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US005097056A
United States Patent [191 [11] Patent Number: 5,097,056
Segall et a1. [45] Date of Patent: Mar. 17, 1992

[54] PROCESS FOR THE PREPARATION OF

TRIARYL PHOSPHATES USING H3PO4 AND FOREIGN PATENT DOCUMENTS
HARD CATION AS A CATALYST 178374 1/1966 U.S.S.R. ............................ .. 558/110
2215722 9/1989 United Kingdom .............. .. 5587110
[75] Inventors: Jeane Segall; Leonard M. Shorr, both OTHER PUBLICATIONS
of Haifa, Israel
“Phosphorous and Its Compounds”, vol. 2, edited by
[73] Assignee: Bromine Compounds Ltd., John R. Wazer, Interscience publishers Ltd London
Beer-Sheva, Israel (1961) pp. 1222, 1231, 1232. '
“The Manufacture and Use of Selected Aryl and Alkyl
[21] Appl. No.: 307,892 aryl Phosphate Esters", TASK 1, Feb. 1976, p. 19.
“The Chemistry and Uses of Fire Retardants”, John W.
[22] Filed: Feb. 7, 1989 Lyons, Wiley Interscience, pp. 41-45.
_ _ _ _ _ Priman; Examiner—Mukund J. Shah
1301 Foreign Apphatlon Priority Dam Assistant Examiner-Jyothsna Venkat
Feb. 8, 1988 [1L] Israel ...................................... .. 85349 Attorney, Agent, or Finn-Michael N. Meller
[57] ABSTRACT
[51] Int. Cl.5 .............................................. .. C07F 9/02
[52] 1.1.5. Cl. .............. .. 558/110; 502/213 A process is described according to which triaryl phos
[58] Field of Search ....................................... .. 558/110 phates are prepared by the reaction of one or more
phenols with H3P04, in the presence of a hard cation as
[56] References Cited a catalyst.
_ Novel catalysts
_ and catalyst precursors for
this purpose are described.
U.S. PATENT DOCUMENTS
2,963,506 12/1960 Lewinski ........................... .. 558/110 6 Claims, 2 Drawing Sheets

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US. Patent Mar. 17, 1992 Sheet 1 of 2 5,097,056

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U.S. Patent Mar. 17,1992 Sheet 2 of 2 5,097,056

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 5,097,056
1 2
Examples of materials which liberate a hard cation
PROCESS FOR THE PREPARATION OF TRIARYL when in soluted form are H3BO3, CdSO4.8H2O, Sb2O5,
PHOSPHATES USING H3PO4 AND HARD CATION Mg(OAc)2.4H2O, Mn(OAc);.4H2O, CuSO4.5I-l2O,
AS A CATALYST Zn(OAc)2, COSOaJHzO, ZnS04.7H20, LIZSO4, Fe2(
SO4)3, Mn dimethyl phosphate, Mg diallyl phosphate,
FIELD OF THE INVENTION Mg dimethyl phosphate, MnSO4, MgSO4, Mg(OH)2,
The present invention relates to a process for the Al(OH)3, Al2(SO4)3.l8H2O. The amount of the said
additive needed is generally less than 1-5 wt %.
manufacture of triaryl phosphates. More particularly, According to a preferred embodiment of the inven
the invention relates to an improved process in which
triaryl phosphate of high purity is obtained. tion, the process comprises the steps of:
a) continuously removing and separating the water
BACKGROUND OF THE INVENTION produced in the reaction between H3PO4 and the phe
nol; ~
According to the known art, triaryl phosphates are b) distilling the triaryl phosphate from the reaction
prepared by a process in which POCl3 is reacted with mixture and recycling the intermediate and catalyst to
the appropriate phenol at elevated temperatures in the the reaction mixture. _
presence of large amounts of AlCl3 as a catalyst. Exam Preferably, the separation of the water is effected by
ples of triaryl phosphates to which the present inven means of an inert hydrocarbon, more preferably xylene.
tion is directed are tricresyl, triphenyl, phenylcresyl and The injection of the latter into the system facilitates the
phenyl-i-propylphenyl phosphates. Triaryl phosphates removal of water from the vapors as well as its separa
have a number of industrial applications, such as plasti tion from the condensed distillate. It should be under
cizers for polymers, ?re retardants, lubricant oil addi stood that efficient water separation is especially impor
tives and hydraulic ?uids. tant for the promotion of the reaction. The inert hydro
The processes of the art, however, present several carbon has the advantage of entraining water and
severe drawbacks. Firstly, l-lCl evolves as a waste prod thereby aiding to remove water and to obtain a greater
uct, and the process, among other common disadvan degree of dryness. Efficient drying is important because
tages of acid evolution, requires that glass-lined vessels the tertiary ester obtained in the reaction is easily hy
be employed. Secondly, only relatively low conversion ' drolizable, which leads to a deterioration of the prod
s-of up to about 88%-are usually obtained. Thirdly, net.
aromatic by-products are wasted and, together with the According to another preferred embodiment of the
large amounts of catalyst employed, form wastes which invention at least part of the phenol or phenolic mixture
are burdensome and must be disposed of, because of‘ is fed to the reaction vessel in vapor form. The latent
environmental hazards. heat of phenolic vapors is exploited in this way, to meet
Replacing POC]; by H3P04 potentially solves part of part of the heat requirements of the reaction.
the above-mentioned problems, since the intermediates Also encompassed within the present invention is a
resulting from the reaction can be recycled, the corro catalyst for accelerating the reaction between a phenol
sion problem is eliminated because AlCl3 is not used, and H3PO4, which catalyst comprises a material which
and no HCl evolves, and there is essentially no waste. in solution liberates a hard cation selected from the
This replacement, however, leads to impractically slow group consisting essentially of H3303, CdSOaSI-IZO,
reactions which are not useful from an industrial point Sb2O5, Mg(OAc)2.4I-l1O, Mn(OAc)z.4I-I2O, CuSO4.5
of view. H2O, Zn(OAc);, CoSO4.7H20, ZnSO4.7H2O, Li2SO4,
SUMMARY OF THE INVENTION Fe2(SO4)3, Mn dimethyl phosphate, Mg diallyl phos
phate, Mg dimethyl phosphate, MnSOa, MgSO4,
It has now been found, and this is an object of the M8(OH)2, Al(0H)3, Al2($04)3-l8H20
invention, that it is possible to provide a process which 45 The above and other characteristics and advantages
employs H3PO4 and which can be carried out at attrac of the invention will be better understood from the
tive reaction rates. following illustrative and non-limitative examples.
It is therefore an object of the invention to provide a
process for the preparation of triaryl phosphates from GENERAL WORKUP PROCEDURE.
H3PO4 and the appropriate phenol or phenols, which Phosphoric acid and an excess of the appropriate
permits to employ H3PO4, with all the advantages at phenol or mixture of phenols were introduced into a
tached to it, and still provides industrially acceptable ?ask. The mixture was heated with efficient stirring
production rates and high purity. whereby a solution was obtained. As the reaction pro
The process for the preparation of triaryl phosphates ceeded the water formed was removed by distillation
according to the invention, in which a phenol or a mix 55 with phenolic vapors through a Dean-Stark trap which
ture of vtwo or more phenols is reacted with H3PO4, is contained xylene for easier water separation. Some
characterized in that the reaction is catalyzed by the xylene returned to the column, but large amounts in the
addition of a catalytically effective amount of an addi reactor were avoided so as to maintain high reaction
tive which liberates a hard cation when in soluted form. temperatures. The dry phenol was continuously recy
Preferably, the phenol is present in at least a small stio~ 60 cled into the reaction mixture. Samples of the reaction
chiometric excess. _ product were withdrawn intermittently and analyzed
By “hard cation" is meant the group of cations so by paper chromatography coupled with UN. spectros
classi?ed according to R. G. Pearson [J . Chem. Educa copy. In one instance the reaction product was distilled
tion, 45, pp. 581 and 6430968)]. under reduced pressure and the distillate, consisting of
According to a preferred embodiment of the inven 65 unreacted phenol and TPP was analyzed and identified '
tion, the cation is selected from the group consisting by G.C. in comparison with samples of the pure com
essentially of: B+++, Cd++, Sb+5, Mg++, Mn++, pounds. In another instance the reaction product was
Cu++, zn++, C°+ +, Li+, 1=¢+++, A1+++_ mixed with a ten-fold excess of water, whereby Tri
 5,097,056
3 4
phenyl Phosphate precipitated. After further washing and consists of a 201 reactor made of 316 stainless steel
with water and after drying, an almost colorless prod and ?tted with a turbine stirrer, thermowell and electric
uct was obtained which was found by G.C. to be over heater. Cresol is fed to the reactor 1 from the cresol
99% pure. boiler 2, which consists of a 10 1it., 316 SS vessel, with
electric heater which, when heated, causes cresol va
EXAMPLE 1 pors to ?ow into reactor 1. The separation column 3 has
A series of reaction experiments was carried out, a diameter of 4 inches and a height of 100 cm, and is
according to the general procedure described above, to ?lled with 6X6 mm glass Raschig rings. Numeral 4
test the in?uence of different additives which liberate indicates a standard condenser and numeral 5 a standard
hard cations on the reaction rate. The phenol employed water separator. Numeral 6 is the cresol tank and nu
was cresol and the ester formed in the reaction was meral 7 the over?ow tank. The top of the reactor is
tricresyl phosphate (T CP). In all cases 0.6 wt %, rela connected to the distillation column and the H20 sepa
tive to the cresol, of the additive was employed, and rator which contains xylene. -
was added gradually in three equal portions. The reac Several TCP production runs were carried out in the
tion mixture was assayed after six hours of reaction, to system of FIG. 1. In all the runs 6 l of cresol were
determine TCP concentration. The results of these ex placed in the boiler and 61 of cresol in the reactor. The
periments are set forth in Table I below, which also cresol was refluxed and dried azeotropically prior to the
shows results obtained in the absence of an additive, as introduction of the H3PO4. 820 ml of 92.4% H3PO4
well as with additives comprising non-hard ions, viz., (13.72 moles) were fed into the hot reactor during about
Sb2O3, HgSO4, Ag2SO4, Zr oxalate, for comparison 20 10 minutes, while cresol vapors were circulated in the
purposes. system. Water resulting from both the initial H3PO4 and
from the reaction distilled off and was collected in the
EXAMPLE 2 xylene separator. The results of a representative run
39.2 g (0.4 mole) of 100% H3PO4 were placed in a 250 (Run 5) are shown in Table 11 below.
ml flask, and 177 g (1.3 moles) of o-isopropylphenol and 25 FIG. 2 shows the rate of formation of TCP at various
0.8 g Mg dimethyl phosphate catalyst were added. A 40 heat inputs as a function of M (the molar ratio HZO/H
cm long column (d=5 cm) ?lled with Raschig rings 3PO4), for the above and additional four runs. The re
was attached to the ?ask which was mechanically sults shown in FIG. 2 are self-explicative.
stirred. On top of the column there was placed a Dean The above examples and description have been given
Stark trap ?lled with xylene and a condenser. 30 for the purpose of illustrations and are not intended to
The reaction product after 5.5 hours contained (on a be limitative. Many variations can be effected in the
molar basis): process of the invention, without exceeding its scope.
43.2% tri-isopropylphenyl phosphate; TABLE I
56.8% di-isopropylphenyl phosphate, the rest being
In?uence of Additives on the Rate of TCP formation
the free phenol. The product was free both of H3PO4 35 TCP Formed After Six Hours (mole %)
and of the mono-isopropylphenyl phosphoric acid. Additive TCP formed (mole %)
EXAMPLE 3 None
To a standard reaction set-up there were added 1.6
moles of 100% H3PO4, 4.9 moles of freshly distilled AS2504
(m+p)-cresol, 3.2 g of Mn dimethyl phosphate catalyst Zr oxalate
and 0.7 g of the oxidation inhibitor 2,6-di-tert-butyl-a H 3503
CdSO4.8H2O
methoxy-p~cresol (ex Ethyl Corp). The reaction was
performed under a N2 blanket in order to avoid oxida
tion and discoloration of the cresol. 45
When the reaction yielded 2.7 moles of H20 (accord
ing to 1120 collected) it was stopped and the product
?ashed out at 3-10 mmHg and a maximum pot tempera
ture of 280‘ C. The time required for this ?ash distilla
tion was 1.75 hours. The distillate obtained, 518 g, con 50 R2604);
Mn dimethyl phosphate
tained: 44% cresol and 56% TCP in addition to very Mg diallyl phosphate
small amounts of the oxidation inhibitor and xylene. Mg dimethyl phosphate
The cold trap consisted of a very small amount (~1 g) M11304
of H20 and xylene. M3804
55
EXAMPLE 4
This example illustrates the continuous production of
TCP, using vaporized cresol. The apparatus used is
shown in FIG. 1. The reactor is shown by numeral 1,
TABLE II
ExErimental Results for Run No. 5 ,
Time mole HZO/ Product Analysis (% w/w) Temperature ('C.)
(hrs) mole P H3PO4 MCP DCP TCP Cresol Pot Head
3 1.60 0.7 4 36 19 41 240 203
4 1.72 0.4 3 30 27 34 255 204
5.25 1.92 0.3 4 37 31 32 249 204
 5,097,056
5
TABLE lI-continued
ExEn'mental Results for Run Not 5
Time mole HZO/ Product Analysis (‘7: w/w) Temperature ('C.)
(hrs) mole P H3PO4 MCP DCP TCP Cresol Pot Head
5.75 2.00 0.2 2 25 43 33 243 203
MC? 1: monocresyl phosphate
DCP = dicrsyl phosphate
TCP = tricresyl phosphate

We claim: 3. A process according to claim 2, wherein the addi

1. A process for the preparation of triaryl phosphates, tive is selected from the group consisting essentially of
in which a phenol or a mixture of two or more phenols H3BO3, CdSO4.8l-I2O, Sb2O5, Mg(OAc)2.4H2O,
is reacted with H3PO4, which comprises Mn(OAc)2.4H1O, CuSO4.5H2O, Zn(OAC)z, 00504.7
a) catalyzing the reaction by the addition of a catalyt HZO, ZnSO4.7l-I2O, Li2SO4, Fe2(SO4)3, Mn dimethyl
ically effective amount of an additive which liber phosphate, Mg diallyl phosphate, Mg dimethyl phos
ates a hard cation when in soluted form; phate, MnSO4, MgSO4, Mg(OH)2, Al(OH)3, A12.
b) continuously removing and separating the water (SO4)3.l8H2O.
produced in the reaction between H3PO4 and the 4. A process according to claim 1, wherein separation
phenol; and of the water is effected by means of an inert hydrocar
c) distilling the triaryl phosphate from the reaction 20 bon.
mixture and recycling the intermediate and catalyst 5. A process according to claim 4, wherein the inert
to the reaction mixture. hydrocarbon is xylene.
2. A process according to claim 1, wherein the cation6. A process according to claim 1, wherein at least
is selected from the group consisting essentially of: part of the phenol or phenolic mixture is fed to the
B+++, cd-ir'lr, Sb'i-S, Mg++, Mn++’ Cu++y Zn-F-l', 25 reaction vessel in vapor form.
t t i t ‘
Co++, Lia’, Fe+++, A1+++‘

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45

50

55

65