JP2773290B2 - Plasticizer and alcohol for plasticizer - Google Patents

Description

The present invention relates to a plasticizer and an alcohol for a plasticizer.

Alcohol having 10 carbon atoms (hereinafter referred to as decyl alcohol) is produced by using an olefin having 4 carbon atoms as a raw material and subjecting it to a hydroformylation reaction, aldol condensation and hydrogenation reaction, and is mainly used as a raw material for a plasticizer of a vinyl chloride resin. Used as alcohol.

The present invention relates to a plasticizer and a mixture of decyl alcohol having excellent overall performance as a raw material thereof.

[Conventional technology]

Decyl alcohol is obtained by subjecting a fraction having 4 carbons (hereinafter, referred to as BB fraction) obtained from thermal cracking or catalytic cracking of hydrocarbon oil to a hydroformylation reaction to produce valeraldehydes, which is then subjected to aldol condensation. The reaction can be carried out to produce decenals, which can be further produced by adding water thereto. There are three types of butenes in the BB fraction: 1-butene, 2-butene, and isobutene. Therefore, valeraldehyde obtained by hydroformylation of this is a mixture of n-valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, and pivalaldehyde (2,2-dimethylpropionaldehyde). Therefore, the condensation product of valeraldehydes and the decyl alcohol product obtained by hydroformylation of the BB fraction are generally a mixture of various isomers.

U.S. Patent Nos. 2,292,089 and 3,210,051 disclose 2-propylheptanol derived from the condensation product of n-valeraldehyde and the cross-aldol product of n-valeraldehyde and 2-methylbutyraldehyde. The method of condensation and hydrogenation may be a conventional method, 2-propylheptanol is excellent as decyl alcohol for a plasticizer, and the cross aldol product has a plasticizer performance. Although inferior to 2-propylheptanol, 2-
It has been shown that the performance is not inferior if used as a mixture with propylheptanol up to more than 10%.

JP-A-58-206537 discloses a method for producing decyl alcohol having good plasticizer performance from butenes.
N-valeraldehyde in propylheptanol and 2-
The composition of the valeraldehyde and the condensation conditions for reducing the amount of the cross-aldol product with methylbutyraldehyde to 20% or less are indicated, in which case mainly 2-propylheptanol and n-valeraldehyde and 2 -Performance of binary alcohol mixtures of alcohols from cross aldol products with methyl butyraldehyde.

[Problems to be solved by the invention]

Industrial use high value BB fraction as olefinic feedstock of 4 carbon atoms include butenes (1-butene, 2-butene and isobutene) in addition to, C ₃ hydrocarbons and butadiene, butane and the like, butene concentration Is usually about 40-80% by weight.

The BB fraction further includes a so-called spent BB fraction after most of butadiene is extracted and a so-called spent spent BB fraction in which a part of isobutene is further removed.The butene concentration is about 60 to 90 wt%, respectively. It is about 70-90 wt%. However, in any case, the butenes have very similar physical properties, and separating 1-butene, 2-butene, and isobutene into individual products is costly and industrially extremely disadvantageous. Therefore, it is desirable that decyl alcohol for a plasticizer with good performance can be obtained from a mixed butene containing all of 1-butene, 2-butene and isobutene.

It is known that in the hydroformylation of a C ₄ olefin mixture, if the reaction conditions, catalyst, etc. are appropriately selected, the composition of the valeraldehyde of the product can be selected to some extent. There is no known method for performing the reaction, and after all, n-valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, and pivalaldehyde are all contained, and the composition of the decyl alcohol to be formed is also a variety of isomers. And a mixture of

Accordingly, it has been desired to obtain an isomer-mixed decyl alcohol having good plasticizer performance from four kinds of valeraldehyde in an industrially advantageous manner.

[Means for solving the problem]

In view of the above prior art, the present inventors have conducted intensive studies to solve the problems, and as a result, have found that a cross-aldol product of n-valeraldehyde and 2- or 3-methylbutyraldehyde and n-valeraldehyde The present inventors have found that when a specific proportion of an alcohol having a structure derived from a cross-aldol product with pivalaldehyde is contained, it has a remarkable effect on improving the overall performance of decyl alcohol, and completed the present invention.

That is, the present invention relates to a mixture of alcohols having 10 carbon atoms, wherein 2-propylheptanol (hereinafter, referred to as PRH), an alcohol having a skeleton of a condensation product of n-valeraldehyde and 2-methylbutyraldehyde (hereinafter, referred to as PRH) , A component), an alcohol having a skeleton of a condensation product of n-valeraldehyde and 3-methylbutyraldehyde (hereinafter, referred to as a B component), and a skeleton of a condensation product of n-valeraldehyde and pivalaldehyde. The components of alcohol (hereinafter, referred to as C component) and other alcohol having 10 carbon atoms (hereinafter, referred to as D component) are represented by a molar ratio of A component / PRH = 0.04 to 1 B component / PRH = 0.002 to 0.3 C component / PRH = 0.001 to 0.3 D component / PRH ≦ 0.3, wherein alcohol for plasticizer and esterification reaction between alcohol for plasticizer and carboxylic acid are carried out. The gist is a plasticizer characterized in that:

 Hereinafter, the present invention will be described in more detail.

The alcohol for a plasticizer of the present invention is a mixture of alcohols having 10 carbon atoms, and the above components A to D and PRH are in a molar ratio: A component / PRH = 0.04 to 1 B component / PRH = 0.002 to 0.3 C component / PRH = 0.001 to 0.3 D component / PRH ≦ 0.3. The method for producing the alcohol for plasticizer of the present invention is not particularly limited as long as each of the above components is within the above composition range. For example, a olefin having 9 carbon atoms obtained by copolymerization of olefins such as a reaction of an olefin having 4 carbon atoms and an olefin having 5 carbon atoms or a olefin having 9 carbon atoms obtained by trimerization of propylene or the like has a carbon number of 10 obtained by a hydroformylation reaction and a hydrogenation reaction. Alcohol,
It can also be obtained by subjecting an olefin having 4 carbon atoms to a hydroformylation reaction, an aldol condensation reaction, and a hydrogenation reaction, or an alcohol having 10 carbon atoms, or by adjusting the mixing ratio of each component therefrom.

Hereinafter, the butene fraction is used as the olefin having 4 carbon atoms, and the butene fraction is subjected to a hydroformylation reaction, an aldol condensation reaction, and a hydrogenation reaction.

A butene fraction as a starting material is a BB fraction containing butenes as a main component, and is contacted with a BB fraction obtained by pyrolysis of a hydrocarbon oil such as naphtha or a hydrocarbon oil such as heavy or light oil. Any BB fraction obtained by cracking (eg, FCC) can be used.

Further, a so-called spent BB fraction after removing most of butadiene from the BB fraction obtained by the above-mentioned thermal decomposition or catalytic cracking, and a so-called spent spent BB fraction after further removing a part of isobutene, etc. Can also be suitably used. Also, a mixture of these can be used.

The alcohol for plasticizer of the present invention is a mixture of C10 alcohols having a specific composition, which can be obtained by subjecting the butene fraction to a hydroformylation reaction, an aldol condensation reaction and a hydrogenation reaction as described below. It is.

The hydroformylation reaction is performed according to a conventional method. The hydroformylation conditions are not particularly critical, and any of the conventionally known rhodium method and cobalt method can be used.However, a higher ratio of the α-isomer in the product valeraldehyde is economically advantageous to some extent. is there. As the rhodium source in the case of the rhodium method, any of an organic salt such as rhodium acetate, an inorganic salt such as rhodium nitrate, and a complex such as hydridocarbonyltris (triphenylphosphine) rhodium can be used. As the cobalt source in the case of the cobalt method, organic acid salts such as cobalt laurate, inorganic acid salts such as cobalt nitrate, and complexes such as dicobalt octacarbonyl and hydride cobalt tetracarbonyl can be used.

The reaction pressure is usually normal pressure to 300 kg / cm ² G, the reaction temperature is usually 50 to 150 ° C., the H ₂ / CO ratio is usually 1 to 10 in molar ratio, and the catalyst concentration is usually several ppm. The condition of ~ several wt% is adopted. As the ligand, a trivalent organic phosphorus compound such as triphenylphosphine or triphenylphosphite or an oxide thereof is appropriately used usually in a molar ratio to the above catalyst of 1 to 1000. A solvent may not be used, but 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, aromatic hydrocarbons such as benzene, toluene, 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 dioctyl phthalate are used. Further, aldehydes and alcohols generated by the hydroformylation reaction can be used as the solvent. High-boiling by-products such as polycondensates of aldehydes can also be used.

The reaction can be carried out in either a continuous mode or a batch mode.

Next, the resulting valeraldehyde can be obtained by distillation and its composition can be controlled.

In the hydroformylation reaction, it is known that the reaction rate of butenes differs for each component, and that the ratio of α-aldehyde to iso-aldehyde can be changed to some extent by the reaction conditions.

Therefore, the composition of valeraldehyde can be controlled to some extent by employing appropriate reaction conditions in the above-mentioned hydroformylation reaction. Also,
Each component of valeraldehyde has a boiling point difference of about 10 ° C., and the composition can be controlled by ordinary distillation.

In obtaining the alcohol for plasticizer of the present invention, the composition of valeraldehyde is represented by a molar ratio of 2-methylbutyraldehyde / n-valeraldehyde =
0.02-0.3, preferably 0.05-0.3 3-methylbutyraldehyde / n-valeraldehyde =
0.001-0.05, preferably 0.001-0.03 pivalaldehyde / n-valeraldehyde = 0.0005-0.
05, preferably 0.001 to 0.03 before subjecting to the aldol condensation reaction.

In the aldol condensation reaction, an aqueous alkali solution such as sodium hydroxide or potassium hydroxide is usually used as a catalyst, but amines or the like can also be used. The reaction temperature is
Usually 50 to 150 ° C, reaction pressure is usually normal pressure to several kg / cm ² G,
The reaction time is usually from several minutes to several hours, but it is preferable that the conversion of valeraldehyde is at least about 90% or more, preferably 95% or more for each component.

Condensation rate of valeraldehyde other than n-valeraldehyde is relatively slow, and mutual condensation reaction or dimerization reaction of valeraldehyde other than n-valeraldehyde hardly occurs, but cross-aldol with n-valeraldehyde. reactions occur relatively quickly at the ₅ aldehyde composition gives decenal mixture of desired composition. The desenal mixture is then subjected to a hydrogenation reaction.
The hydrogenation reaction can be performed by a usual method. That is, the reaction is carried out at a reaction pressure of usually normal pressure to 150 kg / cm ² G and a reaction temperature of usually 40 to 300 ° C. using a normal hydrogenation catalyst such as Ni, Cr, Cu or the like.

Then, a mixture of alcohols having 10 carbon atoms of the present invention is obtained by ordinary distillation purification.

The alcohol for a plasticizer of the present invention has a skeleton of a condensation product of n-valeraldehyde and 2-methylbutyraldehyde in addition to 2-propylheptanol (PRH) (A component): Those having a skeleton of a condensation product of n-valeraldehyde and 3-methylbutyraldehyde (component B): Those having a skeleton of a condensation product of n-valeraldehyde and pivalaldehyde (component C): Other alcohols having 10 carbon atoms (component D) (above omitting the hydrogen atom), each component having a molar ratio of A component / PRH = 0.04 to 1.0, preferably 0.05 to 1.0, more preferably 0.1 to 0.7 B component /PRH=0.002-0.3, preferably 0.002-0.3, more preferably 0.002-0.1 C component / PRH = 0.001-0.3, preferably 0.002-0.3, more preferably 0.002-0.1 D component / PRH ≦ 0.3, preferably 0.1 It is the following ratio.

The decyl alcohol mixture obtained as described above is then subjected to an esterification reaction with phthalic anhydride or the like in the presence of a titanium-based catalyst or an acidic catalyst (such as p-trienesulfonic acid) by a conventional method, and the phthalic acid ester or the like is plasticized. Used as an agent. Examples of the plasticizer include aromatic dicarboxylic acids such as pyromellitic anhydride, and trimellitic anhydride, and aromatic carboxylic acid esters obtained by reaction with aromatic carboxylic acids such as adipic acid, azelaic acid, and sebacic acid. Also used as an aliphatic dibasic acid ester obtained by the reaction with

It is known that decyl alcohol containing 2-propylheptanol as a main component is generally superior in heat resistance to alcohols for general-purpose plasticizers such as 2-ethylhexanol, but the electric resistance and the plasticization efficiency are high. In general, they are inferior.

Plasticizer performance needs plasticization efficiency (100% modulus), volatilization loss (heat resistance), low temperature flexibility temperature (cold resistance), kerosene extractability (oil resistance), electrical resistance (insulation), etc. It is not only a matter of a single property, for example, heat resistance. Although there are some which have a conflicting tendency such as the above and the like, it is complicated.However, according to the present invention, a skeleton of 2- or 2-methylbutyraldehyde of decyl alcohol is obtained by forming an isomer mixture having the above specific composition. A plasticizer and an alcohol for a plasticizer having excellent overall performance can be obtained by allowing a small amount of a compound having a pivalaldehyde skeleton to be present.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as the gist is not exceeded.

Reference Example-1 (1) Synthesis of 2-propylheptanol A commercially available pure n-valeraldehyde was subjected to a condensation reaction.

The condensation conditions were as follows: 3% aqueous solution of sodium hydroxide / n-valeraldehyde = 1 (weight ratio) under normal pressure at 95 ° C., reaction time
A batch reaction was performed after 30 minutes. The conversion of n-valeraldehyde was 99.9%. Next, the desenal after liquid-liquid separation was hydrogenated with a nickel-based solid catalyst. Hydrogenation conditions are pressure 100 kg / cm ² G, temperature 100 ° C, catalyst / decenal = 0.1
The reaction was performed for 3.0 hours by a batch reaction (weight ratio). The conversion of desenal was 99.9%. Next, crude 2-propylheptanol was purified by a 30-stage glass Oldershaw distillation column, and the first fraction cut 1%, the main fraction 96%,
Purified 2-propylheptanol was obtained with a residue of 4%.

(2) Synthesis and evaluation of plasticizer 2-propylheptanol obtained in (1) and phthalic anhydride were esterified by a conventional method to obtain a plasticizer. Then, the mixture was mixed with a plasticizer / vinyl chloride resin = 67/100 (weight ratio) to obtain a soft vinyl chloride resin by an ordinary method, and various tests were conducted by an ordinary method. The results are shown in Table 1. Table 1 shows the general-purpose plasticizer di-2-ethylhexyl phthalate (DO
The test results of P) are also described.

Example 1 A spent spent BB fraction having the following composition after removing most of butadiene and isobutene from a BB fraction from a naphtha cracker was continuously hydroformylated.

[Composition] 1-butene 43 wt% 2-butene 22 isobutene 4 butadiene 1.3 C ₃ acids 0.3 Other 29.4 Reaction conditions were a total pressure 7kg / cm ² G, oxo gas partial pressure _{^{4kg / cm 2 G (H 2}} / CO =
1), reaction temperature 100 ℃ Raw material / catalyst liquid = 10 (weight ratio) The residence time in the reactor was 2.0 hours.

After depressurizing the reaction solution, almost all the valeraldehyde produced was recovered by distillation, and the molar ratio of 2-methylbutyraldehyde / n-valeraldehyde =
0.1 3-methylbutyraldehyde / n-valeraldehyde =
0.02 pivalaldehyde / n-valeraldehyde = 0.01.

Next, this aldehyde is directly used at a reaction temperature of 95 ° C.
Aldehyde / 3% sodium hydroxide aqueous solution = 1 (weight ratio)
For 1.5 hours in a 10 l autoclave.

 The conversion of each aldehyde was n-valeraldehyde 99.9% 2-methylbutyraldehyde 99.8 3-methylbutyraldehyde 99.8 pivalaldehyde 98.2.

This decenal mixture was hydrogenated in exactly the same manner as in Reference Example 1 to obtain decyl alcohol, which was purified and evaluated as a plasticizer. The results are shown in Table 1.

Further, the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, and as a result, the molar ratio was A component / PRH = 0.22 B component / 〃 = 0.045 C component / 〃 = 0.022 D component / 〃 = 0.01.

Example 2 Using the same raw materials as in Example 1, the total pressure was 18 kg / cm.
^A hydroformylation reaction was carried out under the same reaction conditions as in Example 1 except that ² G and oxo gas partial pressure were 15 kg / cm ² G (H ₂ / CO = 1), and valeraldehyde was obtained. −methylbutyraldehyde / n-valeraldehyde =
0.5 3-methylbutyraldehyde / n-valeraldehyde =
0.1 pivalaldehyde / n-valeraldehyde was 0.1.

Next, this valeraldehyde was rectified by a 90-stage glass Oldshaw distillation column to partially distill pivalaldehyde, 2-methylbutyraldehyde, and 3-methylbutyraldehyde, and to give a 2-methylbutyraldehyde by molar ratio. / n-valeraldehyde =
0.2 3-methylbutyraldehyde / n-valeraldehyde =
After setting 0.03 pivalaldehyde / n-valeraldehyde to 0.02, a condensation reaction was performed under the same conditions as in Example-1.

 The conversion of each aldehyde was n-valeraldehyde 99.9% 2-methylbutyraldehyde 99.0 3-methylbutyraldehyde 98.5 pivalaldehyde 98.0.

This decenal mixture was hydrogenated under the same conditions as in Reference Example 1 to obtain decyl alcohol, which was purified and evaluated as a plasticizer. The results are shown in Table 1.

Further, the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, and as a result, the molar ratio was A component / PRH = 0.48 B component / 〃 = 0.073 C component / 〃 = 0.05 D component / 〃 = 0.02.

Following composition after removal of the butadiene from the BB fraction from crackers embodiments -3 Naphtha: 1-butene 24.3Wt% of 2-butene 13.1 isobutene 51.5 butadiene 0.02 C ₃ compounds 0.15 Others 10.93 the spent BB fraction as a raw material, The hydroformylation reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was changed to 110 ° C., and the molar ratio of 2-methylbutyraldehyde / n-valeraldehyde =
0.3 3-methylbutyraldehyde / n-valeraldehyde =
Valeraldehyde of 0.03 pivalaldehyde / n-valeraldehyde = 0.04 was obtained.

Next, in Example 1, the condensation reaction was carried out under exactly the same conditions except that the concentration of the aqueous sodium hydroxide solution was changed to 5%. The conversion of each aldehyde was 99.9% for n-valeraldehyde and 2-methylbutyraldehyde. 99.1 3-methylbutyraldehyde 98.3 Pivalaldehyde 97.8.

Next, hydrogenation was performed under the same conditions as in Example 1 to obtain decyl alcohol, which was purified and evaluated as a plasticizer.

 The results are shown in Table 1.

When the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, the molar ratio was A component / PRH = 0.93 B component / 〃 = 0.09 C component / 〃 = 0.12 D component / 〃 = 0.03.

Reference Example-2 Valeraldehyde (before rectification) obtained by the hydroformylation reaction in Example-2 was evaluated as condensation, hydrogenation, purification and plasticizer under the same conditions as in Example-1. .

 The results are shown in Table 1.

 The conversion of valeraldehyde in the condensation was 99.9% for n-valeraldehyde, 92.2 for 2-methylbutyraldehyde, 93.5 for 3-methylbutyraldehyde, 93.5 for pivalaldehyde, and the composition of decyl alcohol was molar ratio: A component / PRH = 1.3 B Component / 〃 = 0.3 C component / 〃 = 0.3 D component / 〃 = 0.03.

Reference Example-3 Decyl alcohol was prepared in the same manner as in Reference Example-1 except that a commercially available mixture of n-valeraldehyde and 2-methylbutyraldehyde at a ratio of 1: 0.1 (weight ratio) was used as a raw material for the condensation reaction. And as a plasticizer. The results are shown in Table 1. In this case, the conversion of valeraldehyde in the condensation was 99.9% for n-valeraldehyde and 99.2 for 2-methylbutyraldehyde.

 The composition of decyl alcohol was molar ratio A component / PRH = 0.22 B component / 〃 = 0 C component / 〃 = 0 D component / 〃 = 0.01.

Reference Example-4 Commercially available n-valeraldehyde, 2-methylbutyraldehyde and 3-methylbutyraldehyde were 1: 0.3: 0.02
Reference Example-except that the raw material was mixed at (weight ratio)
Condensation, hydrogenation, and evaluation as a plasticizer were performed in the same manner as in Example 1. The results are shown in Table 1. The conversion of valeraldehyde in the condensation was 99.9% for n-valeraldehyde, 9-methylbutyraldehyde 99,3-methylbutyraldehyde 98.5. The composition of decyl alcohol was A component / PRH = 0.88 B component / 〃 = 0.58 C component / 〃 = 0 D component / 〃 = 0.03 in molar ratio.

Example-4 A spent spent BB fraction having the following composition after removing most of butadiene and isobutene from a BB fraction from a naphtha cracker was continuously hydroformylated.

[Composition] 1-butene 43 wt% 2-butene 22 isobutene 0.71 butadiene 1.3 C ₃ acids 0.3 Other 32.7 Reaction conditions were a total pressure 9kg / cm ² G, oxo gas partial pressure _{^{4kg / cm 2 G (H 2}} / CO =
1), reaction temperature 100 ℃ Raw material / catalyst liquid = 10 (weight ratio) The residence time in the reactor was 2.0 hours.

After depressurizing the reaction solution, almost all of the valeraldehyde produced was recovered by distillation, and the molar ratio of 2-methylbutyraldehyde / n-valeraldehyde = 0.
1 3-methylbutyraldehyde / n-valeraldehyde = 0.
Pivalaldehyde / n-valeraldehyde was 0.0048.

Next, this aldehyde is directly used at a reaction temperature of 95 ° C.
Aldehyde / 3% sodium hydroxide aqueous solution = 1 (weight ratio)
For 1.7 hours in a 10-liter autoclave.

 The conversion of each aldehyde was n-valeraldehyde 99.9% 2-methylbutyraldehyde 99.8 3-methylbutyraldehyde 97.5 pivalaldehyde 99.4.

This decenal mixture was hydrogenated in exactly the same manner as in Reference Example 1 to obtain decyl alcohol, which was purified and evaluated as a plasticizer. The results are shown in Table 1.

Further, the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, and as a result, the molar ratio was A component / PRH = 0.22 B component / 〃 = 0.004 C component / 〃 = 0.111 D component / 〃 = 0.01.

Example-5 Spent spent BB fraction having the following composition after removing most of butadiene and isobutene from the BB fraction from a naphtha cracker was continuously hydroformylated.

[Composition] 1-butene 43 wt% 2-butene 22 isobutene 0.68 butadiene 1.3 C ₃ acids 0.3 Other 32.7 Reaction conditions were a total pressure 8kg / cm ² G, oxo gas partial pressure _{^{4kg / cm 2 G (H 2}} / CO =
1), reaction temperature 100 ℃ Raw material / catalyst liquid = 10 (weight ratio) The residence time in the reactor was 2.0 hours.

After depressurizing the reaction solution, almost all of the valeraldehyde produced was recovered by distillation, and the molar ratio of 2-methylbutyraldehyde / n-valeraldehyde = 0.
1 3-methylbutyraldehyde / n-valeraldehyde = 0.
003 pivalaldehyde / n-valeraldehyde was 0.0026.

Next, this aldehyde is directly used at a reaction temperature of 95 ° C.
Aldehyde / 3% sodium hydroxide aqueous solution = 1 (weight ratio)
For 1.8 hours in a 10-liter autoclave.

 The conversion of each aldehyde was n-valeraldehyde 99.9% 2-methylbutyraldehyde 99.8 3-methylbutyraldehyde 97.5 pivalaldehyde 99.4.

This decenal mixture was hydrogenated in exactly the same manner as in Reference Example 1 to obtain decyl alcohol, which was purified and evaluated as a plasticizer. The results are shown in Table 1.

Further, the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, and as a result, the molar ratio was A component / PRH = 0.22 B component / 〃 = 0.004 C component / 〃 = 0.006 D component / 〃 = 0.01.

Example-6 A spent BB fraction having the following composition after removing most of butadiene and isobutene from a BB fraction from a naphtha cracker was continuously hydroformylated.

[Composition] 1-butene 57.9wt% 2- butene 7.1 isobutene 0.68 butadiene 1.3 C ₃ acids 0.3 Other 32.7 Reaction conditions were a total pressure 7kg / cm ² G, oxo gas partial pressure _{^{4kg / cm 2 G (H 2}} / CO =
1), reaction temperature 100 ℃ Raw material / catalyst liquid = 10 (weight ratio) The residence time in the reactor was 2.0 hours.

After depressurizing the reaction solution, almost all of the valeraldehyde produced was recovered by distillation, and the molar ratio of 2-methylbutyraldehyde / n-valeraldehyde = 0.
04 3-methylbutyraldehyde / n-valeraldehyde = 0.
Pivalaldehyde / n-valeraldehyde was 0.0025.

Next, this aldehyde is directly used at a reaction temperature of 95 ° C.
Aldehyde / 3% sodium hydroxide aqueous solution = 1 (weight ratio)
For 1.5 hours in a 10 l autoclave.

 The conversion of each aldehyde was n-valeraldehyde 99.9% 2-methylbutyraldehyde 99.8 3-methylbutyraldehyde 97.0 pivalaldehyde 98.2.

This decenal mixture was hydrogenated in exactly the same manner as in Reference Example 1 to obtain decyl alcohol, which was purified and evaluated as a plasticizer. The results are shown in Table 1.

Further, the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, and as a result, the molar ratio was A component / PRH = 0.08 B component / 〃 = 0.004 C component / 〃 = 0.006 D component / 〃 = 0.01.

Example -7 A spent spent BB fraction having the following composition after removing most of butadiene and isobutene from a BB fraction from a naphtha cracker was continuously hydroformylated.

[Composition] 1-butene 59 wt% 2-butene 6.0 isobutene 1.2 butadiene 1.3 C ₃ acids 0.3 Other 32.2 Reaction conditions were a total pressure 5kg / cm ² G, oxo gas partial pressure _{^{4kg / cm 2 G (H 2}} / CO =
1), reaction temperature 100 ℃ Raw material / catalyst liquid = 10 (weight ratio) The residence time in the reactor was 2.0 hours.

After depressurizing the reaction solution, almost all of the valeraldehyde produced was recovered by distillation, and the molar ratio of 2-methylbutyraldehyde / n-valeraldehyde = 0.
03 3-methylbutyraldehyde / n-valeraldehyde = 0.
005 pivalaldehyde / n-valeraldehyde = 0.0014.

Next, this aldehyde is directly used at a reaction temperature of 95 ° C.
Aldehyde / 3% sodium hydroxide aqueous solution = 1 (weight ratio)
For 1.5 hours in a 10 l autoclave.

 The conversion of each aldehyde was n-valeraldehyde 99.9% 2-methylbutyraldehyde 99.8 3-methylbutyraldehyde 99.8 pivalaldehyde 98.2.

This decenal mixture was hydrogenated in exactly the same manner as in Reference Example 1 to obtain decyl alcohol, which was purified and evaluated as a plasticizer. The results are shown in Table 1.

When the composition of decyl alcohol in this case was analyzed by capillary gas chromatography, the molar ratio was A component / PRH = 0.06 B component / 〃 = 0.01 C component / 〃 = 0.03 D component / 〃 = 0.001.

Reference Example-5 In Reference Example-1, in (2), adipic acid was used instead of phthalic anhydride to esterify it by a conventional method to obtain a plasticizer. Next, plasticizer / vinyl chloride resin = 43/100 (weight ratio)
, And made into a soft vinyl chloride resin by an ordinary method, and various tests were conducted by an ordinary method. The results are shown in Table-2. Table-
2 shows the test results of di-2-ethylhexyl adipate (DOA), which is a general-purpose plasticizer.

Example-8 The decyl alcohol obtained in Example-1 was esterified with adipic acid in the same manner as in Reference Example-5 and evaluated as a plasticizer. The results are shown in Table-2.

Example-9 The decyl alcohol obtained in Example-4 was esterified with adipic acid as in Example-8,
Evaluation was made as a plasticizer. The results are shown in Table-2.

Reference Example-6 The decyl alcohol obtained in Reference Example-2 was esterified with adipic acid in the same manner as in Example-8,
Evaluation was made as a plasticizer. The results are shown in Table-2.

[Effects of the Invention] The alcohol for plasticizer of the present invention exhibits excellent overall performance as a plasticizer raw material, and is industrially useful.

Claims (3)

(57) [Claims] 1. A mixture of alcohols having 10 carbon atoms, the alcohol having a skeleton of a condensation product of 2-propylheptanol (hereinafter referred to as PRH) and n-valeraldehyde and 2-methylbutyraldehyde (hereinafter referred to as "PRH"). , A component), an alcohol having a skeleton of a condensation product of n-valeraldehyde and 3-methylbutyraldehyde (hereinafter, referred to as a B component), and a skeleton of a condensation product of n-valeraldehyde and pivalaldehyde. The components of alcohol (hereinafter, referred to as C component) and other alcohols having 10 carbon atoms (hereinafter, referred to as D component) are molar ratio of A component / PRH = 0.04 to 1 B component / PRH = 0.002 to 0.3 An alcohol for a plasticizer, wherein the ratio of C component / PRH = 0.001 to 0.3 D component / PRH ≦ 0.3. 2. The alcohol for a plasticizer according to claim 1, wherein the mixture of alcohols having 10 carbon atoms is obtained by subjecting a butene fraction to a hydroformylation reaction, an aldol condensation reaction and a hydrogenation reaction. 3. An alcohol having a skeleton of a condensation product of 2-propylheptanol (hereinafter referred to as PRH), n-valeraldehyde and 2-methylbutyraldehyde (hereinafter referred to as A component), and n-valeraldehyde. An alcohol having a skeleton of a condensation product with 3-methylbutyraldehyde (hereinafter, referred to as a B component), an alcohol having a skeleton of a condensation product of n-valeraldehyde and pivalaldehyde (hereinafter, a C component), and The other components having 10 carbon atoms (hereinafter referred to as D component) are represented by the following molar ratio: A component / PRH = 0.04 to 1 B component / PRH = 0.002 to 0.3 C component / PRH = 0.001 to 0.3 D component A plasticizer obtained by subjecting a carboxylic acid to an esterification reaction with a C10 alcohol mixture having a ratio of /PRH≦0.3.