
Co-catalyst II of the present invention is not dependent on water 
immiscibility for its promoting effect, and in fact is generally water 
miscible due to the polar hydroxy group. 
Other patents which disclose acid catalysis include U.S. Pat. No. 3,248,404 
(discloses aliphatic and aromatic mono carboxylic acids and their 
halogenated derivatives as catalysts, e.g., acetic acid, chloroacetic 
acid, and benzoic acid in conjunction with a sequestering agent having 
acid complex forming properties); British Pat. No. 1,143,433 (discloses a 
carboxylic acid cation exchange resin as a catalyst); U.S. Pat. No. 
2,870,171 (discloses the use of a tungsten acid deposited on an inert 
support as catalyst); and British Patent Specification No. 754,359 
(discloses the use of inorganic peracids catalysts such as the peracids of 
tungsten, vanadium, and molybdenum as well as heteropoly acids such as the 
heteropolytungstic acids of arsenic, antimony or bismuth). 
British Pat. No. 1,302,441 is directed to a process for epoxidizing olefins 
using hydrogen peroxide and a two component catalyst composition 
comprising as a first component an organo tin compound having at least one 
hydroxyl group or coordination group which can be converted to a hydroxyl 
group in the presence of water or hydrogen peroxide, and as a second 
component, at least one compound containing at least one of molybdenum, 
tungsten, vanadium, selenium, and boron. Suitable solvents for the 
reaction include alcohols, e.g., straight chain alcohols, polyhydric 
alcohols, and cyclic alcohols, as well as epoxides, ketones, and 
furfurals. Halogenated solvents are not disclosed. While this patent does 
not require the use of anhydrous or substantially anhydrous hydrogen 
peroxide, it will be noted that when aqueous solutions of hydrogen 
peroxide are employed, the reaction times vary from 4 to 24 hours. For 
example, at 90% concentrations of H.sub.2 O.sub.2 in water (Examples 1, 2 
and 4-14) the average reaction time is about 13 hours. However at 70% 
H.sub.2 O.sub.2 in water (Examples 15-18) the reaction time is always 20 
hours. In contrast when no water is employed with the H.sub.2 O.sub.2 
(Examples 35-52) reaction times are measured in minutes (e.g. 60 to 360 
minutes). Thus, the activity of the catalyst composition of this patent is 
reduced substantially even at relatively high H.sub.2 O.sub.2 
concentrations in water. 
Further, it was reported in the Chemical and Engineering news issue of 
December 11, 1978 on page 24 that both Produits Chemique Ugine Kuhlmann 
and Union Carbide have each directly oxidized propylene with hydrogen 
peroxide using an arsenic catalyst. In the former process, hydrogen 
peroxide of a 70% concentration is employed and for the latter 90% 
concentration (the author notes that the latter catalyst is adversely 
affected by the presence of water), with no mention of whether any 
additional inert diluent or solvent is present. 
In summary, substantially all of the disclosures on the epoxidations of 
olefins to olefin epoxides, particularly propylene to propylene oxide, in 
which aqueous hydrogen peroxide is used directly in contact with the 
olefin in either the presence or absence of transition metal catalysts, 
have eluded commercial development due to one or more economic 
disadvantages. For example, the aqueous hydrogen peroxide used typically 
must be substantially above 30% in concentration, and/or the selectivity 
to propylene oxide is low, or the amount of time required for the reaction 
is too long. For these reasons, a practical route for direct epoxidation 
of olefins by aqueous hydrogen peroxide is a long-standing goal in 
oxidation chemistry. More specifically, it would be extremely economically 
advantageous to provide a process for epoxidizing olefins using extremely 
short reaction times while simultaneously achieving comparable or better 
yields obtainable with prior art techniques particularly, in a dilute 
aqueous system of H.sub.2 O.sub.2. Extremely short reaction times enable 
one to employ simpler plant designs by drastically reducing the size of 
the reaction vessel. Extremely short reaction times also permit one to 
employ simplified product separation techniques, such as conventional 
product flash-off procedures, wherein product is continually vaporized 
directly from the reaction medium, recovered and isolated. If the reaction 
time is too long, the amount of product vaporized at any given time would 
be too small to make this technique economically feasible. The ability to 
use dilute aqueous solutions of H.sub.2 O.sub.2 would further increase the 
flexibility and improve the economics of the process. 
Accordingly, there has been a continuing search for processes and catalyst 
compositions that permit the use of dilute aqueous H.sub.2 O.sub.2 
containing reaction mixtures, where it is advantageous to do so, and which 
substantially reduce the epoxidation reaction time without sacrificing 
olefin oxide yield to the point where the process becomes uneconomical. 
One response to this search is provided in commonly assigned U.S. patent 
application Ser. No. 387,341, filed June 11, 1982, of M. G. Romanelli, 
which is directed to a process for epoxidizing olefins with hydrogen 
peroxide in the presence of a catalyst composition comprising as a 
Co-catalyst I, at least one Group V element containing compound, said 
Group V element being selected from As, P, Sb, and Bi (e.g., phenyl 
arsonic acid), and as a Co-catalyst II at least one fluorinated compound 
containing an oxygenated functional group such as hexafluoroisopropanol. 
The scope of the fluorinated oxygenated compounds disclosed in this 
application, however, is limited to those compounds wherein the oxygenated 
functional group is located on a saturated aliphatic carbon and not an 
aromatic carbon. While the invention disclosed in this application 
represents a substantial improvement over the aforedescribed prior art 
vis-a-vis the rate and/or selectivity of the epoxidation reaction, 
particularly when employing the hydrogen peroxide as a commercially 
available dilute aqueous solution, there has been a further continuing 
search for alternative compounds which can perform the same function of 
these Co-catalyst II fluorinated oxygenated compounds but which are more 
readily available commercially at a substantially lower cost. The present 
invention was developed in response to this search also. 
SUMMARY OF THE INVENTION 
In one aspect of the present invention there is provided a process for 
reacting at least one olefinic compound having at least one ethylenic 
unsaturation with H.sub.2 O.sub.2, in the presence of a catalyst 
composition in a manner and under conditions sufficient to oxidize at 
least one of said ethylenically unsaturated groups to its corresponding 
epoxide group. The catalyst composition capable of catalyzing the 
epoxidation of olefins with H.sub.2 O.sub.2 comprises at least one 
Co-catalyst I and at least one Co-catalyst II. The composition of each 
Co-catalyst is described hereinafter in detail. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The present invention is directed to catalyst compositions and processes 
for using the same to epoxidize olefins with hydrogen peroxide. 
More specifically, the catalyst composition comprises at least one Group V 
element or Group V element-containing compound collectively referred to 
herein as Co-catalyst I and at least one phenolic, preferably halogenated 
phenolic, hydrocarbon compound referred to herein as Co-catalyst II. 
The Group V element of Co-catalyst I is selected from the group consisting 
of As, P, Sb, and Bi. Co-catalyst I comprises inorganic and organic 
derivative compounds of the Group V elements as well as the elements 
themselves. 
Co-catalyst I is believed to exert its catalytic effect by reacting with 
hydrogen peroxide in-situ to form a catalytic intermediate species having, 
under reaction conditions, an oxidation potential greater than the 
oxidation potential of hydrogen peroxide alone. The term oxidation 
potential as used herein is defined to be the potential of a substance to 
oxidize the ethylenic unsaturation of the olefinic compound to its 
corresponding epoxide. However, the aforedescribed intermediate species is 
believed to be in equilibrium with the H.sub.2 O.sub.2 and Co-catalyst I 
from which it is formed. Co-catalyst II, in some yet undetermined manner, 
is believed to facilitate the formation of this intermediate species even 
in the presence of water, by activating Co-catalyst I. This activated 
Co-catalyst I is believed to possess a greater propensity to react with 
the H.sub.2 O.sub.2 to form the intermediate species and therefore shifts 
the equilibrium reaction which forms said intermediate species in the 
forward direction. Consequently, the particular identity of the 
Co-catalyst I compound selected for use in the present invention is 
dictated and controlled by its possession of the capability of interacting 
with hydrogen peroxide to form said intermediate species under reaction 
conditions. Typical of such compounds which possess this capability are 
those which possess an oxy acid functionality or those which can form an 
oxy acid functionality in-situ. An oxy acid functionality possesses at 
least one oxo (i.e. o=) group and at least one hydroxy group attached to 
the aforedescribed Group V element such as 
##STR1## 
wherein M represents a Group V metal as described herein. In short, 
Co-catalyst I appears to catalyze the oxidation of the olefin by hydrogen 
peroxide through the formation of an intermediate, and Co-catalyst II 
appears to catalyze the formation of the intermediate. 
The following is a representative description of Co-catalyst I compounds 
which are believed to be capable of forming said intermediate with 
hydrogen peroxide although this description is not intended to be 
exhaustive. 
Accordingly, inorganic Co-catalyst I Group V element containing compounds 
include inorganic: oxides, acids such as oxy acids, oxy acid salts, 
halides, oxy halides, thio halides, sulfides, oxy sulfides and metalides. 
Representative inorganic oxides include As.sub.2 O.sub.3, As.sub.2 O.sub.5, 
P.sub.4 O.sub.6, P.sub.4 O.sub.8, P.sub.4 O.sub.9, P.sub.4 O.sub.10, 
Sb.sub.4 O.sub.6, Sb.sub.2 O.sub.4, Sb.sub.4 O.sub.6, SbO.sub.2, Bi.sub.2 
O.sub.3, 5Bi.sub.2 O.sub.3.3UO.sub.3, 2As.sub.2 O.sub.3.12H.sub.2 O and 
mixtures thereof. 
Representative inorganic oxy acids include H.sub.2 [HPO.sub.3 ], H.sub.3 
PO.sub.4, H.sub.4 P.sub.2 O.sub.7, H.sub.3 PO.sub.2, As(OH).sub.3, H.sub.3 
AsO.sub.4, Bi(OH).sub.3, and Sb.sub.2 O.sub.3.(H.sub.2 O).sub.n. 
Representative oxy acid salts include the alkali metal (e.g., Li, Na, K, 
Rb, Cs), alkaline earth metal (e.g., Be, Mg, Ca, Sr, Ba), ammonium and 
tetrahydrocarbyl ammonium, preferably tetra lower alkyl (e.g., C.sub.1 to 
C.sub.10 alkyl) ammonium, salts of the aforenoted oxy acids, including 
NaH.sub.2 PO.sub.4, Na.sub.2 HPO.sub.4, KH.sub.2 AsO.sub.4, K[Sb(OH).sub.6 
], NaBiO.sub.3, Na.sub.3 AsO.sub.4, tetra ethyl ammonium dihydrogen 
phosphate, tetra methyl ammonium dihydrogen arsenate, ammonium dihydrogen 
arsenate and mixtures thereof. 
Representative halides and oxy halides include those represented by the 
structural formulae PX.sub.3, P.sub.2 X.sub.4, X.sub.3 PO, X.sub.3 PS, 
X.sub.2 (O)--P--O--P--(O)--X.sub.2, P(H)a (X)b wherein X is at least one 
halide independently selected from the group consisting of Cl, F, Br, I, 
and a+b is 5, including such compounds as for example P.sub.2 Cl.sub.4, 
P.sub.2 I.sub.4, PHF.sub.4, PH.sub.2 F.sub.3, PH.sub.4 Cl, PCl.sub.3, 
PCl.sub.5, Cl.sub.3 PS, PF.sub.5 ; those represented by the structural 
formulae MX.sub.3 and MX.sub.5 where M is As, Sb or Bi, and X is at least 
one halide as defined above, including such compounds as for example: 
AsCl.sub.3, AsF.sub.3, BiCl.sub.3, SbF.sub.3, SbCl.sub.3, AsF.sub.5, 
SbF.sub.5, SbCl.sub.5, SbCl.sub.3 F.sub.2, SbCl.sub.2 F.sub.3, SbCl.sub.4 
F; those represented by the structural formula MOX wherein M and X are 
defined above including such compounds as for example: SbOCl, BiOCL, and 
AsOCl; KSb.sub.2 F.sub.7, and As.sub.2 I.sub.4. 
Representative thio halides include: SbSCl, AsSCl, BiSF, AsSCl.sub.3 and 
mixtures thereof. 
Representative sulfides and oxy sulfides include: As.sub.2 S.sub.3, 
As.sub.2 S.sub.5, BiOS.sub.2, Sb.sub.2 OS.sub.2 and mixtures thereof. 
Representative examples of suitable metalides include: As.sub.2 Zn.sub.3, 
5Bi.sub.2 O.sub.3.3VO.sub.3, 2As.sub.2 O.sub.3.12H.sub.2 O and mixtures 
thereof. 
The most preferred inorganic Co-catalyst I compounds are those containing 
As as the Group V element, most preferably the As oxides. 
Organic Co-catalyst I compounds include those represented by the structural 
formulae: R.sub.1 ZX'Y, R.sub.1 R.sub.2 ZX', and R.sub.1 R.sub.2 R.sub.3 
Z, wherein: Z is a Group V element in the plus 3 oxidation state selected 
from the group consisting of P, As, Sb, and Bi; R.sub.1, R.sub.2 and 
R.sub.3 which may be the same or different are selected from the group of 
hydrocarbyl radicals consisting of: alkyl, typically alkyl of from about 1 
to about 20, preferably from about 1 to about 10, and most preferably from 
about 1 to about 5 carbons; aryl, typically aryl of from about 6 to about 
14, preferably from about 6 to about 10, and most preferably 6 carbons; 
alkoxy, aryloxy, alkoxyaryl, aryloxyalkyl, aralkyl, alkylthio, arylthio, 
and alkaryl, wherein the alkyl and aryl groups thereof are as described 
immediately above in connection with alkyl and aryl respectively; 
cycloalkyl, typically cycloalkyl of from about 4 to about 20, preferably 
from about 5 to about 15, and most preferably from about 6 to about 10 
carbons; or any two of said R.sub.1, R.sub.2, and R.sub.3 groups together 
can constitute a cyclic hydrocarbon group having a carbon number as 
described for cycloalkyl immediately above; substituted: alkyl, aryl, 
cycloalkyl, alkoxy, aryloxy, alkoxyaryl, aryloxyalkyl, alkylthio, 
arylthio, alkaryl, or aralkyl, wherein said substituents are selected from 
the group consisting of: halogen (i.e., Cl, F, Br, I, most preferably F) 
and nitro, and mixtures thereof; and X' and Y which may be the same or 
different are selected from the group consisting of: hydrogen; halogen 
(i.e., Cl, F, Br, I), hydroxy, alkyl, aryl, alkaryl, and aralkyl, said 
groups being defined as above respectively in connection with R.sub.1 to 
R.sub.3 ; alkoxy wherein the alkyl group thereof is as defined above in 
connection with R.sub.1 to R.sub.3 ; acyloxy 
##STR2## 
mercapto (--SH), alkylthio (--SR.sub.5) and thioacyloxy 
##STR3## 
wherein R.sub.4, R.sub.5, and R.sub.6 are alkyl as defined in connection 
with R.sub.1 to R.sub.3. 
Representative examples of suitable compounds falling within the scope of 
the above structural formulae are provided below in chart form wherein 
each of the variable groups are associated in specific compounds. In the 
following exemplification, the inclusion of a substituent in parenthesis 
indicates it can be substituted on any position in the hydrocarbyl group 
to which it is attached. 
______________________________________ 
FORMULA: R.sub.1 ZX'Y 
R.sub.1 Z X' Y 
______________________________________ 
C.sub.5 H.sub.11 
As H H 
C.sub.6 H.sub.5 
As Cl Cl 
C.sub.5 H.sub.11 O 
As F F 
C.sub.6 H.sub.5 O 
P Br Br 
CH.sub.3.phi. 
P I I 
.phi.CH.sub.2O 
P OH OH 
(Cl)C.sub.5 H.sub.10 
Sb C.sub.5 H.sub.11 
C.sub.5 H.sub.11 
(F)C.sub.5 H.sub.10 
Sb C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
(Br)C.sub.5 H.sub.10 
Sb CH.sub.3.phi. 
CH.sub.3.phi. 
(I)C.sub.5 H.sub.10 
Bi C.sub.5 H.sub.11 O 
C.sub.5 H.sub.11 O 
(NO.sub.2)C.sub.5H.sub.10 
Bi 
##STR4## 
##STR5## 
(C.sub.3 H.sub.7 O)C.sub.5 H.sub.10 
Bi SH SH 
(C.sub.3 H.sub. 7 S)C.sub.5 H.sub.10 
As SC.sub.3 H.sub.7 
SC.sub.3 H.sub.7 
C.sub.6 H.sub.5 S 
P 
##STR6## 
##STR7## 
______________________________________ 
.phi. = Phenyl 
______________________________________ 
FORMULA: R.sub.1 R.sub.2 ZX' 
R.sub.1 R.sub.2 Z X' 
______________________________________ 
C.sub.5 H.sub.11 
C.sub.6 H.sub.5 
As H 
C.sub.6 H.sub.5 
C.sub.5 H.sub.11 O 
P Cl 
C.sub.5 H.sub.11 O 
C.sub.6 H.sub.5 O 
Bi F 
C.sub.6 H.sub.5 O 
C.sub.6 H.sub.5 O 
Sb Br 
CH.sub.3.phi. 
CH.sub.3.phi. As I 
.phi.CH.sub.2 O 
.phi.CH.sub.2 O 
P OH 
CH.sub.3.phi.O 
CH.sub.3.phi.O 
As OH 
(Cl)C.sub.5 H.sub.10 
(Cl)C.sub.5 H.sub.10 
Bi C.sub.5 H.sub.11 
(F)C.sub.5 H.sub.10 
(F)C.sub.5 H.sub.10 
Bi C.sub.6 H.sub.5 
(Br)C.sub.5 H.sub.10 
(Br)C.sub.5 H.sub.10 
Sb .phi.CH.sub.3 
(I)C.sub.5 H.sub.10 
(I)C.sub.5 H.sub.10 
As C.sub.5 H.sub.11 O 
(NO.sub.2)C.sub.5 H.sub.10 
(NO.sub.2)C.sub. 5 H.sub.10 
As 
##STR8## 
(C.sub.3 H.sub.7 O)C.sub.5 H.sub.10 
(C.sub.3 H.sub.7 O)C.sub.5 H.sub.10 
P SH 
(C.sub.3 H.sub.7 S)C.sub.5 H.sub.10 
(C.sub.3 H.sub.7 O)C.sub.5 H.sub.10 
P SC.sub.3 H.sub.7 
C.sub.6 H.sub.5 S 
C.sub.6 H.sub.5 S 
Bi 
##STR9## 
##STR10## * As OH 
C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
As Cl 
______________________________________ 
*R.sub.1 and R.sub.2 together constitute a cyclic hydrocarbon 
______________________________________ 
FORMULA: R.sub.1 R.sub.2 R.sub.3 Z 
R.sub.1 R.sub.2 R.sub.3 Z 
______________________________________ 
C.sub.5 H.sub.11 -- 
CH.sub.3 -- CH.sub.3 -- 
As 
C.sub.6 H.sub.5 -- 
C.sub.6 H.sub.5 -- 
C.sub.5 H.sub.11 
P 
C.sub.5 H.sub.11 O-- 
C.sub.5 H.sub.11 O-- 
C.sub.5 H.sub.11 O-- 
Bi 
C.sub.6 H.sub.5 O-- 
C.sub.6 H.sub.5 O-- 
C.sub.5 H.sub.11 O-- 
Sb 
CH.sub.3 --.phi.- 
CH.sub.3 --.phi.- 
C.sub.5 H.sub.11 -- 
Bi 
.phi.-CH.sub.2 -- 
.phi.-CH.sub.2 -- 
.phi.-CH.sub.2 -- 
P 
(Cl)C.sub.5 H.sub.10 -- 
(Cl)C.sub.5 H.sub.10 -- 
CH.sub.3 -- 
As 
(F)C.sub.5 H.sub.10 -- 
CH.sub.3 -- CH.sub.3 -- 
P 
(Br)C.sub.5 H.sub.10 
CH.sub.3 -- CH.sub.3 -- 
Bi 
(I)C.sub.5 H.sub.10 -- 
C.sub.6 H.sub.5 O-- 
CH.sub.3 -- 
Sb 
(NO.sub.2)C.sub.5 H.sub.10 -- 
CH.sub.3 -- CH.sub.3 -- 
Bi 
(C.sub.3 H.sub.7 O)C.sub.5 H.sub.10 -- 
C.sub.2 H.sub.5 -- 
C.sub.2 H.sub.5 O-- 
P 
(C.sub.3 H.sub.7 S)C.sub.5 H.sub.10 -- 
CH.sub.3 -- CH.sub.3 -- 
As 
C.sub.6 H.sub.5 S-- 
C.sub.2 H.sub.5 -- 
C.sub.2 H.sub.5 -- 
P 
C.sub.6 H.sub.5 -- 
C.sub.6 H.sub.5 -- 
C.sub.6 H.sub.5 -- 
As 
______________________________________ 
Another class of Group V element containing organic compounds are those in 
which the Group V element, represented by Z.sub.1 hereinbelow, is in the 
plus 5 oxidation state. Such compounds include those represented by the 
structural formulae R.sub.1 Z.sub.1 (O)X'Y, R.sub.1 R.sub.2 Z.sub.1 (O)X', 
and R.sub.1 R.sub.2 R.sub.3 Z.sub.1 (O) wherein R.sub.1, R.sub.2, R.sub.3, 
X' and Y are as defined above in connection with the aforenoted structural 
formulae wherein the Group V element is in the plus 3 oxidation state. 
The preferred Group V element containing organic Co-catalyst I compounds 
are those of the structural formulae R.sub.1 Z.sub.1 (O)X'Y wherein X' and 
Y are hydroxyl and R.sub.1 is a halogen substituted, preferably fluorine 
substituted for unsubstituted hydrocarbyl group selected from alkyl, aryl, 
aralkyl, alkoxyaryl, most preferably aryl, said hydrocarbyl groups being 
as defined in connection with R.sub.1 above; and R.sub.1 R.sub.2 Z.sub.1 
(O)X' wherein R.sub.2 is as described in connection with R.sub.1 
immediately above, and R.sub.1, Z, and X' also are as described 
immediately above. 
Also included within the scope of Co-catalyst I are polymers wherein the 
Group V element is located in a group pendant to the polymer backbone. A 
representative example of such a polymeric Co-catalyst I is illustrated by 
the structural formula: 
##STR11## 
wherein Z.sub.1 is as described above, A is independently selected from 
hydrogen and halogen, preferably fluorine, R.sub.1 is a hydrocarbyl group 
selected from alkyl, and aryl said hydrocarbyl groups being as defined in 
connection with R.sub.1 above, (a') is a number of 0 or 1, and n is a 
number which can vary from about 5 to 1000, preferably 5 to 500. 
Representative compounds falling within the scope of the above formulae for 
Co-catalyst I are described below wherein each of the variable groups are 
associated in specific compounds. 
______________________________________ 
FORMULA: R.sub.1 Z.sub.1 (O)X'Y 
R.sub.1 Z.sub.1 
X' Y 
______________________________________ 
C.sub.5 H.sub.11 
As H OH 
C.sub.6 H.sub.5 
As Cl OH 
C.sub.5 H.sub.11 O 
As F H 
C.sub.6 H.sub.5 O 
P Br Br 
CH.sub.3.phi.O P I OH 
CH.sub.3.phi. P OH OH 
(Cl)C.sub.5 H.sub.10 
Bi C.sub.5 H.sub.11 
C.sub.5 H.sub.11 
(F)C.sub.5 H.sub.10 
Bi C.sub.6 H.sub.5 
C.sub.5 H.sub.11 
(Br)C.sub.5 H.sub.10 
Bi .phi.CH.sub.2 
C.sub.2 H.sub.5 
(I)C.sub.5 H.sub.10 
Sb C.sub.5 H.sub.11 O 
C.sub.5 H.sub.11 O 
(NO.sub.2)C.sub.5 H.sub.10 
Sb 
##STR12## 
##STR13## 
(C.sub.3 H.sub.7 O)C.sub.5 H.sub.10 
Sb SH SH 
(C.sub.3 H.sub.7 S)C.sub.5 H.sub.10 
As SC.sub.3 H.sub.7 
SC.sub.3 H.sub.7 
C.sub.6 H.sub.5 S 
As 
##STR14## 
##STR15## 
CH.sub.3CH.sub.2.phi. 
As OH OH 
CF.sub.3CF.sub.2.phi. 
As OH OH 
CH.sub.3CH.sub.2C.sub.6 H.sub.3 F 
As OH OH 
CF.sub.3CF.sub.2C.sub.6 H.sub.2 F.sub.2 
As OH OH 
C.sub.6 H.sub.4 F 
As OH OH 
C.sub.6 H.sub.3 F.sub.2 
As OH OH 
(NO.sub.2)C.sub.6 H.sub.4 
As OH OH 
C.sub.6 H.sub.3 Cl.sub.2 
As OH OH 
CH.sub.3 OC.sub.6 H.sub.4 
As OH OH 
CH.sub.3(CH.sub.2).sub.2 
As OH OH 
CF.sub.3(CF.sub.2).sub.2 
As OH OH 
.phi.(CH.sub.2 ).sub.2 
As OH OH 
C.sub.6 H.sub.3 F.sub.2 
As OH OH 
C.sub.6 H.sub.4 F 
As OH OH 
C.sub.6 H.sub.5 
As OH OH 
C.sub.3 H.sub.7 
As OH OH 
C.sub.6 H.sub.5 
Sb OH OH 
______________________________________ 
FORMULA: R.sub.1 R.sub.2 Z.sub.1 (O)X' 
R.sub.1 R.sub.2 Z.sub.1 
X' 
______________________________________ 
C.sub.5 H.sub.11 
C.sub.5 H.sub.11 
As OH 
C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
As OH 
C.sub.5 H.sub.11 O 
C.sub.5 H.sub.11 O 
As Br 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 O 
P H 
CH.sub.3.phi. 
CH.sub.3.phi. P OH 
(Cl)C.sub.5 H.sub.10 
(Cl)C.sub.5 H.sub.10 
P OH 
C.sub.5 Cl.sub.11 
C.sub.5 Cl.sub.11 
Bi C.sub.5 H.sub.11 
C.sub.5 F.sub.11 
C.sub.5 F.sub.11 
Bi C.sub.5 H.sub.11 
(NO.sub.2)C.sub. 5 H.sub.10 
(NO.sub.2)C.sub.5 H.sub.10 
Bi C.sub.2 H.sub.5 
C.sub.6 H.sub.4 F 
C.sub.6 H.sub.4 F 
Sb C.sub.5 H.sub.11 O 
##STR16## 
##STR17## As 
##STR18## 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
Sb SH 
C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
As SC.sub.3 H.sub.7 
C.sub.3 H.sub.7 
C.sub.6 H.sub.5 
Bi SC.sub.3 H.sub.7 
CH.sub.3 CH.sub.3 As OH 
CH.sub.3CH.sub.2.phi. 
CH.sub.3CH.sub.2.phi. 
As OH 
CH.sub.3CH.sub.2C.sub.6 H.sub.3 F 
CH.sub.3CH.sub.2C.sub.6 H.sub.3 F 
As OH 
CF.sub.3CF.sub.2C.sub.6 H.sub.2 F.sub.2 
CF.sub.3CF.sub.2C.sub.6 H.sub.2 F.sub.2 
As OH 
C.sub.6 H.sub.4 F 
C.sub.6 H.sub.4 F 
As OH 
C.sub.6 H.sub.3 F.sub.2 
C.sub.6 H.sub.3 F 
As OH 
(NO.sub.2)C.sub.6 H.sub.4 
(NO.sub.2)C.sub.6 H.sub.4 
As OH 
C.sub.6 H.sub.3 Cl 
C.sub.6 H.sub.3 Cl 
As OH 
CH.sub.3OC.sub.6 H.sub.2 
CH.sub.3OC.sub.6 H.sub.4 
As OH 
C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
Sb OH 
______________________________________ 
FORMULA: R.sub.1 R.sub.2 R.sub.3 Z.sub.1 (O) 
R.sub.1 R.sub.2 R.sub.3 Z.sub.1 
______________________________________ 
C.sub.5 H.sub.11 
C.sub.5 H.sub.11 
C.sub.5 H.sub.11 
As 
C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
C.sub.6 H.sub.5 
As 
C.sub.6 H.sub.5 O 
C.sub.6 H.sub.5 O 
C.sub.6 H.sub.5 O 
As 
C.sub.6 H.sub.5 
CH.sub.3 CH.sub.3 Sb 
C.sub.6 H.sub.4 F 
C.sub.6 H.sub.4 F 
C.sub.6 H.sub.4 F 
Bi 
NO.sub.2 C.sub.5 H.sub.10 
C.sub.6 H.sub.5 
P 
CH.sub.3 CH.sub.2 
CH.sub.3 CH.sub.2 
CH.sub.3 CH.sub.2 
As 
______________________________________ 
______________________________________ 
##STR19## 
A R.sub.1 a' Z.sub.1 
______________________________________ 
H N/A 0 As 
H C.sub.6 H.sub.4 
1 As 
H CH.sub.2 1 As 
F N/A 0 As 
F C.sub.6 H.sub.4 
1 As 
F CH.sub.2 1 As 
H C.sub.6 H.sub.4 
1 P 
F C.sub.6 H.sub.4 
1 P 
H CH.sub.2 1 Bi 
F CH.sub.2 1 Bi 
H C.sub.6 H.sub.4 
1 Sb 
F CH.sub.2 1 Sb 
______________________________________ 
Also included as suitable Co-catalyst I are those having at least two of 
the aforedescribed Group V elements such as 
1-diphenyl-phosphino-2-diphenyl arsinoethane and 
2-arsenato-ethyl-triphenyl phosphonium bromide. 
The preferred class of organic Group V element containing compounds include 
the arsenic containing compounds. Of this class, the most preferred 
organic compounds include: arsenic triethoxide, phenylarsonic acid, 
diphenylarsinic acid, dimethylarsinic acid, 2-nitro-4-methylphenylarsonic 
acid, 4-methylphenylarsonic acid, n-propyl arsonic acid, 
4-hydroxy-3-nitrophenyl arsonic acid and mixtures thereof. 
Co-catalyst II is selected on the basis of its pK.sub.a, its possession of 
a phenolic functionality and its oxidative stability. The pK.sub.a of a 
compound is a conventional term and as used herein it represents the value 
of -Log K.sub.a where K.sub.a is the dissociation or ionization constant 
of the Co-catalyst as determined in aqueous solution at 25.degree. C. 
Accordingly, it has been found that Co-catalysts II suitable for use in the 
present invention must possess a pK.sub.a of typically from about 5 to 
about 13, preferably from about 6 to about 11, and most preferably from 
about 7 to about 10. 
Generally, the lower the pK.sub.a of Co-catalyst II, the higher will be the 
acidity of the phenolic hydroxy group and its associated co-catalytic 
activity. However, if the pK.sub.a of the Co-catalyst II is below about 5 
it will be sufficiently acidic to cause unacceptable competing side 
reactions such as ring opening of the epoxide product. While compounds 
with such a low pK.sub.a may be effective to impart co-catalytic activity, 
they deleteriously affect the overall yield of epoxide, and hence can be 
self-defeating for the ultimate purpose for which they are employed. 
If the pK.sub.a of the compound employed as Co-catalyst II is above about 
13, (e.g. 2-propanol), it will not possess sufficient co-catalytic 
activity for the purpose of the present invention. 
A further preferred requirement of the Co-catalyst II is that it be 
sufficiently oxidatively stable under reaction conditions such that it is 
not oxidized to any significant extent by the H.sub.2 O.sub.2 during 
epoxidation reaction. Oxidation of Co-catalyst II not only wastefully 
consumes H.sub.2 O.sub.2, but more importantly it also destroys or 
substantially reduces co-catalytic activity. 
While unsubstituted phenols possess a suitable pK.sub.a of about 9.9 and 
exhibit good co-catalytic activity, they generally also exhibit poor 
oxidative stability and will eventually be oxidized to hydroxy or 
polyhydroxy benzenes under reaction conditions. One of the benefits of 
employing a Co-catalyst II which does not participate directly in the 
epoxidation reaction, is that it can be continuously recycled without the 
addition of new Co-catalyst. Consequently, this benefit, to a large 
degree, will be lost if unsubstituted phenols are employed as Co-catalyst 
II and consumed by the oxidant. Thus, while unsubstituted phenols can be 
employed where economics of the process permit, it is preferred to employ 
phenols substituted with substituents capable of stabilizing and/or 
controlling the pK.sub.a of, the phenol parent compound as described 
herein. 
Inert electron withdrawing substituents, such as halogens (most preferably 
Cl), are preferred because they not only lower the pK.sub.a of the phenol 
but they also increase its oxidative stability. However, oxidative 
stability can also be imparted by replacing the reactive hydrogens of the 
aromatic ring with inert hydrocarbyl and other groups described herein. As 
a general rule, the fewer reactive hydrogens on the aromatic ring the 
greater will be the oxidative stability of the phenolic compound. 
Thus, the co-catalysts II of the present invention provide a delicate 
balance between oxidative stability, high co-catalytic activity, 
negligible competing side reactions, and relatively low cost, and by 
appropriately selecting the substituents and/or pK.sub.a of the phenolic 
Co-catalyst II, one is able to tailor the catalytic composition to achieve 
optimum performance from both a process and economic standpoint. 
Co-catalyst II can therefore be broadly defined to comprise an organic, 
preferably completely organic compound having the aforedescribed pK.sub.a 
values and at least one hydroxy group substituted on an aromatic ring. 
Accordingly, suitable Co-catalysts II can be represented by the structural 
formula: 
EQU (X).sub.a --Ar--(OH).sub.b (I) 
wherein Ar represents a substituted or unsubstituted aromatic hydrocarbyl 
group, typically an aromatic hydrocarbyl group having from about 6 to 
about 14 carbons, preferably from about 6 to about 10 carbons, and most 
preferably about 6 carbons, exclusive of substituents, said substituents 
when present being selected from the group consisting of alkyl, typically 
alkyl of from about 1 to about 20, preferably from about 1 to about 10, 
and most preferably from about 1 to about 5 carbons, hydroxy alkyl wherein 
the alkyl group is as defined above, halogenated alkyl wherein the alkyl 
group is as defined immediately above and the halogen is as defined below 
in connection with X, nitro alkyl, alkoxy alkyl, aralkoxy, oxo substituted 
alkyl, and alkoxy carbonyl, wherein the respective alkyl and aryl groups 
are as described immediately above; X is selected from the group 
consisting halogen (i.e. F, Cl, Br and I, preferably Cl and Br, most 
preferably Cl), hydrogen, and nitro, preferably at least one X is halogen; 
the letter "a" represents a number of typically 0 to 5, preferably 1 to 4 
most preferably 2 to 4, the letter "b" is a number of at least 1, 
typically from about 1 to about 4, preferably 1 to about 3, most 
preferably from about 1 to 2 (e.g. 1), the sum of a+b is equal to the 
total number of available carbon bonding sites, i.e., the number of 
replaceable aromatic hydrogens, on the Ar substituted or unsubstituted 
aromatic hydrocarbyl group. 
Preferably X is halogen and when halogen, is preferably located on the 
ortho or para position of the Ar aromatic hydrocarbyl group. 
A narrower more preferred class of Co-catalyst II compounds can be 
represented by the structural formula: 
##STR20## 
wherein R' is independently selected from the group consisting of alkyl of 
from about 1 to about 5; preferably 1 to about 3, most preferably 1 to 
about 2 carbons, and alkoxy wherein the alkyl portion thereof is as 
described above; c is a number of from about 0 to about 5, preferably 1 to 
5, (e.g., 1 to 4) X, a and b are as described above in connection with 
structural formula I; and the sum of a+b+c is equal to the total number of 
available carbon bonding sites on the aromatic ring. 
The most preferred Co-catalysts II is represented by structural formula II 
wherein X is chlorine, "b" is 1, "c" is 0, and "a" is from 1 to 5, 
typically 1 to 4, preferably 1 to 3, e.g., 1 to 2. 
Representative examples of suitable Co-catalysts II include p-chlorophenol, 
o-chlorophenol, m-chlorophenol, 2,4-dichloro phenol, 2,6-dichlorophenol, 
2,4,6-trichlorophenol, 2,3-dichlorophenol, pentachlorophenol, 
pentafluorophenol, p-cresol, phenol, 2,3,5-trimethylphenol, 
2-methoxyphenol, o-nitrophenol, p-nitrophenol 2,4-dinitrophenol, 
2,4-di-t-butylphenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, 
2,4-di bromophenol, 2,6-diiodophenol, 1-nitro-4-chlorophenol, 
2,6-diethoxyphenol, 2,4,6-trifluorophenol, pentamethylphenol 
pentaethylphenol. 
Preferred Co-catalysts II include p-chlorophenol, 2,4-dichlorophenol, 
p-nitrophenol. 
In addition to the above described Co-catalysts II compounds, it is also 
contemplated that polymers having hydroxy groups pendant from an aromatic 
ring, such as hydroxylated polystyrene, may also be employed. 
The Co-catalysts I and/or II may be employed in the present invention alone 
or in association with a heterogeneous support or carrier. Suitable 
supports, typically employed in powder, spherical, tablet, or cylindrical 
form, for the co-catalysts include, for example, silica; alumina; 
silica-alumina; metal aluminates, such as magnesium aluminate, calcium 
aluminate, titania, zirconia, activated carbon, zeolites, magnesium oxide, 
and basic ion-exchange resins. 
When mixtures of Co-catalysts II are employed, it is the pK.sub.a of each 
component within the mixture which is determinative of suitability of that 
component for use in the present invention. 
Co-catalysts I and II are employed to enhance the epoxidation reaction rate 
of olefins and/or selectivity to epoxide, said epoxidation reaction being 
achieved using H.sub.2 O.sub.2 as the oxidant. 
Accordingly, olefins which can be epoxidized using H.sub.2 0.sub.2 and 
which can be employed in the present invention contain at least one 
ethylenic unsaturation and are conventional in the art. Typical of such 
olefins are those represented by the structural formula: 
##STR21## 
wherein R.sub.7, R.sub.8, R.sub.9 and R.sub.10, which may be the same or 
different, are selected from the group consisting of hydrogen; substituted 
or unsubstituted: alkyl, aryl, alkaryl, and aralkyl hydrocarbyl groups, 
said hydrocarbyl groups being preferably as defined in connection with R 
of structural formula I; or any two of said R.sub.7 to 10 groups together 
can constitute a cycloalkyl group typically of from about 4 to about 12, 
preferably from about 5 to about 8 carbons. 
Representative olefins which can be epoxidized and contain at least one 
ethylenic saturation include: ethylene, propylene, butene-1, butene-2, 
isobutene, pentene-1, pentene-2, isobutene, pentene-1, pentene-2, hexene, 
isohexene, heptene, 3-methylhexene, octene-1, isooctene, nonene, decene, 
dodecene, tridecene, pentadecene, octadecene, eicosene, docosene, 
tricosene, tetracosene, pentacosene, butadiene, pentadiene, hexadiene, 
octadiene, decadiene, tridecadiene, eicosadiene, tetracosadiene, 
cyclopentene, cyclohexene, cycloheptene, methylcyclohexene, 
isopropylcyclohexene, butylcyclohexene, octylcyclohexene, dodecyclohexene, 
acrolein, acrylic acid, methyl methacrylate, styrene, cholestrol etc. The 
preferred olefins are propylene, soybean oil, isobutylene, styrene, allyl 
alcohol and allyl chloride. The most preferred olefin is propylene. 
The components in the catalyst composition of the present invention are 
employed in amounts effective to increase yields and/or selectivities of 
epoxide relative to the absence of said components, typically within a 
reaction time of from about 2 minutes to about 5 hours, preferably from 
about 2 minutes to about 2 hours and most preferably from about 2 minutes 
to about 1 hour. 
The process of the present invention is conducted by contacting at least 
one olefin containing at least one ethylenic unsaturation and H.sub.2 
O.sub.2, preferably in a liquid phase, in the presence of said catalyst 
composition under conditions and in a manner sufficient to oxidize at 
least one of said ethylenically unsaturated groups to its corresponding 
epoxide group. 
The H.sub.2 O.sub.2 can be employed in anhydrous form or as an aqueous 
solution. Such aqueous solutions typically will contain from about 3 to 
about 99.9%, preferably from about 20 to about 75%, and most preferably 
from about 20 to about 45% (e.g., 25 to 35%), by weight, H.sub.2 O.sub.2 
based on the total weight of the aqueous solution. While it is generally 
recognized in the art that yields of epoxide product are highest if the 
water content of the reaction mixture is kept to a minimum, it is a 
particular advantage of the present invention that reaction rate 
enhancement and yields are not particularly adversely affected when 
operating at water levels in the aqueous H.sub.2 O.sub.2 solution of about 
60 to 75% (e.g., 70%) by weight thereof including water produced by the 
reaction. 
Consequently, the economics of the overall process are substantially 
increased due to the ability to use commercially produced aqueous 
solutions of H.sub.2 O.sub.2 directly, without the need to concentrate 
such solutions by removing water therefrom. 
While it is generally desirable to employ the reactants (i.e., olefin and 
H.sub.2 O.sub.2) in approximately stoichiometric proportions, e.g., one 
mole of H.sub.2 O.sub.2 per mole of ethylenic linkage to be epoxidized, an 
excess of either reactant is acceptable and in many instances preferable 
since it actually results in easier process control and a more economic 
process. 
The preferred mode of reacting the olefin and H.sub.2 O.sub.2 is conducted 
in a liquid reaction medium and preferably in the presence of a solvent 
miscible with both reactants. While it is not necessary that the reaction 
medium exist as a homogeneous phase, it is preferred that it does. 
Because the Co-catalyst II can be used in excess relative to the effective 
catalytic amount, it can function not only as a Co-catalyst but also as 
the primary solvent for the reaction medium when employed in such excess 
to achieve a homogeneous liquid reaction phase. However, it may be more 
economically advantageous to employ less expensive solvents for this 
purpose. 
Suitable optional solvents are organic, and inert in the reaction mixture. 
By inert as used herein in conjunction with optional solvents is meant 
that the solvent does not deleteriously affect the epoxidation reaction 
relative to its absence, and does not increase the formation of 
non-epoxidized products. Such optional inert organic solvents include 
aromatic hydrocarbons such as benzene, toluene, xylene, benzonitrile, 
nitrobenzene, adiponitrile, anisole, phenyl nonane; saturated aliphatic 
hydrocarbons having from about 5 to about 20 carbons, such as pentane, 
hexane, heptane adiponitrile; halogenated hydrocarbons such as 
1,2-dichloroethane, chloroform, carbon tetrachloride and the like; 
non-fluorinated substituted saturated aliphatic and/or aromatic 
hydrocarbons having from about 1 to about 20 carbons including those 
selected from the group consisting of alcohols such as: methanol, 
propanol, butanol isopropanol, 2,4-di-t-butyl phenol; ketones such as 
acetone; carboxylic acids such as propanoic acid, acetic acid; esters such 
as ethyl acetate, ethyl benzoate, dimethyl succinate, butyl acetate, 
tri-n-butyl phosphate; dimethyl phthalate; and ethers, such as tetraglyme; 
and mixtures thereof. 
Preferred solvents include benzene, toluene, ethyl acetate, ethyl benzoate, 
dimethyl succinate, dimethyl phthalate, tetraglyme, nitrobenzene, 
benzonitrile, and mixtures thereof. 
In carrying out a preferred embodiment of the invention, olefin or olefin 
and H.sub.2 O.sub.2 are introduced into a liquid reaction mixture 
comprising Co-catalyst I, Co-catalyst II and optionally an inert organic 
solvent. Preferably the reaction mixture also contains an aqueous solution 
of the H.sub.2 O.sub.2 prior to introducing the olefin thereto. 
Thus, the initial preferred reaction mixture prior to olefin introduction 
will typically comprise: (a) an aqueous H.sub.2 O.sub.2 solution (as 
defined above) in an amount of from about 0.5 to 25%, preferably from 
about 2 to about 20%, and most preferably from about 5 to about 15%, by 
weight, based on the weight of the reaction mixture exclusive of the 
weight of olefin and Co-catalyst I; (b) Co-catalyst II in an amount of 
from about 10 to about 99.5%, preferably from about 30 to about 90%, and 
most preferably from about 70 to about 90%, by weight, based on the weight 
of the reaction medium exclusive of the weight of olefin and Co-catalyst 
I; (c) inert organic solvent in an amount of from about 0 to about 90%, 
preferably from about 0 to about 50%, and most preferably from about 10 
to about 30%, by weight, based on the weight of the reaction medium 
exclusive of the weight of olefin and Co-catalyst I; and (d) Co-catalyst I 
in an amount sufficient to achieve from about 0.001 to about 2, preferably 
from about 0.005 to about 1.0, and most preferably from about 0.01 to 
about 1.0 g atom of the Group V element in Co-catalyst I per liter of 
reaction medium inclusive of components (a) through (c) recited above. 
If the aqueous solution of H.sub.2 O.sub.2 is added simultaneously with the 
olefin, it is added in amounts sufficient to eventually achieve the 
reaction mixture composition as described above. 
The olefin is introduced into, and contacted with, the reaction mixture in 
an amount and in a manner sufficient to achieve at least an initial molar 
ratio of olefin to H.sub.2 O.sub.2 therein of typically from about 0.8:1 
to about 50:1, preferably from about 1:1 to about 30:1, and most 
preferably from about 1:1 to about 10:1. Thus, in most instances it is 
preferred to maintain an excess of olefin in the reaction mixture. 
The reaction temperature can vary widely although it is preferred to 
maintain the reaction mixture in the liquid phase. Accordingly, typical 
reaction temperatures will vary from about 20.degree. to about 150.degree. 
C., preferably from about 40.degree. to about 120.degree. C., and most 
preferably from about 50.degree. to about 90.degree. C. The reaction 
pressure is not critical and can be atmospheric, sub-atmospheric or 
super-atmospheric. 
Typically, the reaction pressure is controlled in a manner sufficient to 
keep the reactants and Co-catalyst II in a liquid phase. Furthermore, it 
is highly desirable to conduct the reaction under the autogeneous pressure 
generated by the reactants at the temperature selected. 
The process may be run in a batch mode or a stepwise mode or a continuous 
mode where either one or both the olefin or hydrogen peroxide may be added 
simultaneously or sequentially to maintain reactant concentration as they 
are consumed. 
Additionally, the process may be run in either of the aforementioned modes 
by altering the reaction conditions, and/or, the reactant, solvent, or 
catalyst concentrations during the course of the reaction. Thus, the 
process may be run by changing the temperature, pressure, catalyst 
concentration, hydrogen peroxide concentration or olefin concentration. 
The practice of the process of the present invention within the aforenoted 
reaction times is capable of achieving epoxide yields as high as 100%. 
Because the catalyst composition of the present invention greatly increases 
the rate of the epoxide forming reaction, it becomes economically feasible 
to remove the epoxide product as fast as it is formed by, for example, a 
product flash-off technique. This permits immediate removal of the epoxide 
product and substantially reduces the chances for undesirable hydrolysis 
reaction of the epoxide to corresponding glycol to occur. Thus, a volatile 
epoxide may be removed by vaporization from the reaction medium preferably 
by use of a stripping gas. Alternatively, volatile and non-volatile 
epoxides may also be removed by preferential extraction into a separate 
solvent phase which then in turn may be removed from the reaction medium 
preferably by decanting. The reaction mixture from which products and 
by-products have been removed can be recycled for further use in 
epoxidizing olefins. 
Further isolation of the resulting epoxide from volatilized constituents of 
the reaction medium or from the extraction medium can be accomplished by 
fractional distillation to yield the substantially pure epoxide in cases 
where the epoxide is relatively low boiling. 
It is to be understood that while the Group V element containing compounds 
and phenolic compounds are referred to herein generally as co-catalysts, 
the exact mechanistic relationship by which these classes of compounds 
exert their reaction rate reducing effect is not entirely understood. 
Consequently, the use of the term "co-catalyst" is meant to include the 
possibility of a promoter/catalyst type of relationship between each of 
these respective classes of compounds. 
The utilities of the epoxidized products produced in accordance with the 
process of the present invention are well known and include use as 
intermediates in the preparation of polyesters, polyurethanes, detergent 
products, and the like. 
As used herein, percent epoxide selectivity is defined as: 
##EQU1## 
To determine selectivity to by-product, the moles of epoxide in the above 
equation is replaced by moles of by-product. 
Conversion is reported in two forms, namely, conversion of H.sub.2 O.sub.2 
to organic products and total conversion of H.sub.2 O.sub.2 including 
organic products as well as decomposition products of H.sub.2 O.sub.2 such 
as oxygen and water. Total conversion is determined as follows: 
##EQU2## 
Unless otherwise specified, total conversion is determined by iodometric 
titration of residual peroxide remaining after reaction, and conversion to 
organics is determined by gas chromatography. Most of the conversions 
disclosed herein are reported as being determined by two different 
analytical methods because, as is well known, the use of unpassivated 
stainless steel reactors cause decomposition of hydrogen peroxide (see for 
example, "Hydrogen Peroxide" by Schumb, W., Satterfield, R., and 
Wentworth, R., American Chemical Society Monograph, published by Reinhold 
(1955)). This decomposition of hydrogen peroxide can be eliminated or 
minimized to a negligible degree by passivating the stainless steel using 
conventional techniques such as treatment with nitric acid. Consequently, 
for practical purposes the advantages of the present invention are 
observed from conversion to organic products and selectivity of these 
organic products to epoxide. Total conversion is reported herein in the 
interest of completeness but has no real bearing on the performance of the 
process of the present invention. The yield of epoxide can be calculated 
as the product of conversion to organics and selectivity. It is to be 
noted that the analytical methods for determining total % conversion is 
associated with between about a .+-.2 and 4% experimental error, and the 
analytical method for determining % conversion to organics is associated 
with about a .+-.5% experimental error. The above experimental errors are 
believed to account for those data reported herein where % conversion to 
organics is higher than total % conversion. 
The following examples are given as specific illustrations of the claimed 
invention. It should be understood, however, that the invention is not 
limited to the specific details set forth in the examples. All parts and 
percentages in the examples as well as in the remainder of the 
specification are by weight unless otherwise specified. Unless otherwise 
specified, all reactions reported herein below are conducted in a manner 
such that olefin is available for reaction with H.sub.2 O.sub.2 in an 
amount in excess of the stoichiometric amount relative to the H.sub.2 
O.sub.2. Furthermore, while the following examples may be written in the 
present tense it is to be understood that such examples represent work 
actually performed. 
For purposes of background, publications which report pK.sub.a values of 
numerous compounds include "Transactions of the Faraday Soc." Vol. 65, p. 
1004 (1969) by Rochester and Rossoll; "Ionization Constants of Acids and 
Bases" by Albert and Serjeant, published by Methuen, N.Y. (1962); 
"Handbook of Biochemistry", p. J-150 to J-189 C.R.C. Press, Cleveland 
(1968); "Handbook of Proton Ionization Heats", By Cristensen et al, Wiley 
Press (1976); "Ionization Constants of Organic Acids in Aqueous Solution" 
by Serjeant and Dempsey, Pergamon Press (1979); and "A Comparison of the 
Acid Ionization Constants of Para-t-butyl Phenol, Ortho-t-butyl Phenol, 
and 2,4-di-t-butyl Phenol in Water and Methanol", J. Chem. Soc., p. 4603 
(1965).