JPH04356441A - Complex ester of ether-ester - Google Patents

Abstract

PURPOSE:To readily produce low volatile and non-colored compounds having an ether-ester structure, including novel compounds, having various characteristics and a low acid value, and useful as a plasticizer for polyvinyl chloride or as a lubricant at a high rate. CONSTITUTION:A ester selected from (i) a 1-8C alkyl ester of phthalic acid or adipic acid, (ii) an ester of formula I (X is ethylene, etc.; R'' is lower alkyl;(k) is an integer of 1-15) and (iii) octyl trimellitate ester is subjected to an ester exchange reaction with 1-2 equivalents of a mono-triethylene glycol mono 1-16C alkyl benzyl ether in the presence of an alkoxytitanium or a solid polytitanic acid catalyst produced therefrom under vacuum to produce esters of formula II (R' is 1-l6C alkyl, etc.; (m) is 1, 2, 3; (n) is an integer of 0-3 wherein, when (n)is not 0, (m) is (n); (i), (j) are 1, 2; (i+j)=2, 3; Y is phthalic acid, etc.,) including new compounds, while 1-2 equivalents of the alcohol by-produced by the ester exchange reaction is removed.

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a method for producing a plasticizer or lubricant, mainly made of polyvinyl chloride, which has an ether ester structure and has low volatility and various properties.

BACKGROUND OF THE INVENTION Methods for producing phthalic acid diesters and adipic acid diesters are already well known, and are mainly produced by dehydration and esterification reactions. Sulfuric acid and para-toluenesulfonic acid have been used as catalysts in the past, and alkoxy titanium has been used in recent years.

SUMMARY OF THE INVENTION The present invention relates to a method for producing diesters that does not involve dehydration and esterification reactions. A feature of this technology is the use of transesterification especially when producing these desired esters, and its greatest advantage is that the reaction rate is fast and the unit price is lower than that of monofunctional alcohols. The advantage is that the product can be obtained in the required stoichiometric amount without using an excessive amount of ether alcohol, which would be expected to have a high yield. Furthermore, since the product has a high boiling point, it is difficult to separate and purify it by distillation, so a method that does not cause coloring as much as possible is required, but coloring can be prevented and a product with a low acid value can be obtained. Further, by using a high molecular weight ether ester at the end of the polyester, it becomes easy to reduce the volatile content derived from low molecular weight impurities. If the same product is produced by dehydration and esterification, it will take a long time at high temperature to obtain a low acid value, and it will be difficult to prevent coloration.

Means for Solving the Problems The present invention relates to a method for producing a compound having a structure represented by the following general formula. RO(CH2CH2O)mOCO(CH2)4COO(
CH2CH2O)nR
(A-1) RO(CH2CH2O)mOCOC6H4
COO(CH2CH2O)nR
(A-2)RO(CH2CH2O)nO
{CO(CH2)4COOXO}kCO(CH2)4C
OO(CH2CH2O)nR(B) Of these (A-1
, A-1) Some of the esters are presumed to be already known compounds, but some of them include new compounds, especially mixed esters C-1, C-2 (A:n=0) by partial esterification. No synthesis reports are known. RO(CH2CH2O)mOCO(CH2)4COOC
8H17(C-1)RO(CH2CH2O)mOCOC
6H4COOC8H17 (C-2) R in these formulas
is an alkyl group having 1 to 16 carbon atoms and a benzyl group, mainly butyl, hexyl, octyl, and 2-ethylhexyl, m is an integer of 1 to 3, and n is 0.
~3 integer, k is an integer from 1 to 15, and X is H
It shows the alcohol residue of diol described as OXOH. To explain the reaction method in more detail, a di- or tricarboxylic acid ester and a monoalkyl or benzyl ether of ethylene glycol, diethylene glycol or triethylene glycol are used as raw materials. As the ester, a lower ester such as a butyl ester is preferably used as a raw material, but when an octyl ester is used, a product in which one of the octyl esters remains is also obtained. For example, 2 equivalents of diethylene glycol monobutyl ether as a raw material and 0.2 to 2 mol% of alkoxy titanium as a catalyst are added to dibutyl phthalate or dibutyl adipate, and heating is started under reduced pressure at approximately 100 to 200 mmHg with stirring. The reaction starts at 140℃ and 190-20℃.
When kept at 0°C for 1.5 hours, approximately the calculated amount of butanol is distilled out. Finally, the reaction is terminated by raising the reduced pressure to 15 mmHg to perform the theoretical amount of dealcoholization, and the entire reaction is completed in approximately 2.5 hours. The reason why the reduced pressure is not lowered sufficiently at the beginning is because when dibutyl adipate or some butyl cellosolve is used, the raw materials begin to boil, but if the efficiency of fractional distillation is high, the reaction can be carried out under low pressure from the beginning. The transesterification reaction itself is well known, and since the reaction is an equilibrium reaction, the actual reaction rate is the rate at which the produced butanol is distilled and removed from the system. Butanol can be removed under vacuum at about 40℃, while the titanium catalyst used as a catalyst
The temperature at which the reaction progresses is 60°C, and the reaction progresses slowly at 140°C. When performing a transesterification reaction using a titanium catalyst and adding an alcohol to a normal catalyst such as an alkali catalyst, titanium catalyst is used to take advantage of its excellent catalyst properties and is applied to this reaction. Naturally, this catalyst can be used to carry out a dehydrated ester reaction, but when this system of compounds is used, the reaction between ethylene glycol monoalkyl ether, which is the raw material ether alcohol, and A catalyst intermediate is formed, but the rate of esterification reaction is extremely slow compared to alkyl alcohols, probably due to the slow adsorption rate of acids. It is thought that a colored substance is produced, and once colored, the only way to remove it is by distillation, and the present invention was arrived at after studying various methods for producing esters, which are products with a high boiling point. The reaction rate was fast and various products could be easily obtained. When this ether alcohol is used, the dehydration esterification reaction takes more than twice as long as a normal alkyl alcohol, and even if the temperature is raised, it does not reach the speed of an alkyl alcohol. While only coloring progresses, this disadvantage is greatly improved. When these products are used as plasticizers for polyvinyl chloride, the primary feature is that they have low volatility in proportion to their molecular weight, but they also convert ethylene glycol into di- or triethylene glycol and also convert alkyl We have discovered that when the group changes from a butyl or octyl group to a benzyl group, different features emerge depending on the combination, so we will explain the properties by dividing them into groups. Using B for butyl and E for ethyleneoxy as the terminal butyloxyethylene glycol symbol,
For diesters, the symbol D is attached first, and for terminal mixed esters, each group is also written together. Diethyleneoxy as EE,
Triethyleneoxy is abbreviated as DEE, and for reference, terminal ethyl E, phthalate is P, and adipate is A. In this way, the respective produced compounds are DBE
A, DBEEA, DBDEEA, DBEP, DBEEP
, DBDEEP, and DOP (dioctyl phthalate) is expressed as BEEOP. These have improved plasticization efficiency and exhibit plasticity almost equivalent to DOA or DOP, and their low-temperature properties, such as softness temperature, are lowered, and in particular, DBEEA or DBDEEA based on diethylene glycol or triethylene glycol has a higher boiling point, resulting in a lower volatilization loss. In terms of chemical resistance, there was less weight loss due to gasoline solubility and migration to polyethylene was improved. The hexyloxyethylene glycol system symbol is expressed using H instead of B in butyl. DHEA, DHEEA, DHEP, D manufactured
Compared to the butyl ester type, HEEP and HEEOP had medium plasticization efficiency, flexibility and temperature transition. The properties of HEEOP, in which some of the terminal groups are octyl groups, are DO
It shows a mixture with P and intermediate properties, indicating that it can be used as an additive when mixed with diester. It is expressed using the octyloxyethylene glycol symbol by replacing O with B of butyl. Manufactured DOEA, DOEEA, D0EP, DO
EEP has a small volatilization loss corresponding to its molecular weight.In particular, the softening temperature of phthalic acid type is higher than that of adipic acid type, but lower than that of DOP, and DOEEP showed low temperature characteristics of -30°C or lower. DOEA and DOEEA exhibit a softening temperature equal to or lower than that of DOA, and are used as low-volatility low-temperature plasticizers together with phthalate-based plasticizers. DO as a disadvantage
EP and DOEEP had poor plasticization efficiency. It is expressed using the benzyloxyethylene glycol symbol by changing Bz to B. The plasticizing efficiency of the manufactured DBzEA and DBzEEA is comparable to that of DOP, but it is slightly worse than that of DBzEP and DBzEE.
P has poor plasticization efficiency. However, the electrical characteristics are particularly good.
BzEOP has a surface electrical resistance value that is one order of magnitude better than OP.
, BzEEOP also showed better electrical properties than DOP. Furthermore, this system is characterized by much lower volatility, and the results of measurements of dissolution and extraction with gasoline and transferability with polyethylene sheets showed a significant improvement in the amount of dissolution and transfer. As mentioned above, ethylene glycol
Although the properties of alkyl ether-terminated esters of di- or di- and triethylene glycol have been investigated, they can also be applied to other esters, such as diethylene glycol mono- or di- and tri-ethylene glycol partially exchanged with trioctyl trimellitate. Making esters with butyl ether terminals improved the plasticity, flexibility and temperature transition properties to a lesser extent. In addition, from the complex ester 1,3-butanediolbisbutyl adipate (13BBBA), esters in which both ends are changed to benzylethyleneoxy, BzEAXAEBz or butylethyleneoxyethyl, B
EEAXAEEB was manufactured. Here, AXA is the skeleton of complex ester -{CO(CH2)4COCH2CH2CH
(CH3)OCO(CH2)4CO}n-. Furthermore, the polyester has a molecular weight of 858, has a terminal butyl group, adipic acid as the dibasic acid, and 1,3-butanediol as the diol component, and diethylene glycol monobutyl ether or benzyloxyethyl alcohol at the end. A terminal-modified polyester was produced by a transesterification reaction. The result is 160 in the product
-220°C/0.7mm The volatile content was reduced, resulting in less volatilization loss of the molded sheet. By using a benzyl terminal, a polyester with electrical properties superior to DOP was obtained. On the other hand, the butyloxydiethylene glycol terminal resulted in a polyester with a relatively low softening temperature. Diethylene glycol as a polyester component
The use of a mixed diol component of 1,3-butanediol and 1,3-butanediol, and also the mixed use of a mixed dibasic acid as a dibasic acid, is already well known as a method for producing polyester. state Example 1 Dibutyloxyethyl adipate (D
BEA) Add 0.5 g of butyl titanate as a transesterification catalyst to 236 g of ethylene glycol monobutyl ether equivalent to 2 molar equivalents, heat to 120°C and stir, then add 258 g of dibutyl adipate (1 molar amount) and heat at 160-200°C under slight vacuum. The butanol produced by stirring was removed, and after about 1 hour, the degree of vacuum was increased to 20 mmHg to remove the butanol produced by the transesterification reaction, and an almost quantitative amount of 145 g was recovered and the reaction was continued. finished. After completion of the reaction, as a post-treatment method, when the temperature drops to 100℃, add a solvent, add potassium carbonate or dilute solution of soda as an alkali suitable for the acid value, stir at around 80℃ for 20 to 60 minutes, and then add 5g to 15g of activated clay. The mixture was stirred and filtered. Next, washing with water and, if necessary, alkaline washing and washing with water were performed. After removing the solvent by distillation, the product was obtained by distillation under reduced pressure. Examples 2 to 6 The adipic acid series uses dibutyl adipate, and the phthalic acid series uses dibutyl phthalate as a raw material, and the corresponding ethylene glycol
alcohol, diethylene glycol or triethylene glycol
Example 1
The reaction was carried out in the same manner as above, followed by purification distillation to obtain the product, most of which was the residue of vacuum distillation. The plasticization efficiency and low temperature electrical properties versus chemical properties of the products obtained are shown in Table 1. Example 7 Dibutyl phthalate DBP 111.2 g (0.
4 mol), 72 g (0.42 mol) of diethylene glycol monobutyl ether and 52.8 g of 2-ethylhexanol were added in 1 molar equivalent each in the presence of a solid polytitanic acid catalyst, initially at normal pressure, then at 3 mol.
The transesterification reaction was carried out under reduced pressure of 0 mmHg.
g of butanol was collected to complete the reaction. The product was obtained as a distillation residue after work-up. The result of HPLC analysis is BEEB
It was considered to be a mixture of 13% P and 87% BEEOP. The viscosity at 21°C and the results when used as a plasticizer are listed in Table 1.
Table 1 Abbreviations
Formula 1) Viscosity 2)
Plasticization efficiency 3) Boiling point example 1 DBEA (A
-1, R:C4H9 n=1) 12
42.5 164/1mmHg Example 2
DBEEA (A-1, R:C4H9 n=2)
34 44.9 20
0-205/1mmHg Example 3 DBDEEA (
A-1, R: C4H9 n=3) 74
45.7 Example 4 DBEP (A-2,R:
C4H9 n=1) 38 48.9 Example 5 DBEEP (A-2,R:C4H9 n
=2) 63 51.1 Example 6 D
BDEEP (A-2,R:C4H9 n=3)
85 53.1 Example 7 BEEOP
(C-2,R:C4H9 n=2) 119
49.7 Control Example 1 DOA
23 44 Control Example 2 DOP
75 50 4
) Softness temperature 5) Electrical resistance 6) Heating loss 7) PE
8) Kasoline Example 1 -46.0
8.5X108 25.77 5.0
4 17.60 Example 2 -46.0
6.0X108 9.01 2.1
7 17.42 Example 3 -39.9
5.9X108 6.44 1.4
6 15.00 Example 4 -20.8
1.2X1010 16.16 2.6
6 13.20 Example 5 -21.0
3.8X109 4.79 1.5
8 11.80 Example 6 -17.8
3.0X109 4.41 0.8
4 9.30 Example 7 -24.5
3.0X1010 7.10
14.90 Control Example 1 -43.0
3.4X109 17.86
14.92 Control Example 2 -22.3
4.8X1010 15.70 5.7
0 17.411) Viscosity: Plasticizer solution viscosity at 20°C, 2) Plasticization efficiency: 50PHR sheet and 80P
DO calculated from surface hardness measurements using HR sheet
The amount of plasticizer used to achieve the same hardness as the surface hardness of P50PHR was defined as the plasticization efficiency value. 3) The values listed in parentheses are boiling point values obtained by distillation under reduced pressure. Anything not listed is a plasticizer obtained as a distillation residue at 250° C./1 mmHg. 4) Softness temperature: Measured temperature for 50PHR sheet according to JIS standard. 5) Electrical resistance: Surface electrical resistance value of 80PHR molded sheet, 6) Heating loss: 50PHR molded 1mm sheet at 160℃
The sample was placed in a hot air circulation heating furnace, and the % loss on heating after 2 hours was measured. 7) PE: % migration weight loss from a plasticized sheet by crimping a polyethylene sheet at 10 kg/cm2. 8) Gasoline: After dipping in gasoline at 60°C for 48 hours and drying for 24 hours, the % elution loss was measured. same as below. Examples 8-11, 13-16 and 17-20 Monohexyl ether of ethylene glycol or diethylene glycol
(8-11), mono-2-ethylhexyl ether (13-16), or monobenzyl ether (17-
20) Using 2 molar equivalents of each, add the theoretical amount of butanol produced by transesterifying a mixture with 1 mol of dibutyl adipate or dibutyl phthalate at 160-200°C under reduced pressure using a titanium catalyst. After the reaction is completed and the catalyst is deactivated, decatalyzed, washed with alkali, and washed with hot water according to conventional methods, the volatile matter is removed under reduced pressure, and the product obtained mainly as a residual liquid is removed. The properties and results when used as a plasticizer are shown in Table 2 (
8-11), Table 3 (13-16), Table 4 (17-2
0). Example 12 1 mole equivalent of 102 g of diethylene glycol monohexyl ether was added to 390 g of 1 mole of DOP to carry out a transesterification reaction. The reaction solution was treated in a conventional manner and then distilled under reduced pressure to separate the fractions at 180-200℃/0.6mmHg and 200-225℃, and the gas chromatograph analysis results for each showed that the former was DOP and hexyl ethylene. Oxyethyl 2-ethylhexyl phthalate is a 53:47 mixture with HEEOP, the latter being a 62:38 mixture of HEOP.
It was a mixture of EOP and DEEOP. Examples 21-22 Transesterification reaction was carried out by adding 65 g 0.6 mol of ethylene glycol monobenzyl ether or 0.6 mol 91.2 g and 109 g 0.72 mol of diethylene glycol monobenzyl ether to 0.6 mol 234 g of DOP. After obtaining a product, volatile components were removed at 250° C./0.5 mmHg to obtain BzEOP and BzEEOP. These ester mixtures are also not pure described compounds;
Although they were mixtures with diesters, their properties are listed in the table.
Table 2 Abbreviations
Formula 1) Viscosity 2) Plasticization efficiency 3) Boiling point Example 8 DHEA (A-
1,R:C6H13 n=1) 19 48
．． 5 215-225/1mmHg Example 9 DHEEA (A-1,R:C6H13
n=2) 27 48.0 Example 10 DH
EP (A-2, R:C6H13 n=1) 68
51.1 Example 11 DHEEP (A-2
, R:C6H13 n=2) 78 54.
7 Example 12 HEEOP (C-2,R:C6H13
n=2) 95 51.0
HEEOP-DHEEP (62:38)
108 49.7
4) Softness temperature 5) Electrical resistance 6) Heating loss 7) P
E 8) Kasoline Example 8-49.3
1.0X108 14.45
4.26 17.60 Example 9-4
4.3 9.8X108 7.38
2.34 17.41 Example 10
-24.3 1.1X1010 5.
83 6.44 14.91 Example 11
-27.3 4.7X109
4.37 3.43 13.23 Example 1
2 -23.3
8.14 14.91
-24.8
5.74
14.00
Table 3
Formula 1)
Viscosity 2) Plasticization efficiency 3) Boiling point Example 13 DOE
A (A-1, R: C8H17 n=1) 38
57.2 210-220/0.
5mmHg Example 14 DOEEA (A-1, R:C
8H17 n=2) 54 58.9 Example 15 DOEP (A-2,R:C8H17 n=1
) 67 60.5 Example 16 DOEE
P(A-2,R:C8H17 n=2) 122
62.3 4) Softening temperature 5
) Electrical resistance 6) Heating loss 7) PE 8) Kasoline Example 13 -47.8 3.3X
109 11.23 6.30
17.60 Example 14-38 3
．． 7X109 4.82 3.42
15.0 Example 15 -27.8
2.5X1010 4.72 5.4
2 17.9 Example 16 -29.3
6.5X109 3.20 3
．． 16 17.9
Table 4

1) Viscosity 2) Plasticization efficiency Example 17
DBzEA (A-1, R:C7H7 n=1)
85 49.3 Example 18 DBzEEA(
A-1, R: C7H7 n=2) 129
55.4 Example 19 DBzEP (A-2, R:C
7H7 n=1) 464 58.1 Example 20 DBzEEP(A-2,R:C7H7 n=2
) 322 62.3 Example 21 BzE
OP (C-2,R:C7H7 n=1) 268
54.4 Example 22 BzEEOP(C-2
, R:C7H7 n=2) 121 52.
5 BzEEOP(C-2,R
:C7H7 n=2) 243 54.7
4) Softness temperature 5) Electrical resistance 6
) Heating loss 7) PE 8) Kasoline Example 17
-21.3 4.3X1010
4.58 1.59 10.25 Example 18 -21.5 3.6X1010
4.45 1.08 6.9
9 Example 19 -4.3 1.8X1
012 3.06 1.02
4.84 Example 20 -4.3 3.
5X1011 3.40 0.69
-0.25 Example 21 -4.5
2.6X1012 3.10
14.90 Example 22 -5.5
2.1X1011 9.64
9.38
-8.0 3.
25 5.41 Example 2
3 Products BEEDOTm and DBEEOT obtained by performing a transesterification reaction using 1 molar equivalent of trimellitic acid trioctyl ester and adding 1 molar equivalent or 2 molar equivalents of diethylene glycol monobutyl ether
The properties of the product BDEEOTm, also obtained using 1 molar equivalent of triethylene glycol monobutyl ether, are shown in Table 5.
Table 5
1) Viscosity
2) Plasticization efficiency example 23 BEEDOTm (A-2
', R: C4H9 n=2) 250 59.8 Example 24 DBEEOTm (A-2', R: C4H9
n=2) 201 56.5 Example 25 BDE
EOTm (A-2', R:C4H9 n=2) 25
0 59.4 4) Softness temperature 5) Electrical resistance 6) Heating loss Example 23 -17.
3 6.3X1011 1.71 Example 24 -14.8 0.8X1011
1.49 Example 25 -15.5
2.9X1010 1.87 Examples 26-27 Using 1, butanediol bisbutyl adipate, which is a composite ester, as a raw material at 220-225°C/0.5 mmHg, 183.2 g of 0.4 mol thereof and diethylene glycol monobutyl ether A mixture of 130 g of 0.8 mole or 0.8 mole of ethylene glycol monobenzyl ether and 86.4 g of ethylene glycol monobenzyl ether was subjected to a transesterification reaction using a titanium catalyst and treated in the same manner as described above to obtain a distillation residue. The products BEEAXAEEB and BzEAXAEBz were obtained. Example 28 3 moles of 1,3-butanediol 4 moles of adipic acid 2 moles of butanol and an excess of 2 moles of butanol obtained by dehydration esterification reaction.
A polyester mixture with a terminal butyl group produced with the aim of m = 3 (HPLC results are a mixture of polyesters from n = 1 to n = 11) 0.2 molar equivalent (molecular weight 85
43.2 g of ethylene glycol monobenzyl ether (0.4 molar equivalent) was added to 172 g of ethylene glycol monobenzyl ether (as No. 8), and a transesterification reaction was carried out to obtain the product BzEAXAEBz. Example 2
The results of 6-28 are shown in the table below.
Table 6
1) Viscosity 2) Plasticization efficiency Example 26 BEEAXAEEB
(C-1,R:C4H9 n=2) 192
48.9 Example 27 BzEAXAEBz (C-1
, R:C7H7 n=1) 233 52.
2 Example 28 BzE(AX)3AEBz(C-1:
n=2) 611 61.4 Control Example 3 13BBBA
46 40.0
4) Softening temperature 5) Electrical resistance 6) Heating loss 7) PE 8) Kasoline Example 26-2
6.0 3.9X109 4.74
1.26 10.20 Example 27
-15.8 1.9X1010 3.
15 0.88 5.56 Example 2
8 -11.5 2.5X1010
2.0 0.71 Control example 3
-30.0 3.5X109 5.0
2 7.99 14.77 Example 29 Monomethyl and monoethyl ether of ethylene glycol, diethylene glycol and triethylene glycol
Similar diesters were prepared using DBP and DBA.
I made more. The products are in particular adipate esters and D
EEP has a high solubility in water, and when washed with water, the yield was significantly reduced, and when used as a plasticizer, the plasticizer oozed out onto the surface of the plasticized sheet. Among them, DEDE
The viscosity of EP is 116CP, and the plasticization efficiency is 51.9, which is 80P.
In the case of the HR sheet, the plasticizer leached out onto the surface, but no leaching was observed in the case of 50 PHR. Summary of starting materials and products for the examples
starting material
Product formula No.
．． Ester component Ether component
1 H9C4OCO(CH2)4COOC4H9
HO(C2H4O)1C4H9 BuO(C2
H4O)1COACOO(C2H4O)1Bu2H
9C4OCO(CH2)4COOC4H9 HO(C
2H4O)2C4H9 BuO(C2H4O)2
COACOO(C2H4O)2Bu3H9C4OC
O(CH2)4COOC4H9 HO(C2H4O)
3C4H9 BuO(C2H4O)3COACO
O(C2H4O)3Bu4 H9C4OCOC6H4
COOC4H9 HO(C2H4O)1C4H9
BuO(C2H4O)1COPhCOO(C2
H4O)1Bu 5 H9C4OCOC6H4COOC
4H9 HO(C2H4O)2C4H9
BuO(C2H4O)2COPhCOO(C2H4O)
2Bu 6 H9C4OCOC6H4COOC4H9
HO(C2H4O)3C4H9 BuO(
C2H4O)3COPhCOO(C2H4O)3Bu
7 H17C8OCOC6H4COOC8H17 H
O(C2H4O)2C4H9 BuO(C2H4
O)1COPhCOOC8H17 8 H9C4OCO
(CH2)4COOC4H9 HO(C2H4O)1
C6H13 HxO(C2H4O)1COACOO
(C2H4O)1Hx 9 H9C4OCO(CH2)
4COOC4H9 HO(C2H4O)2C6H13
HxO(C2H4O)2COACOO(C2H4
O)2Hx10 H9C4OCOC6H4COOC4H
9 HO(C2H4O)1C6H13 Hx
O(C2H4O)1COPhCOO(C2H4O)1H
x11 H9C4OCOC6H4COOC4H9
HO(C2H4O)2C6H13 HxO(C2
H4O)2COPhCOO(C2H4O)2Hx12
H17C8OCOC6H4COOC8H17 HO(
C2H4O)1C6H13 HxO(C2H4O)
2COPhCOOC8H17

HxO(C2H4O)2COPhCOO(
C2H4O)2Hx13 H9C4OCO(CH2)4
COOC4H9 HO(C2H4O)1C8H17
OcO(C2H4O)1COACOO(C2H4O
)1Oc14 H9C4OCO(CH2)4COOC4
H9 HO(C2H4O)2C8H17 OcO
(C2H4O)2COACOO(C2H4O)2Oc1
5 H9C4OCOC6H4COOC4H9 H
O(C2H4O)1C8H17 OcO(C2H4
O)1COPhCOO(C2H4O)1Oc16 H9
C4OCOC6H4COOC4H9 HO(C2
H4O)2C8H17 OcO(C2H4O)2C
OPhCOO(C2H4O)2Oc17 H9C4OC
O(CH2)4COOC4H9 HO(C2H4O)
1CH2C6H5 BzO(C2H4O)1COACO
O(C2H4O)1Bz18 H9C4OCO(CH2
)4COOC4H9 HO(C2H4O)2CH2C
6H5 BzO(C2H4O)2COACOO(C2H
4O)2Bz19 H9C4OCOC6H4COOC4
H9 HO(C2H4O)1CH2C6H5 B
zO(C2H4O)1COPhCOO(C2H4O)1
Bz20 H9C4OCOC6H4COOC4H9
HO(C2H4O)2CH2C6H5 BzO(C
2H4O)2COPhOO(C2H4O)2Bz21
H17C8OCOC6H4COOC8H17 HO(
C2H4O)1CH2C6H5 BzO(C2H4O)
1COPhCOOC8H1722 H17C8OCOC
6H4COOC8H17 HO(C2H4O)2CH
2C6H5 BzO(C2H4O)2COPhCOOC
8H17
BzO
(C2H4O)2COPhCOOC8H1723 C6
H3(COOC8H17)3 HO(C2
H4O)2C4H9(1) BzO(C2H4O)2C
OC6H3 (COOC8H17) 224 C6H3 (C
OOC8H17)3HO(C2H4O)
2C4H9(2) (BzO(C2H4O)2CO)2
C6H3COOC8H1725 C6H3(COOC8
H17)3HO(C2H4O)3C4H
9(1) BzO(C2H4O)3COC6H3(CO
OC8H17) 226 BuOCOACOOXOCOA
COOBu HO(C2H4O)2C4H9
BuO(C2H4O)2OCOACOOXOCOAC
OO-
-(C2
H4O)2Bu27 BuOCOACOOXOCOAC
OOBu HO(C2H4O)1CH2C6H5
BzO(C2H4O)1OCOACOOXOCOACO
O-
-(C2H
4O) 1Bz28 BuOCOACOOXOCOACO
OXO- HO(C2H4O)1CH2C6H5 B
zO(C2H4O)1OCOACOOXOCOACOOO
XO- -COACOOXOCOACOOOBu
-COA
COOXOCOACOO(C2H4O)1Bz29H
9C4OCOACOOC4H9 HO(C
2H4O)1-3CH3 MeO(C2H4O)1
-3COACOO-

-(C2H4O)1-3Me H9C4OCO
ACOOC4H9 HO(C2H4O)1
-3C2H5 EtO(C2H4O)1-3COAC
OO-
-(C2
H4O)1-3Et H9C4OCOPhCOOC
4H9 HO(C2H4O)1-3CH3
MeO(C2H4O)1-3COPhCOO-

-(C2H4O)1
-3Me H9C4OCOPhCOOC4H9
HO(C2H4O)1-3C2H5 EtO
(C2H4O)1-3COPhCOO-

-(C2H4O)1-3Et Examples and general formula {R(OCH2CH2)mOCO}iY{
Relationship with symbol definition of CO(OCH2CH2)nOR'}j. No. R m i Y n R' j
No. R m i Y n R
' j 1 Bu 1 1 A 1 B
u 1 17 Bz
1 1 A 1 Bz 1 2 Bu
2 1 A 2 Bu 1
18 Bz 2 1 A
2 Bz 1 3 Bu 3 1 A
3 Bu 1
19 Bz 1 1 Ph 1 Bz
1 4 Bu 1 1 Ph 1 Bu
1 20 Bz 2
1 Ph 2 Bz 1 5 Bu
2 1 Ph 2 Bu 1
21 Bz 1 1 Ph
0 Oc 1 6 Bu 3 1 Ph
3 Bu 1 22
Bz 2 1 Ph 0 Oc 1
7 Bu 1 1 Ph 0 Oc 1
Bz 2
1 Ph 0 Oc 1 8 Hx 1
1 A 1 Hx 1
23 Bz 2 1 Tm 0
Oc 2 9 Hx 2 1 A 2
Hx 1 24
Bz 2 2 Tm 0 Oc 110
Hx 1 1 Ph 1 Hx 1
25 Bz 3 1
Tm 0 Oc 211 Hx 2 1
Ph 2 Hx 1
26 Bu 2 1 P1 2 B
u 112 Hx 2 1 Ph 0
Oc 1 27 Bz
1 1 P1 1 Bz 1 H
x 2 1 Ph 2 Hx 1
28 Bz 1 1 P
2 1 Bz 113 Oc 1 1
A 1 Oc 1
29 Me 1-3 1 A 1-3 Me
114 Oc 2 1 A 2 Oc
1 Et 1
-3 1 A 1-3 Et 115 Oc
1 1 Ph 1 Oc 1
Me 1-3 1 Ph
1-3 Me 116 Oc 2 1 Ph
2 Oc 1
Et 1-3 1 Ph 1-3 Et 1
(Bu=butyl, Hx=hexyl, Oc=octyl, P
h=phthalic acid residue, Me=methyl, Et=ethyl)

Claims (5)

[Claims] Claim 1: a) C1 to C of phthalic acid or adipic acid
8 alkyl ester, b) C5-C6 aliphatic saturated dicarboxylic acid and formula HO-X-
Formula R, in which both dicarboxylic acid ends of an ester dicarboxylic acid having repeating units 1 to 15 are esterified with a monohydric alcohol at the dicarboxylic acid ends formed by polymerization with diol of OH.
”O{CO(CH2)3-4COOXO}kCO(CH
2) 3-4COOR" (wherein X is an unsubstituted or lower alkyl-substituted ethylene group or a polymethylene group up to C4, or a residue of diethylene glycol or dipropylene glycol, and R" is a lower is alkyl, k
is an integer from 1 to 15); and c) octyl trimellitate ester. Adding 1 to 2 equivalents of mono(C1-C16) alkyl or benzyl ether and carrying out the transesterification reaction under reduced pressure in the presence of an alkoxytitanium or a solid polytitanic acid catalyst made from alkoxytitanium to produce an exchanged The general formula {R(OCH2CH2)mOC
O}iY{CO(OCH2CH2)nOR'}j
(A) [In the formula, R and R' are the same or different,
independently a C1 to C16 alkyl group or a benzyl group, m is an integer of 1 to 3, and n is an integer of 0 to 3, provided that when n is not 0, m = n, i and j are integers of 1 to 2, provided that i+j is 2 or 3, and Y is a phthalic acid residue, an adipic acid residue, a trimellitic acid residue, or the ester dicarboxylic acid. a residue, provided that i+j is 3 when Y is a trimellitic acid residue. Claim 2: Ethylene glycol, diethylene glycol, or triethylene glycol mono(C
2. The process as claimed in claim 1, wherein 1-C8) alkyl ethers are used. 3. Butyl of ethylene glycol, diethylene glycol or triethylene glycol,
2. A process according to claim 1, wherein hexyl, octyl or benzyl ether is used. [Claim 4] 1,3- or 1,4-butanedio-
ethylene glycol, and their alkyl-substituted diols, or ether alcohols such as diethylene glycol, propylene glycol, and dipropylene glycol, dibasic acids such as adipic acid or glutaric acid, and terminal alcohols. 2. The process as claimed in claim 1, wherein the complex ester or polyester, preferably made from butanol, is used as the alcohol. [Claim 5] General formula {R(OCH2CH2)mOCO}iY{CO(O
CH2CH2)nOR'}j (A) [In the formula, R and R' are the same or different, and independently C1 to C16
It is an alkyl group or a benzyl group, m is an integer of 1 to 3, and n is an integer of 0 to 3, provided that when n is not 0, m=n, and i and j are 1 An integer of ~2, provided that i+j is 2 or 3,
Y is a phthalic acid residue, an adipic acid residue, a trimellitic acid residue, or repeating at the dicarboxylic acid terminal formed by polymerization of a C5-C6 aliphatic saturated dicarboxylic acid and a diol of the formula HO-X-OH. Units 1 to 15, formula -{CO(CH2)3-4COOXO}kCO(CH2
)3-4CO- (wherein, is an integer of ), provided that when Y is a trimellitic acid residue, i+j is 3]
A plasticizer consisting of an ester having a terminal ester of an alkyloxyethylene glycol having the following.