JPH03169887A - Diphosphonic acid ester compound and its preparation and application - Google Patents

Abstract

NEW MATERIAL: A compound of formula I (m₁ is an integer of 0-2; n₁ is an integer of 2-m₁; m₂ is an integer of 0-2; n₂ is an integer of 2-m₂; 0<m₁+m₂<4; R means H or 1-8C alkyl; R' means 1-18C alkyl; and X means H, OH).

EXAMPLE: 1-hydroxy-ethylidene-1,1-diphosphonic acid mono-2-ethylhexyl ester.

USE: A catalyst for the oxidation of cyclohexane, etc.

PROCESS: A solid diphosphonic acid of formula II is dissolved in a solvent (desirably chosen from water, methanol, and ethanol). The resulting solution is added into an alcohol of the formula, R'OH under atmospheric pressure, desirably at 160-170°C for esterification.

COPYRIGHT: (C)1991,JPO

Description

[Detailed description of the invention] field of invention The present invention relates to novel diphosphonic acid ester compounds.

More particularly, the present invention relates to new types of diphosphonic acid ester compounds, methods for their production, compositions containing them, and uses thereof.

Accordingly, one object of the present invention is to provide a new and useful diphosphonate compound, and another object of the present invention is to provide a method for producing such a diphosphonate compound.

Still another object of the present invention is to provide a composition containing a diphosphonate compound for use in catalysts.

A further object of the invention is to provide the application of such diphosphonic ester compounds and compositions containing them for catalyzing the oxidation of hydrocarbons, in particular the oxidation of cyclohexane, etc.

Structure of the Invention The diphosphonic acid ester compound of the present invention is novel and can be represented by the following general formula (1).

p-0(OH)m+(OR')n+ R-C-X (1)P-
0 (OH) + z (OR') nt (wherein = 0
,! or 2, dynamic = 0. 1 or 2 m. and duck,
are not both 0 or both 2; n H =2 ”
+*m,=2-m2; R=H or either alkyl of 1-8 carbon atoms, R'=alkyl of 1-18 carbon atoms, and X=H or OH) esters or triesters or mixtures of the three, preferably diesters of diphosphonic acid esters).

rRj in formula (1) is preferably linear/branched alkyl having I4 or l-6 carbon atoms, more preferably l-
Alkyl having 3 carbon atoms, for example methyl.

"R" in formula (1) is preferably straight chain/branched alkyl having 6-14 carbon atoms, even more preferably 2-
A branched alkyl having 8-12 carbon atoms, such as ethylhexyl.

rXJ in general formula (1) is preferably OH.

General formula (1) PO (OH) I++ (OR') r++R-
C-X (1) 1 p - 0 (OH) at (OR') nt (where m++mt+n++nt+R+R' and the definition of X are,
The method for producing the diphosphonic acid ester compound of formula (same as above) is based on the general formula (2
) P-0(OH) R-C-X (2) P-0(O
H) Dissolving the solid diphosphinic acid represented by the formula (wherein R and
General formula (3) R'OH (3) (wherein R' has the same meaning as in formula (1)) is added to the alcohol represented by formula (1), and an esterification reaction occurs, which is represented by general formula (+) Substances are obtained.

In the phosphinic acid of formula (2), preferably R is H or 1-
Alkyl having 6 carbon atoms, more preferably R
is alkyl having 1-3 carbon atoms, for example methyl and X is OH. The alcohol of formula (3) is preferably one in which R' is an alkyl having 6-14 carbon atoms, more preferably a branched alkyl having 8-12 carbon atoms, such as 2-ethyl. Both the diphosphinic acid of formula (2) and the alcohol of formula (3) are commercially available.

The temperature of esterification is 150°C to 200°C, preferably 160°C to 170°C.

The solvent for dissolving the diphosphinic acid may be selected from methanol, ethanol and water, with water being preferred.

In order to increase the yield, the diphosphinic acid is preferably poured slowly into the alcohol under stirring.

Another aspect of the invention relates to compositions containing the diphosphonic esters of the invention.

The composition consists of a diphosphonate compound of the invention and one or several transition metal salts, the molar ratio jj l
° 20, preferably between I: 3-10 νl"-.,
, cobalt, copper, maginotum, vanadium, chromium and molybdenum or mixtures thereof, with cobalt being preferred.

The composition can be prepared by simply mixing the diphosphonate compound and the transition metal salt.

Effects of the Invention The compounds of the invention, alone or in the form of a composition, can be used for the oxidation of hydrocarbons, such as the catalytic oxidation of cyclohexane, the oxidation of p-xylene and paraffin.

Regarding the oxidation of hydrocarbons, there are basically two methods known per se in industry: organic salt catalytic oxidation in the solution phase and non-catalytic oxidation. When used, the diphosphonate compounds of the present invention improve both processes.

In the case of a non-catalytic process, the addition of the diphosphonic acid ester of the invention suppresses side reactions and thus improves the yield.

In the case of a catalytic process, the addition of the compound of the present invention can enhance the catalytic activity of the corresponding metal ion, reduce oxidation, prevent cake formation, and extend continuous production for two cycles, resulting in improved yield. .

The amount of the compound of the invention added as a co-catalyst may vary from 0.0 l to 10 ppm, but is preferably from 0.05 to 5 ppm.

The compositions of the invention can also be added directly as catalysts in the case of catalytic processes. Its concentration is between 0.1 and 100 ppm, preferably between 0.5 and IOp.
It is pm.

The compounds of the invention as catalysts and compositions containing them are particularly suitable for the economical operation of cyclohexane oxidation.

When conventional cobalt-based catalysts are commonly used, yields are always less than 80% and heavily cake-based. Furthermore, if the pyrophosphate spreads over the reaction walls, it must be closed to clean up the cake build-up, which not only obstructs production but also causes severe environmental pollution.
Production will only last for two months.

On the other hand, the diphosphonic acid ester compound of the present invention is
Improving the catalytic activity of cobalt ions for the oxidation of cyclohexane, suppressing overoxidation, without requiring changes in the parameters and equivalents of the catalytic cobalt in the process.
It is possible to prevent the production of large amounts of cake and equipment coagulation, extend the period of non-stop operation, and improve the yield of alcohols and ketones.

In the case of cyclohexane oxidation, the amount of the compound of the present invention used is 0. The amount used can vary from 0.1 to 10 ppm, preferably from 0.5 to 5 ppm, whereas when using the composition of the invention, the amount used is from 0.1 to 100 ppm, preferably from 0.5 to loppm.

In addition, the diphosphonic acid esters of the present invention can also be used as complex extractants for metal ions and coagulants for epoxy resins.

The following examples merely illustrate some aspects of the invention and are not intended to limit the scope of the invention.

Example 1 3.500xl2 of 2-ethylhexanol was added to 500
0*(!), heated with a hot plate from the bottom, aerated air through the contents and stirred. Circulating cooling water was installed. When the temperature reached 160°C, HEOP (i.e. 1-
A solution of hydroxyethylidene-1,1-diphosphinic acid (hereinafter similarly abbreviated) was slowly added. On the other hand, 2-
Ethylhexanol and water are boiled (azeotropically), the steam is passed through a coil, condensed, and sent to a decanter, where the water is removed from the bottom from the system, and the upper 2-ethylhexanol condensate is returned to the reactor for circulation. I let it happen. The amount of solid HEDP in solution added to the system for each batch was 1
．． It was 1009.

Feed continued for approximately 2 hours, after which the system was refluxed for 30 minutes until all residual water had distilled out. After the reaction, about 4. OOOi
12 progenitor product was produced in the flask.

The product obtained by cooling is immersed in the same amount of water and 4.00
03112 cyclohexane was added. When left to stand, the contents separate into two layers, with a small amount of unreacted diphosphinic acid and sulfuric acid (catalyst) present at the bottom, and the upper oil layer is then vacuum distilled to distill water, cyclohexane, and 2-ethylhexanol from the top. About 2,000 g of product was obtained at the bottom.

The product has a melting point of -39°C and a decomposition point of 215°C. Field decontamination mass spectrometry (FDMS)
From a series of test results such as , infrared spectroscopy (IR) and nuclear magnetic resonance (NMR), the main components were I-hydroquine-ethylidene-1,1-diphosphonic acid mono-2-ethylhexyl ester, 1 with very small amounts of impurities. -Hydroxy-ethylidene-1,1-diphosphonic acid di-2- containing 1,1-diphosphonic acid tri-2-ethylhexyl ester and 2-ethylhexanol
It was proven to be ethylhexyl ester. ! −
Hydroxyethylidene-1.1 = diphosphonic acid di-2
- Ethylhexyl ester was proven to be a new compound (see below).

1017cm 1218cm 13801463c
-m εtc. NMR: 0.83ppm 1.24pPm3
．． 95ppmFDMS m/z: 341[M1+Na] 453[M2+Na]5 6
5 [M3 +Na] ■R: In the formula, M1 = 1-hydroxyethylidene-ll-diphosphonic acid mono-2-ethylhexyl ester M2 = 1-hydroxyethylidene-l. 1-diphosphonic acid di-2-ethylhexyl ester M3 = 1-hydroxy-ethylidene-l,l-diphosphonic acid tri-2-ethylhexyl ester Example 2 As a comparative example of Example 1, 3,500 ml of 2-ethylhexanol and 1 .1009 solid HEDP 5,0
Add to a 00xff three-necked flask, heat from the bottom with a hot plate, and stir while bubbling nitrogen through the contents. At the top of the flask a decanter and a spherical concentrating coil were connected with cooling water circulating through the jacket of the coil. When the temperature reaches between 130 and 200°C, the solution begins to boil and the reaction begins, but with a very slow rate of esterification. The results showed that only a small amount of HEDP ester was formed. In fact, it is believed that the main reaction was the dehydrogenation of 2-ethylhexanol resulting in the formation of large amounts of 2-ethylhexene.

Example 3 As a comparative example to Example I, a sample of 3.5003IQ containing mainly esterifiable compounds including cyclobentanol, n-pentanol and cyclohexanol obtained as a by-product in the process of producing oil 5,000 light oil
The mixture was poured into an xC three-necked flask, heated from the bottom with a hot plate, and the contents were stirred by bubbling nitrogen through the contents. At the top of the flask a water decanter and a ball-shaped condensing coil were fitted with cooling water circulating through a jack in the coil. When the temperature reached 140° C. and the solution began to boil, the HEDP dissolved in water was slowly added. While the gas oil and water solubles are boiling (azeotrope), the steam flows through the coil to a decanter where it is condensed, where the water is taken out of the system at the bottom and the upper gas oil condensate is returned to the reactor. I put it in a bracket. Solid HED in solution added to the system for each batch
P was 200g. Feed continued for approximately 2 hours, after which the system was refluxed for 30 minutes until all residue had distilled off.

After the reaction, about 3,500xQ of crude product was produced in the flask.

The product obtained by cooling was immersed in the same amount of water, and
0i (7) cyclohexane was added. When left to stand, it separated into two layers. A large amount of unreacted diphosphinic acid and a small amount of sulfuric acid (catalyst) were present at the bottom, and the oil layer at the top was
T″X 4:l″ 11-7 distillate, water, cyclohexane 1″L′. 11. ＋ ＊． +. A very small amount of the product HEDP pentyl ester (approximately 10?) was obtained at the bottom. Yields of useful diphosphonates are very low.

Example 4 3,500 ml of lauryl alcohol at 5,00 ml
The mixture was placed in a 0 mL three-necked flask, heated from the bottom with a hot plate, and the contents were stirred while nitrogen was bubbled through.

At the top of the flask, a decanter and a ball-shaped condensing coil are fed with cooling water circulating through the jacket of the coil. When the temperature reaches 160 °C, first 50 ml of p-xylene is added, then HBOP −
1.1-Diphosphinic acid) was slowly added. The lauryl alcohol, p-xylene and water begin to boil (azeotrope) and the vapor flows through the coil where it condenses into a decanter where the water is taken out of the system at the bottom and the lauryl alcohol, p-xylene in the upper layer - The xylene condensate was recycled back to the reactor. The amount of solid HBOP in the solution added to the system per each batch was 1.500 g. The crude product is soaked and distilled, and finally 2,4
00 g of product, 1-hydroxybutylidene-1.
1-diphosphonic acid lauryl ester was obtained.

PO(OH)2 PO(OHXOC
,H. ．． )CH3H? -C-OH +2C. ffi
HtsOH=C3H7-C-OH +2Ht
OPO(OHh PO(OH)(
OC+tHzs) Example 5 Add 100 ml of benzene to a 250 ml separatory funnel, then add 1 g of cobalt cycloalkanoate, which is suspended evenly in the benzene phase, then
Cobalt ions were extracted into the aqueous phase after adding 2 ml of a 2% solution of diphosphinic acid in hexane. at this point
1 g of HEDP di-2-ethylhexane ester is added to extract the cobalt ions in the lower water layer into the upper oil layer.

Example 6 50g of general purpose epoxy resin was mixed with stirring.
g of HBDP dilauryl ester. After heating to a temperature between 160 and 200° C. for 40 minutes, the resin was fixed and molded and all targets met the test standards.

Example 7 This is a comparative example of Example 8 and is as follows.

8. Cyclohexanone by cobalt-catalyzed oxidation of hexane. In the industrial unit for production of OOOt/g, sodium pyrophosphate spread on the reactor walls due to inertization. The cyclohexane feed was 36 m'/h and the air flow was 2.
It was 1 O O Nm3/h. During cyclohexanone dissolution, cobalt salt in the form of cycloalkanoate was continuously fed into the system to bring the cobalt ion concentration in the oxidation system to 0.
Control to 26 ppm weight or 2k
g of cobalt cycloalkanoate (approximately 8% cobalt ion) was mixed into 2II+3 cyclohexane daily. Weighed 2ffl3 of the cobalt salt cyclohexane solution produced and placed it in a No. 3 metering bomb. 1 reactor at a constant rate over 24 hours. The system pressure is IMPa. g. The reaction temperature was 154±2°C. The oxidation process of cyclohexane proceeded smoothly. The exhaust gas from the oxidation contained 2.5% oxygen as sampled in a gas sampling bottle. By visual inspection, the sample appeared cloudy with a small amount of tan solution at the bottom of the bottle and some particles of the same color adhering to the bottle walls. After the next steps, saponification, distillation of the oxidation products and dehydrogenation of the cyclohexanol, 3.3. 1 t
An average output of 27.1 t/d of cyclohexane was obtained with consumption of /d. After approximately two months of continuous operation in this manner, the operation was stopped for 24 hours, the system was cleaned, and then restarted. This is because the large volume created in the reactor and connecting pipes eventually clogged the system. During cleaning, large amounts of soda water were consumed in the reactor and pipes in combination with manual cleaning of the buildup.

Example 8 This is an 8. cobalt catalyzed oxidation of cyclohexane.
000 t/g of the composition as a catalyst in an industrial unit for the production of cyclohexanone, the same unit as in Example 7, but without using sodium birophosphate as a deactivator.

Cyclohexane supply is 36m'/h, air is 2,1
The cobalt salt in the form of ncroalkanoate, which is mixed with the diphosphonate ester in the cyclohexane solution, was fed continuously to the system. The cobalt ion concentration in the oxidation system was 0.0 NII1"/h. 26 ppI controlled at 1 weight and the molar ratio of cobalt ions to diphosphonate ester is 7:l or 2 kg of cobalt cycloalkanoate (approximately 8% cobalt ions)
and 150 ml of diphosphonic acid ester, mainly HE
DP di-2-ditylhexane ester was mixed into 2 m3 of cyclohexane daily. The cobalt salt/diphosphonic acid ester in the cyclohexane solution of 2+++' produced was weighed and placed in a No. 2 metering bomb. 1 oxidation reactor at a constant rate over 24 hours. System pressure is set to IMPa. g. The reaction temperature was controlled at 154±2°C. The oxidation process of cyclohexane proceeded smoothly. The exhaust gas from oxidation was sampled in a glass sampling bottle.
Contained 2.0% oxygen. By visual inspection, the sample was bright clear with a small amount of colorless solution at the bottom of the bottle, which proved to be acidic water. As the oxidative conversion rate increased, crystalline hexane diacid white particles were visible adhering to the bottle wall. After the next steps, saponification, distillation of oxidation products, dehydrogenation of cyclohexanol, etc., 34.7t
An average output of 30.2 t/d of cyclohexanone was obtained with consumption of /d of cyclohexane. Compared to Example 7, the output per unit time increased by 10%, and the total yield increased by 5%. After one year of continuous operation of this process, there was no resin build-up in any of the reactor or pipes. Operations continued, but maintenance did not require annual scheduled closures. When opened without cleaning, there was no evidence of accumulation inside the fixtures or pipes, and the interior walls were as shiny as when they were first installed. It was confirmed that the unit could be operated continuously for at least one year without changing the unit.

Example 9 Cyclohexanone/by non-catalytic oxidation of cyclohexane
In the usual manufacturing process of cyclohexanol, sodium birophosphate is used as a deactivating agent and spreads in the reactor, which generates sodium ions or conversely, which causes side reactions and results in low yields. In the same unit, instead of spreading sodium pyrophosphate on the wall, a small amount of diphosphonate ester, mainly HEDP di-2-ethylhexane ester, is added to reduce the concentration of diphosphonate in the reaction to 0. The oxidation system No. 3 was controlled to 3 ppm weight. All process parameters were kept unchanged except for feeding the I reactor. Thereby there was no more accumulation in the system. In addition, the oxidation product became colorless and side reactions were reduced. As a result, the total yield of alcohol/ketone production increased by 2%.

Example 10 Conventional process for producing higher alcohols/ketones by paraffin oxidation, e.g. C I2-C +sC by oxidation of paraffins,! - C +s In the alcohol production process, similar problems of fouling and clogging of equipment and pipes hinder normal operation. However, its concentration is about 0. The paraffin oxidation reactor is freed from buildup by adding HEDP di-2-ethylhexane to the feed stream to maintain a 3 ppm weight or by using a 5 to I molar ratio of catalyst metal ions to diphosponate ester. , the yield of useful product increased by 3%.

Example 11 In a commercially operated unit for the production of 1.000 t/g p-toluic acid by oxidation of p-xylene, a similar problem of fouling/clogging inside the equipment/pipes exists. All process/equipment parameters were adjusted to include cobalt catalyst concentration,
By simply adding HEDP di-2-ethylhexane ester into the feed stream such that its concentration is maintained at 0.5 ppm - 3 ppm weight without any changes including reaction pressure, temperature supply and air flow etc. None was found in the vessel, and the overall yield of the target product, p-toluic acid, was increased by 3%.

Claims (1)

[Claims] 1. Compound of formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, m_1 = 0, 1 or 2, n_1 = 2 - m_1;
m_2=0.1 or 2, n_2=2-m_2; 0<m_
1+m_2<4; R is H or alkyl having 1-8 carbon atoms; R' is alkyl having 1-18 carbon atoms;
2. A compound according to claim 1, wherein R' is H or OH)2 and R' has 6-14 carbon atoms. 3. A compound according to claim 2, wherein R is H or alkyl having 1-6 carbon atoms. 4. The compound of claim 3, wherein X is OH. 5. The compound of claim 4, wherein R' is branched alkyl having 8-12 carbon atoms. 6. The compound of claim 5, wherein R has 1-3 carbon atoms. 7. The compound of claim 6, wherein R' is 2-ethylhexyl. 8. The compound of claim 7, wherein R is methyl. 9. The compound according to claim 1, wherein m_1 and m_2 are both 1. 10. Formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) (In the formula, R and Formula (1), which is characterized in that the esterification reaction is carried out by adding R'OH (3) (wherein R' has the same meaning as in claim 1) to the alcohol of formula (3) at normal pressure. , chemical formulas, tables, etc.▼(1) P-O(OH)m_2(OR')n_2 (In the formula, m_1, m_2, n_1, n_2, R, R',
and X have the same meanings as in claim 1). 11. The method of claim 10, wherein the esterification temperature is in the range of 150 to 200°C. 12. The method of claim 11, wherein the solution of diphosphinic acid is added slowly under stirring. 13. The method of claim 12, wherein the solvent is water. 14. Claim 1, wherein the solvent is methanol or ethanol.
Method 2. 15. The method according to claim 13, wherein the temperature of the esterification reaction is 160-170°C. 16, R is H or alkyl having 1-6 carbon atoms, R
Claim 1 wherein ' is alkyl having 6-14 carbon atoms.
The method according to any one of items 0 to 15. 17, R is alkyl having 1-3 carbon atoms, R' is 8
16. A method according to any one of claims 10-15, wherein X is OH, a branched alkyl having -12 carbon atoms. 18, R is methyl, R' is 2-ethylhexyl, X is O
16. The method of any one of claims 10-15, wherein H. 19. Use of a compound according to any one of claims 1 to 9 in catalyzing the oxidation of hydrocarbons. 20. Claims 1-9 regarding the oxidation catalytic action of cyclohexane
Uses of the compound according to any one of the following. 21. The use according to claim 19 or 20, wherein the compound is used as a catalyst. 22. The amount of compound used is from 0.01 to 10 ppm
The use according to claim 19 or 20. 23. The use according to claim 19 or 20, wherein the amount of compound used is from 0.05 to 5 ppm. 24. Use of the compound of any one of claims 1-9 as a complex extractant. 25. Use of the compound according to any one of claims 1-9 as a coagulant for epoxy resins. 26. A composition for oxidizing hydrocarbons, comprising the compound according to any one of claims 1 to 9 or a mixture thereof and a transition metal salt. 27. The composition of claim 26, wherein the molar ratio of compound to transition metal salt is between 1:1-20. 28. The composition of claim 27, wherein the transition metal salt is selected from cobalt, copper, magnesium, vanadium, chromium and molybdenum salts or mixtures thereof. 29. The composition of claim 27, wherein the molar ratio of compound to transition metal salt is between 1:3-10. 30. The composition of claim 29, wherein the transition metal salt is a cobalt salt. 31. Use of the composition of any one of claims 25-30 as a hydrocarbon oxidation catalyst.