JPS58134053A - Manufacture of dialkylcarbonates - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carbonates using a catalytic reaction to produce dialkyl cargenates from bamboo.

It is known that carbon dioxide and aliphatic alcohols react with the aid of tin sibutyl alkoxides as catalysts to separate water and yield the corresponding dialkyl carbonates. This reaction is catalyzed by 11 CO, + 2Ros; Ro-c-oR-1-H! .

Proceed according to the following. The esterification equilibrium is dominated by the starting material η, <n<iゎ, 3. ,) The yield is 8 lower [ya.・(
1・□Ni-ffki et al., Po ``l-・3., Praprits
ta, Amur, Chem.

1\SaC,, Div, Polym, Chum, 20
(1979), pp. 146-149, or 197
See Japanese Published Application No. 79/&012 of November 18, 2009].

The present invention relates to an improvement to this process which provides even higher yields.

Therefore, in the present invention, the monohydric fatty acid group alcohol can be used in an amount of 0 to 300
The present invention relates to a process for the preparation of V alkyl carnates in the presence of a catalyst, characterized in that the reaction is carried out with carbon dioxide in the presence of molecular sieves at a temperature of 1 to 3000 par.

The carbon dioxide used is, for example, in gaseous form.

Generally, this reaction uses an autoclave into which the alcohol, catalyst and molecular sieves are added and then filled with, for example, gaseous carbon dioxide to the desired pressure and then heated to the reaction temperature. After depressurizing and opening the autoclave, the carbonate formed can be isolated by conventional methods.

Suitable monohydric aliphatic alcohols for the process are linear primary alcohols, spheroidal alcohols or secondary alcohols, especially C.

~C1°-Alkanols, such as ethanol, methanol, chrononol, ingulonol, butanol, hexanol, 2-ethylhexanol, 2-methylgulonohexanol, 3-methylbutanol, amyl alcohol and 2-butanol, and Cs' %-c,.

- cycloalkanols, such as cyclohexanol,
It is.

Examples of suitable catalysts according to the invention are compounds of the main and cape groups 1 to 1 and the subgroups VIIM and 11 of the photoelectric period J111 table [Hallman (/-10L l etn
, ann) - Wiberg, Textbook of Inorganic Chemistry (17tt h-r, bxch ch
Anorganischemn Chgmie), 37
-39th edition, published by Walter De Ruyter & Kanno, Bell lJ/1ss6#).

Suitable main group 1 and subgroup 1 compounds according to the invention are not only salts but also covalent compounds of metals of these groups of the periodic table, such as LtBr, butyllithium, LiCL.
, Lil, Na0CHB, CsC1゜Ag0CC)-
CH, etc. may also be used.

Suitable compounds of main group n and subgroup 2 according to the invention include soot-like as well as covalently bonded compounds of the metal symbols of these groups of the periodic table, such as MgCl,, Be ((j-co-cH
@ ) t % Grignard compounds, ZnCL.

Zn5U4. My(QC, Hl), etc. may be used.

Compounds of the main group Meng and subgroup Ca are suitable according to the invention, in particular covalent compounds of these elements of the periodic table, such as B(O'eHs)a*B(Ce#s)s
*Al (OR), (R=aliphatic or aromatic hydrocarbon group), etc.

Suitable main group and subgroup compounds according to the invention include the elements rumanium, tin, lead, titanium and citanates (e.g. tetrabutyl orthotitanate), orthotitanates (e.g. echetetraphenyl orthostanate). ) etc.

Suitable main group V and subgroup (I) compounds according to the invention are in particular #t■ bond compounds of the elements of these groups of the periodic table;
For example, amines (e.g., -1'zoazabicyclooctane), phosphines (e.g., triphenylphosphine or F-n-octylphosphine), phosphines/oxides (e.g., triphenylphosphine oxyto)
etc.

In accordance with the present invention, the main group Ⅰ and the subgroup ① of subgroup V1]; joint groups include not only covalent compounds of the elements of these groups of the periodic table, apart from oxygen, but also ferrochemical compounds, It may also be thioethers, such as diphenyl sulfide.

Suitable compounds of subgroup 1 according to the invention may be covalently bonded compounds of the elements of this group of the Periodic Table, as well as sooty compounds (for example manganese(II") acetate).

Suitable subgroup compounds according to the invention □ can be not only covalent compounds of the elements of this group of the periodic table, but also sooty compounds, such as iron (N-acetylacetonate).

Combinations of the above compounds are also coupled catalysts for the process according to the invention, in which the electron-donating and electron-accepting properties of the catalyst combination have to be mutually exclusive, i.e. electron donor and deuteron acceptor. Must use body combinations.

Examples of such combinations are aluminum alcoholates combined with amines, phosphines, phosphites or phosphine oxytos, lithium #i combined with ortho titanates, and thioethers. It is a phase of madanesium alcoholate that has been considered.

Suitable catalysts according to the invention are used in amounts of from 10-a to 5 molty, preferably from 0.1 to 3 molty, with respect to the number of moles of the particular alcohol used; This applies not only to the use of catalysts, but also to the combination of catalysts.

Molar ratio of catalyst types in catalyst combination I: 1r3=-
It can be varied between 3:1, for example 1:1.

Suitable catalysts have the general formula %) [wherein M# represents Sn, Zr or Ti, -R1 represents Ct-Cta-alkyl, *rrtc, -c,
.

-aryl, R1 Cl-C1a-alkyl, c, -c,. -aryl or "t-C18-acyl (1, X is /% o
If 7, SH, = 0 / 2 t = S / 2, '1 * "! t "S and n4 are 0, 1, 2°3 or 4 - 6E, s, +n, -) - The sum of n and + is always 4]. Especially when M#=S%, father-in-law.

= 1 or 2, Me = Ti over Zr, n
,=4.

Examples of particularly suitable catalysts are dialkyltin dialkoxides, such as sibutyltin dibutyrate or ti,ybutyltinV laurate, tetrabutyl orthotitanate and tetrabutylorthotitanate.
The molecular sieves used according to the invention are known and
・1・.

(e.g. German Published Specification No. λB 50.32)
No., column 3, lines 28-65 and Ul1man%
S E? 1cyklop&die dartgchni
schenChamig), 4th edition, vol. 17, 9-18
White.

Particularly appropriate molecular behavior is its groove (chan↑+e1g
) are zeolites having a negative polarity of 3 to 474'.

The coughing method can also be performed using a molten S diluent. Suitable solvents or diluents are all liquids that are inert to the reaction.

The method uses a pressure of between 1 bar and 1.000 mbar, in particular between 1 bar and 1.00 mbar. OOO pearl's carbon dioxide pressure ≠ 1 is used, lO pearl ~ S OO no? -L, especially 25-300
Pearl is preferably used.

The process is carried out at temperatures between 0 and 3100°C. However, once the reaction is performed, especially at 100-220°C, (7) 11
J1faFt, ! ,ll! 4. tC@＊'lWrt
l1M is between 130 and t8n°C.

The reaction time can be between 2 and 100 hours, especially between 10 and 60 hours, and especially between 24 and 48 hours.

The amount of molecular sieve used in the process according to the invention must be selected in each case such that the water separated off during the reaction can be collected in the trap.

It is also possible to use slightly more or less molecular sieves than are needed to capture water.

In a special variant, the reaction is carried out in several stages, preferably up to 5 stages, and after each stage the reaction solution is separated from the molecular sieve and treated with a new molecular sieve. The amounts of carbonate obtained in the examples below always refer to the amount of alcohol used.

Examples Example 1 Aliphatic alcohol (25,9 2-ethylhexanol = 1935 mmol) was added to 1! It was added to a 200 d laboratory autoclave along with 1I medium (&3 g diptyltin dilauret = 5.5 mmol to 3 mol) and water removal material (4A molecular weight of sol I). The air contained in the autoclave was removed by repeatedly introducing carbon dioxide and purifying the autoclave. Next, introduce 55 parts of COI, invert the autoclave [7 parts to mix its contents, and heat to 160°C.
It was heated for 66 hours. Thereafter, the autoclave was cooled silently, excess CO1 was released, and the carbonate content produced was determined by gas chromatography.
Established. The so(2-ethylhexyl) carbonate content is determined by mf14, with respect to the amount of alcohol used (this is also calculated as such in the examples below).
Met.

Example 2 The feed rate was the same as in Example 1. A 2501111 capacity laboratory autoclave was used. Reaction temperature is 220℃
and the reaction time was 18 hours. Yield is 2
It was Q2%.

Example 3 1,25N 2-ethylhexanol (=9.6 mmol), α083I subbutyltin dilaurate (=α1
4 mmol to 1.5 mol) and ? , 59 were used as starting material.

Use a 10-volume high-pressure autoclave, in which 300
Q. CO8 was introduced in the armpit. The reaction temperature is 200
℃ and reaction time was 42 hours. The yield is 16.6%? "fart.

Example 4 The supplier was the same as Example 1. ! ! A Gotlt laboratory autoclave was used. The reaction was interrupted at 160° C. with a reaction interval of 18 hours, and in each case the 4 reaction solutions were separated from the molecular sieve and treated with a new molecular sieve.
Then, a new COl was introduced. After four reaction cycles, the nate yield was 60.1%.

Example 5 (Comparative example) 125 g of 2-ethylhexanol (=96 mmol)
and λ7I! Sibutyltin dilaurate (=45 mmol=47 mol qb) was added to 50 tones of xylene and human
o, a g's #, #'-zocyclohexyl-cal?
With soimide (=50 mmol), the force [ieda] was placed in a 250 m/each laboratory autoclave.

The reaction solution was heated to 45 Parr GO! at room temperature. 6 under pressure
Stir/bread for 6 hours. Carbonate yield 4=t, &
It was 1ch.

Implementation Example 6 (Comparative Example) M! The amounts were the same as in Example 5. A 200 liter laboratory autoclave was used. The reaction temperature was 80°C and the reaction time was 66 hours. A carbonate of 4% was obtained.

Example 7 (Comparative example) The supply amount was the same as in Example 5. 200 - React in a laboratory autoclave. Reaction temperature: 120°C; reaction time: 9 hours. Kerr's nate yield was near, 3%.

Example 8 4α45I n-butanol (=545.65 mmol), 1.6111 dibutyldimethoxytin (=S, 46
3A molecular sieves of 5011 and 5011 were treated with 55 par of COI in a 200-volume laboratory autoclave. The reaction time was 91 hours, and the reaction temperature was 155°C. The &-(n-butyl)carnate yield was 220% (area).

Example 9 1Q, 71-heptatool of ON (=86.05 mmol) and 1.27 N of dibutyldimethoxytin (=
4.30 mmol = 5 mol%) with 50 g of xylene and 50 g of molecular sieves in a 250-volume laboratory autoclave at 55 bar CO! Processed with. The reaction temperature was 155°C and the reaction time was 50 hours. Di(n-heptyl) carbonate yield H19,
It was 4% ([#qA).

Example 10 Same snoring as 9. 9.62 j' of cyclohexanol (=
96.08 mmol) as alcohol.

The reaction time was 91 hours, and the reaction temperature was 155°C.
Met. The no (cyclohexyl) carbonate yield was 4.0% (area %).

Example 11 50-251 in xylene! 2-Ethylhegi? /-
(=19197 mmol), 5Ojl(7)3A molecular sieve and 2.84.9 zirconium zolobire-'
) (=8.loammol=45 mol%) was treated with 55 pars of CO2 in a 200-volume laboratory autoclave. The reaction time was 69 hours, and the reaction temperature was 15
The temperature was 5°C. A yield of 6.15% (area %) glue (2-ethylhexyl)carnate was obtained.

Example 12 I in xylene of 50-jl to 2-ethyl of Z5fI
'l/-k (=9L9BS remol),! SO# 3A molecular sieve and 440.9 tetrabutylorthotitanate at 200F! 5 l/vol in a laboratory autoclave
It was treated with 5 pearl co,,,:. After 53 hours at 150°C, 9.1% (area fl!ch) of di(2-ethylhexyl) carbonate was produced.

Example 13 The process and process were the same as in 11. MmH1 used
7,25- diptylaluminum hydride (=I
) iBAH) 20% strength solution in toluene/z2sII
of triphenylphosphine (=a7 mmol=4 mol %). 421t! After the reaction time between 4.
0% no(2-ethylhexyl) carbonate was obtained.

Example 14 The quantities and steps were the same as in 12. The catalyst used was 3.6 g F non-tBAR 20% strength solution in toluene/'1.35 II triphenyl phosphite (=434 mmol - 5 mol %). The yield of mono(2-ethylhexyl) carbonate after the reaction between 93H'1 and 10% was 10%.

’, l:.

Example 15 The amounts and steps were the same as in 12. One catalyst for 1φ was a 20% strength solution of 36-diEAH in toluene/a
44,9 triethylamine (=434 mmol=45
(mol%). After a reaction time of 75 hours, the carbonate yield was 20%.

Although the invention has been described in detail for purposes of illustration,
It should be understood that such claims are for that purpose only, and that other modifications within the spirit and scope of the invention are within the scope of the claims, and are therefore limited to, by those skilled in the art. It is easy to understand that it can be done.

Patented Dejima style Beyer Akchenr Zellshaft

Claims (1)

[Claims] 1. Dialkyl in the presence of a catalyst, characterized in that monohydric alcohols are reacted with carbon dioxide in the presence of molecular sieves at a temperature of 0 to 300 °C and under a pressure of 1 to 3000 par. Carbonate manufacturing method. 2. The method according to claim 1, wherein the cough molecular sieve is a zeolite characterized in that its grooves have a diameter of 3 to 4 A. 2. The method according to claim 1, wherein the λ reaction is carried out in several stages. The method according to claim 1, wherein the pressure is between 1 and 1000 par. The method according to claim 4, wherein the pressure is 1-500 par. a The method according to item 1, wherein the temperature is 100 to 220°C, %P: 60% range. 7. The method according to patent-ψ range item 6, wherein the temperature is 130 to 180°C. & The catalyst has the general formula % formula %) [In the formula, Me ij Sn , Zr straddling Ti is shown, R, f
C1-Cll-alkyl or C, -C. -aryl, R, represents C1-C1@-alkyl, C5-cto-aryl or Ct-Cts-acyl [7, ・X
indicates Haloke 0, SR, = 0/2 straddle = S/2, and bamboo 1 w ``* s '' m and n4 are independently 0, . 1, 2, '3 or 4, but n, -)
The method according to claim 1, wherein the sum of -s, +n, -)-s is always 4. 9. The method of claim 8, wherein e, M- indicates outside S, and sl is 1 or 2. 9. The method of claim 8, wherein lo, M- represent Ti or Zr, and n$ is 4. lt, the catalyst is selected from the group consisting of diptyltin dibutyrate, subbutyltin zolaurate, tetrabutyl orthotitanate and tetrabutyl orthotitanate.・, 1 12 The monovalent aliphatic alcohol is (:', -c,, -
2. The method of claim 1, wherein the method is selected from the group consisting of alkanols and C,-C1°-cycloalkanols.