WO2003055842A1

WO2003055842A1 - Process for producing composite mixed ester

Info

Publication number: WO2003055842A1
Application number: PCT/JP2002/006083
Authority: WO
Inventors: Satoshi Matsumoto
Original assignee: Japan Science And Technology Agency
Priority date: 2001-12-25
Filing date: 2002-06-18
Publication date: 2003-07-10
Also published as: KR20040058190A; CN1285564C; KR100619575B1; JP3907470B2; JP2003183372A; CN1608046A; TW588043B

Abstract

A process for producing a composite mixed ester suitable for use as a plasticizer having improved nonvolatility as compared with dibasic acid diesters which have excellent general-purpose plasticizer properties and have been used in a large amount but have come to be regarded as endocrine disruptors. The mixed ester is equal to the dibasic acid diesters in production cost and performance even when it contains none of these diesters. Also provided is a composition. Dibasic-acid diesters volatilize according to their vapor pressures, while polymers have nonvolatility and reduced toxicity according to their molecular weights. However, polymers have poor plasticizer performance. Although composite esters having an intermediate molecular weight may meet the requirement, they are difficult to produce and have poor profitability. The process comprises subjecting acids, a diol, and a terminal alcohol to dehydrating esterification and subsequently subjecting the excess alcohol to transesterification. Thus, a composite mixed ester is advantageously produced, which is a composition represented by (R(PX)1-2(AX)n-1AR) and which contains residues of the two dibasic acids bonded in such a manner that one or two residues of one of the acids and one or two residues of the other occur alternately.

Description

Method of producing heterogeneous composite ester

The present invention relates to a process for producing a heteroconjugate ester. Here, the compound ester is represented by a composition formula of R (AX) nAR (where n represents a positive number of 1 or more), and in this formula, a compound ester corresponding to n = l, COMPLEX ESTER (R AXA In contrast to R), it can be considered as a concept of love as COMPOSITE ESTER. Prior art

Hereinafter, in the present specification, R and O each represent a monohydric alcohol (for example, kactanol), and A and P each represent a dibasic acid (for example, A is adipic acid and P is a phthalic acid). X) represents a diol (for example, ethylene glycol or propylene glycol). Description of unreacted terminal groups (hydroxyl group and carboxyl group) in these and ester bond in the product in which they are esterified is omitted. There may be a risk.

Complex esters are generally obtained by the reaction of diol dibasic acid-terminated monohydric alcohols of the composition, and they are produced as a mixture of compounds having different degrees of polymerization where n = 1 to 7, and the ratio is the degree of polymerization It is manufactured as a mixed composition whose amount decreases in proportion in series as the number increases. As for the composition, its distribution varies depending on the production method in particular, so the composite ester produced by controlling the distribution should be regarded as a different composition from that produced without consideration. Control the characteristics of the product.

The present invention is a method of improving the method for producing a different type of complex ester (JP-A-7-330664) and reducing the width of its distribution (Japanese Patent Application No. 2 0 0 1-1 1 9 2 5) 2) To propose a method of production with the aim of preventing the formation of the by-produced dibasic acid diester RAR or RPR completely by adopting only 2), or in a very small amount. Two different dibasic acids produced, adipic acid, HOCOACOOH And a method for producing the general formula R (PX) ₂ (AX) ₀ ^ AR by using phthalic anhydride P (CO) ₂₀ or other succinic anhydride S (CO) ₂₀ etc. The present invention relates to heterogeneous compound esters produced in

Regarding control of molecular weight distribution of ester and formation of diester, consider first the ester reaction of three components (R, A, X):

2 {R + A + X + A + R} → 2 RAXAR (1)

{R + A + X + A + X + A + R} + {R + A + R} → R {AX} ₂ AR + RAR (2)

(1) According to the formula, 4 moles of acid A and monoalcohol R and 2 moles of diol X produce 2 moles of n = 1 (1), but in the same number of moles the reaction of formula (2) When n occurs, n = 21 moles and 1 mole of diester are formed. The reactions of (1) and (2) occur simultaneously, so even if the reaction is conducted for the purpose of (1), an amount of RAR corresponding to the number of n will always be produced. Since this by-produced diester can be produced by an amount which deviates from the target degree of polymerization, the degree of polymerization corresponding to the diester can be obtained. If the control of molecular weight distribution can therefore suppress the formation of diester and can eliminate it, the product of the target molecular weight polymerization degree can be obtained, and the dispersion of the polymerization degree is already 2 or less. An application was filed (Japanese Patent Application 2001-11925 2).

The method has problems with the reaction mode and the amount of alcohol used in excess during Ethenollich. If ROH is used in excess, the ester exchange reaction also proceeds simultaneously with the esterification reaction, and the terminal of the polyester once formed The reaction of ROH produces RAR, so that the target degree of polymerization can not be obtained. The present invention was found to be capable of controlling the degree of polymerization by limiting the amount of R0H used, and the conditions such that the complex ester and the ester alcohol coexist. By carrying out esterification in this way, it became possible to produce polyesters with a molecular weight distribution of 2 or less.

It has been thought that the value of n is small and it is possible to reduce the RAR by-product but it is impossible to prevent it completely, in the case of the complex complex ester, but the reaction molar ratio should be well controlled and reacted. In particular, it is possible to produce a product of the desired degree of polymerization according to a preparation process which does not use more than the necessary ROH, in particular using the above-mentioned active catalyst and RAR It became possible to prevent by-products.

In the above patent application, an excess amount range was defined as 0.2 to 2 times the theoretical amount, but even at a low rate, the reaction proceeds sufficiently in particular when the active catalyst (Japanese Patent Application No. 2000-147554) is used Useful esters are found to be produced and are therefore also relevant to the use of the invention. With regard to the prevention of the generation of by-product diester, transesterification has been carried out from the perspective of the prior art that it has been produced in such a large amount that it can be targeted for low polymerization esters for the reasons already described, and can not be completely eliminated. As a general method, we proposed a method that can produce different types of complex esters by the following method (Japanese Patent Application No. 2000-147554). ROH + P (CO) 20 → RPH → + HOXOH → RPXOH

2ROH + HOCOACOOH → mRAR → + RPXOH → R (PX) nAR + ROH + + RAR (3) That is, the above-mentioned reaction formula is made to react the phthalic anhydride and the monoalcohol, and then the diol is reacted by Partially forms ester alcohols of phthalic acid, including compound esters. This is added to an excess amount of adipic acid diester prepared separately to carry out an alcohol transesterification reaction to obtain a product, and the remaining excess diester RAR can be distilled off to produce a heterocomposite ester. (Equation (3)). At this time, if the amount of RAR in the transesterification reaction is small, the degree of polymerization of the product rises and the viscosity becomes high, and for the purpose of an excellent plasticity ester, using about 2.5 molar amount, for example, the diol component is 1 For 2-propanediol, a low viscosity 450 centipoise heterogeneous composite ester product is produced with an excellent degree of polymerization of about 1.4. The component formula from the method of preparation is that terminal alcohol R0 H is recorded as 0 (PX _p ) _1-4 AO in kactanol 00H, but as a component of the polymer the incorporation of R (PXPX) AR and RPXPR due to its method of preparation Is considered. In addition, although the inventor of the present invention could not prevent the by-production of the diester in the dehydration esterification reaction of the hetero-type composite ester, the composition would be deviated from the purpose by producing it on the premise of its production. They were manufactured and evaluated for their performance and found to have excellent properties, and a patent application for use as a plasticizer was made (JP-A-7-3306 74). However, because of the large removal requirement of RAR, there is a need for a manufacturing technology that reduces the amount of by-product RAR. Problem that invention tries to solve

The composite ester is conventionally obtained as a composition having a distribution of polymerization degree and contains a highly polymerized composition, so that particularly in the case of a phthalic acid composite ester, the viscosity is high and the plasticization efficiency extremely deteriorates when used as a plasticizer. The compound ester of PXAX composition equivalent to the copolymerization of phthalic acid and adipic acid was studied for the purpose of a low plasticizer and excellent plasticizer, but the production method free of byproducts with a high degree of polymerization was not possible, especially the high degree of polymerization. The dibasic acid diester can be produced as a by-product of degree of removal, and removal of the diester is necessary. Removal of the phthalate results in deterioration of the product acid number due to thermal decomposition. It has become. Both are used as superior plasticizers and low viscosity additive processing aids. Plasticizers that are regarded as problems of environmental hormones are required. In the production of these complex esters, when producing a composition that does not contain n = 3 or more high molecular weight oligomers, the terminal alcohol is efficiently reacted to form a low polymerization composition. It is considered that the terminal alcohol is an ester with an acid because a transesterification reaction results in a high polymer. When the ability to esterification was insufficient, the excess could not be controlled. The use of a particularly good catalyst has led to an understanding of the reaction, which has become a method of determining the reaction mode and producing an excellent composition. Means to solve the problem

That is, the present invention comprises a first step of reacting a first dibasic acid, an excess of a diol and a monohydric alcohol at a reaction temperature of 160 ° C. or lower (in this step, the main reaction is carried out at 1 to 2 minutes). (2) It is preferable to proceed approximately 3), 2) A second step in which a second dibasic acid and a monohydric alcohol are separately reacted at an equivalent ratio of approximately 1: 1 (this step is to remove the excess used diol) The reaction is preferably carried out under a reduced pressure of 0.2 to 1 mm Hg), the third step of reacting the products of the first step and the second step (in this step, additional reaction molar equivalents are added) It is preferable to carry out the dehydration esterification reaction using an excess of alcohol to the acid using a diol to lower the acid value sufficiently to carry out the esterification; Step 4) transesterification of the product under reduced pressure (this step is the production of the third step Remaining in response to excess during the addition E generated in Esuteruihi The purpose is to react sterol alcohol with the main component. The compositional formula R (PX) 卜₂ (AX). This method is a method for producing a heteroconjugate ester represented by ~ iAR (wherein R represents a monohydric alcohol, A and P represent a dibasic acid, and X represents a diol, and the description of the ester bond is omitted). This heterogeneous complex ester is subjected to a dehydration ester reaction between an excess of alcohol component and acid to acid to lower the acid value, and the ester alcohol mainly formed or remaining from the diol component corresponding to the excess amount. It is produced by transesterification with ester. In addition, the composition formula of the hetero compound composite indicates the ratio of the components, not the arrangement of the components.

In the present invention, the composition formula R (PX) ₂ (AX) O AR (wherein R represents a monohydric alcohol, A and P represent a dibasic acid, and X represents a diol, and the description of the ester bond is omitted). It is a hetero-complex ester represented by), which is a hetero-complex ester not having a PXPX structure. In addition, this different complex ester is represented by: RAR, 1 to 1 ^ and 18

X may not be included or may not be contained in a small amount.

The first dibasic acid is preferably adipic acid, and the second dibasic acid is preferably phthalic acid. The diol is preferably a difunctional alcohol having 2 to 6 carbon atoms or a polyalkylene glycol having 6 or less carbon atoms, for example, propanediol, 12,13,14-butanediol, and dipropylene Dariko. It is a mixed diol with nore. Embodiment of the Invention

The manufacturing method of the present invention will be described in each step.

First step: The dehydration esterification reaction of the first dibasic acid (A, for example, adipic acid) in the presence of an excess amount of diol (X) is usually carried out at a lower temperature (160 ° C. or less, preferably 140 to 150 °). C) will generate many AXs. Under these conditions, add monohydric alcohol (R) little by little and proceed the reaction. After the reaction of 2 ノ 3 to 3 4 proceeds, the catalyst is added, the temperature is raised, and the ester dehydration esterification proceeds at 190 to 210 to completely lower the acid value, and the first dibasic acid (adipine) Di-diesters (RA R) -free, diol diesters (XAX) and ester alcohols (RA) A mixed product consisting of X) is obtained. In this stage, unreacted diol (X) and monohydric alcohol (R) are removed because the pressure is usually reduced.

At this stage, R reacts preferentially to X, and the amount used determines the composition of the product. Excessive use X is removed under reduced pressure at a low temperature of 0.2-2 O mmHg. This temperature is determined by the pressure, and it is more effective to use as low a pressure as possible. However, if you try to completely remove X, XAX becomes de-XAXA and the degree of polymerization increases, and under normal conditions, it is formed ^ ^ ίΑΧ)) ^ It becomes ^ ^ and is not preferable.

Second step: Separately, an anhydride reaction of a second dibasic acid (P, for example, phthalic acid anhydride) and a terminal alcohol (R) is carried out approximately 1: 1 to produce a second dibasic acid (phthalic acid) To obtain the monoester (RP) of

Stage 3: The ability to add the Stage 2 product to the Stage 1 reaction system to continue the reaction or Add the Stage 1 product to the Stage 2 reaction and add the reaction When it is allowed to continue, the ester is formed by the reaction of the monoester (RP) of the second dibasic acid (phthalic acid) with the ester alcohol (RAX) and the diol diester (XAX) of the first dibasic acid (adipic acid). The reaction proceeds.

In this reaction, it is preferable to carry out the reaction of dehydrating esterification reaction with an acid and an alcohol in a reaction amount suitable for the target composition. The total alcohol equivalent is preferably 0.5 to 20% more than the acid equivalent. It is taken into the reaction system by transesterification of the plate. At this stage, the alcohol added to lower the acid value (specific example of diol addition second method) is esterified by the reaction with the acid to substantially eliminate the ester alcohol RPX or RAX is It remains in the esterification product together with the amount used in excess. Dehydration reaction, which produces an excess of alcohol equivalent to the acid equivalent, proceeds with an excellent reaction rate even at the end of the reaction, especially with active catalysts, and the acid reacts quantitatively. In the case of an ester mixture in which the acid value is not sufficiently lowered, the transesterification reaction in the next step does not proceed extremely.

Step 4: Further reducing the pressure of the reaction system subsequent to Step 3, the main products of Step 3 (RAXPR and RPXAXPR) and the ester alcohol remaining in Step 3 (esters produced by reaction with RAX) Products from all combinations with alcohols (RPXAX as well as RPX for X addition) can be made, but the reaction is mainly at the site of RA Is determined to take precedence. In this way, heterogeneous mixed esters (composition formula R i PXJ ^ iAXJ o ^ AR can be obtained, but most of them are main products. The ester alcohol of the transesterification reaction corresponds to the excess alcohol content. The amount of the product expected to be produced is RAXAXPR, RPXAXAXPR, RPX (AX) (^ AXPR, RAXPXAR, RPXAXPXAR, RPPXXAXPR etc., and their degree of polymerization is 2 and 3). However, phthalic acid in the whole molecule including these is prepared as a mixture having a composition of 1 to 2 adipic acid which also has a composition of 1 to 2. Particularly, the compound described in the final product of PXPX structure by-product is its Depending on the amount, the viscosity increases rapidly in response to the amount, but in transesterification, the reaction with RP is higher than the reaction with RA, because the reaction temperature is higher and those with RA structure are preferentially reacted. , RAXPR in the main products involved in the reaction As those large proportion of, ing a composition having a low viscosity.

In this composition, any composition is prepared by changing the composition ratio of phthalic acid and adipic acid, and the price of phthalic acid is lower than that of adipic acid. The more acid units, the more desirable the product.

According to the method of the present invention, it was possible to produce different complex esters, but by forming a different complex ester of mainly P XA X structure in which two kinds of acids are linked alternately, the degree of polymerization is high, the polyester structure is not included, The viscosity is as low as 400 to 60 centioise by producing a heterocomposite ester which has no or only a slight amount of sterically hindered PXPX structure such as phthalic acid. It was found to be a mixed ester of viscosity. In the case of linear dibasic acid esters containing a lot of phthalic acid, the volatility relative to the molecular weight of the phthalic acid diester when used as a plasticizer is completely resolved, and the plasticity has a somewhat higher viscosity. Is improved due to the structure and becomes equivalent to the diester, and the flexibility is combined with the linear dibasic acid adipic acid, and its water resistance is greatly improved, and the weather resistance due to phthalic acid is combined and an excellent plasticizer It became possible to use it.

The present invention is composed of four components of phthalic acid, adipic acid, difunctional diol and monohydric alcohol, which are expected to have excellent performance as a plasticizer, and mainly composed of two kinds of acids alternately joined to form a general formula W PX ^ ^ It relates to a heterogeneous complex ester represented by AX ^ AR. That is, It is obtained from a dibasic acid anhydride using an ester alcohol which is produced by partially reacting a diol diester of dipic acid and a terminal monoalcohol, and additionally adding a diol corresponding to the reaction molar amount. Reaction with a monoester produces a heterocomplexed ester and an ester alcohol, which are transesterified into the desired heterocomplexed ester. This method provides a highly efficient production method for producing a very small amount of acid diester which is a by-product, which can not be achieved with complex esters. General Formula R (PX) About AXi ^ AR Ri PX ^^ AO stands for an arbitrary mixture of RPXAXPA and RPXA0 (where AX i is the 100% purity of the force XAX described in the example) It is virtually impossible to manufacture, so it corresponds to its purity degree of polymerization and is a figure calculated with the AXAXA mixing ratio, and the corresponding increase in (AX) is: Zero is a perfect 100% theory It is a value that can be expressed as an increase in the percentage of AX in the ester mixture.

This composition contains a very small amount of high polymer, but as the whole composition, it means a composition made of 1 or more of phatalic acid and 2 or more of keadilipic acid in the molecule, and a composition containing almost no PXPX from its production method. is there. Such a composition is also possible by other methods described in this patent, particularly by the reaction rate and method, and the method is not particularly limited. We previously filed a method for obtaining a product containing PXPX structure but not containing (PX) ₃ or more by transesterification using RPX made from phthalic acid and terminal alcohol and diol (Japanese Patent Application No. 2000- 1 4 7 5 5 4). Furthermore, in the description of the same format as that of the present application as the hetero-complex ester, a composition of R (PX) m (AX) n AO m = 0.3 or more and n = 0.3 or less was filed (Japanese Patent Application Laid-Open No. 7-330664), The composition ratio of (PX) is not included at all, and it is shown that the performance of the composition having an average total composition ratio of 0.3 or more is evaluated to maintain excellent performance and water resistance. The composition of the present application may be in the range from the figure as a heterogeneous conjugated ester, but in the case of (PX) it is a complete heterogeneous conjugated ester including at least one or more random polymers, the former being described by polymers In contrast to the above, the composition of the present application relates to a composite ester composition mainly composed of alternating polymerization polymers. It has not been described in detail, as it was not possible to completely prevent by-production of the adipic acid diester by the dehydration esterification reaction followed by the transesterification reaction of the excess alcohol component according to the same procedure as the present application using RPX. Of the present application _{_{R (PX) 1. 2 (}} AX) 0. Not limited particularly also ₁ AR is manufactured manufacturing method thereof. Example

The present invention will be illustrated by the following examples, which are not intended to limit the present invention. The reaction at the laboratory scale is described below as an example for the preparation of CXPXp.sAO using 2-ethylhexanol (denoted by the symbols octalol, O or OOH) for the terminal alcohol.

1 mole (146 g) of adipic acid and 1, 2-propanediol (propylene glycol, abbreviated as HOX _p OH) 2. 5 moles (190 g, an excess of one required) to the dehydration ester reaction 1 The reactor was put into a three-necked L reactor, and nitrogen substitution was carried out under reduced pressure, then toluene as a small amount of 2 Oml of azeotropic solvent was added, and heating to 140 to 160 ^ was carried out with heating to initiate dehydrating esterification reaction. The esterification reaction is carried out by adding 0.5 mol (65 g) of 2-ethylhexanol in small portions during the outflow of 27 ml of water from the distillation of 9 ml of water, and the distilled diol is a reaction. The reaction was carried out while returning to the vessel. Since propylene glycol is distilled off azeotropically with water, one molar amount is excessive, and water distilled off azeotropically is a 30 to 40% aqueous solution. After completion of the addition, check for distillation of 27 ml of water, add 2 mmol (0.7 g of tetrabutoxytitanium) separately prepared titanium catalyst, raise the reaction temperature to 180 to 190 ° C, and continue the dehydration esterification reaction. After 1 to 2 hours, the reaction is completed, and the next reaction is performed.

Since excess propanediol is distilled off at 190 ° C., it is preferable to simultaneously measure the acid value, and preferably by high-performance liquid chromatography (HPLC), as well as the purity of the component diol esterene HOXpAX _P OH, and the ester alcohol 0AX _P 0H by measuring the residual amount of H0X _P 0H, obtain assumptions data during the next stage reaction. The target products are 0.5 moles of diol ester and 0.5 moles of ester alcohol. In this reaction, if the reaction of octanol is rapidly and rapidly added, the diester DOA is by-produced, so DOA is not generated! It is necessary to add to some extent. Furthermore, since AX, which is the reaction product of adipic acid and a diol, produces AXA or AXAX in a sequential reaction, it is necessary to carry out the reaction in the presence of an excess of X. Temperature for that control It is necessary to select a temperature of 140 to 160 ° C. where the down reaction proceeds slowly. This reaction is uncatalyzed with adipic acid and is a reaction for 2 to 4 hours. Since propanediol is rapidly distilled off by azeotropic distillation with water if it exceeds 150 ° C., the excess amount changes depending on the reaction temperature, and therefore, it is recycled after being calculated by correcting the distillate. To use. In the case where the amount of excess is small and the progress of the reaction is rapid, the diol diester polymer HO (XpA) nX _p OH is obtained, and the value of n rises to about 1.4, which can be confirmed by HPLC. On the other hand, the diol can be removed under reduced pressure from the reaction product, and the value of n polymerization degree can be calculated by calculation from the weight of the remaining product. Concentration under reduced pressure gives a theoretical weight of the residual product of 2 8 9 g, which gives an approximate product. However, at 2 8 5 g, the composition is a mixture of 0.5 AXOH and 0.4 4 7 HO (XA) ^ ^ ΧΟΗ Is calculated.

Formation reaction of iron oxide (second step reaction): 1.5 moles (222 g) of phthalic anhydride and 1.5 moles (195 g) of 2-ethylhexanol as a dilution solvent The anhydride reaction was carried out by stirring g at a temperature of 1000 ° C. or less for 3 hours. Although this reaction is an exothermic reaction and the product is monooctyl phthalate (abbreviated as OPH), the reaction temperature rises rapidly due to the heat generation during the reaction, and it is particularly notable if the amount of reaction does not result in dilution. It becomes more than ° C. The reaction at this high temperature is by-product of dioctyl phthalate D O P, which also affects the purity of the phthalic anhydride, but the anhydride and phthalic acid will remain. The residual anhydride causes a decrease in catalyst activity, but in the reaction with a diol, in particular, the phthalic acid diol diester HOXPXOH can be formed and PXPX can be formed in the next stage reaction, which may cause a viscosity increase. It is desirable that high purity OPH be obtained. The reaction amount of 0 PH is determined by the purity of the diol diester and ester alcohol.

OPH reaction liquid 1. 300 molar amount (490 g) is used and placed in a 2 L three-necked reactor, and the above 1 molar reactant of adipic acid is added with stirring and remaining anhydride and catalyst After the reaction, the catalyst solution of 2 to 5 millimoles is added. The activation catalyst is prepared by dissolving tetraalkoxytitanium in toluene, a small amount of propanediol, or octanol, adding and mixing a mixed solution of 4 to 20 times the molar amount of a water-soluble diol and water, An activated catalyst is produced (Japanese Patent Application No. 2 00-1 4 7 5 5 4). 1 9 0 2 1 When the dehydrating esterification reaction is carried out with O 2, the acid value decreases in the primary reaction, and its half life is 15 to 25 minutes. If the rate of decrease of the acid amount is slow and the reaction rate is stagnant, the degree of polymerization is high at the time of production of the diol diester, and the remaining diol is removed to lower the total alcohol concentration. The theoretical amount of OH is 0.1 molar excess from the reaction amount, and the reaction surely proceeds to form a low acid value ester mixture. Products with lowered acid value close the reflux opening and gradually reduce the pressure inside the vessel to remove distillate. The azeotropic addition toluene, the remaining volatile matter and the 2-ethylhexanol produced by the transesterification reaction are removed. The transesterification reaction proceeds corresponding to this removal, and the reaction is finally completed at a reactor temperature of 210 and a degree of vacuum of 2 to 1 mmHg, but for completeness, including the removal of by-product DOA 0 • It is preferable to lower the pressure to 2 mmHg, and mixing with volatiles is confirmed by heating and stirring under low pressure conditions.

The theoretical amount of octanol formed is the amount corresponding to the OH excess due to the diol, in this case 0.1 mol, and 13 g will be removed, 1.30 OPH + 0.45)) ^ ^ + The 0.50 response is

i) 0.35 ΟΡΧ (ΑΧ) 1 _ΡΟ ΟΡΧΑΟ + 0.50 + 0.10 ΑΧ (Λ) 1 _ΟΗ ΟΗ →

0.35 ΟΡΧ (ΑΧ) ₁ ΡΟ + 0.40 ΟΡΧΑΟ + 0.1 Λ (ΑΧ 0.45 1 _ΆΧΡ 0 ϋ) 0.45 0.45 (ΟΡΧ) ΑΧ _{: ι} + 0.40 0 + 0.1 ΟΑΧΟΗ →

Two reactions are expected: 0.45 ΟΡΧ (ΑΧ) ₁ ΡΟ + 0.30 ΟΡΧΑΟ + 0.1 の. Thus, the product is a mixture of at least 5 to 6 different complex esters as described, and if the transesterification proceeds sufficiently, the ester alcohol responsible for the product volatiles is completely gone.

On the other hand, D Α may be by-produced by the esterification reaction of adipic acid, but it is prevented under the above reaction conditions, and DOP can be prevented under good reaction conditions with anhydride and reaction conditions. . In the transesterification reaction, once generated butanol is reacted with the terminal ester of the product to produce DOP or DO A, ROH produced by the transesterification reaction does not react with the product again. As such, it is necessary to remove it quickly, and it is necessary to carry out transesterification under reduced pressure. This ester exchange reaction is preferentially performed at the AX or PX site of ester alcohols and esters. It is further understood that the reaction at the AX site is more easily reacted, and the viscosity of the product can be prepared as a correspondingly lower viscosity product.

The reaction product is cooled to 100 ° C., and a small amount of diluent and a small amount of water are added and stirred to hydrolyze the titanium, which is adsorbed by the addition of activated clay and filtered to remove the catalyst residue. The volatiles were then removed in vacuo to give 622 g of product, a viscosity of 210 centistokes and a viscosity of 21. The produced ester has no moles of DOA and DOP, and the number of moles of the reactant is the number of moles of adipic acid and n is the mole of phthalic acid mole / didipic acid mole, so that if the diester is not completely formed, the above The composition of the reaction product is expressed as c ^ PX ^ AO. Since the number of moles of the diol diester is low and the correction 0) _{_1.. 37} (^). .... A composition formula having a molecular weight of 0, 61 and a number of moles of 0,95 is calculated. The heterozygous complex ester to be produced is mainly an alternating complex ester, and the bond of the adjacent acid is a structure of PXA in the heteroacid, and in particular, the complex ester bond of phthalic acid alone represented by PXP is at least 700 centipoise. Since it becomes a highly viscous ester, the increase in the viscosity of the product can be controlled by minimizing its formation to make it a useful ester. On the other hand, in the production of diol diesters, OPXOH may be by-produced in the reaction with the remaining diol, and 0PXPX is produced in the transesterification reaction, so that it is a mixture with a complex ester having an 0AX end. In that case, it becomes 0 PXAX and can suppress the rise in viscosity. Therefore, the ratio of the diol ester of adipic acid to the ester alcohol used is 1: 1, but 9: 1 power, etc. may be 1: 9 and the amount of OPH reaction at the time of chewing is different. Using stoichiometric amounts and having a degree of polymerization of (PX) 1-2 as the composition of the product is a factor for obtaining the useful low viscosity product of the present invention.

However, if the degree of polymerization of (PX) n is 1 or less, monoesters of linear dibasic acids can not be selectively formed, and diester is by-produced and a removal step is required. Although it is possible to partially replace linear fatty acids with 0PH, it is possible to use anhydrides as monoesters. In this method, diol diester and estenoleanoleconone 1: 9 are prepared for the purpose of producing 0.1 HOXAXOH and 0.9OX0H as a reaction of 1 monole with OPH.

0. 1 OPXAXPO + 0. 8 OPXAO + 0. 1 OAXOH → 0.1 OPXAXPO + 0.7 OPXAO + 0.1 OPXAXAO or 0.1 OPXAXOH + 0.9 OPXAO → 0.1 OPXAXAXPO + 0.8 OPXAO The product of this reaction is a mixture of 4 to 6 kinds of products, and the composition is a product close to ΟίΡΧ. ^ Ο Will be obtained. In the actual reaction, even if the addition reaction of the terminal alcohol is strictly carried out in the production of the adipate alcohol, the partial formation of DO DO can not be prevented, and the removal is not necessary. The reaction mole number of the substance is less than the theoretical amount, and as a result, the value of n deviates by more than 1 and the OPH reaction amount also needs to be reduced. DOA needs to be removed, but it is a condition for producing volatile products.

As a second method, a method is employed in which the dehydration esterification reaction is carried out by using an excessive amount of OPH to be used and adding an equivalent amount of diol HOXOH. As an example of the above reaction, 1.6 moles of phthalic anhydride (237 g) and 2-ethyl hexanol (208 g) are used to prepare 1.6 moles of phthalic acid monoester 0PH, Using adipic acid ester prepared in the same manner, diorole ester 0.424

Add a 1 to 1 mixed reaction solution with 0.5 ester alcohol OAX _p OH (show the degree of polymerization by gravimetric method), start the dehydroesterification reaction in a 2 L reactor, and respond to the OPH excess The reaction is carried out using an additional 0.16 mol (12. 2 g) of 12-propanediol as the amount to be added, but additionally using 0.1 mol 7. 6 g of propanediol for the preparation of the activated catalyst. went. That is, 1.7 g (5 millimoles) of tetrabutoxytitanium is added to 7. 6 g and dissolved, and a mixture of 1 g of ethylene dallycol water and 1 g of water is added and an activation catalyst formed by stirring is added 160 The reaction proceeds at a half-life rate of 15 to 25 minutes when dehydrating ester at ~ 210 ° C and esterifying at the end with an additional 6.1 g of pupandiol as the acid value decreases. After 2 to 3 hours, the acid value can be reduced to 0.1 or less.

Then, the pressure in the reactor is reduced to 2 to 0.2 mmHg at the end to remove volatiles and to remove otatanol formed by the transesterification reaction. After confirming that DOA is free, the reaction is terminated. The product is cooled to 100 ° C., a small amount of water and a dilution solvent are added, the mixture is stirred, activated clay is added, the catalyst residue is adsorbed, the catalyst is removed by filtration and the catalyst is removed again. 675 g of product were obtained. Heterogeneous complex S obtained The viscosity of the tellurium is a low viscosity product of 520 centistokes at 2 and its plasticization efficiency is estimated to be 50 to 52 against the DO P 50 when used as a polyvinyl chloride plasticizer from the conventional experimental course As the characteristics of phthalate adipate, it can be judged from the previously reported results (described in JP-A-7-330684) that it can be used as a non-volatile plasticizer which is excellent in water resistance and weather resistance and hardly loses its volatility.

This reaction is

1.6 0PH + 0.42 H 0 X (XA) _{L 18} 0 H + 0.5 0 AX 0 H + 0.26 H 0 X 0 H →

In esterification

0.42 OPX (AX)! ₁₈ P0 + 0.5 0 PXA 0 + 0.26 0 PX0 H →

In the next stage exchange reaction

0.42 OPX (AX)! ₁₈ P0 + 0.24 0 PXA 0 + 0.26 0 PXAXP0 or

In esterification

0.32 OPX (AX)! ₁₈ P0 + 0.5 0 PXA 0 + 0.160 PX 0 H + 0.1 0 P (AX) i ₁₈ 0 H + 0.1 0 PXP 0 in the next stage exchange reaction

0.32 OPX (AX) _{L 18} AXP0 + 0.240 PXA 0 + 0.16 0 PXAXP0

In the lower reaction estimated according to + 0.1 0 P (AX) _{L 18} AXP 0 + 0.1 0 PXP 0, the product of the structure of (PXP) is formed, and the reaction can not be ignored, and the amount to test 0PH or H0X0H in excess is There is a limit. In the case of theoretical reaction, the product is a reaction of 1.6 mol and 1 mol, and its composition becomes 0 (PX) ₁₅ A0, but the compositional correction of the degree of polymerization of diol is 0) ₁₇₃乂₁₎ ) . ₀ ^ 0 Molecular weight 740 0. 92 It is calculated to be a monomer. The amount of 0PH used varies depending on the amount of alcohol added during adipic acid ester alcohol production, and when 0AX is large, the amount of 0PH and H0X0H corresponding to the excess amount of 0PX naturally becomes considerably larger than 0.1 molar amount . However, the product of the PXPX structure needs to be increased so that the viscosity does not increase rapidly.

Diorgesterl made from 1 mole of adipic acid and the product of ester alcohol 2 to 8 and 1.8 mole of diol corresponding to 1 .8 mole fatty acid monoester are added with 1 mole of complex ester Ester alcohol is dehydrated when 0.6 mol is made and the esterification reaction is an excess of alcohol in the amount of 0.6 mol, and the acid is completely esterified, Transesterification will then yield ( _{0 (} p _{X) 18} A ₀₎ . The desired product is OPXAXPO, but partly because of OPXPXAXPO, the viscosity of the product is somewhat higher.

(0.2 XAX + 0.8 0 AX) + (1.2 0 PH + 0.6 0 PH) + 0.6 H 0 X 0 H →

0.2 0PXAXP0 + 0.8 0PXA0 + 0.60PX → 0.8 0PXAXP0 + 0.2 0PXA0

The heterogeneous complex ester of the present invention represented by the formula R (PX) ^ ₂ AR according to the present invention, which partially contains PXP and byproducts such as DO A or DOP at the time of production, is described (3) According to the formula, it can be made by transesterification of adipic acid diester with RPX, in which case (PXPX) is by-produced, so it is necessary to use a large excess of diester, and its recovery cost is a problem. The present invention is characterized in that it can not be made into diesters but can be made in extremely small amounts, but it can also be produced by the method described in the next step using the method of the present invention. It can not be carried out strictly, and even if the reaction is carried out for the purpose, the by-product of the diester can not be prevented since it becomes a mixture of diester and unreacted adipic acid. In the reaction of adipic acid and a monohydric alcohol which becomes a terminal alcohol under normal conditions, the product is a monoester, a diestenole, and an unreacted acid of about 1/3 monole each. Although the conditions of the specific product are not described based on the above results, the ester formula formed as an esterified byproduct according to the method of the present invention according to the following formula is subjected to a transesterification reaction to give a composition formula R (the target product PX) Complex esters of ^ aAR can be produced.

About the first stage adipic acid

3 H 0 C 0 (CH ₂ ) ₄ C 00 H + 3 R 0 H → H 0 C 0 AC 00 H (abbreviated as A) + RAH + RAR

About the second stage phthalic acid

P (C0) ₂ 0 + 匪 → RPH

RPH + H0X0H → RPX0H (or RPX)

(3) Removal of RPX0H In order to prevent the formation of R (PXPX) 0H by R0H, the phthalic acid ester alcohol formed by removing excess alcohol under reduced pressure (0.3 匪 Hg) is used. When dehydrating esterification reaction is performed using 10% excess

3.3 RPX + A + RAH + RAR → RPXAXPR + RPXAR + RAR + 0.3 RPX

Next, when transesterification is performed → RPXAXPR + 0.7 RPXAR + 0.3 RPXAXPR + RAR

1. 3 RPXAXPR and zero. 7 can mixed composition R (PX) mixture of _1-65 AR 2 moles with one mole of RAR and RPXAR the above reaction.

In this reaction, the diol may be reacted first to produce RPX using excess alcohol, and either method can partially reduce PXPX, resulting in a somewhat higher viscosity of the product. On the other hand, even if the temperature is changed to suppress the by-product of the RAR diester in the first step reaction, the by-product of the RAR diester can not be completely prevented, but the by-product amount of the RAR diester is reduced. I can do it.

The present invention relates mainly to a method for producing a heterogenous composite ester having a structure in which adipic acid and phthalic acid are alternately bonded, and the composition is mainly a method for producing a composition of W PX ^ AO. In particular, it is difficult to quantitatively produce diol ester and ester alcohol in the reaction of adipic acid, in particular, the reaction conditions, temperature conditions, and the product composition differ depending on the reaction amount, and the volatility of the diol component during production is It greatly affects. 12-Propanediol is the most industrially inexpensive and useful power S, easy to azeotropic distillation, difficult to control the composition of the product. In contrast, dipropylene glycol, 2-ethyl 13-hexanediol, and 16-6-hexanediol are less volatile and are easier. It is necessary to consider the volatility of 12-, 13-, and 14-butanediols, and ethylenedalicol requires the use of a large excess like propanediol. It is also practically possible to use a diol component in combination with a diol corresponding to the purpose of use. The use of the terminal alkyl alcohol is not particularly limited to 2-ethyl, xanol, and may be various alcohols prepared by the ortho method as well as mixed compositions. The method of this reaction is a method that effectively utilizes a dibasic acid monoester using phthalic acid anhydride and can be applied to other maleic acid, oxalic acid and hydrophthalic acid, and partially fatty acids. May be mixed and used.

When using plasticizers, DOA is easily volatilized but used as a low viscosity specification. In addition, DOP volatilizes in 4 weeks at 70 to 80 ° C, and in outdoor type films volatilizes almost half in 1 year, but has been used as a useful high plasticizing plasticizer. It may also be used as a processing diluent for polyester plasticizers. When it is used as a non-volatile plasticizer, partially mixed use of D OA and DOP actually increases the loss of volatilization but mostly remains and is used as a non-volatile plasticizer. There are no practical problems with residual DOA and DOP as minor components. Therefore, a small amount of ROH is used as an excess as a production method, and the reaction molar ratio is strictly controlled. It is not limited to the products to be However, if D.sub.OA and D.sub.OP are not only volatile but also have a large impact on the biological environment as an environmental hormone, the hetero-complex ester of the present invention has a large molecular weight and biological activity such as volatility and permeability. It is considered to be a polymer which has no action and weak bioactivity and is useful as a plasticizer that does not contain any environmental hormones, and is a plasticizer equivalent to DOP, water resistant, and non-volatile which retains weather resistance. It is considered to be an excellent plasticizer.

Claims

The scope of the claims

1. A first step of reacting a first dibasic acid, an excess of a diol and a monohydric alcohol at a reaction temperature of 160 ° C. or less, and the molar ratio of a second dibasic acid to a monohydric alcohol separately about 1 Composition comprising the second step of reacting in 1, the third step of reacting the products of the first step and the second step, and the fourth step of transesterification of the product of the third step under reduced pressure Formula R (PX) ₂ (AX). AR (In formula, R is a monohydric alcohol, A and P represent a dibasic acid, X represents a diol, The description of an ester bond is abbreviate | omitted.) The manufacturing method of hetero compound ester represented by these.

2. The method according to claim 1, wherein the first dibasic acid is adipic acid, and the second dibasic acid is phthalic acid.

3. The method according to claim 1, wherein the diol is a difunctional alcohol having 2 to 6 carbon atoms or a polyalkylene glycol having 6 or less carbon atoms.

4. The method according to any one of claims 1 to 3, wherein the reaction temperature is 140 to 150 ° C.

5. The method according to any one of claims 1 to 4, wherein the second step is performed under a reduced pressure of 0.2 mm Hg.

6. Composition Formula R (PX)) ₂ (AX) ₀ ^ _X AR (wherein, R represents a monohydric alcohol, A and P represent a dibasic acid, and X represents a diol, and the description of the ester bond is omitted.) A heterogeneous complex ester represented by and which does not contain a PXPX structure.