JPS5824532A - Preparation of aldehyde - Google Patents

Abstract

PURPOSE:To prepare an aldehyde by the hydroformylation reaction of an olefin using a highly active low-phosphorus catalyst composed of an Rh compound and a styrene oligomer containing specific diphenylphosphino group as trivalent organophosphorus compound. CONSTITUTION:In the preparation of an aldehyde by the reaction of an olefin compound with carbon monoxide and hydrogen in the presence of a trivalent organophosphorous compound and a rhodium compound, a diphenylphosphino group-containing styrene oligomer is used as said trivalent organophosphorus compound. The styrene oligomer has a number average polymerization degree of 3-350, especially 4-100, contains the structural unit of formulaIin an amount of 5-100mol%, and contains styrene oligomer as the principal skeleton. Preferably, the diphenylphosphino group-containing styrene oligomer is composed of 40-100mol% structural unit of formula II, 0-40mol% structural unit of formula III (X is halogen) and 0-40mol% structural unit of formula IV. EFFECT:The catalyst exhibits high n/i ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing alda and do by the human tetraformation reaction of olefins using a novel catalyst system.

The human tetraphonation reaction of olefins catalyzed by a tetradium-J-class phosphine complex is well known.
Ru.

(British Patent No. 1 Try Bait No. 1, Special Public Shojiter 10710
However, in this method, the production ratio of linear isomer/branched isomer (hereinafter abbreviated as φ) of the generated aldehyde is small, and it is difficult to obtain a large amount of KFi to obtain the industrially important linear isomer. It is necessary to coexist a tertiary phosphine ligand in the reaction system.

In the do-tetraformylation reaction, aldehyde oligomers produced by side reactions such as aldol condensation of aldehydes and tertiary phosphine oxidation products are used.
Because the high-boiling byproducts of phosphine oxides gradually accumulate in the catalyst solution, a portion of the catalyst solution is normally discharged continuously or intermittently to the outside of the system to remove the components contained in the discharged catalyst solution. By replenishing the rhodium and tertiary phosphine complex and tertiary sphine in an amount commensurate with the amount of the catalyst, it is usual to prevent the accumulation of the high boiling point by-products in the system as well as the activity a# of the catalyst. It is the law. The use of large amounts of tertiary phosphine.

With the increase in the amount of tertiary phosphine to be replenished, it is not only economically disadvantageous but also operationally difficult, such as installing a recovery system 1 for the tertiary phosphine in the discharged catalyst liquid.
It has the disadvantage of being complicated.

On the other hand, using rhodium catalyst and low concentration of phosphine, high n/
Methods for obtaining the i ratio include a method using a monodentate ligand (JP-A Sho!!-/2/7//, JP-A Sho-Nazi 39007) and a method using a phosphine ligand bonded to crosslinked polystyrene (Bud AC8 !9102 (l def 6)) have been proposed, but all of them have the disadvantage of slow conversion speed compared to tertiary phosphine systems.

In order to overcome the drawbacks of the prior art as described above, the present inventors conducted extensive research and found that when a diphenylphosphino group-containing styrene oligomer is used as a ligand for a rhodium catalyst, The present invention was completed by discovering that high activity and high n/i ratio can be obtained.

That is, the present invention provides a method for producing an aldehyde by reacting an olefin compound with carbon monoxide and hydrogen in the presence of a trivalent organophosphorus compound and a rhodium compound, which is expressed as a trivalent organophosphorus compound by the Shimohi formula (1). The number average degree of polymerization of the styrene oligomer, which is the basic skeleton, is 3 to 3.
An aldehyde characterized by using a diphenylphosphino group-containing styrene oligomer having 0. ! ! It lies in the construction method.

The present invention will be explained in detail below.

The trivalent organic phosphorus compound used in the present invention has from ! to 100 moles of structural units represented by the following formula (D), and the number average degree of polymerization of the styrene oligomer, which is its basic skeleton, is from 3 to 1.
10 (hereinafter abbreviated as oligophosphine).

Preferably, the structural unit represented by the formula (I) of the bait 0-/00 molti, the structural unit represented by the following formula (1) of the O-a O molti, and the structural unit represented by the following formula of the bait Q molti. It is something that you have. The number average degree of polymerization of the styrene oligomer that is the basic bone S is preferably 100 to 100.

The diphenylphosphino group-containing styrene oligomer F
(i) Diphenylphosphinostyrene is produced by a low polymerization method or by introducing a diphenylphosphino group into the phenyl nucleus of a styrene oligomer, but preferably the latter method is used.

The raw material styrene oligomer is obtained by decomposing polystyrene by heat or the like or by low polymerization of styrene monomer. In particular, styrene oligo i- having a polymerization degree targeted by the present invention can be easily obtained by an anionic low polymerization method using butyllithium as a starting agent.

In addition, a commercially available styrene oligomer having the degree of polymerization targeted by the present invention can be used as a raw material that is easy to handle.

The method of introducing diphenylphosphino groups into the styrene oligomer can be directly applied to the known method shown in the following formula, but the introduction rate of diphenylphosphino groups (
It is preferable to carry out phosphination rate) tflll.

Halogenated styrene oligo in formula (B)! -is,
For example, a styrene oligomer is reacted with a simple halogen such as bromine in the presence of zinc chloride in a chloroform-acetic acid mixed solvent, or a styrene oligomer is reacted with a simple halogen such as bromine in the presence of thallium acetate in a carbon tetrachloride solvent. By letting it be set for seconds. In the former method.

Styrene oligomers with a low degree of polymerization are completely substituted with halogen, but styrene units with a high degree of polymerization remain unsubstituted.

The amount of non-halogenated styrene unit (1) is preferably small! It should be less than 0 mol. If there is too much Unirad that is not halogenated, the amount of phosphorus that is ultimately introduced into the lambda tyrene oligomer will be reduced.
If it is preferable that n/i decreases in the hydrophorylation reaction.

□゛Also, in the former, about 10% of the halogen substitution positions are at the p-position, and about 10% are at the o-position. In the latter method, the degree of halogen substitution is almost the same as in the former method, but all halogens (11f) are introduced by substitution at the p-position Kll.

(M) The lithiated styrene oligomer in 2 can be obtained by a method in which a styrene oligomer is reacted with Kn-butyllithium in the presence of M, M, M', He-tetramethylethylene cyazine, halogenated styrene #9=r mer A method of reacting halogenosterene oligo i- with metal lithium can yield wheat flour.

In order to produce oligophostuines from lithiated styrene oligomers, diphenylphosphine such as chlorodiphenylphosphine is added dropwise to the reaction product liquid obtained by the lithiation, followed by slight heating.

As the reaction progresses, the precipitate of the lithiated styrene oligomer gradually disappears, so after the precipitate has completely disappeared, cool it and drain the reaction solution into methanol. is obtained as a white precipitate.

IL for producing oligophosphine from halogenated styrene oligomers: Dissolve these oligomers in a solvent such as tetrahydrofuran, add dropwise a solution of lithium diphenylphosphine in tetrahydrofuran, and heat. 7
~! After heating and stirring for a period of time, the mixture was cooled and one reaction solution was discharged into methanol, yielding a white precipitate of oligophosphine.

It is preferable that the halogen is completely substituted with the diphenylphosphino group, but the residual rate of the halogen is less than or equal to aO mol as the structural unit (II), preferably #i coσ
It must be less than molti. If the residual rate of halogen increases, n/i or reaction rate will decrease in the hydroformylation reaction, which is undesirable.

KFi to obtain an oligophosphine consisting of 100% of the structural units represented by formula (1) described above may be obtained by low polymerization of diphenyl (vinylphenyl) phosphine, which is known for the conversion of bromostyrene to diphenylphosphine.

Thus, the number average degree of polymerization of the styrene oligomer is J~J
Evening 0. Preferably, the phosphine conversion rate is between da and 100! ~1
00 molar, preferably %0 to lσ0 molar, of oligophosphine can be obtained.

The oligophosphine of the present invention has a number average polymerization f3~3!00
Specific Ili! The basic skeleton is a styrene oligomer of 0. Preferably Kat~t.

selected within the range.

Oligophosphine is used by introducing it into a hydroformylation reactor together with a suitable rhodium source, and then hydrogen and -
Examples include a method in which K111 is formed in the presence of a mixed gas of carbon oxide, and a method in which a complex is formed with rhodium in advance.

As a suitable rhodium source, a complex containing rhodium and phosphine such as RhH(Co)(Pφ, - means phenyl group) may be used.
Easily available rhodium compounds such as rhodium in organic acids such as rhodium acetate or rhodium in free form such as rhodium nitrate and rhodium sulfate can be used by dissolving them in an appropriate solvent.

As a method for forming a complex with the oligophosphine in advance, it is possible to apply a method of complex formation between a rhodium compound and a tertiary phosphine, which has been widely studied in the past, but coordination with a monovalent rhodium complex is possible. Particularly preferred is the production method by child exchange. As a heptavalent rhodium complex.

Typically Rh'H(co)(pφ, )1, Rh(oA
c) (00)(Pφ,).

(MuCFi, means acetyl group), ("Rhcz(
cycloocte/ )1 )1, (Rh(OAc)(/,
! -cyclooctadiene)), Cuhcz(c
o), )*, (Rh(oAc)(CO)*)e
Examples include. Ligands such as tertiary phosphines, olefins Ws, and carbon oxide contained in these complexes are easily exchanged with the ligands of the present invention to form oligophosphine-coordinated rhodium complexes.

There is no particular limit to the amount Fi used of the rhodium compound, but it is usually 5
The concentration in the reaction zone is 0.0 in terms of rhodium metal. /8
9-co f/t, preferably Fi/IIIP~/1/
Selected within the range of 1.

The olefinic compound used as a reaction raw material in the method of the present invention is an organic compound having an olefinic double bond in one molecule, and specifically, edelene, tetrapyrene, butene-7°pentene, etc. -7, hexene-7, octene-7, dodecene-7, olefinic hydrocarbons having 2 to 20 carbon atoms such as styrene, el-methylstyrene, and cyclohexene, acrylonitrile, allyl alcohol, vinyl acetate, and methyl acrylate.

Examples include olefinic compounds having a functional group such as methyl methacrylate.

Although it is essential to use a reaction solvent in carrying out the reaction, the reaction is usually carried out in the presence of a solvent that is inert to the hydroformylation reaction and that dissolves the oligophosphine-coordinated rhodium complex compound.

Preferred specific examples include aromatic hydrocarbon compounds such as benzene, toluene, xylene, and dodecylbenzene, acetone,
Examples include ketones such as diethyl ketone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and esters such as ethyl acetate, ethyl propionate, and di-n-octyl phthalate. Furthermore, from an economic point of view, it is also possible to use a high boiling point substance consisting of aldehydes as products or aldehyde oligomers as Fi by-products as a solvent. In any case, in this reaction system, it is necessary that the catalyst system consisting of the rhodium compound and oligophosphine be substantially dissolved.

As for the reaction conditions, the reaction temperature is in the range of room temperature to θOC, preferably 0 to 1707:.

The reaction pressure is normal pressure to 300 atm, preferably Fi- to 10 atm. When the pressure is low, n/i tends to be large.

The molar ratio of hydrogen and carbon monoxide (FiJCO') is 10//
~l/10, preferably l/l-6//.

Hereinafter, the present invention will be explained by reference examples and examples. Number average wage rate of styrene oligomer in the present invention (lower w
) is measured as follows. It was measured by gel permeability chromatography under the following conditions.

Model used: IILO-40/MU (manufactured by Toyo Soda Co., Ltd.) Column: GMaa (Cofeet) Komoto (manufactured by Toyo Ichida Co., Ltd.) Conditions Developing liquid Tetrahydrofuran ('rHF)
Open temperature JrC Detector R engineering standard sample Pressure Chemicals standard polystyrene cord, j X10' 000 00 3 l da l O In addition, for the styrene oligomer of M (Taooo Co., Ltd. J), two columns asooooH/ (J feet) (manufactured by Toyo Soda Co., Ltd.) were used (the measurement conditions were the same). '), the molecular weight was confirmed.

Reference Example - (Synthesis of styrene oligomer) The styrene oligomer, which is the raw material for the oligophosphine used in the present invention, can be easily obtained by an anionic low polymerization method of styrene. Its synthesis method involves diluting a hexane solution of commercially available butyl lithium manufactured by Merck & Co. (approximately 0N) with THν to obtain a solution of approximately O,A normality.
: Cool to 100 mL, stir vigorously, add a predetermined amount of a mixed solution of styrene monomer and THF (volume ratio: 1:J) dropwise from the outside, and continue stirring for 1 hour. Then,
The polymerization reaction is stopped by dropping this reaction solution into 1x distilled water, and the styrene oligomer is extracted and separated from the solution. Styrene oligo with the desired degree of polymerization by adjusting the molar ratio of butyllithium and styrene monomer! -, but further as desired.

Kutoege column chromatography method (silica gel as a packing material,
A styrene oligomer having a degree of polymerization suitable for the present invention can be obtained by performing fractionation by molecular tK using a mixed solution consisting of benzene and n-hexane as a developing solution.

Also, styrene oligo! - is a commercially available styrene oligo with the desired degree of polymerization! - Alternatively, commercially available styrene oligomers can be separated by the above-mentioned column chromatography method and used as styrene oligomers having a desired degree of polymerization.

Number average table of styrene oligomers used in the present invention - 7 Reference example - (Introduction of phosphino group) The oligophosphine used in the present invention was prepared by the nuclear bromination and hiff bromine of the styrene oligomers shown in Reference example -/. It can be obtained from K by substitution with 7 diphenylphosphine groups. An example of its synthesis method is:

Styrene oligomer9. /lori4roformsu0il/
then dissolved in glacial acetic acid O1E/, anhydrous zinc chloride/
2. Add st. While shielding the above solution from light, a mixed solution consisting of bromine/Dif and tetrafluoroform was added dropwise, and the mixture was stirred at room temperature for 70 hours.

Next, a mixture of bromine /#, /f and chloroform was added dropwise, and after stirring at room temperature for 10 hours, one reaction solution was heated under reduced pressure (approximately 30 μHe) to remove unreacted bromine and chloroform. To leave. 00 tons of this pot residual liquid
Bromine-containing styrene oligo! − is obtained.

A predetermined amount of the above bromine-containing styrene oligomer (approximately 70 atomic bromine) is added to Tl! Dissolved in IIF JσW11.

T111ν of diphenylphosphine trilithium synthesized from diphenylphosphine chloride and metallic lithium
A predetermined amount (7.7 times equivalent to bromine) of the solution (OAe j mol/l) is added, heated to tO to 60C, and stirred for d hours. Next, the reaction solution was added dropwise to an equal volume of methanol, and the precipitate was deposited to obtain oligophosphine.

Elemental analysis values of the oligophosphine obtained by the above synthesis method and used in the present invention are shown in Table 1.

The infrared absorption spectrum (KBr) derived from the diphenylphosphino group of the oligophosphine of Cholera was observed as follows.

/j? 7cln-"(s), 14taOon-'(8
), /ldeQcm-'(a<), t too
cm-' (yx), 7tOan-'' (8).

7zOeWI-'(s) Reference Example-3 The rhodium source used in the present invention is a rhodium salt or
Although it is possible to use a valent rhodium complex or the like, it is also possible to form a complex with the oligophosphine shown in Reference Example 1 in advance and use this as the rhodium source.

As an example of complex formation, a predetermined amount of (Rh(OAe)(/,
r-cyclooctadiene)], benzene solution (approximately 1 free atom Rh/l) at room temperature,
``C Rh obtained by soaking for 1 hour
A solution of (oAc) (co), ) is dropped into a predetermined amount of a benzene solution of oligophosphine (about 10 ot/l), and stirring is continued at room temperature for 1 hour. Next, the reaction solution was dropped into 10 times the amount of n-hexane, and the precipitate was dried using a P weir to obtain a rhodium complex having oligophosphine as a ligand. The infrared absorption spectrum of the rhodium complex is l? ! 0-19♂OCIn” has a sharp absorption of carbonyl coordinated to rhodium, /400,1 JIO tan
Nearby there is an absorption derived from the carbonyl group of acetic acid. Furthermore, /Q9Q6n K has an absorption derived from the diphenylphosphino group of oligophosphine.

Table 3 shows the elemental analysis values of the above rhodium complex used in the present invention.
Shown below.

Reference Example DA A rhodium complex having an oligophosphine as a ligand used in the present invention can be prepared by a method other than that shown in Reference Example 3.

Synthesized by a known method (HRh(Co)(Pφ,),
]θ, -4! f (θ as Rh, -Deda atom) and the oligophosphine 8011 (J■ atom as P) shown in Reference Example-1 Experimental Example/4 (Table 2) were dissolved in benzene yawl and heated with argon at room temperature. After stirring the bait for an hour under airflow,
When the solution was dropped into n-hexane at 00d in the evening, a precipitate was deposited, and when the precipitate was taken and dried, it was found to have a weight of 0.9 JF.

The elemental analysis values of the carcass sediment are C76.07, Hj, Shikochi,
Pde, 34IIRh 3. a7cI,,Br t,7
0f! It was s.

Example-l~? The following reaction was carried out using a rhodium complex having the oligophosphine shown in Reference Example 3 (Table 3) as a ligand.

Predetermined amount of rhodium complex shown in Table-D and toluene jOw
The autoclave was charged into a magnetically stirred stainless steel autoclave having an internal volume of 0.theta.1, and the autoclave was sealed. After that, the inside of the autoclave was purged with nitrogen, and propylene O and chloride were pressurized. Then, when the temperature inside the autoclave was raised to 1 °C, the pressure inside the autoclave became 13 ky/cd gauge. A mixed gas consisting of hydrogen and carbon oxide (volume ratio/l)
pressure in the autoclave to /rky/dl
I used it as a gauge. Next, reduce the temperature inside the autoclave by /2
Stirring was continued while maintaining the autoclave at 0 CIC, and a mixed gas consisting of hydrogen and carbon oxide (volume ratio 1:/) was replenished so that the pressure inside the autoclave was /rkf/dl gauge, and the reaction was carried out for a predetermined time. After the reaction is complete, use a Gask four-mad graph.

As a result of analyzing the product, it was found that the table -
The reaction results shown are obtained. In addition, the reaction rate determined from the supply rate of the supplied mixed gas consisting of hydrogen and carbon oxide can be approximately approximated by a first-order rate equation for the propylene concentration, and the resulting ninth-order rate constant is listed in Table D. did.

In Comparative Example 1 and Co-Example 1, (
1! Rh(CIO)(Pφ3)s] Using a predetermined amount and a commercially available amount of triphenylphosphine, the reaction was carried out in exactly the same manner for a predetermined time, and the results are listed in Table 1.

Comparative Example 7 was carried out using a P/Rh ratio similar to that of Examples 1 to 7, and although the reaction activity was high, the Vi ratio was only J/J.

Comparative Example 1 is the result of using a large excess of triphenylphosphine with respect to rhodium (P/Rh ratio = @/su), but in a reaction using triphenylphosphine as a ligand, such a large amount of High n for the first time with phosphine
/i ratio. In that case, compare with Comparative Example-7 and p
The activity of the dium oxide is significantly reduced. Moreover,
While using such a large amount of phosphine, Example-2
~7 (P/Rh ratio = 7~a0), still n/Rh ratio = 7~a0)
1 ratio is small, and the superiority of the present invention is clear.

Comparative Example 3 Using commercially available non-crosslinked polystyrene (9#!θO), a soluble oligophosphine having a primary elemental composition was obtained by the method shown in Reference Example-C.

0: r2.22%, H: evening, tochi, P: 10
．． 0-1Br: 8th Next, when a rhodium complex having the above-mentioned sribophosphine as a ligand was synthesized by the method shown in Reference Example 3, a rhodium complex insoluble in benzene was produced. The infrared absorption spectrum of the rhodium complex is shown in Reference Example-3, and there is no significant difference Fi from that of the rhodium complex used in the present invention, and its composition is O: 77, Tata%, H: t, t /e
4. ? : De, bait, Br: /, r3%, Rh
: j,! It was a flathead.

A rhodium complex having the diphenylphosphino group-containing polystyrene as a ligand 0. Corat was used, and the rhodium complex of Experimental Example/7 (Reference Example-3) was not used in Example-7, but 6,! When a time reaction was carried out, the results shown in Table 1 were obtained. That is, the reaction activity is significantly lower than that of Examples 1 to 7, and no superiority can be found in the n/i ratio.

Example-! In Example 1, the reaction was carried out in exactly the same manner except that the mixture ratio of the hydrogen and carbon oxide gases initially injected after heating was changed to 6:1. Aldehyde yield 0.7g, n/1 ratio? , /≦,propanda, kl#i3. It was ko/hr.

Using the method shown in Example-De Example-/, using a rhodium acetate solution (manufactured by Nippon Engelhard Co., Ltd.) as Rh, without using a rhodium complex having oligophosphine as a ligand, 20■ and Reference Example-C were prepared. Experimental Example-74 (Table 2) Add the oligophosphine shown in K (P = 0.3? Da atoms P/Rh atomic ratio = 9) and carry out the reaction in the same manner for 2 hours. Butyraldehyde yield? 6. θchi.

n/L ratio, 72, k, xz j, / hr-'' was obtained.

Example 10 In Example 2, the reaction was carried out in the same manner for 5 hours except that the oligophosphine was used as 83/r (P as J, t de ■ atom P/Rh atomic ratio =, 2o). As a result, butyraldehyde yield? %, /chi, n/i = x a, 70°k,
We obtained θrihr to w.

Example-// In Example-D, the oligophosphine was 0.6 tatay (p
Using Yarihiro ■ atoms, P/Rh atomic ratio = lσ), the pressure inside the autoclave during one reaction is! σkg/c
Assume that the reaction was carried out in the same manner for 3 hours except that a mixed gas consisting of hydrogen and -carbon oxide was supplied to obtain the d gauge. Chi, n/i =
J,/θ,k,==/,7jhr”.

Example - The pressure inside the autoclave was 117 kl.
/d gauge. Next, a mixed gas consisting of K, hydrogen and -carbon oxide (volume ratio 1:1) was replenished so that the pressure inside the autoclave was 12 kg 101 gauge, and J
, as a result of the reaction for r hours, the butyraldehyde yield was 6.
．． 7%, nli ratio I7 bait =/, Jr.

Example-/J In Example-/, without using the lysium complex shown in Reference Example-3, the experimental example of Reference Example-1-/OK was used as the oligophosphine 0-30/f (as P 0.97W
9 atoms) and ("Rh (oAe) (1, nasik tetraoctadiene)), za, /sy (as nh / Owg
, P/Rh atomic ratio wto) in the same manner as above,
If the reaction was carried out for an hour, the yield of butyraldehyde would be t.

Obtain n/1 ratio J, 7 t, k, #i, SJ hr-
"Met.

In Example-l-゛Example-/, when the rhodium complex shown in Reference Example-J was used, the rhodium complex shown in Reference Example-1 was used.
/37f (as Rh, bait, #I9, P/Rh atomic ratio wx f, de) and in the same manner, a 1-hour reaction was carried out, and the butyraldehyde yield was 7! ,t,! l/
1 ratio! , 06f obtained, k, x5. jl+ and nine.

Applicant: Mitsubishi Kasei Koto Co., Ltd. 1951. Mr. Haruki Shimada, Commissioner of the Japan Patent Office, 1981, Patent Application No. 12311
No. 63 No. 2 Name of the invention Process for producing aldehydes 3 Person making the amendment (t5Pg) Mitsubishi Chemical Industries, Ltd. 4 agents 〒100 (and 1 others) 5 Subject of amendment ``Detailed description of the invention'' column of the description 6 Amendment Q Contents (1) “Example-“ on page 37, lines 3 to ix of the specification
Example 1 By the method shown in Example 1, rhodium acetate solution (manufactured by Nippon Engel-Ruth Co., Ltd.) was used as iRh 20■ and Reference Example 2 without using a rhodium complex having oligophosphine as a ligand. Experimental Example-7
As a result of the time reaction, the butyraldehyde yield μ, 1
%, n/i = p, 70-k, = 1. o r h
I got r-'k. ” (3) In the second line from the bottom of page 31, “
``Example-ii'' is corrected to ``Example-10J.''

(4) On page 32, line g, "Example L12" is corrected to "Example-1l".

(5) On the 32nd page line, the text "In Example-1/" is corrected to "In Example-io".

(6) In the third line from the bottom of page 32, the text ``Example-/3'' is corrected to ``Example-/2j.''

(7) On page 33, line g, "Example-1 Hiro" is corrected to "Example-73."

that's all

Claims (3)

[Claims] (1) In a method for producing an aldehyde by reacting an olefin compound with a monoxide compound and hydrogen in the presence of a monovalent organophosphorus compound and a tetradium compound, the structural unit represented by the following formula as a monovalent organophosphorus compound of! -100 mole of vomiting. A method for producing an aldehyde characterized by using a diphenylphosphino group-containing spray/oligomer whose number average degree of polymerization of the styrene oligomer, which is the basic skeleton, is J to JIO. (2) The diphenylphosphino group-containing spray/oligomer has a structural unit represented by the formula
A patent characterized in that the number average degree of polymerization of the styrene oligomer, which is the basic skeleton, is 3 to JtO. Method according to claim 1 (3) The number average degree of polymerization of the styrene oligomer is d~100
The method according to claim 11 or 2, characterized in that