JPH0436251A - Alcohol for plasticizer - 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 [Field of Industrial Application] The present invention relates to an alcohol for plasticizer. Specifically, the present invention relates to a mixed alcohol of an alcohol having 9 carbon atoms and an alcohol having 10 carbon atoms, which exhibits excellent properties in heat resistance, cold resistance, and electrical insulation, as an alcohol for use as a plasticizer for vinyl chloride resins. It is.

[Conventional technology]

Conventionally, carbon is produced by dimerization, hydroformylation, and hydrogenation of a 4-carbon fraction (hereinafter referred to as BB fraction) obtained in large quantities from thermal cracking or catalytic cracking of hydrocarbon oil. The alcohol number 9 contains an alcohol with a carbon number of 9 derived from an olefin with a carbon number of 8 containing a quaternary carbon atom produced by dimerization of isobutene in the BB fraction, so it can be obtained by esterification etc. It is known that when used as a plasticizer, the plasticizer performance, particularly cold resistance and plasticization efficiency, is significantly reduced.

[Problem to be solved by the invention]

Therefore, there are two methods: a method in which isobutene is separated in advance using advanced separation technology and then dimerized, and a method in which a co-dimerization reaction with n-butene is selectively progressed under specific dimerization reaction conditions (Japanese Patent Publication No. 57-27088). ) have been proposed, but all of them have many disadvantages such as a separation process that is industrially disadvantageous and a complicated catalyst system.

On the other hand, using the BB fraction as a raw material, hydroformylation reaction,
Alcohols having 10 carbon atoms produced by aldol condensation and hydrogenation reactions are used as raw material alcohols for plasticizers.

In the production of the above-mentioned alcohol having 10 carbon atoms using the BB fraction as a raw material, it is conceivable to use the unreacted BB fraction during the hydroformylation reaction of the BB fraction as a raw material for the above-mentioned alcohol having 9 carbon atoms. . However, the composition of the BB fraction in this case usually contains a large amount of isobutene (10% or more) and a small content of n-butene (15% or less), so co-dimerization of n-butene and isobutene is difficult. It becomes difficult. Moreover, since the reaction product of the hydroformylation reaction of the BB fraction contains oxygen-containing compounds such as valeraldehyde, methanol, and water, the influence of the presence of these compounds must be taken into consideration on the dimerization reaction. .

Therefore, the problem was how to obtain an alcohol for a plasticizer that is economical and also provides a plasticizer with excellent overall performance.

[Means to solve the problem]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above-mentioned problems.

That is, the present invention provides: (1) an alcohol having 10 carbon atoms (hereinafter referred to as IDA) obtained by subjecting butenes to a hydroformylation reaction, an aldol condensation reaction, and a hydrogenation reaction; and (2) unreacted alcohol in the above hydroformylation reaction product. 1-butene 0.1 to 15% by weight, 2-butene 1.
Carbon number obtained by subjecting recovered butenes having a composition of 0 to 70% by weight, 1.0 to 50% by weight of isobutene, and 30% by weight or less of other hydrocarbons having 4 carbon atoms to dimerization, hydroformylation reaction, and hydrogenation reaction. 9, which is a mixed alcohol with an alcohol containing 5% by weight or more of an alcohol containing quaternary carbon in the molecule (hereinafter referred to as INA), where the weight ratio of IDA and INA is 1) < I D
A/INA=0.01-0.6 (7) The gist of the present invention is an alcohol for plasticizer, characterized in that it is in the range of A/INA=0.01-0.6.

The present invention will be explained in more detail below.

IDA constituting the alcohol for plasticizer of the present invention is an alcohol having 10 carbon atoms obtained by subjecting butenes to a hydroformylation reaction, an aldol condensation reaction, and a hydrogenation reaction.

Butenes include mixtures containing l-butene, 2-butene, and isobutene, such as BB fraction obtained by thermal cracking of hydrocarbon oils such as naphtha, or catalytic cracking (FCC, etc.) of hydrocarbon oils such as heavy and light oils. Any of the resulting BB fractions can be used.

Furthermore, the so-called spent BB fraction (hereinafter referred to as BBS fraction) obtained after removing most of the butadiene from the BB fraction obtained by the above-mentioned thermal cracking or catalytic cracking, and after further removing a portion of isobutene. The so-called spent BB fraction (hereinafter referred to as BBSS fraction)
etc. can also be suitably used.

Furthermore, the above BBS fraction or BBSS fraction is preliminarily treated with Pd.
Depending on the catalyst, the normal temperature is 20~100" C1 pressure normal pressure~
The treatment is carried out under conditions of 10 kg/dG to selectively remove trace amounts of compounds with two or more double bonds or triple bonds in the molecule, such as butadiene or acetylenes contained in each fraction. Hydrogenated ones are preferable.

Mixtures of these can also be used.

The hydroformylation reaction is carried out according to conventional methods. The hydroformylation conditions are not particularly critical either (any of the conventionally known rhodium methods and cobalt methods can be used).

As the rhodium source in the case of the rhodium method, organic salts such as rhodium acetate, inorganic salts such as rhodium nitrate, or complexes such as hydridocarbonyltris(triphenylphosphine)rhodium can be used. As a cobalt source in the cobalt method, organic acid salts such as cobalt laurate, inorganic acid salts such as cobalt nitrate, and complexes such as dicobalt octacarbonyl and hydridocobalt tetracarbonyl can be used.

The reaction pressure is usually normal pressure to 300 kg/cjG,
The reaction temperature is usually 50 to 150°C 1Hz/
The CO ratio is usually a molar ratio of 1 to 10°, and the catalyst concentration is usually several ppm to several wt%. As the ligand, trivalent organic phosphorus compounds such as triphenylphosphine and triphenylphosphite, and their oxides are appropriately used in a molar ratio of usually 1 to 1000 to the above catalyst. Although it is not necessary to use a solvent, a solvent can be used if necessary. Any solvent can be used as long as it dissolves the catalyst and does not adversely affect the reaction. For example, benzene, toluene,
Aromatic hydrocarbons such as xylene and dodecylbenzene; alicyclic hydrocarbons such as cyclohexane; ethers such as dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and tetrahydrofuran; esters such as diethyl phthalate and dioctyl phthalate etc. are used. Moreover, aldehydes and alcohols produced by the hydroformylation reaction can also be used as a solvent. High-boiling by-products such as polycondensates of aldehydes can also be used.

The reaction method can be carried out either continuously or batchwise.

The reaction product liquid is first separated by distilling off unreacted butenes in a distillation column at normal pressure using a conventional method, and then the bottoms from the distillation column are fed to a vacuum distillation column to remove the produced Cs aldehyde (valeraldehyde). ) is separated from the catalyst liquid.

Each component of valeraldehyde in the product has a boiling point difference of more than ten degrees Celsius, and mixed valeraldehyde can be separated into each component by distillation.

In the aldol condensation reaction, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide is usually used as a catalyst, but amines and the like can also be used. Reaction temperature is usually 50 to 150°C1 Reaction pressure is usually normal pressure to several kg
/afl G, the reaction time is usually several minutes to several hours.

The produced acenals are purified by distillation and then subjected to a hydrogenation reaction, but they can also be subjected to a hydrogenation reaction without being purified by distillation.

The hydrogenation reaction can be carried out in a conventional manner.

That is, using a conventional hydrogenation catalyst such as Ni, Cr, Cu, etc., the reaction pressure is usually normal pressure to 150 kg/cell G, and the reaction temperature is usually 40 to 300°C.

Next, an alcohol having 10 carbon atoms (
IDA) can be obtained.

In addition, INA constituting the alcohol for plasticizer of the present invention is obtained by recovering butenes from the reaction product in the hydroformylation reaction of butenes described above. - 1.0 to 70% by weight of butene,
Carbon number obtained by dimerizing, hydroformylating and hydrogenating recovered butenes having a composition of 1.0 to 50% by weight of isobutene and 30% by weight or less of other hydrocarbons having 4 carbon atoms such as isobutane and normal butane. Alcohol containing quaternary carbon in the molecule! It is an alcohol containing 5% by weight or more of carbon dioxide.

Usually, it is obtained by distilling the above-mentioned hydroformylation reaction product of butenes and distilling off and recovering unreacted butenes, and the composition is 0.1 to 15% by weight of 1-butene, preferably 2-butene. ~15% by weight, 2-butene 1.0~
70% by weight, preferably 2-70% by weight, isobutene 1
．． 0 to 50% by weight, preferably 3 to 20% by weight, and 30% by weight or less, preferably 20% by weight or less of other C4 hydrocarbons are subjected to dimerization, hydroformylation and hydrogenation reactions.

There are no particular restrictions on the distillation conditions as long as a product having the above composition can be obtained.

In addition, in the above-mentioned hydroformylation reaction of butenes, for example, the reaction temperature is 90 to 110'C1, preferably 90
~100°C1-carbon oxide partial pressure 1~3kg/cii G
, preferably 1 to 1.5 kg/dG, to increase the conversion rate of 1-butene to 80% or more, preferably 90%.
The conversion rate of 2-butene and isobutene was maintained at 20%.
% or less, preferably 5% or less, unreacted butenes can be separated economically using an atmospheric distillation column, and valeraldehyde, methanol,
The content of oxygen-containing compounds that have an unfavorable effect on the dimerization catalyst, such as water, should be 1100 pp or less, preferably 30 pp.
m or less.

The typical composition of the recovered butenes subjected to the dimerization reaction is 4 to 6% by weight of 1-butene, 6 to 50% by weight of 2-butene, 9 to 20% by weight of isobutene, and other carbonized carbon atoms with a carbon number of 4. The hydrogen content is 0 to 20% by weight, and the oxygen-containing compound content is 30 ppm or less.

The distillation conditions for the above-mentioned atmospheric distillation are usually atmospheric pressure to 3.
kg/dlG, the number of distillation column plates is usually 10 to 20, preferably 9 to 14, and the reflux ratio is usually 3 to 10, preferably 3.
It is in the range of ~5.

The dimerization reaction of the recovered butenes is carried out by a known method using a Ni-based catalyst or the like.

The hydroformylation reaction of octene is carried out according to a conventional method.

The hydroformylation conditions are not particularly critical either, and either the rhodium method or the cobalt method can be used, which has almost the same conditions as the hydroformylation reaction of butenes employed in producing the above-mentioned IDA.

The hydrogenation reaction of the produced nonylaldehyde can also be carried out by a conventional method under the same conditions as the hydrogenation reaction of acenals, as described above, and then an alcohol having 9 carbon atoms (INA) can be obtained by ordinary distillation purification. .

The INA obtained as described above contains 5 to 20% by weight of alcohol with 9 carbon atoms containing quaternary carbon in the molecule, and generally, when used as a plasticizer alone, this INA , cold resistance, and plasticization efficiency are quite low.

In the plasticizer alcohol of the present invention, the above-mentioned ID
The weight ratio of A and INA is IDA/INA=0.01~
0.6, preferably 0.02-0.4, more preferably 0.03-0.3, most preferably 0°06-0.3
This makes it possible to obtain an alcohol for plasticizers with excellent overall performance.

The point at which IDA and INA are mixed is IDA and INA.
In addition to NA products, it is also possible to mix crude alcohol after hydrogenation reaction and before distillation purification to adjust the above ratio by distillation purification, or to mix acenals and nonylaldehyde to be subjected to hydrogenation reaction. After carrying out a hydrogenation reaction, the above ratio can also be adjusted by distillation purification.

If the weight ratio of IDA/INA is less than 0.01, the plasticization efficiency and cold resistance will not be improved, and if it exceeds 0.6, the plasticization efficiency and cold resistance will decrease, which is not preferable.

The alcohol for plasticizer of the present invention obtained as described above is used as an ester plasticizer by an esterification reaction with a carboxylic acid such as phthalic anhydride, an acid such as phosphoric acid, or a derivative thereof by a conventional method.

The performance of plasticizers is as follows: ■ Plasticization efficiency (100% modulus) ■ Volatilization loss (
■ Low temperature flexibility temperature (cold resistance) ■ Kerosene extractability (oil resistance) ■ Electrical resistance (insulation) It is necessary to comprehensively evaluate such factors as a single property, such as heat resistance. However, according to the present invention, it is possible to industrially advantageously obtain an alcohol for plasticizers having overall excellent performance.

[Examples] The present invention will be described in more detail below based on Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example 1 (1) Production of IDA After removing most of butadiene and isobutene from the BB fraction from a naphtha cracker, Pd/Af was further removed.
After partial hydrogenation of dienes and acetylenes using a Z off type catalyst, a spent BB fraction having the following composition was continuously hydroformylated.

[Assembly]

1-Butene 44.3 wt%2-
Butene 22 Isobutene 4 Butadiene O Class 03 0.3 Other hydrocarbons with 4 carbon atoms 29.4 Reaction conditions are total pressure cuff kg/ailG, oxo gas partial pressure 4 kg/c
dc (H,/C0=1) Reaction temperature 100°C (Solvent xylene raw material/catalyst liquid = 1.0 (weight ratio) Reactor residence time 2.0 hours. 1-butene, 2-butene and isobutene The conversion rates were 90%, less than 1%, and 2%, respectively.

After depressurizing the reaction solution, unreacted butenes are distilled off and recovered in an 11-stage atmospheric distillation column, and then the bottoms from the distillation column are separated into catalyst liquid and valeraldehyde in a vacuum distillation column. separate,
The composition of the produced valeraldehyde is adjusted so that the molar ratio is 2-methylbutyraldehyde/n-valeraldehyde=
0.5 3-methylbutyraldehyde/n-valeraldehyde=
A mixed aldehyde of 0.1 pivalaldehyde/n-valeraldehyde = 0.1 was obtained.

Next, this aldehyde was subjected to a linearization reaction for 1°5 hours at a reaction temperature of 95° C. and normal pressure in a 1042 autoclave at a reaction temperature of 95° C. and normal pressure and an aldehyde/3% aqueous sodium hydroxide solution=1 (weight ratio).

The conversion rate of each aldehyde is n-valeraldehyde 99.9%2-methylbutyraldehyde 99.83-methylbutyraldehyde 99.8pivalaldehyde
It was 98.2.

This decenal mixture was hydrogenated using a Ni-based solid catalyst. Hydrogenation conditions are pressure 100kg/aiG, temperature 120°
A batch reaction was carried out for 3.0 hours at a C1 catalyst/decenal ratio of 0.1 (weight ratio). The conversion rate of decenal was 99.9%.The initial distillate was 1%, the main distillate was 95%,
Purified decyl alcohol was obtained with 4% residue in the pot.

In addition, when the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, the molar ratio of component A/2-propylheptatool = 1.3 component B/
2-propylheptatool-0,30 component/2-propylheptatool-0,3D component/2-propylheptanol=0.03.

Here, component A is 2-propyl-4-methylhexanol, component B is decyl alcohol having a skeleton of an aldol condensate of n-valeraldehyde and 3-methylbutyraldehyde, and component C is n-barrel. Component D represents decyl alcohol having a skeleton of an aldol condensate of aldehyde and pivalaldehyde, and component D represents other decyl alcohols.

(2) Production of INA■ Synthesis of octenes After gas-liquid separation of the hydroformylation reaction product liquid obtained in the hydroformylation reaction of Example 1 (1), the reflux ratio was 5 in a 10-stage distillation column at normal pressure. The unreacted butenes were distilled out and recovered.

Composition> 1-Butene 4.8 wt%2-
Butene 67.6 Isobutene
11.0 Other hydrocarbons with 4 carbon atoms 16
．． 6C, aldehyde 30ppmH1O2
0PPm The recovered butenes recovered in this way were transferred to a SUS with a volume of 1ON.
4 kg of the above C4 fraction, 5.5 g of an n-hexane solution of nickel octoate (Ni content: 6 wt%), and 11.3 g of ethylaluminum dichloride were charged into a manufactured induction stirring autoclave under a nitrogen atmosphere, and the mixture was heated at 40°C. The reaction was allowed to proceed for 7 hours.

After the reaction, 340 g of 5 wt% H, SO, aqueous solution was added,
After deactivating the catalyst, octenes were obtained by liquid-liquid separation.

The obtained octene contains quaternary carbon, 9
It contained wt%.

The above reaction was performed three times.

(2) Obtaining an octene fraction by distillation The octenes obtained in (1) above were rectified at normal pressure in an all-Gusho type distillation column with an inner diameter of 50 mm and 20 plates. 5.8 kg of octene fraction with a tower top temperature of 108-127°C
Obtained.

■ Synthesis of INA Volume 10 In a US autoclave with a nitrogen atmosphere, the octene fraction 2 obtained in the following (■) was added. Add Okg and 20 g of dicobalt octacarbonyl, maintain the total pressure at 160 kg/dG with oxo gas with H2/C0 = 1, and
The reaction was carried out at 0°C. After 2 hours, gas absorption stopped, so the reactor was rapidly cooled, a 3% NaOH aqueous solution was injected, the cobalt catalyst was deactivated, the reactor was further cooled, the oxo gas was depressurized, and the entire reaction solution was taken out. , liquid-liquid separation was performed to obtain an organic phase.

Next, an aldehyde having 9 carbon atoms and an alcohol were obtained by simple distillation under reduced pressure at a pressure of 10 Hg. The total yield of aldehyde and alcohol was 99%.

Next, in a SUS autoclave with a capacity of 10 f, the entire amount of the obtained liquid from the simple distillation and 160 g of the nickel-supported solid catalyst were charged in a nitrogen atmosphere, and the total pressure was 90 kg/cd using hydrogen gas.
The hydrogenation reaction was carried out at a reaction temperature of 150°C. 5
After a period of time, gas absorption stopped, so it was rapidly cooled, the hydrogen gas was depressurized, the reaction solution was taken out in its entirety, the solid catalyst was filtered off, and it was rectified using an all-Gusho type distillation column with an inner diameter of 35 m and 20 plates. . Reflux ratio is 3, pressure is 10m*Hg
Met. Cut 0.5% of initial distillate and 3% of pot residue to 96.
5% was obtained. The yield of INA through hydrogenation reaction and rectification was 95%.

(3) Synthesis of mixed alcohol and synthesis and evaluation of plasticizer The IDA and INA obtained in (1) and (2) above are ID
A mixed alcohol and phthalic anhydride mixed at a ratio of A/INA=0.087/1 were esterified by a conventional method to obtain a plasticizer. Then plasticizer/vinyl chloride resin = 60/10
0 (weight ratio), a soft vinyl chloride resin was prepared by a conventional method, and various tests were conducted by a conventional method. Table the results =
1. Table 1 also shows test results for di-2-ethylhexyl phthalate (DOP), a general-purpose plasticizer.

Examples 2 to 4 and Comparative Example 1 The same procedures as in Example 1 were carried out except that the mixing ratio of IDA/INA was changed as shown in Table 1. The results are shown in Table-1.

Comparative Example 2 Example 1 was carried out in the same manner as in Example 1 except that INA obtained in (2) was used alone and a plasticizer was synthesized in (3). The results are shown in Table-1.

Comparative Example 3 Example 1 was carried out in the same manner as in Example 1 except that IDA obtained in (1) was used alone and a plasticizer was synthesized in (3). The results are shown in Table-1.

Comparative Example 4 (1) Synthesis of octenes C4 fraction after removing butadiene and isobutene from the BB fraction obtained from a naphtha cracker (6% by weight of isobutene, 43% by weight of 1-butene, 25% by weight of 2-butene) %, 25% by weight of butanes, 1% by weight of others) was dehydrated using Molecular Sieve 13X, and then placed in a 10f capacity SUS induction stirring autoclave under a nitrogen atmosphere. 4kg of the dehydrated C4 fraction and octanoic acid. 5.5g of nickel n-hexane solution (Ni content 6wt%)
and 11.3 g of ethylaluminum dichloride were charged and reacted at 40°C for 7 hours.

After the reaction, 340 g of 5 wt% H, SO, aqueous solution was added,
After deactivating the catalyst, octenes were obtained by liquid-liquid separation.

The octenes contained 1 wt% of quaternary carbon.

The above reaction was performed three times.

(2) Obtaining octene fraction by distillation The octenes obtained in (1) above are
It was rectified at normal pressure in an all-Gusho type distillation column. The octene fraction with a tower top temperature of 108 to 127°C was heated to 5.8 k.
I got g.

(3) Synthesis of INA and plasticizer and evaluation volume 1
The octene fraction 2. obtained in (2) above was placed in a 0f SUS autoclave under a nitrogen atmosphere. Add Okg and 20 g of dicobalt octacarbonyl, maintain the total pressure at 160 kg/dG with oxo gas of Hz/C0 = 1,
The reaction was carried out at °C. After 2 hours, gas absorption stopped, so the reactor was rapidly cooled, a 3% NaOH aqueous solution was injected, the cobalt catalyst was deactivated, the reactor was further cooled, the oxo gas was depressurized, and the entire reaction solution was taken out. , liquid-liquid separation was performed to obtain an organic phase.

Next, an aldehyde having 9 carbon atoms and an alcohol were obtained by simple distillation under reduced pressure at a pressure of 10 kg Hg. The total yield of aldehyde and alcohol was 99%.

Next, in a SUS autoclave with a capacity of 101 cm, the entire amount of the obtained liquid from the simple distillation and 160 g of the nickel-supported solid catalyst were charged in a nitrogen atmosphere, and the total pressure was 90 kg/dG with hydrogen gas.
The hydrogenation reaction was carried out at a reaction temperature of 150°C. After 5 hours, gas absorption stopped, so it was rapidly cooled, the hydrogen gas was depressurized, the entire amount of the reaction liquid was taken out, the solid catalyst was filtered off, and an all-Gusho type distillation column with an inner diameter of 35 tubes and 20 plates was added. It was rectified with The reflux ratio was 3, and the pressure was 10° Hf. 96.5% by cutting initial distillation 0.5% and pot residue 3%
was obtained as INA. This INA was evaluated alone as a plasticizer in the same manner as in Example 1 (3). The results are shown in Table-1.

〔Effect of the invention〕

According to the present invention, it is possible to provide a mixed alcohol of an alcohol having 9 carbon atoms and an alcohol having 10 carbon atoms, which is industrially advantageous and has excellent overall performance as a raw material alcohol for a plasticizer.

Claims (1)

[Claims] (1) [1] An alcohol having 10 carbon atoms (hereinafter referred to as IDA) obtained by subjecting butenes to a hydroformylation reaction, an aldol condensation reaction, and a hydrogenation reaction; 1-butene 0.1-15% by weight, 2-butene obtained by recovering butenes from the reaction
Obtained by dimerizing, hydroformylating, and hydrogenating recovered butenes having a composition of 1.0 to 70% by weight of butene, 1.0 to 50% by weight of isobutene, and 30% by weight or less of other C4 hydrocarbons. A mixed alcohol with an alcohol having 9 carbon atoms and an alcohol containing 5% by weight or more of quaternary carbon in the molecule (hereinafter referred to as INA), where the weight ratio of IDA and INA is An alcohol for plasticizer, characterized in that IDA/INA is in the range of 0.01 to 0.6.