JPH08157418A - Diol diester and conjugate ester and polyester produced by using the diester - Google Patents

Abstract

PURPOSE: To provide a process for producing a nonvolatile high-molecular plasticizer having low volatility, free from the problem of hardening of a polyvinyl chloride resin caused by the evaporation of plasticizer after the use over a long period and useful especially for polyvinyl chloride film. CONSTITUTION: A conjugate ester or a polyester of formula I (X is a diol residue; A is adipic acid residue; P is phthalic acid residue; R is a 4-10C alkyl; m and n are each >=0; m+n>0) is produced from adipic acid, phthalic acid, a diol and a 4-10C monofunctional saturated aliphatic alcohol. In the above process, a part or total of the diol is made to react with a part of phthalic acid or phthalic acid or their lower alkyl ester in excess of diol and the produced diol diester of formula II and/or formula III p is a polymerization degree) are used as the diol components. Preferably, the conjugate ester compound is composed of a unit containing phthalic acid residue and a unit containing adipic acid residue and the polymerization degree of the unit containing phthalic acid residue is >=0.3.

Description

Detailed Description of the Invention

[0001]

[Explanation of Symbols] In the present specification, O may represent oxygen or an ester-bonded octyl residue.
P represents a phthalic acid residue. The diols are indicated by the following abbreviations. 1,2-Propanediol = X _P ; Ethylene glycol = X _E ; Diethylene glycol = X _DE ; Dipropylene glycol = X _DP ; 1,3-Butanediol = X _13B ; 1,4-Butanediol = X _14B ; 2- Ethylhexanediol = _X2E ; Tripropylene glycol = _XTP . Although A represents an adipic acid residue, it may mean a dicarboxylic acid in general unless otherwise specified. Occasionally, an abbreviation symbol is used in which the -O-CO- moiety of the ester bond adjacent to X, A and P is omitted.

[0002]

FIELD OF THE INVENTION The present invention is applied to polyvinyl chloride, which has low volatility and prevents hardening due to volatilization of a plasticizer for long-term use, and is especially used for a polyvinyl chloride film. To a method for producing a high molecular weight plasticizer. The present invention also relates to a heterogeneous unit composed of a unit containing a phthalic acid residue and a unit containing an adipic acid residue, which is excellent in water resistance such that a unit containing a phthalic acid residue has a degree of polymerization of at least 0.3 or more. Regarding complex esters.

[0003]

BACKGROUND OF THE INVENTION The compounds described in this invention which are useful as plasticizers have the structure shown in the general formula below. RO (COACOOXO) _n (COPCOOXO) _m COACOOR where R is a residue of a commonly used alkyl alcohol, X is a residue of diol, and m and n are 0 or more, which represents the degree of polymerization, and m + n is Greater than zero. The dibasic acids used are phthalic acid, referred to herein as HOCOPCOOH, and saturated aliphatic dicarboxylic acids, primarily adipic acid, referred to as HOCOACOOH. The alcohols also used are the difunctional alcohol HOXOH as well as the monofunctional alcohol ROH. The compounds, namely complex esters and heterogeneous complex esters, are produced from them and have excellent properties of water resistance, volatility resistance and migration resistance when used as a plasticizer.

Here, the complex ester is a mixture of compounds represented by the general formula of RO (COACOXO) _n COACOOR, in which m is 0 in the above general formula, and essentially, the number of n is 1-7. Although the degree of polymerization is not described, the chemical formula has already been reported in the journal of the American Chemical Society of 1930 (JACS 52: 3221). The inventor of the present invention has conducted manufacturing studies and composition ratio studies on the single complex ester (Polymer Thesis Collection 47,177 (1990)). Further, a method of producing a complex ester by a transesterification reaction is disclosed in JP-B-1-25733, and a dehydration esterification reaction is disclosed in JP-B-4-51540 and US Pat. No. 4,661,622. Further, a complex ester composed of different dibasic acids is referred to as a heterogeneous complex ester, and its production method is disclosed in JP-A-62-234044, and a method by dehydration esterification reaction in consideration of molecular weight distribution is disclosed in JP-A-5155810. Also as a diol component
It has also been found that the use of 2-ethyl-1,3-hexanediol improves water resistance.

Polyester plasticizers have reduced volatility corresponding to their molecular weight. If it has a high molecular weight of 1500 or more, its viscosity is high, and when it is used as a plasticizer for vinyl chloride, its plasticity is poor. Also, it is not easy to make a low ester having a low acid value during production. On the other hand, although the complex ester has low viscosity and high plasticity, ROCOACOOR which is adipic acid diester

[0006] A large amount of by-product (abbreviated as DOA in the text) is disadvantageous. In particular, in consideration of the molecular weight distribution, and as a method for producing a desired complex ester mixture of n, a complex ester having a controlled distribution can be obtained by an esterification reaction in which octanol is sequentially added under the condition of excess DOA by-product. Things have been found. That is, according to the technique described in JP-A-5-1558102,
When general 1,3-butanediol is used as the diol, when aiming at n = 2.5, almost 93% of the adipic acid used becomes a complex ester, and when n = 3 or more, almost 97%. Has been found to be the desired complex ester. When producing a complex ester having n = 3 or less, particularly a small number of n, it is necessary to increase the amount of adipic acid diester by-produced. The high-molecular-weight oligomer-free complex ester has low viscosity and high plasticity and low volatility corresponding to the molecular weight, and thus has a possibility of being used as a very excellent plasticizer.

In a general method of esterification reaction, it is common sense to use a large amount of alcohol with respect to acid.
If it is not used, the terminal rate is slow and therefore a low acid number product cannot be obtained. When an excessive amount of monofunctional alcohol is used in the production of complex ester, ester alcohol is by-produced, which greatly affects the molecular weight and distribution, but it is not preferable, but it is unavoidable to use it in a small amount to lower the acid value. To be done. Even in the case of polyester, if ester ester is not sufficiently reacted to react with ester alcohol, the remaining ester alcohol is reduced by heating,
It has been found to reduce water resistance, electrical properties, and other plasticizer performance, and it has already been found that a transesterification reaction must be carried out last when producing a complex ester by a dehydration esterification reaction. ing.

[0008] Conventionally, the transesterification reaction in the production of the complex ester described above (Japanese Patent Publication No. 4-51540 and US Pat. No. 4,661,622).
Then, it has been considered that up to 200 ° C is sufficient. It has been found that it is necessary to carry out the transesterification reaction at a high temperature and a low pressure in addition to the method described, and that it is significantly improved by the high temperature treatment up to 250 ° C. In addition, particularly in the production of a complex ester having a low degree of polymerization and a small number of n, the amount of diester produced as a by-product is predicted in advance, and the number of reaction moles is controlled by assuming that the amount other than the by-product is reacted to produce the desired product. It was also found that the production can produce a complex ester having an intended average molecular weight.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a heterogeneous composite ester and a method for producing the composite ester through the formation of a diol diester.

The first characteristic, the diol component used in the complex ester is expected to become a softer plasticizer as its molecular length becomes longer.
Butanediol, 1,4-butanediol, 1,6-hexanediol and the like have been studied, and ethylene glycol, propylene glycol and polymers thereof have also been studied. However, ethylene glycol and propylene glycol have been avoided because they are volatile and difficult to react quantitatively. In the method of the present invention, even lower diol can be advantageously used as a raw material.
Therefore, the present invention is an economical method for producing a complex ester using an inexpensive diol component. Propylene glycol has a boiling point of 190 ° C. and is easily volatilized in the esterification reaction and the transesterification reaction. As a result, the polymerization degree of the product is significantly lower than the intended polymerization degree, and at the same time, the yield of the product is reduced. In order to improve the difficulty of the esterification reaction, a dibasic acid was previously reacted with an excess amount of a diol to produce a diol diester, and a method for producing a complex ester using this as a diol was examined. As a result, the present invention has been completed.

The degree of polymerization of the diol diester used is controlled by the reaction amount ratio of the acid and the diol. The larger the excess amount of the diol is, the smaller the degree of polymerization p is, that is, closer to 1, and the molar amount of the acid is smaller. The p-value increases as it approaches the quantity. The degree of polymerization and the average molecular weight of the diol diester thus obtained were calculated, and the reaction molar ratio of acid to diol was 2: 1.
The p value is 1.8 to 2.3, and the molar ratio is 4: 1 to 7:
The reaction of 1 gives 1.05 to 1.3. If necessary, a diol is added to adjust the average molecular weight, and a diol diester having an appropriate degree of polymerization is produced, and the reaction is carried out.

HOCOACOOH + HOXOH → HOX {AX} _p OH (In the description of the specification, ester bonds adjacent to X, A and P-
O-CO- part may be omitted and described)

The diol diester is not limited to those produced from propanediol, and other diols and mixtures of diols can be used, and they can be selected depending on their characteristics.

In order to facilitate understanding of the reaction formula, the adipic acid residue is A and the phthalic acid residue is P. X is the alcohol residue of the diol, and OcO is 2-ethylhexanol.
It is described as H, DOP is described as OPO, dioctyl adipate is OAO, and diol is X (OH) ₂ .

Kind of reaction for producing complex ester of the present invention a ) Complex ester forming reaction by transesterification method is represented by the following formula. OAO + HOX {(A or P) X} pOH + OAO → O (AX) _n (PX) _m AO + 2 OcOH (2) b) The transesterification method of the heterogeneous complex ester is represented by the following formula. OAO + HOX (PX) pOH + {HOX (AX) pOH} + OAO → O (PX) _m (AX) _n AO + 2OcOH (3) c) The dehydration esterification method of sequential addition is represented by the following formula. 2 HOCOACOOH + HOX (PX) pOH + {HOX (AX) pOH} + 2ROH → O (PX) _m (AX) _n AO (4) di) In the reaction system with phthalic acid, the anhydride is represented by PO. And 2 PO + HOX (AX) pOH → HPX (AX) pPH + 2OcOH → OPX (AX) pPO (5).

In the examples, etc., in which complex esters having different molecular weights and viscosities are described, the product compound is O (PX) _m (AX) _n A
Expressed as O, the degree of polymerization m of the unit containing the phthalic acid residue and the degree of polymerization n of the unit containing the adipic acid residue, which are found from the experimental results, are given. On the other hand, the diols used for the production of diol diesters are described by adding a symbol to each X for the following purposes. 1,2-Propanediol = X _P ; Ethylene glycol = X _E ; Diethylene glycol = X _DE ; Dipropylene glycol = X _DP ; 1,3-Butanediol = X _13B ; 1,4-Butanediol = X _14B ; 2- Ethylhexanediol = _X2E ; Tripropylene glycol = _XTP .

Second Feature A second effect of producing a complex ester using diol diester is that the molecular weight distribution of the product can be controlled. As described above, the first feature is to minimize the volatilization of the diol during the reaction, but the reaction can also control the molecular weight distribution. Use of an excess amount of octanol in the reaction process causes a transesterification reaction to cause isomerization into lower complex esters having different molecular weights, resulting in a wide molecular weight distribution. However, according to the method of the present invention in which diol diester is used and the reaction is carried out under reduced pressure while removing octanol, a complex ester of a fraction having a narrow molecular weight distribution and containing the most n = 2 compounds can be synthesized for the first time. In this reaction method, by-product of OPO in by-product diester can be prevented.

Requirement for Obtaining Target Product with Narrow Molecular Weight Distribution Instead of the diol component in the general production method of complex ester, diol diester is simply added to the reaction system to carry out dehydration esterification reaction or transesterification reaction. You can go. However, in any case, the molar ratio of the alcohol component and OAO at the time of the transesterification reaction is important in order to control the molecular weight distribution and obtain the product having the desired degree of polymerization. Therefore, it is necessary to predict the amount of OAO in advance based on the experimental results and use it in excess so that it remains unreacted. In these reactions, a transesterification reaction other than the purpose proceeds, so the post-addition method of diol performed under reduced pressure is the most preferable reaction method.

The unintended reaction is considered to be that the transesterification reaction (6) between OAXAXOH and octanol, which is considered as an intermediate, proceeds at the same time as described below, and the octanol produced by the post-addition method is removed from the reaction system. For the first time except
The formation of the reaction product n = 2 was confirmed by the formula (2) '. OAO + HOXPXOH + OAO → OAX (PX) AO + 2OcOH (2) 'HOXAXOH + OAO → OAXAXOH + OcOH (6-1) OAXAXOH + OcOH → 2 OAXOH (6-2) OAXOH + OAO → OAXAO + OcOH (6- 3) OAXAXOH + OcOH → OAXAO + HOXOH (6-4) OAXAXAO + OcOH → OAXAXOH + OAO (6-5)

The intermediate ester alcohol of the formula (6) can also be formed from the product OAXAXAO, and as a result of these side reactions, the ratio of n = 1 in the product increases, and the distribution is measured to show that n = 1. It is considered that the complex ester mixture has a distribution that decreases geometrically in accordance with the number of n, (2) and
In the reaction of (2 '), n = 2 is a reaction that should originally be produced, but n = 1
It is thought that this is the cause of the formation of reaction products mainly containing. In contrast, the use of diol diester of phthalic acid prepared by using ethylene glycol or propylene glycol as the diol component is particularly remarkable.
The ratio of n = 2 was greater than n = 1, and the reaction according to the formula (2) ′, which was the main reaction, proceeded. Even when a diol diester of adipic acid is used, a product with a large n = 2 can be obtained under specific conditions, but many side reactions occur. In any case, a complex ester product containing a large proportion of the product of n = 2 can be obtained only when the reaction product is obtained under the condition that octanol is removed under reduced pressure. In this reaction, when HOXPXOH was used, all of the reactions described in (3)
There will be no by-products.

When the reaction is carried out in a reduced pressure addition mode, the OPO by-product can be reduced to 0.5% or less, but when the transesterification reaction is carried out using the reaction mixture, OPO is converted into the by-product diester by 2%. ˜5%, and when the reaction mixture is used to obtain the reaction product under dehydration esterification conditions, 20% or more of OPO is by-produced in OAO, and phthalic acid and diol of HOXPXOH are mixed. The bond is converted to an octyl ester by undergoing a transesterification reaction. In such a case, m and n in the product deviate from the objective, and there are considerable variations in the production conditions.
In particular, since the by-product OAO is desired to be reused in the reaction system, it is necessary to separate OPO.

On the other hand, in the dehydration esterification reaction, the presence of a constant excess of diol diester naturally leads to the reaction represented by the above formula (6), so that not only the molecular weight distribution but also the deviation from the target molecular weight is large. By adopting the sequential addition method of adding according to the progress, these problems can be overcome, the quantitative reaction can be promoted, and the deviation from the purpose can be minimized.

Third Feature The third feature is that the complex ester of phthalic acid alone has extremely high viscosity as the degree of polymerization thereof increases, which is extremely disadvantageous as a plasticizer. Therefore, it is preferable to use a polyester having a viscosity as low as possible, but adipic acid has a strong acid strength and is easily hydrolyzed, so that the water resistance is poor. A complex ester partially containing phthalic acid is preferable for the purpose of improvement, but the type of the block polymer of the phthalic acid ester referred to as a polymer compound has a high viscosity. However, when the reaction with phthalic acid is carried out using diol diester, the composition is presumed to be mainly an alternating copolymer type. In reality, oligomers are formed during the reaction and the molecular weight is (XAXP) m +
Since it has a high molecular weight in the form of n, it is necessary to obtain a product with a small proportion, but by selecting a quantitative reaction mode, a low-volatile complex ester with a large proportion of complex ester with a suitable viscosity can be obtained. Can be manufactured.

When used as a plasticizer, the high-boiling point complex ester may be used as a main component in a mixture with general DOP or DOA, so that it can be produced and used as a mixture, but as a complex ester, It is considered that a plasticizer with excellent water resistance is required in consideration of volatility and long-term use.
When propanediol is used as the diol component having an acid polymerization degree of 0.3 or more, which is particularly inexpensive, the water resistance is remarkably maintained by forming a complex ester having 0.5 to 0.6 or more. You can Already add phthalic acid to 0.
The complex ester having 5 or more has water resistance,
Reported at the polymer discussion forum. However, among them, propanediol compounds have not been investigated, but they have been confirmed this time and relate to those compounds.

Next, the manufacturing method will be specifically described. Production of diol diester The production method of diol diester HOXAXOH or HOXPXOH is carried out by transesterification of an excess 4 to 7 molar amount of diol with a lower diester of adipic acid or phthalic acid or phthalic acid adipic acid. By direct dehydration transesterification reaction, dealcoholization or dehydration reaction is carried out in the presence of a titanium catalyst, and finally the diol is distilled off under reduced pressure to obtain a diol diester in the form of HOX (AX) _p OH.

The amount of diol used has a great influence on the degree of polymerization p of the product, and the value is close to 2 in the equimolar relationship.
In the case of aiming at a low volatility and high plasticity plasticizer, it is preferable that the number of p is small, and a large excess of 4-7 molar equivalents of diol is used. P = 1.03 to 1.2 at 7 molar equivalents
Therefore, the molecular weight increases depending on the diol distillation conditions. p
It is preferable to add an amount of diol corresponding to = 1 and use the same molecular weight, but it is also possible to add a correction amount to the diol during the reaction or to use it at the same time. (A
In order to control n of X) n, it can be used by changing to another diol. For this purpose, a mixture of different diols is used to control the softening temperature when used as a plasticizer, such as HOXPXOH or H
It can be carried out at the same time as the purpose of adjusting the molecular weight of OXAXOH. It is necessary to control the removal amount because p is increased by raising the temperature and de-dioling when the excess amount of diol is distilled off.

Using phthalic acid diol diester
Features HOXPXOH is mainly used to improve the poor water resistance caused by adipic acid when complex ester is used as a plasticizer, and the value of m is 0.3 to 3.0. As the amount increases, the viscosity rises sharply and the plasticizing efficiency deteriorates. In particular, the amount of m of (PX) m in the heterogeneous complex ester is determined by the usage ratio of HOXPXOH,
In addition to directly adding and mixing other diols to react,
It is also possible to control the reaction rate by using a mixed diester with HOXAXOH, and when the mixture is used, its viscosity decreases, deoxidizing treatment becomes easy, and it is easy to use. In the ethylene glycol-based propanediol-based combination with the diol component, the water resistance is insufficient if the m of (PX) m is 0.3 or less, and under severe conditions under high humidity, deterioration due to hydrolysis occurs and Precipitation can be seen in the.

Component of diol The diol component is related to the above-mentioned water resistance, electrical characteristics and flexible temperature. Octanediol has good performance but high price, ethylene glycol has good price but poor water resistance. However, it is necessary to use them according to their characteristics. The performance of the composite ester using propylene glycol and dipropylene glycol was almost satisfactory among many experimental examples. Especially, when propylene glycol was used, the reaction efficiency of the diol was 9% for the first time by this method.
It can be set to 0% or more, and in comparison with its performance, it has become an excellent method for producing an inexpensive complex ester.

Polymerization Degree of Complex Ester The polymerization degree of the complex ester depends on the reaction molar ratio of the diester component DOA and the diol. Therefore, when a low volatility and a plasticity equivalent to or slightly worse than DOP is aimed for as a composite ester for a plasticizer, it is preferable to produce the product with a viscosity of 500 cP or less and m + n up to about 3. . Further, for the purpose of mixing with a general-purpose plasticizer, a medium molecular weight m + n of about 8 to 9 produced by minimizing diester by-products is used. A polyester having a molecular weight of about 2000 can be produced. On the other hand, a polyester having a small amount of p may be transesterified with a diester such as dibutyl adipate in advance to obtain a polyester diol, and then a polyester may be obtained under the conditions of the present invention.

The degrees of polymerization m and n are calculated as follows. The diester by-produced by distillation was confirmed by GC analysis to confirm DOP and DOA, the average molecular weight was calculated, and the value was used to calculate the number of moles of the by-produced diester.
The diester recovery rate q corrected by the ester recovery rate is calculated, and the reaction amount [1−q] of the reacted A and P is calculated. On the other hand, m + n = [X] / {[1-q]-[X]} is calculated using the reaction amount [X] of the diol after subtracting the unreacted amount recovered in octanole or in the esterification reaction. M = [P] / from the reaction amount [P] obtained by subtracting the amount recovered as DOP from the amount of phthalic acid used.
{[1-q]-[X]} is calculated, and m is subtracted from m + n to calculate the value of n.

From the amount of diol "X" and the amount of dibasic acid [A] or [P] reacted in exactly the same manner, p = [A] / {[X]
-[A]} calculates the degree of polymerization p of the diol diester.

In describing the examples, the viscosities of the compounds obtained by performing these calculations are described.
In addition, the volatility when used as a plasticizer is described as the volatilization loss of 180 degrees, and a part of the volatility is measured by the JIS method using a 50PHR sheet, and various diols are used for comparison. The results of measuring the water resistance when the components are used (1% soap water immersion 60 ° C. 48 hours 72 hours weight loss after drying at 60 RH) are described. Their volatility is 1/7 or less in comparison with DOP, and the softening temperature is high corresponding to the molecular weight and is influenced by the phthalic acid content of the diol.
It was about -20 to -12 degrees.

Water- and migration-resistant heterogeneous complex ester and polyester
Stells will be described in relation to its water resistant to migration heterogeneous complex esters and polyesters. As a method for producing a complex ester having a controlled molecular weight distribution, it has been found that the molecular weight can be controlled by sequentially adding octanol, which is a terminal alcohol, during the dehydration esterification reaction. See Japanese Patent Laid-Open No. 5-1558102. Also in this case, the ester alcohol is formed in the presence of a large amount of octanol and the distribution is deteriorated. There is a feature that can reduce. On the other hand, when the water resistance to migration of the heterogeneous composite ester described above was examined, it was found that the heterogeneous composite ester exhibited excellent water resistance to migration resistance as compared with the complex esters containing no phthalic acid.
In the reaction, the use of phthalic acid diol diester was able to greatly improve the disadvantage that the reaction rate of phthalic acid was slow. Not only does the viscosity of polyester containing phthalic acid increase, but the terminal phthalic acid of the polyester is not esterified because the esterification reaction rate of phthalic acid is slower than that of adipic acid, so it is removed by alkali washing. Although it is difficult to obtain a polyester having a low acid value, it is possible to easily obtain a polyester having excellent water resistance to migration by this method. Comparing the above-mentioned transesterification method and the sequential addition dehydration esterification method, in the former case, in order to reduce the contamination of DOP in the by-product diester, the addition method of diol diester was adopted and the reaction time was very short, and the product Although it is suitable for the production of complex esters having low viscosity, it has a disadvantage that a large amount of DOA is recovered. On the other hand, in the latter case, DOA is a by-product during the production of high molecular weight polyester and relatively high molecular weight complex ester.
(In this case, DOP is mixed in), the reaction molar ratio of adipic acid and diol diester is 5: 3. The degree of polymerization m + n of the product is 3.5 or more, and the by-product ratio becomes 3 for the first time. %, But in a 2: 1 reaction, 11 to 17% of diester is by-produced. As a disadvantage, the whole reaction rate is slow, and a technique for obtaining a colorless product by properly using an appropriate octanol addition time and a catalyst usage amount is required, and if wrong, a by-product amount immediately increases and a molecular weight increases.

Molecular Weight Calculated Diol Diester Next, the molecular weight calculated diol diester will be described. The diol diester described in the present invention was used by calculating the average molecular weight, and in all cases, the reaction proceeded according to the reaction molar amount. Like the complex ester, the distribution naturally decreases as the ratio gradually increases from n = 1, and it is not possible to accurately measure the average molecular weight due to insufficient separation by HPLC. If it is the same as in the case of ester, it will be exactly the same as the calculated average molecular weight. Therefore, it is considered that the diol diester thus produced is also used as other industrial raw material such as a polyester polyol component for polyurethane.

When phthalic acid is changed to adipic acid to produce a terminal phthalic acid type complex ester, the viscosity of the terminal octanol complex ester becomes 7,000 CP even if m of (PX) m is 3 using the above symbols. The viscosity is high, and the plastic performance deteriorates rapidly as the molecular weight increases. (PXAX)
It is considered that the viscosity is low and the water resistance of phthalic acid can be utilized to obtain a polymer of an alternating copolymerization system which is a repeating unit of. That is, the terminal alcohol group of diol diester corresponding to XAX is reacted with phthalic acid by an anhydride reaction, and then octanol is sequentially added to esterify the terminal acid group, and finally, transesterification reaction is performed, As a product, 10-20 mol% of the phthalic acid used was DO, due to the influence of excess octanol and the difficulty of quantitative reaction of the anhydride reaction, as described above.
P was produced as a by-product, and as a result, the viscosity of the product complex ester increased. However, when the reaction mole number of phthalic anhydride is used in excess of 5 to 30% in advance, the by-produced DO
By producing it as a mixture with P, it is possible to produce a product having a relatively low viscosity and a high proportion of complex ester in the mixture, and by using propanediol having a short molecular length instead of dipropylene glycol, A relatively low viscosity product was also obtained. These products are DO
Since it is a mixture with P, the volatility of DOP remains, but DO
It has been found that after P volatilizes, it can be used as a complex ester mixture having a low volatility corresponding to the complex ester ratio.

Examples will be described below.

EXAMPLE Use of 1,2-propanediol diester of phthalic acid

Example 1 1 mol of adipic acid, 146 g, 320 g of 2-ethylhexanol (octanol), 2.45 mol were put in a dehydration esterification reactor 190
The mixture was heated and stirred at −240 ° C., water generated was removed, and 1 hour later, 0.45 g of tetrabutoxytitanium was added, and the mixture was heated and stirred while measuring the acid value. After 2 hours, after confirming the acid value of 0.1, the system was switched to a distillation apparatus and 54 g of excess octanol was distilled off under mild depressurization. Then separately prepared HOX _P PX _P OH, 0.167 mol, 47 g and H
OX _13B OH, 0.1667 mol, a mixture of 15g at 190-240 ℃ 80mmHg
Octanol was added to the reaction solution under reduced pressure of 20 to 20 mmHg, and finally transesterification was sufficiently performed at 0.5 mmHg to recover 47 g of octanol. (HOX _P PX _P OH was prepared as follows: 1 mol of phthalic anhydride, 456 g in 148 g, 6
After adding 1 mol of 1,2-propanedil HOX _P OH and heating and stirring at 100 ° C for 1 hour and a half, the reaction temperature was raised and the distillate was distilled under reduced pressure every 15 minutes to remove water and returned to the reactor for dehydration. An esterification reaction was performed. The acid value became 0.09 after 7 hours, and the reaction was completed. HOX _P OH was distilled off under reduced pressure below 110 ° C. to give 261.5 g of product. Insufficient amount than calculated amount except analytical use amount of 6.18g 1
4.5 g was added to produce 276 g of HOX _P PX _P OH. The composition was calculated as p = 1.236, and 0.809 mol and 0.191 mol of HOX _P O
The mixture with H can be handled as a molecular weight of 282 and 0.979 mol.

The complex ester reaction solution was added with 3 mL of 5% alkaline aqueous solution at 100 ° C. to hydrolyze the catalyst, filtered with activated clay, washed with alkali and washed with water, and distilled to 160 to 210 ° C. /
156.1 g of the distillate was removed at 0.4 mmHg to obtain 152.7 g of the product as a residual liquid at 265 ° C./0.4 or higher. OAXPPX _P AO, 0.167 mol, OA
X _13B AO 0.167 mol Total 222.0 g OAO by-product 123 g calculated to 123 g of ester recovery, therefore corrected OAO by-product amount 0.461 mol reacted [A + P] = 1 + 0.167-0.461 = 0.706 reaction Used for [Xp + X ₁₃ ] = 0.166 × 3 = 0.5, n = 0.5 / (0.706-
0.5) = 2.43, m = 0.167 / (0.206) = 0.81, product is O (AX _P ).
_0.81 is calculated as _{(PX P) 0.81 (AX 13} ) 0. 8 1 AO. Its viscosity is
It was 362 cP at 21 ° C. Using this plasticizer at 50 PHR and using a molded product made of polyvinyl chloride resin with 2 PHR of organotin stabilizer, the surface hardness was measured and the plasticization efficiency was measured. 50 PHR was judged to be equivalent. Weight loss at 160 ℃ for 2 hours is 2.1%
It is less than 1/8 of DOP 17%, and the water resistance value (48 hours 1
% Weight loss after dipping for 72 hours in 60% soapy water) is 0.99
The water resistance was almost the same as that of the DOP value of 0.8 to 1.2.

Example 2 Reaction (4) In exactly the same manner as in Example 1, 1 mol of DOA was prepared and p =
1.24 HOX _P PX _P OH, 0.167 mol, 47 g was added dropwise to the reaction under reduced pressure and treated as before to give 248 g DOA and 105.6 g product, calculated as O (AX _{P P} ) _1.30 (PX _P ) _1.30 AO, and its viscosity is 401 cP high-performance liquid chromatography analysis peak 1; 44%, peak 2; 52%, peak 3;
The peaks were 3% and 4th peak; 1%, and in the phthalic acid system, the ratio of abnormal reaction of n = 1 generation was small.
Water resistance is excellent as the value of m is large.
% Soft temperature was -9.5 ° C.

Example 3 Reaction (2) 0.16 mol of HOX _P PX _P OH (45.1 g) was added to 0.64 mol of DOA, and the mixture was heated and stirred to carry out transesterification mainly at atmospheric pressure. This diol diester is dimethyl phthalate
2/3 moles and 4 moles of propanedyl were transmethanolized by transesterification using 5 g of titanium catalyst to give p =
1.158 The molecular weight is 314. 5.7 g of 1,3-butanediol is added to adjust the average molecular weight to be 284. The OAO fraction 126.2 g obtained in this reaction was confirmed to have DOP of 13.6%. For 110.5 g of a product of 265 ° C or higher / 0.4 mmHg, the calculated composition is O (AX _P ) _1.51 (PX _P ) _0.84 AO, and the viscosity is
It had a water resistance of 0.56, a loss on heating of 1.76%, a flexible temperature of -9.0 ° C, and the performance was excellent except that DOP was by-produced during manufacturing.

Example 4 Reaction (4) 0.92 mol 134.3 g adipic acid and 0.08 mol diol diester Same as in Example 3 HOX _P PX _P OH 22.6 g and
1,3-butanediol 0.24 mol 21.6 g 156 g 1.2 mol
Adipic acid was added to carry out a dehydration esterification reaction. Five
After an hour, the acid value was 0.09, and transesterification was performed under reduced pressure to recover 21 g. The same post-treatment and distillation were carried out as in Example 1 to obtain 138.9 g of DOA fraction. However, 1/4 or more of the used phthalic acid containing 5.25% of DOP was distilled off as DOP without reaction. 140.8 g of product was obtained as a residual liquid, the composition of which was O (AX _P ) _0.51 (PX _P ) _0.30 (AX ₁₃ ) _1.22 AO, viscosity 192 c
The water resistance of P is 1.22, which is somewhat worse than that of DOP, but the performance is almost the same, the flexible temperature is -20.5, the volatilization loss is 2.8%, and the volatility is high.The diol component is a mixture of HOX _P OH and HOX ₁₃ OH. Therefore, it was cold-resistant and excellent in performance.

Example 5 Reaction (2) 1 mol of DOA was added at 200 ° C. to 230 ° C. under a reduced pressure of 20 mmHg.
0.2 mol HOX _P PX _P OH 55.4 g and HOX _DP OH 0.15 mol 20.1 g
The mixture was sequentially added to carry out a transesterification reaction. The product is
DOA 138.0 g and 376 cP residual liquid 173.0 g
O (AX _P ) _0.89 (PX _P ) _0.89 (AX _DP ) _1.66 AO, water resistance 0.88
Volatile loss 2.31% Soft temperature -14.0 ° C, no DOP by-product, and excellent product performance.

Example 6 Reaction (4) Propaneyl 7 mol 532 g in 2/3 mol phthalic anhydride
Add the mixture and stir at 100 ℃. Adipic acid 1/3 mol 48.6g
Was added and a dehydration esterification reaction was carried out at 200 to 240 ° C.
The acid value became 0.08 after 6 hours, and HOX _P OH was distilled under reduced pressure to obtain a diol diester with p = 1.07, which was corrected with HOX _DP OH and used. HOX _P AX _P OH-HOX _P PX _P OH (1: 2) Molecular weight 283.2 0.25 mol to 20 mmHg under reduced pressure at 200-230 ℃ DOA
The reaction was carried out by adding dropwise to 1 mol of 370 g, and 59 g of octanol was added.
Was recovered (91%). Treated as in Example 1, DOA 201.5
g Residual liquid 176.2 g and its viscosity was 421 cP. Its composition is O (AX _P ) _1.62 (PX _P ) _0.81 AO and its plasticization efficiency is 52.
0.50 Loss on heating 2.07% Flexible temperature -12 ° C.

Example 7 Reaction (4) 1 mol of adipic acid (146 g) was added with 6 mol of 456 g of 1,2-propanediol, and 1.8 g of tetrabutoxytitanium was added at the end of the reaction to carry out a dehydration esterification reaction. After 4 hours, the acid value became 0.1 or less and then distilled at 110 ° C. or less to obtain diol diester HOX _P AX _P OH as a residual liquid. 250.9
Correct the g deficiency by adding 15.1 g of HOX _2E OH to obtain the molecular weight.
Used as 266. 200 to 0.86 moles 318.2g DOA
The de-octanol transesterification reaction was carried out while adding at a relatively fast rate under a reduced pressure of -240 ° C / 20 mmHg. The calculated n was 2.76, but the result by high performance liquid chromatography was 61.9% for n = 2 and the average molecular weight was 696n = 1.75.
It was found that about 20% of 0.065 mol of propanediol was distilled off during the transesterification reaction. The product has a viscosity of 174 cP, a soft temperature of -22 ° C, and a heating loss of 2.80%.
The water resistance was 2.36. Reduce pressure to 50 for similar reactions.
The result obtained at -80 mmHg was a complex ester O (AX) _2.76 AO having a viscosity of 213 cP and n = 2.76. The water resistance was 2.46. The softening temperature was -20 ° C, the water resistance was 2.46, and the weight loss on heating was 2.18%. When used as a plasticizer, the water resistance was somewhat poor. The result of HPLC was n = 2.89 with an average molecular weight of 908, but the product distribution in this case was n = 1: 34.2%, n = 2; 23.6%, n = 3; 14.4%,
n = 4; 8.2%, n = 5; 4.4%, and the molecular weight distribution of the usual complex ester decreased as the number of n increased.
Depending on the reaction conditions, especially for the diol diester of adipic acid HOXAXOH, an abnormal reaction was likely to proceed, and a large amount of n = 1 was observed. However, the efficiency of HOX _P OH improved when the addition rate was slow and progressed almost quantitatively.

Ethyl glycol diester of phthalic acid
Using Use Example 8 Reaction (4) phthalic anhydride 1 mol of 148g and Echirenku Bu recall 7 mol 434g from dehydration esterification reaction product was obtained by distillation in a subsequent vacuum performed 258g Le as 1 mole. HOX _E PX _E OH 0.
O (AX _E ) from 16 mol and HOX _2E OH 0.08 mol DOA 0.84 mol
_{0.81 (PX E) 0.81 (AX} 2E) 0 .4 AO, to obtain its viscosity 425CP.
Flexible temperature -15.5 ℃ Water resistance 2.31 Although the water loss was improved to 2.35% by heating, the use of ethylene glycol resulted in poor water resistance.

Example 9 Reaction (4) As in Example 7, from HOX _E PX _E OH 0.14 mol 1,3-butanediol 0.187 mol O (AX _E ) _0.98 (PX _E ) _0.98 (AX ₁₃ ) ₀₈₀ AO,
A viscosity of 329 cP was obtained, and the flexibility temperature was -16.0 ° C, the water resistance was 1.58, and the weight loss on heating was 2.47%.

Example 10 Reaction (4) Same as before HOX _E PX _E OH 0.163 mol 1,4-butanediol X _14B
0.13 mol and 1 mol DOA were used for addition reaction under reduced pressure.
O (AX _E ) _0.95 (PX _E ) _0.55 (AX _14B ) ₀₄₆ AO, viscosity 237 cP, flexible temperature -19.0 ° C, and heating loss 3.40% were obtained.

1,3-Butanediol Diester of Phthalic Acid
The acid value and the reaction continued by adding tetrabutoxytitanium 1.2g Use Examples 11 and 12 0.8 moles phthalic anhydride 118.4g 4.8 mole of 1,3-butane diol mixture subjected to heat dehydration esterification reaction of Le 0.1
And The diol was distilled under reduced pressure to obtain a product with p = 1.04. 1 mole 370g DOA 0.167 moles 48.3g HOX
_13B PX _13B OH was added at 200 ° C./25 mmHg to carry out a transesterification reaction to remove 37 g (96%) of octanol. Example 1
After work-up and distillation according to the usual procedure described in
105.5 g of product was obtained and the calculated composition was O (AX _13B ) _1.31 (PX
_13B ) _1.31 AO analysis by HPLC n = 1; 20.7%, n = 2; 3
1.9%, n = 3; 17.9%, n = 4; 9.95%, n = 5; 5.0%, n = 6; 2.3% distribution, with a large proportion of n = 2 but a proportion of n = 1 There were also many. Its viscosity was 569 cP. Also DOA 1 mol
In contrast, the reaction product with 0.234 mol of HOX _13B PX _13B OH is O (A
X _13B ) _2.05 (PX _13B ) _2.05 AO had a distribution peak at n = 2 and its viscosity was 839 cP. Both of them were good in water resistance and loss on heating, but were expected to have a relatively high softening temperature. X
It can be seen that the viscosity increases sharply as the molecular structure of the PXPX shape increases.

Dipropylene glycol phthalic acid
Use of Stell Example 13 To 3 mol of dipropylene glycol HOX _DP OH and 0.5 mol of dibutyl phthalate BPB, 3 g of tetrabutoxytitanium was added, and the mixture was heated and stirred at 220-230 ° C under reduced pressure to remove 71 g of butanol thus formed. Exchange reaction, 110-11
Diol was removed at 5 ° C / 0.5 mmHg, and diol diester HOX _DP PX _DP OH 196.6g Calculated n = 1.03 3.6g
The above diol was added and corrected. 370 g of 1 mole
The DOA and 0.167 mol of HOX _DP PX _DP OH 66.3 g were added under reduced pressure to carry out the transesterification reaction to give 230.4 g of DOA and 137.0 g.
g of distillation residue was obtained, and its viscosity was calculated by 432 cP calculation.
O (AX _D P) _1.0 (PX _DP ) _1.0 AO, water resistance 0.88 Heat loss 2.09
% Soft temperature was -12.0 ° C.

Example 14 The diol diester obtained in Example 13 HOX _DP PX _DP OH
0.116 mol 53.1 g and HOX _DP OH 0.116 mol 17.8 g 0.8 mol
Transesterification was carried out by adding 200-230 / 25 mmHg to DOA. DOA (130.8 g) and a residual liquid (159.7 g) were obtained, and the viscosity was 299 cP and the composition was O (AX _DP ) _1.55 (PX _DP ) _0.78 AO. The water resistance of the molded product is 1.20 and the weight loss due to heating is 2.25.
The softening temperature was -18.0 ° C.

Examples 15-17 4 mol 536 g dipropylene glycol and 0.267 mol 39.5
The mixture of g phthalic anhydride was heated and stirred at 100 ° C for 1.5 hours to react with the anhydride, and the molar ratio of phthalic acid was 0.5 times.
33 mol of adipic acid was added and the mixture was heated and stirred to carry out a dehydration esterification reaction. After 1 hour, the reaction was carried out while adding 2 g of titanium catalyst and removing dipropylene glycol, and after 3 hours, the acid value was adjusted to 0.08. Distilled under reduced pressure at 120 ℃ or less to remove the diol and calculate 280.1g as residual liquid p = 1.3
Got 44. It was corrected by adding 27.1 g of HOX _DP OH and treated as an average molecular weight of 385. Dioctyl adipate DOA 0.8 mol 300 g of diol diester 1: 2
Change the moles of the mixture HOX _DP PX _DP OH-HOX _D PAX _DP OH (1: 2).
0.2 mol 77 g, 0.24 mol 92.3 g, 0.28 mol 107.7 g were added under reduced pressure to carry out transesterification reaction to obtain DOA 144.8 g,
127.0g, 97.8g residual liquid 162.5g, 182.0g, 206.9g were obtained. Their composition is O (AX _DP ) _2.74 (PX _DP ) _0.55 AO, O (AX
_DP ) _3.30 (PX _DP ) _0.65 AO and O (AX _DP ) _3.35 (PX _DP ) _0.67 AO
The viscosity is 326cP, 334cP, 393cP, water resistance 0.91, 0.89,
0.69 Heating loss is 2.61, 2.03, 2.65 Flexible temperature is -19.5,
The temperatures were -19.0 and -16.5 ° C.

Dipropylene glycol adipic acid
Use of Stell Example 18 HOX _DP AX _DP OH was prepared by transesterification using 3.2 mol of dipropylene glycol HOX _DP OH (429 g) and 0.8 mol of dibutyl acrylate BAB (206.4 g). 1 at 145-185 ° C
Under a reduced pressure of 00-25 mmHg, the mixture was heated and stirred with 1.8 g of a titanium catalyst to remove butanol produced, and an ester exchange reaction was performed. 117 g of distillate was obtained, the reaction was completed, and 1
254.7g as a residual liquid after removing diol at temperatures up to 20 ℃
By calculation, n = 1.80 was obtained. HOX _DP (AX _DP ) _1.80 OH As a molecular weight of 573, 0.111 mol of 63.6 g was used, and 3 times its mol was 0.37 mol. Transesterification was carried out under reduced pressure using 137 g of DOA. Product is a by-product DOA 45.9g Residual liquid
113.8g Its viscosity is 360 cP and the product is O (AX _DP ) _2.44 AO
The water resistance was calculated to be 2.20. Theoretically n = 1.8
Therefore, n = 2.8 is generated, but the experimental result shows that n = 2.4 and HOX (AX) _P OH advances the retroreaction with a smaller molecular weight. Therefore, in the case of adipic acid alone system, it is not necessary to use diol excessively, and it is possible to use a large one of p, but in the system in which phthalic acid is mixed, the phenomenon of retroreaction in which n decreases cannot be confirmed. .

Diethylene glycol of phthalic acid
Was prepared from using Example 19 Diethylene glycol 6 moles of phthalic anhydride 1 mole of ether, HOX _DE PX _DE OH 0.2 mol, 64.4 g and 1,3-butanediol 0.15 mol, using a mixture of 13.5 g, 1 mol DOA
And transesterification was performed under reduced pressure. D as product
182.4 g of OA 168.5 g was obtained as a residual liquid. Its composition is O
(AX _DE ) _1.10 (PX _DE ) _1.10 (AX _13B ) _0.83 AO, the viscosity of which is evaluated as 376 cP PVC plasticized sheet, water resistance 2.16, heat loss 2.55%, flexible temperature -16.5
At ℃, the cold resistance was good, but the water resistance was poor.

Pair-translocating hetero-complex ester and octa
Production Example by Sequential Addition Method of Nool Example 20 Reaction (3) Propylene glycol 304 g 4 mol to phthalic anhydride 1/3 mol 4
9.4 g was added and the mixture was heated with stirring at 100 ° C. for 1.5 hours. Then, 2/3 mol of adipic acid (97.4 g) was added to carry out a dehydration esterification reaction. 1 hour later, 1.5 g of titanium tetrabutoxide was added, and the reaction was proceeded while removing water in propanediol.
The temperature was raised and the reaction was carried out at 230 ° C. Acid value after 2.5 hours 0.12
And the reaction was completed. As a result of distilling at 110 ° C or lower under reduced pressure, 252.7 g of product was obtained, and the calculated polymerization degree was obtained.
p = 1.267 The average molecular weight was 320.

0.3 mol of this propanediol diester
A mixture of 96 g and adipic acid 0.4 mol 58.4 g is put in a dehydration esterification reactor and heated and stirred, and the reaction proceeds at 200-230 ° C. 0.2 mol 26 g of octanol is added according to the distilling of water.
The reaction proceeded while being added while distilling water from 5/8 equivalent to 6.5 / 8 equivalent. As a catalyst when the reaction progressed about 80%
0.34 g of tetrabutoxy titanium was dissolved in 4 g of excess octanol and added little by little, and the acid value became 0.1 after 3 hours. D produced as a by-product by post-treatment and distillation as in Example 1
OA 0.2g excluding product 149.2g 0.15 mol 8
A 9.8% yield was obtained. Its viscosity was 1671 cP and the calculated composition was 0 (AX _P ) _5.53 (PX _P ) _1.27 AO. The water resistance test result is 1.7, the weight loss on heating is 1.0%, and the softening temperature is -5 ℃.
The transfer rate from 0PHR to 20PHR PVC sheet (weight loss% of the laminated press sheet after 12 hours) is 3% of DOP.
1.1% for polyethylene and 0.84% for polyethylene with a DOP value of 9.5%.

Example 21 Propanediol diester described in Example 20.
3 mol and 0.4 mol of dipropylene glycol were mixed and used, and the molar ratio of adipic acid was changed to 0.8 mol, 0.2 mol of octanol was added to 13/16 mol of water equivalent to 14.5 / 16 mol.
Sequential addition dehydration esterification reaction was performed up to the equivalent amount. The post-treatment was carried out in the same manner as before to collect 0.3 g of DOA as a product to obtain 216.6 g of a polyester product. Its viscosity is
At 4354 cP its composition is O (AX _P ) _4.27 (AX _DP ) _4.0 (PX _P ) _2.53 AO
Met. Corresponding to the molecular weight, the migration rate is low and PVC0.
It was 4% and polyethylene 0.8%.

Example 22 Prepared similarly to the propanediol diester described in Example 20 and corrected with dipropylene glycol, p = 1.
The diol diester of 07 and dipropylene glycol were used, and the molar ratio with adipic acid was changed to 0.3 mol + 0.2 mol.
Using 0.6 moles, using 0.2 moles of octanol,
The water was distilled off from 8.5 / 12 molar equivalents to 10.2 / 12 molar equivalents to carry out dehydration esterification reaction. The product had a DOA of 0.20 g and a polyester product viscosity of 196.06 g of 1812 cP and a calculated composition of O (AX _P ) _4.02 (AX _DP ).
_{It was 2.01} (PX _P ) _2.01 AO. The water resistance was 1.0, the migration rate to PVC was 1.1%, and that to polyethylene was 1.4%.

Example 23 Molar ratio of adipic acid and phthalic acid prepared as in the previous example
Propane diol diester produced 1: 2, average molecular weight 275.3, 0.3 mol, 82.6 g and adipic acid 0.6 mol, 87.6 g
In addition, 0.6 mol of octanol was sequentially added between the water distillation of 1.2 / 4 mol equivalent and the water distillation of 3/4 mol equivalent, and dehydration esterification reaction was carried out to obtain 3.28 g of DOA and 197.0 g of product. Got.
Calculated n = 2.06 and its composition is O (AX _P ) _1.37 (PX _P ) _0.68 A
O, the viscosity was 265 cP. Water resistance of 1.2 and migration rate against PVC
Was 1.4% and polyethylene was slightly higher at 3.0, but it was significantly less than DOP.

Example 24 0.3 mol 44.4 g of phthalic anhydride and 6 mol of 456 g of propanediol were mixed, deoxidized, and heated and stirred at 100 ° C. to react the anhydride. Next, 0.7 mol of 102.2 g adipic acid was added to increase the reaction temperature, and the propanediol, which was distilled at a temperature of up to 210 ° C., was removed, and the water was removed by sequentially distilling under reduced pressure to return the propanediol to the reaction system.
Twenty minutes after the start of the reaction, 0.8 g of tetrabutoxytitanium catalyst was added, and the acid value was adjusted to 0.1 after 3 hours. 75-90 ℃ / 0.6 mmHg
After distilling propanediol, the degree of polymerization was calculated to be 1.111 from the weight of the remaining reaction solution, and the molecular weight was 289.3.
The following reaction was carried out. A mixture of propanediol diester 0.21 mol 60.8 g, adipic acid 0.35 mol, and 51.1 g was deoxygenated and stirred under heating to carry out a dehydration esterification reaction (reaction molar ratio = diol diester: adipic acid: octanol =
3: 5: 4) and distilling 3/10 equivalents of water to 6.5 / 10 0.14 mol 18g octanol 7/10 to 9.0 / 10
The remaining 0.14 mol of octanol was sequentially added during the water distillation of. Finally, an excess amount of 9.5 g was added in four portions and added to reduce the acid value to 0.1. 200 after reaction
Transesterification was performed at ℃ / 0.5 mmHg to remove a little octanol generated. Water and a small amount of alkaline water were added to inactivate the catalyst, and the activated clay was filtered, washed with alkali, and then distilled under reduced pressure. The distillate (DOA) distilled up to 265 ° C / 0.5 mmHg is 1.9 g and the residual liquid is 127.8 g.
Including the amount used for analysis, the ester recovery rate was 99% and the by-product dibasic acid ratio was 0.9%. The product has a viscosity of 409 cP and its composition is O (AX _P ) _2.58 (PX _P ) _0.74 AO, and the water resistance test result is 1.0, which is almost equivalent to DOP, and the flexibility temperature is -14 ° C. It was a drug. The reaction ratio of the dibasic acid varies greatly depending on the method of sequential addition, and even in the reaction ratio of this example, the DOA by-product ratio varies from 0.9% to 13% in this description, and the amount of excess octanol used. Including the above, the strict addition timing of octanol was a factor for obtaining a quantitative reaction product.

Example 25 X prepared with a molar ratio of phthalic acid to adipic acid of 1: 2
A PX-XAX mixture was prepared according to the previous example. At that time, the reaction temperature was raised and the dehydration esterification reaction was carried out while removing propanediol to obtain the product. Using the calculated p = 1.498 molecular weight of 354.6, a complex ester was produced by the sequential addition esterification method. Diol diester
Start the reaction with a mixture of 0.3 mol 106.4 g adipic acid 0.45 mol 65.7 g, and successively add 0.3 g of octanol 39 g from the distillation of 3.5 / 6 mol of water to the distillate of 5/6 mol of water. Then, dehydration esterification reaction was performed. DOA 8.53g was by-produced, and the product was 151.05g Corrected with a recovery rate of 84.6% based on the theoretical amount of ester, the DOA by-product amount was calculated and reacted.
+ P = 0.877, n = 5.90 , m = 0.79 composition _{O (AX P) 5.11 (PX} P) 0. 7 9
The AO viscosity was 466 cP. The water resistance is 0.94, which is an excellent value, and its migration rate is 1.50% for PVC and 0.97% for PE, and the softening temperature is somewhat higher at -5.0 ° C. Was an excellent plasticizer.

Example 26 Diol diester prepared by transesterification method from 6 mol of dipropylene glycol and 1 mol of dibutyl phthalate. Using an average molecular weight of 398.4, 0.194 mol of 77.1 g
And adipic acid 0.38 mol 56.6 g of a mixture was used to initiate the dehydration esterification reaction, and 0.388 mol of octanol was added between the distillation of 1.8 / 4 equivalents of water and the distillation of 3/4 equivalents of water.
50.4 g was sequentially added, and finally a small amount of excess octanol was added to lower the acid value and terminate the reaction. The product is 20.9 g D
OA, 7.5g DOP and 112.0g product, the viscosity is just 100
It was 0 cP and its composition was O (AX _DP ) _1.55 (PX _DP ) _1.93 AO. High phthalic acid content means excellent water resistance and its value is 0.67
Met

Example 27 Mixed diol diester having a molecular weight of 420 p = 1.11 prepared by reacting 6 mol of dipropylene glycol with 1 mol of phthalic acid and then adding 0.5 mol of adipic acid to carry out dehydration esterification reaction. Was used to carry out dehydration esterification. Diol diester mixture 0.2 mol 84 g Adipic acid 0.44 mol Start the reaction with a mixture of 64.3 g and between the distillation of 5.4 g of water and the distillation of 12 g
0.48 mol 62.4 g of octanol was added, and finally an excess amount of octanol was added to reduce the acid value, and the ester exchange reaction was followed by decatalytic treatment and distillation to obtain volatile matter as DOP DOA.
44.6 g of a mixture and 100.6 g of product were obtained. Its viscosity is 699
It was cP. The water resistance when used as a plasticizer was 1.05.

Example 28 5phthalic anhydride 55.5 g 0.375 mol and molecular weight 577 p = 1.1
7 dipropylene glycol diadipate 86.6g, 0.1
After reacting a toluene solution with 5 mol at 80-120 degrees,
A dehydration esterification reaction was carried out by adding 75 mol 48.75 g of octanol. At the end, an excess amount of octanol (9.8 g) was added little by little to lower the acid value, and finally octanol generated by the transesterification reaction was removed, followed by washing with a decatalytic water and distillation to remove volatile components. Its viscosity was 735 cP. Further distillation yielded DOA 15.8 g DOP 37.7 g and complex ester O (PX) _1.87 (AX) _3.34 PO, 1950 cP.

A mixture of 735 cP with a diester is slightly less plasticizing than DOP to obtain the same surface hardness.
It was necessary to use a relatively large amount, but although it contained DOP and DOA as volatile components, the volatilization loss was almost 1/3 of that of DOP, and it could be used as a volatile plasticizer, and the water resistance was An excellent value was obtained at 1.10.

Example 29 Terminal octanol when using a mixture of diol diester XAX and XPX 2: 1 used in preparing O (AX) _n (PX) _m AO by sequentially adding octanol The ratio molar amount of adipic acid and the reaction molar ratio of diol diester used with respect to 2 and the molar amount of unreacted dibasic acid (q value) are shown in the table below. As a reference example, the q value when directly using 13-butanediol was described. As a result, when diol diester was used, the q value was much smaller and the amount of DOA by-produced was less, and the reaction ratio of dibasic acid was improved.

Example of use of diol diester Reaction molar ratio 2: 2.3: 1.3 2: 2: 1 2: 2.5: 1.5 2: 3: 2 (O: A: X) (3: 3.5: 2) (4: 5: 3) By - product DOA% q value 17-18% 11-12% 7% 3% Use example of 1,3-butanediol Reaction molar ratio 2: 2: 1 2: 2.5: 1.5 2: 3: 2 2: 4 : 3 2: 5: 4 (O: A: X) (4: 5: 3) By -product DOA% q value 22-27% 18% 11-12% 5% 3%

Summary of Examples Quality RO (COACOOXO) _n (COPCOOXO) _m COACOOR migration% Simplified chemical formula of Example product Water resistance ¹⁾ Weight loss on heating ²⁾ PVC ³⁾ PE ⁴⁾ Control DOP 0.8-1.2 17% 3 9.5 1 O (AX _P ) _0.81 (PX _P ) _0.81 (AX ₁₃ ) _0.81 AO 0.99 2.1% 2 O (AX _P ) _1.30 (PX _P ) _1.30 AO 0.90 2.2% 3 O (AX _P ) _1.51 (PX _P ) _0.84 AO 0.56 1.76% 4 O (AX _P ) _0.51 (PX _P ) _0.30 (AX ₁₃ ) _1.22 AO 1.22 2.8% 5 O (AX _P ) _0.89 (PX _P ) _0.89 (AX _DP ) _1.66 AO 0.88 2.31% 6 O (AX _P ) _1.62 (PX _P ) _0.81 AO 0.50 2.07% 7 O (AX) _2.76 AO 2.36 / 2.46 2.18% 8 O (AX _E ) _0.81 (PX _E ) _0.81 (AX _2E ) _0.4 AO Inferior 2.35% 9 O (AX _E) ) _0.98 (PX _E ) _0.98 (AX ₁₃ ) ₀₈₀ AO 1.58 2.47% 10 O (AX _E ) _0.95 (PX _E ) _0.55 (AX _14B ) ₀₄₆ AO 3.40% 11 O (AX _13B ) _1.31 (PX _13B ) _1.31 AO Good Good 12 O (AX _13B ) _2.05 (PX _13B ) _2.05 AO Good Good 13 O (AX _DP ) _1.0 (PX _DP ) _1.0 AO 0.88 2.09% 14 O (AX _DP ) _1.55 (PX _DP ) _0.78 AO 1.20 2.25 15 O ( AX _DP ) _2.74 (PX _DP ) _0.55 AO 0.91 2.61 16 O (AX _DP ) _3.30 (PX _DP ) _0.65 AO 0.89 2.03 17 O (A X _DP ) _3.35 (PX _DP ) _0.67 AO 0.69 2.65 18 O (AX _DP ) _2.44 AO 2.20 19 O (AX _DE ) _1.10 (PX _DE ) _1.10 (AX _13B ) _0.83 AO 2.16 2.55% 20 O (AX _P ) _5.53 ( PX _P ) _1.27 AO 1.7 1.0% 1.1 0.84 21 O (AX _P ) _4.27 (AX _DP ) _4.0 (PX _P ) _2.53 AO 1.0 0.4 0.8 22 O (AX _P ) _4.02 (AX _DP ) _2.01 (PX _P ) _2.01 AO 1.0 1.1 1.4 23 O (AX _P ) _1.37 (PX _P ) _0.68 AO 1.2 1.4 3.0 24 O (AX _P ) _2.58 (PX _P ) _0.74 AO 1.0 2% or less 1.50 0.97 25 O (AX _P ) _5.11 (PX _P ) _0.79 AO 0.94 26 O (AX _DP ) _1.55 (PX _DP ) _1.93 AO 0.67 27 − 1.05 28 O (PX) _1.87 (AX) _3.34 PO 1.10 1/3 of DOP ^{1) 2)} See Example 1 ^{3) 4)} Example 20 reference

Claims (7)

[Claims] 1. One or two dicarboxylic acids selected from adipic acid and phthalic acid or their alkyl esters; 1,2-propanediol, ethylene glycol,
Diethylene glycol, dipropylene glycol, 1,2-
From a diol selected from butanediol, 1,3-butanediol, 1,4-butanediol, 2-ethylhexanediol, tripropylene glycol, and a C _{4 to} C ₁₀ saturated aliphatic monofunctional alcohol, Formula RO (COACOOXO) _n (COPCOOXO) _m COAC
OOR [wherein, X is the same or different residue of the diol, A is adipic acid residue, P is phthalic acid residue, R is C
_{4 to} C ₁₀ alkyl group, n and m represent a number of 0 or more, provided that m + n is larger than 0], the complex ester or polyester of Part and a part of phthalic acid or adipic acid or a lower alkyl ester thereof are reacted in excess of the diol to give a diol diester of the formula A and / or A ′. [Where X is as defined above and p is the degree of polymerization of the diol diester] and used as the diol component. 2. The method according to claim 1, which comprises producing a complex ester or a heterogeneous complex ester by carrying out a dealcohol transesterification reaction between a diol diester of a dicarboxylic acid and an adipic acid diester. 3. A dicarboxylic acid selected from adipic acid or phthalic acid or an alkyl ester thereof; 1,2-
Propanediol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-ethylhexanediol,
Starting from a diol selected from tripropylene glycol, as well as a C _{4 to} C ₁₀ saturated aliphatic monofunctional alcohol, said diol or part thereof and phthalic acid or adipic acid or their A part of the lower alkyl ester is reacted with an excess of the diol to give a diol diester of the formula A and / or A '. [Where X is the residue of the diol and p is the degree of polymerization of the diol diester], and the dicarboxylic acid diol diester (A) and / or (A ′)-containing di-
Reaction with phthalic acid or adipic acid or an alkyl ester thereof and the monofunctional alcohol to give a compound of the formula RO (COACOOXO) _n (COPCOOXO) _m COAC.
OOR [In the formula, X is a residue of the diol, A is an adipic acid residue,
P lid - Le acid residue, R represents produce C ₄ -C ₁₀ alkyl groups, although m and n is a number of 0 or more, provided that m + n is a condition that is greater than 0] complex ester or polyester In the method, the saturated aliphatic monofunctional alcohol is sequentially added to proceed the reaction. 4. A diol of the formula HOXOH and a HOCO of the formula
By reacting ACOOH with a dicarboxylic acid,
In producing diol diester compositions consisting of molecules of various degrees of polymerization of compounds of formula HOX (COACOOX) _p OH, the formula p = [A] / {[X]-[A]} or [X] /
[A] = (1 + p) / p [where p is the degree of polymerization of the diol diester greater than 1 and 2 or less, [X] is the molar concentration of the diol, and [A] is the molar concentration of the dicarboxylic acid] and The diol diester, which comprises reacting the diol with the dicarboxylic acid while adjusting the molar ratio of the dicarboxylic acid to the diol calculated from the degree of polymerization p of the diol diester to be adjusted to 1: 2. A process for producing a calculated molecular weight composition of a mixture. 5. A unit comprising a phthalic acid residue and an adipic acid residue produced by the method according to claim 1, wherein the unit comprising a phthalic acid residue has a degree of polymerization of 0.3 or more. A complex ester compound composed of units. 6. The method according to claim 1, wherein the monofunctional saturated aliphatic alcohol is 2-ethylhexanol. 7. A plasticizer containing a substance produced by the method according to any one of claims 1 to 3.