JP2765071B2 - Alcohol for plasticizer - Google Patents

Description

The present invention relates to an alcohol for a plasticizer. More specifically, the present invention relates to a mixed alcohol of an alcohol having 10 carbon atoms and an alcohol having 9 carbon atoms, which has excellent overall performance as a plasticizer raw material alcohol.

[Conventional technology]

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 vinyl chloride resin. Used as alcohol.

An alcohol having 9 carbon atoms (hereinafter referred to as nonyl alcohol) is obtained by subjecting a olefin having 8 carbon atoms (hereinafter referred to as octene) obtained by dimerizing an olefin having 4 carbon atoms to a hydroformylation reaction and a hydrogenation reaction. This is mainly used as a raw material alcohol for a plasticizer of a vinyl chloride resin.

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. It is produced by reacting to produce decenals, which are further hydrogenated. 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. However, by purification of butenes or distillation separation of aldehydes,
It is also possible to obtain decyl alcohol containing only one or several isomers.

U.S. Pat.Nos. 2,921,089 and 3,121,051 include n-
It describes 2-propylheptanol derived from the condensation product of valeraldehyde and decyl alcohol derived from the cross-aldol product of n-valeraldehyde and 2-methylbutyraldehyde. Means that a normal method may be used.
Propyl heptanol is excellent as a decyl alcohol for plasticizers, and the cross aldol product has a plasticizer performance inferior to that of 2-propyl heptanol, but has
It has been shown that the performance is not so inferior when used as a mixture up to more than 10% with propylheptanol.

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.

It is also known that nonyl alcohol using octene as a raw material is used as a plasticizer alcohol as disclosed in British Patent No. 789,777.

[Problems to be solved by the invention]

The performance of a C10 alcohol (hereinafter, referred to as IDA) as a plasticizer obtained by subjecting a C4 olefin to a hydroformylation reaction, an aldol condensation reaction, and a hydrogenation reaction is a general-purpose plasticizer alcohol. 2
Although it has the greatest feature of low volatility as compared with ethylhexanol, it has drawbacks in other performances such as plasticizing efficiency and electric resistance. In particular, the plasticizing efficiency is directly related to the cost of the plasticizer, and a poor one is industrially disadvantageous.

Therefore, development of decyl alcohol for plasticizer which overcomes these drawbacks and has excellent overall performance has been desired.

[Means for solving the problem]

In view of the above prior art, the present inventors have conducted intensive studies to solve the problem, and as a result, by mixing a specific nonyl alcohol with a specific ratio to IDA, the overall performance of decyl alcohol is significantly improved. We have found that we can do this and completed the present invention.

That is, the present invention relates to 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 a carbon number obtained by dimerizing butenes. A mixed alcohol with an alcohol having 9 carbon atoms (hereinafter referred to as “INA”) obtained by subjecting an olefin of 8 to a hydroformylation reaction and a hydrogenation reaction,
And a weight ratio between IDA and IDA is in the range of INA / IDA = 0.001 to 0.4.

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

The IDA constituting the alcohol for the plasticizer of the present invention is a C10 alcohol obtained by subjecting butenes to a hydroformylation reaction, an aldol condensation reaction, and a hydrogenation reaction.

As the butenes, 1-butene, 2-butene, and isobutene are each used alone, as well as in the catalytic cracking of hydrocarbon oils such as BB fractions or heavy and light oils obtained by thermal cracking of hydrocarbon oils such as a mixture thereof or naphtha. Any of the BB fractions obtained by FCC etc. 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 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.

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, an oxide thereof, or the like is generally used as appropriate in a molar ratio of usually 1 to 1000 with respect to the above catalyst. 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.

Each component of valeraldehyde in the product has a boiling point difference of more than 10 ° C., and the mixed valeraldehyde can be separated into each component by distillation.

In the aldol condensation reaction, it is usually used as an aqueous alkali solution such as sodium hydroxide and potassium hydroxide and a catalyst, but amines and 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.

The produced desenals are subjected to a hydrogenation reaction after being purified by distillation, but may be subjected to a hydrogenation reaction without purification by distillation.

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, C10 alcohol (IDA) can be obtained by ordinary distillation purification.

INA constituting the alcohol for the plasticizer of the present invention,
It is a C9 alcohol obtained by subjecting a C8 olefin obtained by dimerizing butenes to a hydroformylation reaction and a hydrogenation reaction.

Octene can be obtained by dimerizing butenes by a known method such as a nickel-based catalyst. The butenes described above
The same raw materials as IDA are used.

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

The hydroformylation conditions are also not particularly critical,
Any of the rhodium method and the cobalt method under almost the same conditions as the hydroformylation reaction of butenes used in the production of IDA can be used.

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

The alcohol for plasticizer of the present invention has a weight ratio of IDA to INA of INA / IDA = 0.01 to 0.4, preferably 0.02 to 0.4, more preferably 0.03 to 0.3, and most preferably 0.06 to 0.3. As for the mixing time, not only the IDA and INA products but also the crude alcohol after the hydrogenation reaction and before the distillation and purification can be mixed and adjusted to the above ratio by distillation and purification, and the mixture is supplied to the hydrogenation reaction. After hydrogenation reaction after mixing the decenals and nonyl aldehyde,
The above ratio can also be adjusted by distillation and purification.

If the weight ratio of INA / IDA is less than 0.01, the plasticizing efficiency and the electric resistance are not improved, and if it exceeds 0.4, the plasticizing efficiency and the electric resistance are undesirably reduced.

The alcohol for a plasticizer of the present invention obtained as described above is used as a plasticizer by an esterification reaction with phthalic anhydride or the like by a conventional method.

Decyl alcohol is generally known to be superior in heat resistance to alcohols for general-purpose plasticizers such as 2-ethylhexanol, but is generally inferior in electrical resistance and plasticization efficiency.

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 contradictory tendencies such as those described above and are complicated, according to the present invention, it is possible to obtain an alcohol for a plasticizer having excellent overall performance.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless departing from the gist thereof.

Reference Example 1 (1) Synthesis of IDA 1-butene was subjected to a hydroformylation reaction by a batch reaction in a 10-autoclave. The reaction conditions were as follows: total pressure 10 kg / cm ² G, oxo gas partial pressure 4 kg / cm ² GH ₂ / CO = 1, reaction temperature 95 ° C. Raw material / catalyst liquid = 3 (weight ratio) The reaction time was 3.0 hours.

After the autoclave was cooled and depressurized, the entire reaction liquid was recovered and batch-distilled in a 50-stage Oldershaw distillation column to obtain n-valeraldehyde.

The distillation conditions were such that the top pressure was normal pressure, the reflux ratio was 3.0, a small amount of unreacted 1-butene and 2-methylbutyraldehyde were cut off as the first fraction, and the main distillate was 99.97% pure n.
-Valeraldehyde was obtained. The impurity was xylene 0.03%.

 The obtained n-valeraldehyde was subjected to a condensation reaction.

A batch reaction was carried out at 90 ° C. under normal pressure with 3% aqueous sodium hydroxide / n-valeraldehyde = 1.5 (weight ratio) for a reaction time of 30 minutes. The conversion of n-valeraldehyde was 99.9%. Next, the desenal after gas-liquid separation was hydrogenated with a nickel-based solid catalyst. Hydrogenation conditions were as follows: pressure 50 kg / cm ² G, temperature 120 ° C, catalyst / decenal = 0.
The reaction was carried out at 1 (weight ratio) by a batch reaction for 3.0 hours. 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 95%,
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 = 60/100 (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.

Reference Example 2 Reference Example 1 was repeated except that a mixture of n-valeraldehyde obtained in (1) of Reference Example 1 and 2-methylbutyraldehyde at a ratio of 1: 0.1 (weight ratio) was used as a raw material for the condensation reaction. Was evaluated as decyl alcohol as a plasticizer. The results are shown in Table 1. The conversion of valeraldehyde in the condensation in this case was n-valeraldehyde = 99.9% 2-methylbutyraldehyde = 99.2%.

The composition of decyl alcohol was as follows.

(Composition)

2-propylheptanol 81.3wt% 2-propyl-4-methylhexanol 17.9wt% Other isomeric decyl alcohol 0.8wt% Reference Example 3 After removing most of butadiene and isobutene from the BB fraction from naphtha crackers Of the following composition 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 18kg / cm ² G, oxo gas partial pressure _{^{15kg / 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, the composition of valeraldehyde produced was adjusted by distillation, and the molar ratio of 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 is directly used at a reaction temperature of 95 ° C.
Aldehyde / 3% sodium hydroxide aqueous solution = 1 (weight ratio)
For 1.5 hours in an autoclave of 10 hours.

The conversion of each aldehyde was n-valeraldehyde 99.9% 2-methylbutyraldehyde 92.2 3-methylbutyraldehyde 93.5 pivalaldehyde 91.8.

This decenal mixture was hydrogenated in 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.

The composition of the decyl alcohol in this case was analyzed by capillary gas chromatography, and it was found that the molar ratio was A component / 2-propylheptanol = 1.3 B component / 〃 = 0.3 C component / 2-propylheptanol = 0.3 D component. /〃=0.03.

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

Reference Example 4 (1) C ₄ fraction after the removal of butadiene and isobutene from BB fraction obtained from a cracker of synthetic naphtha octenes (isobutene 6
% By weight, 43% by weight of 1-butene, 25% by weight of 2-butene, 25% by weight of butanes and 1% by weight) were dehydrated with a molecular sieve 13X. Then, under a nitrogen atmosphere in a SUS induction stirring autoclave having a capacity of 10 under nitrogen atmosphere, 4 kg of the above-described dehydrated C ₄ fraction, an n-hexane solution of nickel octanoate
5.5 g (Ni content 6 wt%) and 11.3 g of ethyl aluminum dichloride were charged and reacted at 40 ° C. for 7 hours.

After the reaction, 340 g of a 5 wt% H ₂ SO ₄ aqueous solution was added to deactivate the catalyst, and then octenes were obtained by liquid-liquid separation.

 The above reaction was performed three times.

(2) Obtaining the octene fraction by distillation The octenes obtained in the above (1) were rectified at normal pressure in an Oldershaw type distillation column having an inner diameter of 50 mm and 20 stages. 5.8 kg of an octene fraction having a top temperature of 108 to 127 ° C. was obtained.

(3) Synthesis of INA and synthesis and evaluation volume of plasticizer 10
Under an atmosphere of nitrogen, 2.0 kg of the octene fraction obtained in (2) above and 20 g of dicobalt octacarbonyl were added to a SUS autoclave, and the total pressure was increased to 16 with oxo gas of H ₂ / CO = 1.
It was kept at 0 kg / cm ² G and reacted at 140-150 ° C. After 2 hours, the gas absorption had ceased.
After injecting an aqueous NaOH solution to deactivate the cobalt catalyst, the system was further cooled, and the oxo gas was released. After that, the entire reaction liquid was taken out and separated into liquids to obtain an organic phase.

Then, an aldehyde and an alcohol having 9 carbon atoms were obtained by vacuum coal distillation at a pressure of 10 mmHg. The total yield of aldehyde and alcohol was 99%.

Next, in a SUS autoclave having a capacity of 10, a total amount of the obtained liquid obtained by the simple distillation and 160 g of the nickel-supported solid catalyst were charged under a nitrogen atmosphere, and the total pressure was maintained at 90 kg / cm ² G with hydrogen gas.
A hydrogenation reaction was performed at a reaction temperature of 150 ° C. Five hours later, the gas absorption ceased, so the mixture was quenched. After the hydrogen gas was released, the entire amount of the reaction solution was taken out, and the solid catalyst was removed. Rectified.
The reflux ratio was 3, and the pressure was 10 mmHg. 0.5% of first distillate and 3% of kettle remaining were cut to obtain 96.5%.

The yield of INA through hydrogenation and rectification was 95%. This INA was evaluated as a plasticizer in the same manner as in (2) of Reference Example 1 and evaluated. The results are shown in Table 1.

Examples 1 to 3 The decyl alcohol (IDA) obtained in Reference Examples 1 to 3 was obtained by using the INA obtained in (3) of Reference Example 4 and INA / IDA = 0.2 (weight ratio).
The plasticizer was used as a plasticizer in the same manner as in (2) of Reference Example 1 and the performance was evaluated. The results are shown in Table 1.

Example 4 In the hydrogenation reaction of desenal in Reference Example 2, after mixing with an aldehyde and an alcohol having 9 carbon atoms at a ratio of 1: 1 (by weight) before the hydrogenation reaction in (3) of Reference Example 4, Hydrogenation was performed in the same manner as in (1) of Reference Example 1 to obtain a mixed crude alcohol.

This mixed crude alcohol was subjected to batch distillation using an 60-stage Oldershaw distillation apparatus. Conditions are 10mmHg, Hook temperature 14
The temperature was 0 to 160 ° C and the reflux ratio was 5.0. An initial distillation cut of 0.5% by weight, an INA-IDA fraction mainly composed of INA, an INA-IDA fraction mainly composed of IDA, and a bottom residue of 4.0% by weight were obtained based on the charged liquid. This IDA
Was measured by capillary gas chromatography to find that it was 8.0 wt%.

The INA-IDA fraction mainly composed of IDA was esterified in the same manner as in (2) of Reference Example 1 and evaluated as a plasticizer. The results are shown in Table 1.

Example 5 In the hydrogenation reaction of the desenal mixture in Reference Example 3, the mixture was mixed with the aldehyde and alcohol having 9 carbon atoms before the hydrogenation reaction in (3) of Reference Example 4 at a ratio of 1: 1 (by weight). After hydrogenation and batch distillation in the same manner as in Example 4, an INA-IDA fraction mainly composed of IDA was obtained and evaluated as a plasticizer. INA-IDA mainly based on this IDA
The INA in the fraction was 12.3 wt%. The results are shown in Table 1.

Example 6 Mixed crude alcohol. Set the reflux ratio of the distillation conditions to 1.0
Example 4 was carried out in exactly the same manner as in Example 4, and after obtaining an INA-IDA fraction mainly composed of IDA, evaluation was made as a plasticizer. The INA in this IDA-based INA-IDA fraction is 25.9
wt%. The results are shown in Table 1.

Comparative Examples 1-3 Same as Example 1 (Comparative Example 1) and Example 2 (Comparative Example 2) except that the mixing ratio of INA and IDA was set to INA / IDA = 0.005 (weight ratio). Comparative Example 3 was performed in the same manner as Comparative Example 3. The results are shown in Table 1.

Comparative Examples 4 to 6 The same as Example 1 (Comparative Example 4) and Example 2 (Comparative Example 5) except that the mixing ratio of INA and IDA was set to INA / IDA = 0.5 (weight ratio). Comparative Example 6 was performed in the same manner as Comparative Example 3. The results are shown in Table 1.

[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.

Continuation of front page (56) References JP-A-62-267341 (JP, A) JP-A-61-243845 (JP, A) JP-A-58-98350 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) C07C 31/125 C07C 29/141 C07C 29/38 C08K 5/10 C08K 5/05

Claims (2)

(57) [Claims] 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 a C8 alcohol obtained by dimerizing butenes. Is a mixed alcohol with an alcohol having 9 carbon atoms (hereinafter referred to as "INA") obtained by hydroformylation reaction and hydrogenation reaction of olefin, wherein the weight ratio of INA to IDA is INA / IDA = 0.01 to 0.4. The alcohol for a plasticizer characterized by the above range. 2. The alcohol for a plasticizer according to claim 1, wherein the weight ratio of INA to IDA is in the range of INA / IDA = 0.02 to 0.4.