JP2765072B2 - Alcohol for plasticizer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an alcohol for a plasticizer. More specifically, the present invention relates to a C9 alcohol (hereinafter referred to as "INA") having excellent heat resistance, cold resistance and electrical insulation properties as an alcohol for a plasticizer of a vinyl chloride resin. It relates to a mixed alcohol with an alcohol having 10 carbon atoms.

[Conventional technology]

A butane-based fraction having 4 carbon atoms obtained by thermal cracking of naphtha or catalytic cracking of heavy and light oils
It is called "butene fraction". INA) obtained by performing a hydroformylation reaction and a hydrogenation reaction using an olefin having 8 carbon atoms (hereinafter referred to as "octenes") obtained by dimerizing the olefin as a raw material for a plasticizer of a vinyl chloride resin. Suitable use is already known. Also, as disclosed in GB 789777, IN
It is also known that A has excellent heat resistance and is suitable as an alcohol for a plasticizer.

Also, alcohols having 10 carbon atoms (IDA) obtained by hydroformylation, aldol condensation and hydrogenation of butenes are disclosed in U.S. Pat. Nos. 2,921,089 and 3,12.
No. 1,051 describes 2-propylheptanol derived from the condensation product of n-valeraldehyde and decyl alcohol derived from 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 plasticizer, and the cross aldol product has a plasticizer performance compared to 2-propylheptanol. Although it is inferior, it is shown that the performance is not so inferior when used as a mixture of up to more than 10% with 2-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.

[Problems to be solved by the invention]

However, the performance of INA as a plasticizer is superior to 2-ethylhexanol, which is a general-purpose plasticizer alcohol, in terms of its volatilization loss and low-temperature softening temperature. Had drawbacks.

Therefore, it has been desired to develop an INA for plasticizer which overcomes these drawbacks and has excellent overall performance.

[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, mixing INA with a specific alcohol having a specific carbon number at a specific ratio, as a plasticizer for INA. The present inventors have found that the overall performance can be improved and completed the present invention.

That is, the present invention relates to an alcohol having 9 carbon atoms (hereinafter referred to as “INA”).
And alcohols having 10 carbon atoms (hereinafter referred to as "IDA") obtained by subjecting butenes to a hydroformylation reaction, aldol condensation reaction and hydrogenation reaction, wherein the weight ratio of IDA to INA is IDA. / INA = the alcohol in the range of 0.01 to 0.2, wherein the alcohol is for a plasticizer.

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

The INA constituting the alcohol for the plasticizer of the present invention is produced by a conventionally known method, and is obtained, for example, by subjecting an olefin having 8 carbon atoms (hereinafter referred to as octene) to a hydroformylation reaction and a hydrogenation reaction.

The raw material octene can be obtained by a method of dimerizing butenes by a known method using a nickel-based catalyst or the like.
It can also be obtained by a low polymerization reaction of ethylene.

The octene hydroformylation reaction is carried out 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 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.

The hydrogenation reaction of the produced nonyl aldehyde can be carried out by a usual method. That is, the reaction is usually carried out at normal pressure to 150 kg / cm ² G and at a reaction temperature of 40 to 300 ° C. using a normal hydrogenation catalyst such as Ni, Cr and Cu.

Next, alcohol having 9 carbon atoms (INA) can be obtained by ordinary distillation purification.

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

The raw material butenes include 1-butene, 2-butene, and isobutene, as well as their mixtures, and the catalytic cracking of hydrocarbon oils such as BB fractions or heavy and light oils obtained by thermal cracking of hydrocarbon oils such as naphtha. (FCC etc.)
Any of the BB fractions obtained by the above 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 conditions can be carried out under conventionally known conditions substantially the same as in the case of INA described above. It is only necessary to obtain valeraldehyde or valeraldehyde mixture corresponding to butene.

In the aldol condensation reaction, a conventionally known method may be used, and an aqueous alkali solution such as sodium hydroxide or potassium hydroxide can be used as a catalyst, but amines or the like can also be used. The reaction temperature is usually from 50 to 150 ° C., the reaction pressure is usually from normal pressure to several kg / cm ² G, and the reaction time is usually from several minutes to several hours.

The hydrogenation reaction of the produced desenals can be carried out by the usual method as described above for INA, and then the alcohol having 10 carbon atoms (IDA) is obtained by ordinary distillation and purification.

The alcohol for the plasticizer of the present invention has a weight ratio of INA to IDA of IDA / INA = 0.01 to 0.2, preferably 0.02 to 0.2, but the mixing time is limited to IDA and INA.
Not only the products of the above, but also the crude alcohol before the distillation and purification after the hydrogenation reaction can be mixed and adjusted to the above ratio by distillation and purification, or the decenals and nonylaldehyde to be subjected to the hydrogenation reaction can be mixed. After carrying out the hydrogenation reaction, the above ratio can be adjusted by distillation and purification.

If the mixing ratio of IDA / INA is less than 0.01, the electric resistance is not improved, and if it exceeds 0.2, the plasticizing efficiency, heat resistance and 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.

INA is generally known to be superior in heat resistance and low-temperature softening temperature compared to general-purpose plasticizer alcohols such as 2-ethylhexanol, but is generally inferior in electrical resistance and plasticization efficiency. ing.

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 conflicting 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, but the present invention is not limited to the following Examples as long as the gist is not exceeded.

Reference Example 1 (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 made of SUS induction stirring type autoclave of volume 10 under a nitrogen atmosphere, C ₄ fraction 4kg after the dehydration mentioned above, n- hexane nickel octoate
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, the catalyst was removed, 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.

(2) Synthesis of INA In a SUS autoclave with a capacity of 10 in a nitrogen atmosphere,
2.0 kg of the octene fraction obtained in the above (2) and 20 g of dicobalt octacarbonyl were added, and the mixture was reacted at 140 to 150 ° C. while maintaining the total pressure at 160 kg / cm ² G with oxo gas of H ₂ / CO = 1. After 2 hours, the gas absorption had ceased.
% NaOH aqueous solution to inactivate the cobalt catalyst,
After further cooling and releasing the oxo gas, the entire reaction liquid was taken out and separated into liquid to obtain an organic phase.

Then, aldehyde and alcohol were obtained by simple distillation under reduced pressure 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.
The reaction was performed at a reaction temperature of 150 ° C. Five hours later, the gas absorption ceased, so it was quenched, the hydrogen gas was released, the entire reaction solution was taken out, the solid catalyst was removed, and the inside diameter was reduced to 35.
The fraction was rectified in an mm × 20-stage Oldershaw distillation column. The reflux ratio was 3, and the pressure was 10 mmHg. First stay 0.5%, pot remaining 3%
Was cut to obtain 96.5%. The yield of INA through hydrogenation and tax distillation was 95%.

(4) Synthesis and evaluation of plasticizer The INA obtained in (3) 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-
The test results of 2-ethylhexyl phthalate (DOP) are also described.

Reference Example 2 A spent spent BB fraction having the following composition after removing most of butadiene and isobutene from a BB fraction with 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 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 the produced valaldehyde 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 desenal mixture was hydrogenated with a nickel-based solid catalyst. The hydrogenation conditions were as follows: pressure 100 kg / cm ² G, temperature 120 ° C., catalyst / decenal = 0.1 (weight ratio) by batch reaction.
A time reaction was performed. The conversion of desenal was 99.9%. Next, the product was rectified by a 30-stage glass Oldershaw distillation column, and the initial fraction 1% and the bottom 3% were cut to obtain a main fraction 96%.

The composition of the obtained IDA was analyzed by a capillary gas chromatograph. A component / 2-propylheptanol = 1.3 B component / 2-propylheptanol = 0.3 C component / 2-propylheptanol = 0.4 D component / 2-propylheptanol = 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-valeraldehyde. Represents a decyl alcohol having a skeleton of an aldol condensate of phenol and pivalaldehyde, and the component D represents other decyl alcohol.

This IDA was evaluated as a plasticizer as in (4) of Reference Example 1. The results are shown in Table 1.

Reference Example 3 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% 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%.

A mixture of the obtained n-valeraldehyde and 2-methylbutyraldehyde at a ratio of 1: 0.1 (weight ratio) was subjected to a condensation reaction.

The condensation conditions were as follows: 90 ° C. under normal pressure, 3% aqueous sodium hydroxide solution / valeraldehyde = 1 (weight ratio), reaction time 12
A batch reaction was performed at 0 minutes. The obtained decenal mixture was used as decyl alcohol (IDA) in the same manner as in Reference Example 2 and evaluated as a plasticizer. The results are shown in Table 1. In this case, the conversion rate of valeraldehyde in the above condensation reaction was n-valeraldehyde = 99.9% 2-methylbutyraldehyde = 99.2.

 The isomer composition of IDA was 2-propylheptanol 82.0 wt% 2-propyl-4-methylhexanol 17.3 and other isomers decyl alcohol 0.7.

Examples 1 and 2 A mixture of the IDA obtained in Reference Examples 2 and 3 with the INA obtained in (3) of Reference Example 1 and IDA / INA = 0.1 (weight ratio) was used as a mixture of (4) in Reference Example 1. ) Was evaluated as a plasticizer in the same manner as in (1). The results are shown in Table 1.

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

This mixed crude alcohol was subjected to batch distillation using a 60-stage Oldershaw distillation apparatus. Conditions are 10mmHg, pot temperature 140-160
° C and a reflux ratio of 10. 0.2 wt cut for first charge
%, INA-IDA fraction mainly composed of INA, IN mainly composed of IDA
An A-IDA fraction and a still residue of 4.3 wt% were obtained.

IDA in the INA-IDA fraction mainly composed of INA was measured by capillary gas chromatography and found to be 4.76% by weight.

This INA-IDA fraction mainly composed of INA was esterified in the same manner as in (4) of Reference Example 1 and evaluated as a plasticizer. The results are shown in Table 1.

Comparative Example 1 The same procedure was performed as in Example 1 except that the mixing ratio of INA and IDA was changed to IDA / INA = 0.005 (weight ratio). The results are shown in Table 1.

Comparative Example 2 The same procedure was performed as in Example 1 except that the mixing ratio of INA and IDA was set to IDA / INA = 0.3 (weight ratio). 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] An alcohol having 9 carbon atoms (hereinafter referred to as "INA").
And alcohols 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, wherein the weight of IDA and INA is The ratio is IDA / INA = 0.01
Alcohol for a plasticizer, which is in the range of ~ 0.2. 2. The alcohol for a plasticizer according to claim 1, wherein the INA is an alcohol having 9 carbon atoms obtained by hydroformylation and hydrogenation of an olefin having 8 carbon atoms.