JPH07330670A - Improved process for producing composite ester and esters - Google Patents

Abstract

PURPOSE:To obtain a composite ester having low volatility and excellent plasticizing property and useful as an additive for a polyvinyl chloride film to prevent the hardening of the film caused by the evaporation of plasticizers after the use for a long period by using the ester in an amount calculated from a reaction formula. CONSTITUTION:(A) Adipic acid, (B) a monohydric alcohol of formula ROH (R is a monohydric alcohol residue) and (C) a diol of formula HOXOH (X is a diol residue) are subjected to dehydrative esterification reaction first in the absence of a catalyst and then using a titanium catalyst. The obtained product is subjected to dealcoholating transesterification reaction e.g. by the direct addition of the diol to obtain a composite ester of formula I ((n) is a real, number of 1-7) and a by-produced mixture of a monohydric alcohol and an adipic acid ester. The composite ester is separated from the mixture. The amounts of the component B and the component C relative to the component A are theoretically determined from formula II and formula III ((q) is estimated or experimentally determined ratio of by-produced ester; (m) is a value calculated by formula IV).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a high-molecular-weight plasticizer having low volatility and excellent volatility and plasticity, which is added to a polyvinyl chloride film which is hardened by volatilization of the plasticizer for long-term use. Manufacturing method.

The plasticizer compound produced by the method of the present invention has a structure represented by the following general formula. _{RO (CO (CH 2) 4} COOXO) n CO (CH 2) 4 COOR (I) where residues of alkyl alcohol R is commonly used, X is acid residue of a diol, n represents 1-7 It is a real value. These are dibasic acids (HOCOACOO), which are mainly adipic acid.
H), difunctional alcohols (diols), and monofunctional alcohols, which are small complex esters of n and large polyesters of n (hereinafter may be simply referred to as complex esters), represented by the general formula ( I). The present invention relates to a method of making these n small complex esters or n large polyesters.

[0003]

BACKGROUND OF THE INVENTION Complex esters are essentially prepared as a mixture of compounds having the general formula RO (COACOOXO) _n COACOOR where n is 1-7. Such a complex ester has already been reported in the journal of the American Chemical Society of 1930 (JACS 52: 3).
221). The inventors of the present invention have conducted research on production of a single complex ester among such esters and research on the composition ratio of the complex ester mixture. Journal of Polymer Science 47,177 (1990). The present inventor has further investigated a method of producing a complex ester by a transesterification reaction (Japanese Patent Publication 1-25733), a dehydration esterification reaction (Japanese Patent Publication 4-51540, USP 4661622), and a complex ester composed of different dibasic acids. Is referred to as "heterogeneous complex ester" and its production method (Japanese Patent Laid-Open No. 62-234044) has been applied, and a method by dehydration esterification reaction in consideration of molecular weight distribution is described in Japanese Patent Laid-Open No. 5-155810. 2 as the diol component
A patent application was filed because an ester having excellent water resistance can be obtained by using -ethyl-1,3-hexanediol.

When compared with polyester plasticizers, these complex esters have a lower volatility than polyester plasticizers, depending on their molecular weight. However, regarding the use as a plasticizer, if the molecular weight is 1500 or more, its viscosity is too high, and if it is used as a plasticizer for vinyl chloride, the plasticity performance is poor, and it is not easy to produce a low ester having a lowered acid value. ROCOACOOR (II), a complex ester with low viscosity and high plasticity, but adipic acid diester
(Hereinafter, abbreviated as diester or DOA)
The amount of by-product is large and the disadvantages cannot be avoided. In addition, the production technology of the product, especially considering the molecular weight distribution, or the target n
Although the technology for producing a complex ester mixture having values has not been established, the present inventor studied a method for producing a terminal octyl-based complex ester and a method for obtaining a complex ester having a controlled molecular weight distribution by sequential addition esterification reaction. I found it. That is, refer to the above-mentioned Japanese Patent Laid-Open No. 5-1558102. According to the technology described here, when using general 1,3-butanediol as a diol at present, when aiming at n = 2.5, almost 93% of the adipic acid used becomes a complex ester, It was also found that, when n = 3 or more, almost 97% became the target complex ester.

[0005]

Since the complex ester is always obtained as a mixture of oligomers, its molecular weight distribution is important for obtaining the intended effect. Further, particularly when a complex ester having a small number of n is produced, the amount of by-produced adipic acid diester is large, and a production method for avoiding this is a problem. Also, if a complex ester containing no high-molecular weight oligomer is produced, it is used as an excellent plasticizer having low viscosity and high plasticity, low volatility corresponding to the molecular weight, and low volatility.

In the esterification reaction, it is common knowledge that the alcohol is used in a large amount relative to the acid, and unless it is used, the terminal rate is slow and it is difficult to obtain a low acid value product. is there. In complex esters, when a monofunctional alcohol is used as the alcohol corresponding to such excess amount, ester alcohol ROCOACOOXOH
However, it is not preferable because the molecular weight distribution becomes wide.
It has been used unavoidably for lowering the acid value. Further, what was found in the course of the above-mentioned research is that even in the case of a complex ester, if a sufficient transesterification reaction is not carried out, a slight amount of mixed ester alcohol may cause a decrease in heating, water resistance, electrical characteristics, and other plasticizers. It was found to reduce performance. It has been found that it is necessary to carry out the transesterification reaction at a higher temperature and a lower pressure than that of the conventionally described method, and that the high temperature treatment at 250 ° C. significantly improves the plasticizer performance. In particular, it was found that a complex ester can be easily obtained by utilizing the transesterification technique, and the present invention was completed after various studies.

[0007]

Improvements in the Prior Art In the above patent application, the present inventor has examined the method for producing a complex ester, including industrial problems, but the present invention has been improved particularly in the technique for producing a complex ester. It is the one that raises the method.

The reaction mode is described by the following formula. (1) HOCOACOOH + 2ROH → ROCOACOOR ROCOACOOR + m HOXOH → [RO (COACOOX) pOH] → RO (CO (C
H ₂ ) ₄ COOXO) _n CO (CH ₂ ) ₄ COOR (I) + 2m ROH + q ROCOACO
OR (II) (2) HOCOACOOH + m HOXOH + 2-m ROH → m ROCOACOOXOH
+ {(1-q) / (n + 1) + q} ROCOACOOR → → RO (CO (CH ₂ ) ₄ COO
XO) _n CO (CH ₂ ) ₄ COOR (I) + m ROH + q ROCOACOOR (II)

In connection with the above reaction, the diester (ROCO
Japanese Patent Publication No. 1-25733 describes a method of transesterification between ACOOR) and diol (HOXOH). This is a technique for improving the reaction molar ratio of a diester and a diol to produce a target complex ester. In order to produce a complex ester by reacting with excess alcohol, ester alcohol ROCOACOOXOH and diester (D
Preparation of a mixture with OA) by a dehydration esterification reaction is described in Japanese Patent Publication No. 4-51540. One of the schemes of the present invention is the three components used (dicarboxylic acid, diol, monoalcohol) as described in the examples.
The reaction proceeds in a molar equivalent amount without using an excess amount, but the reaction is started without a catalyst during the reaction, and a titanium catalyst is added when about 80 to 90% of the acid has reacted. The feature is that the acid value is sufficiently lowered in a short time. This method is also applied to the method for producing the diester used in the above transesterification reaction, and the titanium catalyst is effectively used as a catalyst for the transesterification reaction.
In this esterification method, the reaction rate in the dehydration esterification reaction is high in the third step in the dehydration esterification reaction, especially when the scale of the reaction is large, and the dehydration rate in the presence of the catalyst in the latter stage is high. The esterification reaction is a first-order reaction, and by utilizing the fact that the terminal acid value is predicted and the LOG concentration and time are in a substantially proportional relationship, the esterification reaction effectively utilizes the performance of the titanium catalyst. The timing of addition is related to the alcohol and acid equivalent ratio in the reaction solution, and it is good when the acid at the end of the reaction decreases and the alcohol equivalent ratio becomes large, which minimizes the deactivation of the titanium catalyst and improves the efficiency. The esterification reaction can proceed well. When the catalyst is added from the beginning, the reaction is apparently fast on the laboratory scale, but on the industrial scale the reaction time is inversely proportional to the initial concentration, the relative speed is slow and the reaction is long, and only the non-catalytic reaction, The reaction at the end of the reaction is slow, and a long reaction time is required to achieve a low acid value.

On the other hand, especially when ROH is a high-boiling alcohol such as octanol, heptanol, or oxoalcohol, the problem was how to deal with the dealcoholation transesterification reaction.
The purpose could be achieved by increasing the degree of vacuum to 0.2 mmHg. As a result of studying the temperature of these transesterification reactions, it has been described previously (Japanese Patent Publication 1-25733).
At a temperature up to ℃ and a degree of reduced pressure of about 25 mmHg, the reaction is more quantitatively promoted, residual low volatile components are removed, and it is insufficient to maintain water resistance when used as a plasticizer, It was found that the condition of this transesterification reaction is an essential factor. In this way, it was possible to achieve a technique for producing a composite ester and a polyester by an esterification reaction.

Next, the reaction molar ratio will be described. When carrying out the transesterification reaction, ester alcohol and DO
The molar ratio of A is an important factor, and when a transesterification reaction is carried out with the composition ratio thereof being 1: 1, a composite ester having an average molecular weight corresponding to an average n of about 2-3 is formed. Generate and DO in proportion to the increase in the number of n
A is a byproduct. The ratio q value of the by-produced DOA, which was experimentally confirmed, was predicted or calculated in advance, and the amount of diol required for the adipic acid (1-q) reacting as a complex ester was m = (1
-q) × n / (n + 1) as well as monofunctional alcohol (2-m) for the reaction composition of ester alcohol and diester
A mixture of m: {(1-q) / (n + 1) + q} was prepared by a dehydration esterification reaction according to the above-mentioned method, and optionally, DOA was added to adjust the reaction ratio, or a reaction intermediate Is regarded as an ester alcohol, the amount of diol used is calculated in the same manner, and dealcoholation transesterification reaction is carried out, and finally n = (amount of reacted diol) / (amount of reacted dibasic acid−reacted geo) -Amount) to obtain a product by carrying out a transesterification reaction for the purpose of arbitrary value of n.

The proportion of DOA (diester) produced as a by-product is
The reactivity was somewhat different depending on the type of diol used, and the value was also different depending on the reaction temperature. In particular, as the value of n becomes smaller near 1, it is necessary to increase the proportion of the by-product DOA, and it is impossible to obtain n = 1 in practice.
Only = 1.5 or more complex ester can be made. Here, when n = 1.5 to 1.8, the DOA byproduct ratio is 70 to 50%, and this is described as q = 0.7 to 0.5. When n = 1.8 to 2.0, the DOA byproduct ratio is 50 to 30%. Yes n =
In 2.0 to 2.5, the DOA byproduct ratio is 35 to 20%, and n = 2.
In 5 to 3.5, the DOA byproduct ratio is 20 to 10%, and n = 3.5.
At ~ 5, the DOA by-product ratio is 10 to 5%, and n = 5.
In the above, the DOA byproduct ratio is 5% or more. The amount of DOA by-product with respect to n is as described above, and the diol so that the amount of adipic acid (1-q) excluding the amount of by-product is reacted to form a complex ester to obtain the desired product having n. By controlling the amount of the compound used according to the formula m = (1-q) × n / (n + 1) to carry out the reaction, the desired complex ester of n is determined to have a viscosity and an average molecular weight corresponding to its molecular weight. It can be manufactured. Although the molecular weight distribution can be measured by a liquid chromatograph or GPC method, HPLC was used here. N = 1, 2, by HPLC
The weight fractions of 3, 4, 5, 6, 7 were obtained, Mw and Mn were calculated, and the deviation from the purpose was examined. When the amount of diol distilled off by the transesterification reaction is taken into consideration, the values are in good agreement and the deviation is small. A complex ester having a distribution of Mw / Mn corresponding to the width of the complex ester molecular weight distribution up to about 1.2, and producing a complex ester having an arbitrary value of n within the defined range, that is, an arbitrary molecular weight You can do it.

The amount of DOA as a by-product is the above ester alcohol.
Depends on the reactivity of le and DOA, these are 1: 1
If 100% reaction occurs, only n = 1 will be produced,
In reality such a thing can never happen. Assuming that 10% of the complex ester of n = 1 is n = 2, the amount of complex ester having n larger than 1 and n larger than 1 is obtained so as to obtain DOA of 0.5 × 0.1 corresponding to the number of moles. DOA corresponding to is produced as a by-product. When n = 2 is possible, the following equation is obtained. ROCOACOOXOH + ROCOACOOR → 0.5RO (CO (CH ₂ ) ₄ COOXO)
₂ CO (CH ₂ ) ₄ COOR + 0.5DOA When a complex ester having a low value of n = 1 to 2 is intended, the reaction ratio of ester alcohols is higher than that of ester alcohols and DOA. More and as a result DO
A: The amount of by-products is large. The DOA byproduct amount is a q value obtained for each n by the above experiment. Determining the value of q for each n means, in terms of content, the molar ratio of ester alcohol and DOA (m: 1
This is equivalent to determining −m) for each value of n. That is, the molar ratio of the reaction is n ester alcohol: DOA 1.5 to 1.8 1: 4 to 2 1.8 to 2.0 1: 2 to 1 2.0 to 2.5 1: 1 to 0.75 2.5 to 3.5 1: 0.75 to 0.5 3.5 to 5 1: 0.5 or less 5 or more means that the reaction is performed at a reaction ratio of 1: 1 / n. The molar ratio of ester alcohol and DOA is determined by the esterification reaction, but a mixture with a high concentration of ester alcohol is prepared in advance, and the molar ratio is adjusted by adding and mixing DOA before the transesterification reaction. It may be carried out, and the target product can be produced by controlling the proportion, an example of which is described in Example 3. Meanwhile 1,3-
When using a volatile diol such as butanediol, it may be difficult to control the reaction amount.
In such a case, the molecular weight of the product may be lowered, but the composition before the transesterification reaction should be RO (C
It is also possible to obtain a product by carrying out a transesterification reaction after carrying out the reaction with the addition amount of ROH being 2-pm so as to form a mixture of OACOOX) ₂ OH and DOA. Although the description of Example 5 was intended to reduce the amount of dediol in the transesterification reaction, some diol was desorbed with a small amount, and as described in Example 8, the larger the number of n, the more. Since the amount of desorption increases, the one with a large number of P is advantageous. The rate of dedioling in the transesterification reaction varies, and it is necessary to control the type of diol, the reaction temperature, and the rate thereof.

The diols used here may be diols having a low boiling point, and diols having a high molecular weight and low volatility can be easily used, but are suitable for imparting physical properties when used for the purpose of a plasticizer. Diole is used, the general one
3-butanediol and propanediol, and their oligomers such as polyethylene glycol and polypropylene glycol, and other 1,2-, 1,3-, 1,4-,
1,6-alkanediol is used. It is not particularly limited to the example.

[0015]

EXAMPLES Examples will be described below. In the Examples, the degree of polymerization n is described by using the symbol [O (AX) _n AO] corresponding to the structural formula of the complex ester (I).
The plasticization efficiency of plasticized polyvinyl chloride when using these complex esters corresponds to the viscosity, and the lower the viscosity is, the better the plasticity is. However, at 500 cP, the plasticization efficiency is equivalent to that of DOP 50 parts. Shows almost the same or excellent plasticity at 45 to 55, and by using a complex ester, the weight loss on heating of the plasticized sheet at 160 ° C. for 2 hours is 1-2%, which is significantly improved from 15% of DOP. I got the result.

Example 1 Di2-ethylhexyl poly (2.8) (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) _2.8 CO (CH ₂ ) ₄ COOC ₈ H
₁₇ ; Simplified formula: O (AX) _2.8 AO adipic acid 148.1 g (1.014 mol) and 1,3-butanediol 6
The dehydration esterification reaction was started using a mixture of 3.2 g (0.676 mol + excess 2.36 g), and 175 g (1.346 mol) of 2-ethylhexanol was added to 5/6 according to the amount of water distilled. It was divided and added sequentially (the reaction molar ratio of adipic acid: diol: octanol was 3: 2: 4 mol according to the above reaction formula). At the time of distilling 30 ml, 0.003 mmol / kg of titanium catalyst and a small amount of toluene as an azeotropic solvent were added, and after two and a half hours, the esterification reaction was terminated with an acid value of 0.08. The amount of water distilled was 37.2 g, and 1.2 g of diol was distilled. Reaction temperature 220 ~
The temperature was kept at 240 ° C., the distilling toluene and octanol were removed, the degree of pressure reduction was gradually increased, and finally the vacuum pump was switched to completely remove the heated volatile matter until the DOA refluxed. Distilled octanol is 76.1g, of which 9.6% of 1,3-
Butanediol was confirmed. After cooling to 100 degrees, 0.2g N
After adding 1 g of an aqueous solution containing aOH, filtering the activated clay, washing with alkali and washing with hot water, distilling under reduced pressure, DOA fraction 64.13 g, residual liquid of 270 ° C / 0.3 mmHg or more 19
0.16 g was obtained. The viscosity at 21 ° C. was 287 cP.

When the molecular weight of the reaction product intended for the title n = 2 was measured by high performance liquid chromatography,
Mw = 927, n = 2.79, Mn = 878, n = 2.24, Mw / Mn = 1.05. The formula m = (1-q) × n / (n + 1) described in the claims of the present invention
The calculation of the amount of diol used according to the above is as follows.
The amount of by-product DOA is 18 mol%, and the required amount of diol is 1.014 × (1-0.18) × 2.5 / 3.5 = 0.5 for 1.014 mol of adipic acid.
It was 939 mol, that is, 53.45 g, and 9.7 g of this was used as an excess amount of the diol distilled azeotropically during the dehydration esterification reaction and an excess amount of the diol produced as an azeotropic component during the transesterification. Expected product is n = 2.5, molecular weight 8
70, 1.014 × (1-0.18) /3.5=0.238 mol, 207.06 g,
The amount of DOA produced as a by-product is 370 × 0.18 = 66.6 g. The product recovery rate was 92.7%, which was calculated from the experimental results.
The by-product rate of A was 64.13 / 370 / 0.927 / 1.014 = 0.1843, 18.4 mol%, and the adipic acid used in the reaction was 1.014 × (1-0.184
3) = 0.8271 mol, the diol used in the reaction is (63.2-1.2-7
6.1 × 0.096) /90=0.6077 mol, calculated from these n =
It was 2.77, which was exactly the same as the Mw value.

Example 2 Di2-ethylhexyldi (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) 2 CO (CH ₂ ) ₄ COOC
₈ H ₁₇ ; Simplified formula: 0 (AX) ₂ AO [153.3 g (1.05 mol)] adipic acid, [48.2 g (0.504 mol) +
Excess amount of 2.8g] 1,3-butanediol and 104g of 2-ethylhexanol were used to start the dehydration esterification reaction, and the reaction was carried out at 180-220 ℃, and the water distillation amount was 1/5 molar equivalent. The dehydration esterification reaction was carried out while adding 52 g of octanol and the remaining 52 g of octanol (total of 1.6 mol) when the amount was 1/2 to 3/5 equivalent. The reaction rate was estimated to be 28% DOA by-product, the diol requirement was calculated to be 1.05 × 0.78 × 2/3 = 0.504, and the expected product was 0.252 moles of complex ester with n = 2, 194.04 g. The raw DOA is 0.294 mol, 108.78 g. The distilled water was returned to the reaction system several times to allow 1,3-butanediol to sufficiently react, and when the final 32 ml of water was distilled, the polyol polytitanic acid solid catalyst 0.003 mmol / Kg
Toluene was added as an amount, as well as a small amount of azeotropic solvent. 50 minutes after the catalyst was added, the acid value became 0.1 1 hour and 55 minutes after the reaction was started. The total amount of water distilled was 36 g plus an excess of 1.5 g, 1,3-butanediol was distilled with just 1.5 g of water and the molar amount of diol used in the reaction was 0.5644 mol. After completion of the reaction, the temperature was raised to 240 ° C., and 2-ethylhexanol distilled by the transesterification reaction was analyzed by GC to confirm the time when the amount of 1,3-butanediol was reduced, and the pressure was gradually reduced to remove octanol. Distillation was performed, and finally, a vacuum pump was used to reduce the pressure to 0.3 mmHg, and DOA was refluxed at a reaction solution temperature of 220 ° C. to completely carry out a transesterification reaction. The distillate weighs approximately 65 g, and the 1,3-
Butanediol (4.9%, 3.2 g) was removed without reaction. Finally, the reaction amount was 0.4830 mol.

The temperature of the reaction solution was lowered to 100 ° C., 1 ml of water containing 0.2 g of caustic soda was added, and the mixture was stirred for 5 minutes, then filtered through activated clay to remove catalyst residue, and washed with alkali and hot water. After distillation, 112.47 g of a fraction (mainly DOA) of 180 to 220 ° C./0.3 mmHg and 164.77 g of a high boiling point ester of 270 / 0.3 mmHg or more were obtained. The recovery rate of ester for the target product was 91.55%, and by-product D corrected using this value was obtained.
The ratio of OA was 31.6 mol%.

The reacted adipic acid is 1.05-0.3320 = 0.7180
Mol, and n = 0.4830 / (0.7180-0.4830) = 2.06. On the other hand, the molecular weight distribution of the obtained complex ester was analyzed by HPLC.
When measured according to the method, Mw = 794, n = 2.12, Mn = 731,
n = 1.81 and Mw / Mn = 1.09. 21 ℃ of this complex ester
Has a viscosity of 181 centipoise cP and 50 PHR.
And 80 PHR sheet (a sheet obtained by adding and kneading a plasticizer at a ratio of 50 parts or 80 parts with a stabilizer of 0.5 PHR per 100 parts of polyvinyl chloride resin), which is calculated from the surface hardness and is equivalent to DOP50PHR The efficiency was 48.5 when calculated as the plasticizing efficiency, which is the amount of the plasticizer for indicating the firmness. Therefore, an excellent DOP as a plasticizer
It showed better plasticity than (di-2-ethylhexyl phthalate). The weight loss on heating at 160 ° C. for 2 hours was 1.6% by weight, and the volatility was greatly improved compared to the same test value of 15.0% for DOP. On the other hand, it has excellent cold resistance at a soft temperature of -22 ° C according to JIS Crushberg method using 50 PHR, and as its water resistance, it is soaked in soapy water at 60 ° C for 48 hours and then dried. Weight change after 48 hours D
Compared with OP, the value is 1.8 for 1.2% of DOP
% Showed no significant decrease in water resistance.

Example 3 Di2-ethylhexyldi (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) ₂ CO (CH ₂ ) ₄ COOC
₈ H ₁₇ ; O (AX) ₂ AO Adipic acid 164.1 g (1.124 mol), 1,3-butanediol [5
4.2 g (0.5320 mol) + 6.4 g excess], 111 g of 2-ethylhexanol was used to start the dehydration esterification reaction, and the remaining 2-ethylhexanol was divided into 222.similar to the previous examples.
9 g (1.71 mol) was added, and finally 0.43 g of titanium catalyst was added to carry out a dehydration esterification reaction. DOA byproduct forecast = 29
% (120.6 g), diol consumption = 1.124 × 0.71 × 2/3 mol,
With the product n = 2, 0.266 mol (204.8 g), after 130 minutes of reaction, the acid value became 0.08, the amount of water distilled was 43.4 g, and the diol reacted excessively by 3.4 g. For the purpose of correcting the amount of DOA, 31.1 g was added and a transesterification reaction was carried out at 200 to 240 ° C / 750-0.3 mmHg. Distilled octanol was 69.1 g, which was analyzed by GC.
4.9% diol (3.42 g) was confirmed. The temperature was lowered to 100 ° C, a small amount of alkaline aqueous solution was added, activated clay was filtered, washed with alkali, washed with water, and then distilled under reduced pressure to obtain 138.7 g of DOA and
194.2g of the residual liquid at ℃ / 0.3mmHg or more was obtained with a recovery rate of 93.5%. The by-product ratio of DOA to adipic acid used is 3
3.1%, the number of moles of adipic acid used in the reaction = 0.
It was 807 mol, the number of moles of diol = 0.532 mol, and n = 1.93. The viscosity of this complex ester at 21 ° C. is 174 cP, H
The result of the molecular weight distribution measurement by PLC is Mw = 744, n = 1.87,
Mn = 716, n = 1.73 and Mw / Mn = 1.04.

Examples 4-8 Di2-ethylhexyl poly (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) _n CO (CH ₂ ) ₄ COOC
₈ H ₁₇ ; O (AX) _n AO According to Example 2, the results for n = 1.5, 2.0, 2.5, 3.0, 3.5, 7.5 are listed in the list together with Experimental Examples 1 to 3 in ascending order of the number of n. The -th table relates to production conditions, 1) target n value, 2) q value of DOA ratio by-product, 3) reaction molar ratio (A: X: O for adipic acid, diol, ROH), 4 ) DOA theoretical by-product amount g number, 5) The theoretical complex ester production amount g is described, where the values of X and O are as follows: Calculated amount of diol = mol adipic acid × m {m = (1-q) × n /
From (n + 1)}, octanol amount = adipic acid mol x (2-
pm) or (amount of adipic acid-amount of diol) × 2 + amount of diol. The second table shows, for reaction products, 1) n by calculation of the product, 2) molar production of DOA by-produced, 3) A mole of adipic acid reacted, 4) X mole of reacted diol, 5) Number of DOA g formed, 6) g number of complex ester, 7) viscosity cP at 21 ° C., 8) average molecular weight Mw and n by HPLC, Mn and n, Mw / Mn value, 9) ester alcohol at the time of transesterification The molar ratio of DOA is described as OAX: OAO.

The production conditions carried O (AX) _n AO-product O (AX) n of DOA theoretical stoichiometric complex S. Examples of _n AO DOAq A: X: O-product weight g Tel generation amount g 4 1.5 0.55 1.160: 0.313: 2.007 120.6g 236.1g (3) 2.0 0.29 1.124 + 0.084: 0.532: 1.71 151.9g 204.8g (2) 2.0 0.28 1.05: 0.504: 1.596 108.78g 194.04g 5 2.5 0.24 1.220: 0.662: 1.44 # 108.3g 230.5g 6 2.5 q = 0.15 0.825: 0.50 + 6g: 1.15 45.78g 174.0g (1) 2.5 q = 0.18 1.014: 0.5939: 1.330 66.6g 207.6g 7 3.5 q = 0.10 1.05: 0.74: 1.37 38.85g 224.50g 8 8 q = 0.05 0.95 : 0.89 + 6g: 0.565 # 17.6g 197.8g

Reaction product By-product Reaction- produced Complex 21 ° C. Viscosity Example n DOAq A X DOAg Ester g (cP) (continued) 4 1.49 54.9 0.5233 0.3135 116.2 226.2 111 (3) 1.93 33.1 1.208 0.532 138.7 194.2 174 (2) ) 2.06 31.6 0.7180 0.4830 112.47 164.77 181 5 2.52 24.0 0.9262 0.6633 101.22 214.38 238 6 2.6 20.5 0.6558 0.4750 59.79 150.07 281 (1) 2.77 18.4 0.8238 0.6077 64.14 190.16 287 8.7 3.5 9.7 0.948 0.739 34.67 207.50 18475 18.7 7.5 3.6 0.9153 Examples (continued) Mw n Mn n Mw / Mn OAX: OAO 4 690 1.60 660 1.45 1.05 1: 2.66 (3) 744 1.87 716 1.73 1.04 1: 1.27 (2) 794 2.12 731 1.81 1.09 1: 1.08 5 856 2.43 774 2.02 1.11 1: 0.92 #; OAXAX: OAO, P = 2 6 910 2.70 804 2.17 1.13 1: 0.57 (1) 928 2.79 818 2.24 1.13 1: 0.47 7 1088 3.59 925 2.78 1.18 1: 0.42 8 1: 0.137 #; P = 2, -X = 2.6%

(1) Di 2-ethylhexyl poly (3) (tripropyleneoxy adipate) C ₈ H ₁₇ O {CO (CH ₂ ) ₄ COO (CH ₂ CH (CH ₃ ) O) ₃ O} of Example 9 ₃ CO (CH ₂ ) ₄ COOC ₈ H
₁₇ ; O (AXTp) ₃ AO adipic acid 90.25 g (0.618 mol), tripropylene glycol 72.00 g (0.375 mol), 2-ethylhexanol 56.
The dehydration esterification reaction was carried out using 8 g of the mixture, and 2-ethylhexanol was added to 28.4 g when the water was distilled off by 1/5, and further 3
-When the amount is -4/5, the remaining amount is 28.4g, total 0.89mol is added, and 20% of D
The reaction was carried out using the molar amount calculated as the source of OA by-product as the reaction molar ratio. Finally tetrabutoxy titanium
Add 0.003 mmol / Kg amount, remove almost calculated amount of water,
Two hours later, the dehydration esterification reaction was terminated with an acid value of 0.08. Then, the mixture was heated and stirred at 240 ° C., the pressure was gradually reduced to remove octanol produced, and finally the pressure was reduced to 0.4 mmHg to complete the reaction. After-treatment distillation by a conventional method, DOA 40.36g,
150.36 g of a product having a temperature of 270 ° C. or higher / 0.3 mmHg was obtained. Its viscosity is
393 cP at 21 ℃, reacted adipic acid 0.502 mol, tripropylene glycol 0.375 mol, calculated n = 2.95
Met.

(2) Di-2-ethylhexyl poly (2) (2-ethyl-1,3-hexanediyl adipate C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH (C ₂ H ₅ )) of Example 9 CH (C ₃ H ₇ ) O) ₂ CO (CH ₂ ) ₄ CO
OC ₈ H ₁₇ ; O (AX2E) ₂ AO DOA The by-product amount was set to 30%, and the reaction was carried out using 0.86 mol of adipic acid. The molar amount of 2-ethyl-1,3-hexanediol used was m = 0.86 × (1-0.3) × 2/3 mol, 0.4013 plus 0.5 g, and 2-ethylhexanol (0.86 × 2-m) = The reaction was carried out according to Example 2 using 1.32 at 220-240 ° C.
The reaction was performed under reduced pressure of 760-0.4 mmHg. The amount of by-product DOA is 8
8.71 g, complex ester obtained 156.02 g as a high boiling point of 270 ° C./0.3 mmHg or more, DOA by-product ratio 31% per mole, reacted adipic acid 0.593 mol, diol 0.400 mol, n = 2 .
1, the viscosity at 21 ° C. was 292 cP, the plasticization efficiency was 50.5 when blended with polyvinyl chloride resin and the plasticity was examined, showing plasticity almost equivalent to DOP, and the heating loss of 50 PHR plasticized PVC sheet was 160. The value at 2 ° C. for 2 hours was extremely excellent at 1.3%, the water resistance in 60 ° C. soap water immersion was equivalent to that of DOP, and the migration to PE and PVC was less than that of DOP.

Example 10 Diisodecyl poly (2) (2-ethyl-1,3-hexanediyl adipate C ₁₀ H ₂₁ O (CO (CH ₂ ) ₄ COOCH ₂ CH (C ₂ H ₅ ) CH (C ₃ H ₇ )) O) ₂ CO (CH ₂ ) ₄ C
OOC ₁₀ H ₂₁ ; iD (AX) ₂ AiD 20% Diisodecyl adipate was produced by post-adding dibutyl adipate as a diester in order to facilitate the transesterification reaction. 0.75 mol of adipic acid, 0.5 mol of 2-ethyl-1,3-hexanediol (73
g), using 1 mol of isodecyl alcohol, Example 2
The reaction was carried out in the same manner as above, and after 3 hours and 10 minutes, the acid value was adjusted to 0.08. 0.188 mol (48.4g) of dibutyl adipate was added here, and the mixture was heated and stirred at 200 to 240 ° C to collect the butanol produced, and finally to collect the isodecanol which volatilizes at 200 ° C / 0.5mmHg, and to collect 34.1g of the ester. An exchange reaction was performed. Post-treatment according to the usual method, vacuum distillation, 180 ~ 230 ℃ /
56.66 g of 0.2 mmHg DIDA fraction was obtained and a product of 270 ° C./0.2 mmHg was obtained. Its viscosity is 403.5 cP at 21 ° C., the adipic acid used in the reaction is 0.938 mol, the amount used in the complex ester is 0.938-0.133 = 0.805 mol, n = 1.64, and the by-product DIDA is 17.4%. Met. When used as a plasticizer, the plasticizing efficiency was 53.5, and the performance was somewhat inferior, but the volatility and water resistance were excellent.

Direct transesterification reaction Examples of direct transesterification reaction are described below. In particular, Examples 11 and 12 describe an integrated production method from raw materials. In the following examples, DOA is described as a raw material.

Example 11 Di2-ethylhexyl poly (1.6) (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) _1.6 CO (CH ₂ ) ₄ COOC ₈ H
₁₇ ; O (AX) _1.6 AO Adipic acid 109.5 g (0.75 mol) and 2-ethylhexanol
292.5 g (2.25 mol) was placed in a dehydration esterification reactor and heating and stirring was started. Water evaporates as the temperature rises, and the temperature is kept up to 200 ° C for the purpose of preventing discoloration.
The reaction temperature is gradually raised to 230 ° C from l (70%), and when 22 ml, 0.003 mmol / Kg of titanium catalyst and 0.41 g of titanium catalyst are added together with a small amount of octanol, the catalyst is added, the acid value starts to be measured, and the primary reaction rate After 50 minutes, the acid value became 0.08 and the dehydration esterification reaction was completed. The time to finish was 90 minutes. Instead of the distiller, distilling slightly reduced pressure (about 10mm water silver pillar) under octanol and reaction solution DOA (0.75 mol). With the by-product DOA ratio of 0.4, the amount of 1,3-butanediol added was m = (1-0.4) × 1.5 / 2.5 × 0.75 = 0.27, and 24.3 g was put in the reactor to start the transesterification reaction. Calculated amount of octanol is 2m = 0.54mol (70.2g), by-product DOA
Is 0.4 × 0.75 = 0.3 mol (111 g), complex ester n = 1.5,
It has a molecular weight of 670 and (1-0.4) /2.5×0.75=0.18 mol (120.6 g). The amount of 1,3-butanediol distilled azeotropically was refluxed while conducting GC analysis, and after 1.5 hours, the decrease was reduced, the degree of reduced pressure was reduced, and the octanol produced was distilled to obtain 85% of the calculated amount at 25 mmHg. 70 ml of octanol was distilled. Change to vacuum pump depressurization and proceed transesterification reaction at reaction temperature 220 ℃ / 0.3mmHg, finally 65.4g (93%) octanol, 4.2%
A recovered liquid containing 1,3-butanediol was obtained. The unreacted recovered 1,3-butanediol was 2.73 g, and the reacted diol was 0.240 mol. Lower the reaction mixture to 100 ℃ and add NaOH.
A 0.2 g / 0.5 ml aqueous solution was added, and the mixture was stirred for 3 to 5 minutes, filtered with activated clay, washed with alkali and water, distilled under reduced pressure, and distilled at 180 to 220 ° C./0.3 mmHg DOA131.81
g (0.356 mol) was obtained. 91.73 g of the target complex ester was obtained as a high boiling point ester of 270 ° C./0.3 mmHg or higher. The recovery rate of the ester was 96.5%, and the DOA corrected using this value
Recovery was 0.369 mol, 49.2% per mol. The DOA used in the reaction was 0.75-0.369 = 0.381, thus the complex ester n = 0.240 / (0.381-0.240) = 1.70. H
Mw = 689, n = 1.60, Mn = 657, n = measured by PLC
The viscosity at 1.44, Mw / Mn = 1.05, and 21 ° C. was 114 centipoise (cP).

Example 12 Di2-ethylhexyl poly (1.9) (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) _1.9 CO (CH ₂ ) ₄ COOC ₈ H
₁₇ ; O (AX) _1.9 AO adipic acid 146 g (1 mol) and 2-ethylhexanol 390 g
(3 mol) was placed in a dehydration esterification reactor and heating and stirring was started. As the temperature rises, water distills out, and the temperature is kept up to 200 ° C for the purpose of preventing discoloration.
%), The reaction temperature is gradually increased to 220 ° C., and when 30 ml, 0.003 mmol / Kg 0.54 g of titanium catalyst is added together with a small amount of octanol, the catalyst is added, the acid value is measured, and the primary reaction rate is confirmed. The acid value became 0.08 after minutes, and the dehydration esterification reaction was completed. The time to finish was 110 minutes. The distillation apparatus was replaced with a distiller, and octanol was distilled under mildly reduced pressure (about 10 mm water column) to obtain a DOA (1 mol) reaction solution. By-product DO
As A0.32, the addition amount of 1,3-butanediol is m = (1-0.32)
× 2/3 = 0.453, 40.80 g was put in the reactor and the transesterification reaction was started. Generated octanol calculation amount is 2m = 0.906
Mol, 117.8 g, by-product DOA 0.32 mol, 118.4 g, complex ester n = 2, molecular weight 770, (1-0.32) /3=0.227 mol, 174.5 g
Is. The amount of 1,3-butanediol distilled off azeotropically was refluxed while performing GC analysis, and after 80 minutes, the pressure was reduced, the degree of vacuum was reduced, and the octanol produced was distilled to obtain 85% of the calculated amount at 25 mmHg. 110 ml of octanol was distilled. Change to vacuum pump depressurization, proceed transesterification at reaction temperature 220 ℃ / 0.3mmHg, and finally obtain 109.7g (93%) of octanol distillate, of which 1,3-butanediol is 3.19%. there were. The recovered 1,3-butanediol was 3.49 g and the reacted diol was 0.415 mol. The reaction solution was cooled to 100 ° C, and after adding 0.2g / 0.5ml NaOH aqueous solution and stirring for 5 minutes, it was filtered with activated clay, washed with alkali, washed with water and distilled under reduced pressure to 180-230 ° C / 0.3mmHg. Distilling in
OA128.85g (0.348mol) was obtained, and 275 as the residual liquid.
146.51 g of the target complex ester having a temperature of ℃ / 0.3 mmHg or more was obtained. The ester recovery was 94% and the DOA recovery corrected using this value was 0.370 mol, 37 mol%. The DOA used in the reaction was 1-0.370 = 0.630, thus the complex ester n = 0.415 / (0.630-0.415) = 1.93. HPLC
Mw = 754, n = 1.92, Mn = 699, n = when measured by
The values were 1.64 and Mw / Mn = 1.08. Viscosity at 21 ℃ is 190 cP
Met.

Example 13 Di2-ethylhexyl poly (2.4) (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) _2.4 CO (CH ₂ ) ₄ COOC ₈ H
₁₇ ; O (AX) _2.4 AO 0.75 mol of DOA prepared by dehydration esterification reaction, q = 0.22
As a result, a complex ester of n = 2.5 was prepared. m = (1-0.22) × 2.5
/3.5×0.75=0.417 mol, 37.60 g + excess amount 2.96 g of 1,3-butanediol was added, and by-product DOA 0.22 × 0.75 = 0.165 mol, 61.05 g; complex ester, n = 2.5, molecular weight 870, (1- 0.2
2) /3.5×0.75=0.167 mole, transesterification reaction was performed for the purpose of 145.41 g. The transesterification reaction was carried out at 220-240 ° C / 750-0.3mmHg in the same manner as in the above example, and the post-treatment distillation was carried out to obtain 121.08g of 61.3g DOA and 0.166mol of DOA and 275 ° C / 0.3mmHg or more of composite ester. It was Ester recovery rate is 8
8.3%, corrected by-product amount of DOA 0.188 mol, 25.0 mol%, reacted DOA 0.75-0.188 = 0562 mol, recovery of diol 4.79% in octanol × 104.13 = 4.98 g, amount of reaction diol 35.58 g, 0.395 mol, thus n = 0.395 for complex ester
/(0.562-0.395)=2.37. M as measured by HPLC
When w = 858n = 2.44, Mn = 777, n = 2.04, and Mw / Mn = 1.10, the viscosity at 21 ° C. was 239 cP.

Results of use as plasticizer (Example 13) 50 PHR and 80 PHR sheets (50 parts or 8 with 0.5 PHR stabilizer per 100 parts polyvinyl chloride resin ).
A sheet obtained by adding and kneading a plasticizer at a ratio of 0 part)
Calculated from the surface hardness of DOP (dioctyl phthalate, which is used as a general plasticizer), the amount of plasticizer showing the same hardness as when using 50 PHR is calculated as the plasticization efficiency. 48.2, 51.0,
It has a plasticity of 52.0, which is equivalent to or superior to that of DOP, and the heating weight loss at 160 ° C for 2 hours is 2.2% and 1.8%, respectively.
%, 1.6% by weight, similar test value for DOP 13.0%
The volatility was significantly improved compared to. On the other hand, the softening temperature by the Crashberg method according to JIS method using 50 PHR is -24.0 ° C, -20.8 ° C, and -20.5 ° C, respectively, and it has excellent cold resistance. Keeping time and comparing its water resistance with DOP, the values are 2.1%, 1.6% and 1.5% respectively for 1.2% weight change of DOP.
And did not show a significant decrease in water resistance.

Example 14 Di2-ethylhexyl poly (3.6) (1,3-butanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH ₂ CH (CH ₃ ) O) _3.6 CO (CH ₂ ) ₄ COOC ₈ H
₁₇ 0.75 mol, 277.5 g DOA made by dehydration esterification reaction
Complex esters with n = 4.0 were made with q = 0.05. m = (1-0.0
5) x 4/5 x 0.75 = 0.570 mol, 51.30 g + excess 6.3 g of 1,3-
Butanediol was added, and by-product DOA 0.05 x 0.75 = 0.0375
Mol, 13.88 g, complex ester, n = 4, molecular weight 1170, (1-0.
The transesterification reaction was carried out for the purpose of 05) /5×0.75=0.1425 mol, 166.73 g. The transesterification reaction was carried out at 220-250 ° C / 750-0.3mmHg in the same manner as in the above-mentioned example, and post-treatment distillation was carried out to obtain 128.32g of 22.19g, 0.06mol DOA and 275 ° C / 0.3mmHg or more of composite ester. It was Recovery rate of ester 83.
3%, corrected by-product amount of DOA 0.072 mol, 9.6 mol%, reacted DOA is 0.75-0.072 = 0.678 mol, recovery of diol is 5.65% in octanol × 156 = 8.81 g, amount of reaction diol is 4
8.79 g, 0.542 mol, thus n = 0.54 of complex ester
It was 2 / (0.678-0.542) = 3.98. By HPLC
Mw = 1085, n = 3.58, Mn = 929, n = 2.80, Mw / Mn = 1.17, and the viscosity at 21 ° C. was 547 cP.

Examples 15 to 18 Di2-ethylhexyl poly (n) (tripyreneeneoxyadipate) C ₈ H ₁₇ O {CO (CH ₂ ) ₄ COO (CH ₂ CH (CH ₃ ) O) ₃ O} _n CO (CH ₂ ) ₄ COOC ₈ H
The complex ester obtained by using tripropylene glycol and 2-ethyl 13 hexanediol as the diol component using ₁₇ DOA is shown. Examples 11 to 1
Similar to 3, objective n, expected by-product DOA ratio q value, DOA reaction mole number, g number, diol reaction mole, m value, by-product DO
A calculated value DOAcalc, molecular weight Mw of interest complex esters, moles, as g second number item, n by calculating the resultant complex ester, by-product DOADOA _ob g number, by-product DOA molar corrected with recovered ester% The number, the mol%, the weight of the complex ester, the number A of the reacted DOA, the number X of the reacted diol, the calculated n, and the viscosity cP at 21 ° C. are listed in this order.

Implementation Anticipated DOA reaction (continued) Example n DOAq response mol g number Diol reaction mol m value 15 1.5 0.5 1 370 0.5x1.5 / 2.5 = 0.3 57.6 16 2 0.25 0.542 200.9 (1-0.25) x2 / 3x0. 542 = 0.272 52.1 17 3 0.2 0.75 277.5 (1-0.2) x3 / 4x0.75 = 0.45 86.4 18 6 0.09 0.6 222 (1-0.09) x6 / 7x0.6 = 0.468 89.90 exemplary continued byproduct example DOAcalc Mw mol Number g Number 15 185 823 0.2 164.6 16 0.25x0.542 = 0.1355 50.21gn = 2.0 974 0.1357 132.2 17 0.2x0.75 = 0.15 55.5g 1276 0.15 191.4 18 0.09x0.6 = 0.054 19.98g 2182 0.13 170.20

The exemplary byproduct DOA correction sub composite S. reaction DO reacted Bu 21 ° C. Example n DOA _ob (g) raw DOA mol mol% ether by weight A number of moles A o - Rumoru X Viscosity cP 15 1.60 177.08 51.3 148.78 0.487 0.30 138 16 2.11 48.37 0.143 26.4 118.47 0.400 0.272 214 17 2.74 45.39 0.1358 18.1 177.57 0.6141 0.45 394 18 5.29 14.60 0.043 7.15 160.25 0.600-0.0429 0.468 979 = 0.557

Examples 19-22 Di2-ethylhexyl poly (n) (2-ethyl-1,3-hexanediyl adipate) C ₈ H ₁₇ O (CO (CH ₂ ) ₄ COOCH ₂ CH (C ₂ H ₅ ). CH (C ₃ H ₇ ) O) _n CO (CH ₂ ) ₄ CO
The results of the experiment using OC ₈ H ₁₇ ; O (AX2E) _n AO DOA and 2-ethyl 13 hexanediol as the diol are shown. Item is Example 1
The same as 5-18. Execution Anticipated DOA reaction (Continued) Example n DOAq Reaction mol g number Diol reaction mol m value 19 1.5 0.5 1 370 (1-0.5) x1.5 / 2.5 = 0.3 43.8g 20 2.0 0.3 0.6 222 0.7x2 / 3x0.6 = 0.278 40.9g 21 3 0.17 0.805 297.85 ( 1-0.17) x3 / 4x0.805 = 0.501 73.0g 22 6 0.1 0.6 222 (1-01) x6 / 7x0.6 = 0.463 67.6g embodiment (continued) byproduct example DOAcalc Mw Number of moles g 0.5 0.5 185g 754 (1-0.5) /2.5=0.2 150.8 20 0.3x0.6 = 0.18 66.60g 882 0.7 / 3x0.6 = 0.14 123.48 21 0.805x0.17 50.63g 1138 (1-0.17) / 4x0.805 = 0.167 190.08 22 0.1x0.6 = 0.06 22.20g 1906 (1-0.1) /7x0.6=0.077 146.95

The exemplary byproduct DOA correction sub composite S. reaction DO reacted Bu 21 ° C. Example n DOA _ob (g) raw DOA mol mol% ether by weight A number of moles A o - Rumoru X Viscosity cP 19 1.77 184.40 0.5307 53 131.0 1-0.5307 = 0.4692 0.30 192 20 2.28 65.58 0.1996 33.3 103.26 0.6-0.1996 = 0.400 0.2786 21 3.16 19.19 0.1466 18.2 168.96 0.805-0.1466 = 0.6584 0.50 483 22 5.6 17.96 0.054 9.0 134.43 0.6-0.053 = 0.5462 0.463 1077

Relationship between Product of Example and Symbol of Formula (I) General Formula RO (CO (CH ₂ ) ₄ COOXO) _n CO (CH ₂ ) ₄ COOR (I) Example R X n Abbreviation 1 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) _2.8 O (AX) _2.8 AO 2 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) ₂ O (AX) ₂ AO 3 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) ₂ O (AX) ₂ AO 4-8 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) _{n (1.49-7.5)} O (AX) _n AO 9 no 1) C ₈ H ₁₇ (CH ₂ CH (CH ₃ ) O) _{3 3} O (AXTp) ₃ AO 9 no 2) C ₈ H ₁₇ CH ₂ CH (C ₂ H ₅ ) CH (C ₃ H ₇ ) ₂ O (AX2E) ₂ AO 10 C ₁₀ H ₂₁ CH ₂ CH (C ₂ H ₅ ) CH (C ₃ H ₇ ) ₂ iD (AX) ₂ AiD 11 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) _1.6 O (AX) _1.6 AO 12 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) _1.9 O (AX) _1.9 AO 13 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) _2.4 O (AX) _2.4 AO 14 C ₈ H ₁₇ CH ₂ CH ₂ CH (CH ₃ ) _3.6 O (AX) _3.6 AO 15-18 C ₈ H ₁₇ (CH ₂ CH (CH ₃ ) O) _{3 n (1.60-5.29)} O (AXTp) _n AO 19-22 C ₈ H ₁₇ CH ₂ CH (C ₂ H ₅ ) CH (C ₃ H ₇ ) _{n (1.77-5.6)} O (AX2E) _n AO

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (6)

[Claims] 1. Adipic acid (HOCO (CH ₂ ) ₄ COOH), monoalcohol (ROH), and diol which may be present (HOX).
OH), the first half is non-catalytic, and the second half is a dehydration esterification reaction using a titanium catalyst to give adipic acid diester (ROCO (CH ₂ ) ₄ COOR) or adipic acid diester and ester alcohol ([ ROCO (CH ₂ ) ₄ COOXOH]), and then subjecting the adipic acid diester or the mixture to a de-alcohol transesterification reaction, either directly by addition of the diol or by utilizing an ester alcohol. A complex ester RO (CO (CH ₂ ) ₄ COOXO) nCO (CH ₂ ) ₄ COOR (I) and a reaction mixture consisting of by-produced monoalcohol and adipic acid diester are obtained, and the complex ester is isolated. At that time, (1) HOCO (CH ₂ ) ₄ COOH + 2ROH → ROCO (CH ₂ ) ₄ COOR ROCO (CH ₂ ) ₄ COOR + m HOXOH → [ROCO (CH ₂ ) ₄ COOXOH] →
_{RO (CO (CH 2) 4} COOXO) nCO (CH 2) 4 COOR (I) + 2m ROH + q R
OCO (CH ₂ ) ₄ COOR (II) (2) HOCO (CH ₂ ) ₄ COOH + m HOXOH + 2-m ROH → m ROCO (C
H ₂ ) ₄ COOXOH + {(1-q) / (n + 1) + q} ROCO (CH ₂ ) ₄ COOR → RO
_{(CO (CH 2) 4 COOXO} ) nCO (CH 2) 4 COOR (I) + m ROH + q ROCO
(CH ₂ ) ₄ COOR (II) (wherein X is a residue of diol, R is a residue of monoalcohol, n is a real value of 1-7, and q is a predicted or experimental value. Is the ratio of the by-product diester obtained by, and m is an amount calculated by (1-q) × n / (n + 1). 〕in accordance with,
The amount of by-produced adipic acid diester, q, for each value of n was determined predictively or empirically, and from the established q value for each n, the monoalcohol and di-
A method for producing a complex ester, which comprises determining the amount of use of the ester. 2. From adipic acid (HOCO (CH ₂ ) ₄ COOH), monoalcohol (ROH), and optionally added diol (HOXOH), the first half is non-catalyst and the second half is titanium catalyst. By carrying out a dehydration esterification reaction, adipic acid diester (ROCO (CH ₂ ) ₄ COOR) or adipic acid diester and ester alcohol ([ROCO (CH ₂ ) ₄ COOXO
H]) in a method for producing a product containing a mixture thereof, about 80 to 90% of the reactant reaction amount of the dehydration esterification reaction or the product production amount is reacted without a catalyst, and then a titanium catalyst is used. A method for producing the product having a low acid value, which comprises adding and reacting. 3. Ester alcohol ROCOACOOXOH [wherein A is a dicarboxylic acid residue, X is a diol residue, and R is a monoalkoxy group].
Is a residual group) and a diester ROCOACOOR (A and R are as defined above) by a transesterification reaction,
In the method for producing a complex ester or polyester of the formula RO {COACOOXO} nCOACOOR, the reaction temperature is 170 to 250 in order to prevent the formation of volatile components in the molded product when used as a plasticizer for the molded product. ° C / 760-
A method comprising performing a transesterification reaction under the condition of 0.2 mmHg. 4. The production rate q of a diester produced as a by-product according to any one of claims 1 to 3, and m = (1-q) × n / (n + 1) for adipic acid. The amount of diol is used to make an intermediate ester alcohol and the de-alcohol transesterification reaction is carried out to obtain the formula n = (reacted diol amount) / (reacted dibasic acid amount-
A method for producing a desired n-valued complex ester and polyester from the reacted diol amount). 5. The relation between n and q is 0.70 ≦ q <0.50, 1.8 ≦ n <2.0 when 1.5 ≦ n <1.8 is predicted or experimentally.
When 0.50 ≦ q <0.30 or 0.35, 2.0 ≦ n <2.5
0.20 when 0.30 or 0.35 ≦ q <0.20, 2.5 ≦ n <3.5
When ≦ q <0.10, 3.5 ≦ n <5 0.10 ≦ q <0.05, 5
The method according to claim 1, wherein 0.05 ≦ q is determined when ≦ n 2. 6. The formula RO (CO (CH ₂ ) ₄ COOXO) _n CO (CH ₂ ) ₄ COOR (I) produced by the method according to claim 1, wherein R is a straight chain or a branched chain. a C ₈ -C ₁₀ alkyl group, X is C ₄ -C ₈ alkylene group or _{- (CH 2 CH (CH 3} ) O-) 3
A group, and n represents a number in which the average value of the mixture is in the range of 1.49 to 7.5].