TW588043B - Process for producing composite mixed ester - Google Patents

Abstract

This invention discloses 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

588043 V. Description of the invention (1) Technical field ^ The present invention relates to the manufacture of hetero compound esters. The so-called composite ester is represented by a composition formula of R (AX) nAR (n is a positive number greater than or equal to}), and this formula is compared to the compound _C0MPLEX ESTER (RAXAR) equivalent to n = 1, which is considered to be Other concepts in the form of COMPOSITE ESTER. Prior Art * Hereinafter, in this specification, R and 0 are monovalent alcohols (for example, octyl alcohol), and? To represent a dibasic acid (for example, a is adipic acid and p is a phthalic acid), X is a diol (for example, ethylene glycol and propylene glycol), and unreacted groups are sometimes omitted (hydroxy and carboxyl groups). ), And the ester-bonded complex in the ester-bonded product is generally a mixture of compounds having different degrees of polymerization from n to 1 to 7 obtained by reacting a diol diacid terminal of the composition with a monohydric alcohol, and its A mixed composition type in which the proportion decreases in proportion to the degree of polymerization as the degree of polymerization increases. Regarding its composition, its distribution is changed according to the manufacturing method. Therefore, the composite brew produced by controlling this distribution has a composition different from that of the manufacturer without considering the characteristics of the obtained product. The present invention relates to a manufacturing method for improving the applied hybrid compound s (Japanese Patent Laid-Open No. 7-330684), and proposes a method for reducing the distribution width (Japanese Patent Laid-Open No. 2000-1 1 1 9252) In particular, it is possible to completely prevent the production of diacid RAR or RPR which is a byproduct of dibasic acid, or to make it in a trace amount for the purpose of manufacturing, and to use the two different types of dicarboxylic acid and adipic acid produced by such treatment. Acid, H0C0AC00H and phthalic anhydride P (c〇) 2〇 or other succinic anhydride 8 ((: 0) 2〇, etc., to make the composition of the general formula κ (ρχ) ι ~ 2 (Ax) 〇 ~ iAR system

588043 V. Description of the invention (2) Manufacturing method and hetero-complex ester manufactured by this method. Control of the molecular weight distribution on the S day and the formation of the second brew, first consider the ester reaction of 30% / knife CR, A, X): 2 {R + A + X + A + R} —2RAXAR ⑴ iR + A + X + A + X + A + R} + {R + A + R}-. R {AX} 2AR + RAR (2) According to (1) Formula 4 Mol acid A and monool r and 2 Mol glycol χ A product of η 1 of 2 moles 2 is produced, but if the reaction with the same mole number causes (2), it is 11 = 21 moles and 1 mole. Because the reactions of (1) and (2) are caused at the same time, so even if the reaction is for the purpose of ⑴, it may not be variable = the number of RARe should be equal to the number of n. Instead, it can be changed to correspond to the degree of polymerization of diacetate. Because the distribution of the amount of "two" "can suppress the birth of the two 'purpose, if it can become none, then the application of the small S Japanese clothing manufacturing method (Japanese Patent Application No. 200 1-119252) 〇 / ^ method has a reaction pattern, and Excessive use in vinegarization == Use _ 'to perform the brewing exchange reaction with the hydration reaction, and the reaction of the terminal of 和 and ROH will become RAR in the reaction, so the result is beneficial. The present invention is to discover the use of restricted use: 化, 到;! :: ΐ degree, when the compound ester and ester alcohol coexist under the conditions of 酉 化 衣 is a polyester with a sub-quantity distribution of 2 or less . The aspect of + does not completely prevent the η value in the complex ester from decreasing and decreasing by two Λ. The reaction is carried out through a well-controlled reaction Mole ratio, especially through the use of the aforementioned active catalyst, and the above necessary is not used. 588043 V. Description of the invention (3) The manufacturing method of R0H can produce the product of the desired degree of polymerization, and can prevent the by-product of RAI? In the aforementioned patent application, the range of the excess is specified as a theoretical amount of 0.2 to 2 "Amount", but it was found that even at a low ratio, it can be used in an active catalyst (Japanese Patent Application No. 20000 -1 4 7 5 5 4), in particular, to fully react and produce useful vinegars. Therefore, It is also related to the use of this invention. Regarding the reason for preventing the occurrence of by-product diesters, for the reasons described in the prior art, because a large amount of beer with a low degree of polymerization is produced to a large extent and cannot be completely eliminated, the proposed transesterification method is The method of the following general formula is a method capable of producing a heterocomplex ester (Japanese Patent Application No. 2000-147 4 55 4).

R0H + P (C0) 20 —RPH-~ > + H0X0H — RPX0H 2ROH + HOCOACOOH- ~ > mRAR ~ > + RPX〇H- ^ R (PX) nAR + ROH f + RAR (3) That is, the above The reaction formula is to make a phthalic anhydride react with a monoalcohol, followed by a diol reaction to produce an ester alcohol of phthalic acid that also contains a partial composite ester. A hetero-complex ester can be produced by adding a dealcoholic acid diester produced separately to a trans-alcoholic transesterification reaction to obtain a product and evaporating and removing the remaining excess R A R (Equation (3)). At this time, if the amount of rar in the transesterification reaction is small, the degree of polymerization of the product will increase and the viscosity will increase. If the ester with excellent plasticity is used for about 2.5 moles, for example, the diol component is it propylene glycol. The product XK has an excellent low viscosity of about 1.5 and a low viscosity of 4 5 0 centipoise (centi ρ 0 ise).

Since the composition formula of the manufacturing method is described in the case where the terminal alcohol rqH is octanol ⑻η is 〇 (Ρχρ) ι · 4Α〇, it is considered that R (pxpx) AR caused by this manufacturing method is mixed.

C: \ 2D-〇〇DE \ 91-09 \ 91116007.ptd page 7 588043 5. Description of the invention (4) and RPXPR as polymer components. In addition, the inventors learned that the heteroesters cannot prevent the by-product formation of diesters in the dehydration esterification reaction. However, if the production is carried out under the premise of this formation, heterocomplexes can be produced even if the group is not suitable for the purpose. And evaluate its performance; excellent special 7 33 0 674) / But, because there are many necessary amounts to remove RAR, there is a manufacturing technology to reduce the amount of by-product RAR. This ° The complex ester of the rhyme * 2 to be solved by the invention, in order to obtain a composition with a degree of polymerization distribution and a two-component composition, especially the use of rancid compound vinegar: The agent can be used every day, the plasticization efficiency is extremely poor, review Low viscosity does not mean that it does not contain a high degree of polymerization; together, "the degree of by-products of the dibasic acid is cool. It must be removed. The acid value of the product is deteriorated due to thermal decomposition. The main reason. Anyone who has the problem of environmental hormones, and no one who wants to use it, must pay attention to the importance of environmental protection, and does not contain plasticizers. When manufacturing these composite esters, the south molecular oligomers of ln 1 are manufactured. When the composition of the material is, if the old alcohol is a mountain, * terminal alcohol causes side brewing, if the terminal alcohol is made into a t acid by the reason; and :: then it becomes a high polymer. =. When vinegaring, 'the catalyst function is not enough to a!' Excessive control. In particular, the reaction can be interpreted through the use of Xiao Xi 勰 M, and the determinant A can be used as a medium. 4 4 ^ Use a good catalyst, a reaction pattern, and become an excellent composition.

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5. Method of Invention Description (5). The means to solve the problem is that the present invention is the first stage of the reaction of the first mono-acid, excess diol and mono-alcohol due to the reaction temperature below 160 ° C (this stage is the eight main reaction to The second stage is the second stage: the second stage of the reaction between the acid and the monohydric alcohol in an equivalent ratio of about 1: 1 (this stage is to remove the diol used in the process, and It is better to carry out under reduced pressure of 0.2 ~ 10mmHg), and the third stage of reacting the first stage with the products of the second stage (this stage is used for the reaction of molar equivalents combined with additional diols and the use of excess alcohol with respect to Sa , Carry out dehydration esterification reaction, and fully reduce the acid value into the esterification is better), the third stage of the product under reduced pressure transesterification anti deer ^ the fourth stage (this stage is in the third stage Excessive residues in the product, ^ make the ester alcohol generated by acetic acid react with the main component for the purpose) of the formula 1 ^ (? 乂) 1 ~ 2 (Ya 乂) () ~ 1 八 8 (where, ^ It is a monohydric alcohol, human and? Are dibasic acids, ^ is a diol, and the description of the ester compound is omitted.) This hetero-complex ester can be dehydrated by reacting the excess alcohol component of the acid with the acid to reduce the acid value, and is formed from the corresponding excess diol component or the remaining brew alcohol and the main product. The esters are produced by transesterification reaction. The composition formula of the 'hetero-complex vinegar' is the ratio of the components, not the arrangement of eight. 77 In the present invention, the composition formula is 1 ^) 1 ~ 2 (eight). () ~ 1 ^^ (wherein 1 ^ is a monohydric alcohol, A and P are dibasic acids, X is a diol, and the description of the ester bond is omitted) The hetero compound i is shown to have no ρχρχ structure Mixed with mixed vinegar. The hetero-complex ester contains no or only a small amount of RAR, RPR & RAX.

588043 5. Description of the invention (6), the first dibasic acid is preferably adipic acid, and the second dibasic acid is preferably phthalic acid. The diol is preferably a bifunctional alcohol having 2 to 6 carbon atoms or a polyalkylene glycol having 6 or less carbon atoms. For example, propylene glycol and 1 2, 1 3, 1 4-butane A mixed diol of alcohol and dipropylene glycol. Embodiment of the Invention The shape of the bear of the present invention will be described. Brother Bai Bai · Youyi monobasic acid (A is for example adipic acid) in the presence of excess monoalcohol (X) dehydration esterification reaction at a lower temperature than usual (丨 60 below it, more preferably + 140 ~ 150 ° c), many AX are generated. Under such conditions, the monohydric alcohol (R) is added in a small amount to react. After the reaction of 2/3 ~ 3/4, the catalyst is added, and the temperature is increased, and the ester is dehydrated and esterified at 190 ~ 2 10 ° C, so that the acid value is completely reduced, and the first dibasic acid is not contained. (Adipic acid) diester (RAR) A mixed product consisting of a glycol diester (χΑχ) and an ester alcohol (RAX). This stage is usually reduced in pressure, so unreacted diols (χ) and monoalcohols (R) are removed. In this stage, R is a preferential reaction to X, and the composition of the product is determined according to the amount used, and the excess X is removed under a reduced pressure of low temperature of 0.2 to 20 mmHg. This temperature is more effective if the pressure determined by the pressure is as low as possible, but if you try to completely remove X, XAX will become de-XΑχΑχ and the degree of polymerization will increase. Under normal conditions, the product will become χ (ΑΧ) ι ~~ 4 As bad. And the first stage: In addition, the second dibasic acid (ρ is, for example, phthalic acid) and the terminal release (R) are subjected to an anhydrous reaction at about 1: 1 to obtain the second dibasic acid (phthalic acid). Monoester (RP). ^ Second stage ... If the products of the second stage are added to the relief of the first stage

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588043 V. Description of invention (8) A mixture of components. In particular, the compound finally recorded as a by-product of the ρχρχ structure has a rapidly increasing viscosity corresponding to its weight according to its formation. However, in the exchange reaction of S, the reaction temperature with Rp is higher than the reaction with Rp. And the RA constructor is a priority reaction, so the more the RAXPR ratio in the main product participating in the reaction, the lower the viscosity composition. This composition can be used to make any shellfish by changing the composition ratio of phthalic acid and adipic acid. However, compared to adipic acid, phthalic acid has a lower valence. As long as it can correspond to the viscosity, the phthalic acid unit in the molecule will increase. Many are better products. According to the method of the present invention, it is possible to make a hybrid compound, and by making a hybrid compound brewing the main PXAX structure with two kinds of acids mutually combining, a high degree of polymerization can be produced: it does not contain a polymer brewing structure and has no or only a small amount The acid is a hybrid compound of PXPX structure with steric disorder, and it can be judged that the viscosity is a low-viscosity compound ester of about 400-600 centipoise. There are many units of phthalic acid = S: S said * 'Can be used to solve the problem of plasticity vs. western volume and volatility, and the plasticity is a little bit viscous. The second brewing is of the same degree, and the combination of the adipic acid and adipic acid has softness and greatly improved its water resistance. The linear phthaloic acid has weatherability and can be used as an excellent plasticizer. The present invention is Regarding the properties expected to have plasticity A: It is composed of four components of 70 alcohols, the main i 2 is mutual: combined with the general formula R (PX) 1 ~ 2, and mr is used to make the adipic acid diol two follow the terminal Mono-alcohol part λ i-element = Mono-brewing reaction obtained by adding mellow alcohol produced by mol of diol corresponding to the molar amount of reaction-citric anhydride to make hetero-complex vinegar and vinegar:

C: \ 2D-C0DE \ 91-09 \ 9lll6007.ptd Page 12 588043 V. Description of the invention (9) Transesterification reaction to make the target hetero complex ester. By this method, the method for producing the by-product acid diS, which is impossible for complex S, has been made, and the manufacturing method of k is extremely small. > The efficiency is excellent. Regarding the general formula IKPXWAXXyAR, R (PX) 1 ~ 2a〇 is an arbitrary mixture of sound RPXAXPA and RPXA0, and (AX) ^ is 2 at every f center, ^ a χαχ 〇〇% ^ ^ 11 ± ^ ^ ^, ν! Λζ0 " *

The degree of purity polymerization is increased by the number A: T m (Αχ) unit calculated by the mixing ratio of AXAX. Zero is exactly 100% of the theoretical value. The value is expressed in proportion to the increase in _ZiHe'm. AX of AX This composition contains a very small amount of high polymer, and the total composition of phthalic acid 1 or more is composed of 2 or more adipic acid i or more and: 乂 :: sub-method is a composition containing almost no PXPX Thing. Other methods of such a group ΠΪ may be based on the reaction ratio: ΪΓ method: there is no particular limitation. The method of using acetic acid and terminal alcohol and :: two parties, and using vinegar exchange reaction to obtain the structure containing PXPX, that is, containing no (PX) uu products, has been previously applied. R Oral * * & 彳 一 不 3 (ρχ ) 3 or more, hybrid compound brewed in the Japanese Patent Patent No. 2000 ~ 1 47554). = 0.3 or more η = 0.3 or less \ The description of the style is WR (PX) m (AX) nA〇m 7-330 6 84), and please refer to the product of (Pχ) f (Japanese Patent Special) The total composition ratio of Kaiping is averaged. 1. The ratio is a mixture that does not contain at all to maintain excellent performance. The performance of the composition above 0.3 is shown, and the figures have this range. Although the composition in this case is miscellaneous The compound ester type has more than one complete "complex function f", but (PX) must contain 1 polymer, compared with 2 in this case, the former is random and the product is described as a polymer. The cross-polymerized polymer is mainly mlm C: \ 2D-OODE \ 9I · 〇9 \ 9] I I6007.ptd 3〗 3 588043 V. Compound S composition of the invention description (ίο). Use RPX and the same according to this case The method is to carry out dehydration esterification reaction, followed by the transesterification reaction method of excess alcohol, because it is not able to completely prevent the by-product of adipic acid diester, so it is not described in detail, but what about the production of this case? 1) 2 (eight $) The manufacturing method of () ~ ^ 1 ^ is not particularly limited. Examples Hereinafter, the present invention is illustrated by examples, but it is not intended to limit the present invention. A laboratory scale reaction using 2-ethylhexanol (octanol, denoted by 0 or OOH) as the terminal alcohol and the purpose of preparing ie 0 (P Xp) 5 A 0 is taken as an example and described below.

Put 1 mole of adipic acid (146 g) and 1,2-propanediol (propylene glycol, abbreviated as ΗΟχρΟΗ) 2.5 moles (190 grams, 1 mole more than necessary) into the dehydration reaction 1 A three-liter liter reactor was replaced with nitrogen under reduced pressure, followed by the addition of a small amount of 20 ml of toluene as an azeotropic solvent, and it was heated and stirred at 400-600, and the dehydration and acetation reaction was started. From 9 ml of water to the outflow of 27 ml of water, a small amount of 2-ethylhexanol 0.5 mol (65 g) was added to carry out the vinegarization reaction. Return to the reactor to perform the reaction. Since propylene glycol is distilled azeotropically with water, the amount of 1 mol is excessive, and the water produced by the co-emulsion is an aqueous solution of 30% to 40%. At the end of the addition ^ Recognize 27 ml of water, add another adjusted titanium catalyst 2 millimoles (tetrabutoxycin 0.7 g amount) and increase the reaction temperature to 180-1900c, continue Dehydration reaction. The reaction is completed after 1 to 2 hours, and the next reaction is carried out. Since excess propylene glycol is distilled off at 190 ° C, if the acid value can be measured at the same time, the purity of the component diol with HOXpAXpOH and acetol 〇AXp〇H can be measured by high-speed liquid chromatography (HPLC) and measured simultaneously. Residual of H〇Xp〇H

C: \ 2D-CODE \ 91-09 \ 91116007.ptd Page 14 588043 V. Description of the invention (11) The quantity, to obtain the basic calculation data for the next reaction. The target products are diol diester 0.5 mole and ester alcohol 0.5 mole. In this reaction, if the reaction of octanol is a rapid addition, dioxin D 0 A is by-produced. Therefore, it must be added to such an extent that d 0 A will not be formed. Furthermore, the reaction product Ax of adipic acid and a diol is to form AAXA or AAXAX by sequential reaction, so the reaction must be performed in the presence of an excess of X. In order to control this, the temperature-decreasing reaction must be selected to a temperature of 1 40 to 16 ° C, which proceeds slowly. The reaction with adipic acid is a non-catalyst reaction for 2 to 4 hours. If the dioxin is above 150 ° C, it will be azeotroped with water and quickly removed by distillation. Therefore, the excess amount will change depending on the reaction temperature. Therefore, the distillate fraction is corrected and recycled in the reactor at the same time. In the case where the excess amount is small and the reaction proceeds rapidly, the diol diester polymer Η0 (χρΑ) ηχρ0Η is obtained, and the value is about 14 or more ^, so it can be confirmed by HPLC. On the other hand, the reaction product is decompressed. After removing the diol and calculating the value of the η polymerization degree from the weight of the remaining product, the theoretical weight of the remaining product was reduced to 289 g and approximately the same product was obtained by concentration under reduced pressure, but the composition of 285 g was equal to 0.05. Calculated by a mixture of Αχ〇Η &〇; 447ΗΟ (ΧΑ) 112χ〇Η. The reaction of the formation of OPH (second stage reaction): in phthalic acid

And 2-ethylhexanol} 5 mol (195 5) φ ★ ^ 吴 斗 充 J 1 cn ^. n. Add 150 grams of toluene as a diluting solvent, and stir at a temperature below 100 ° C. This and the pan are subjected to an anhydrous reaction at a temperature of cQk, and the reaction is as thermal and the product is Phthalic acid monooctyl ester, but the reaction temperature is hot on the way and rapidly increased. 1 When diluted, it turns into UOt: above, and it does not produce dioctyl acid dopate D0P 'based on the reaction amount and also affects phthalic acid ::: J = by-products and phthalic acid residues. Residuals of Anhydrous: The degree of pullout ’makes Fu Anshui the cause of reduced catalyst activity

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Because of the reaction between amidine and monoalcohol, it is possible to form a glycolic acid glycol diester H Q χ ρ χ Q Η, which will become PXPX and cause the viscosity to increase in the next reaction, so it is expected to obtain as high purity OPP as possible. The reaction amount of OPH is determined based on the purity of the above-mentioned glycol diamine and S alcohol.

Use 1.30 moles (490 grams) of OPP reaction solution, put 2 liters in three mouths, add the 1 mole of adipic acid reactant, and stir the remaining anhydrous substance to dissolve with the catalyst, then add 2 ~ 5 millimoles of catalyst solution. The activation catalyst is prepared by dissolving titanium tetraalkoxide in ammonium, a small amount of propylene glycol, or octanol, and adding a mixed solution of water-soluble diol and water in a molar amount of 4 to 20 times the molar amount of titanium, and performing a mixing reaction. To make an activated catalyst (Japanese Patent Application No. 2000-147554). If the dehydration esterification reaction is carried out at 190 ~ 21 ° C, the acid

The value decreases in the first order reaction and its half-life is 15-25 minutes. In addition, in the case where the acid is reduced in speed and the reaction rate is stagnated, the degree of polymerization and the remaining diol are removed during the production of the glycol diester, and the total alcohol concentration is reduced. The theoretical amount is to change the amount from 0 to over 0.1 mol in excess, and the reaction is carried out to become a low acid value ester mixture. The product with a reduced acid value was obtained by closing the reflux opening and slowly distilling off the distillate in the vessel. The azeotrope was added with xylene and its remaining volatiles and 2-ethylhexanol produced by the transesterification reaction. The transesterification reaction was performed in response to this removal, and the reaction was finally ended in a reaction state of 210C and a decompression degree of 2 to 10 mmHg. However, in order to make it complete, it also includes the removal of by-product DOA and drops to 0. 2mmHg is preferred. Heat and stir under low pressure to confirm the mixing amount of the volatile portion. The theoretical amount of octanol produced is the amount of diol corresponding to the excess amount of 0H, which is 0.1 mole, removing 13 grams, ’

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Page 17 588043 V. Description of the invention (14) ----- Because the mole number of the diol diester becomes smaller, it is corrected and calculated. (()) (AX) G G5A0 molecular weight 661, mole number 0.95 Mo The composition of the ear. 1. The hetero-complex esters produced are mainly cross-complex esters, and the combination of adjacent acids is the structure of the heteroacid PχΑ. The acetic acid shown by ρχρ is compounded separately. The lowest is also as high as 700 centipoise. Viscosity ester, so by suppressing its production as much as possible, it can be used as a useful ester to control the increase of product viscosity. On the other hand, especially in the manufacture of glycol diesters, the reaction with residual diols may have the possibility of by-product OPX0Η, because 〇ρχρχ is generated in the transesterification reaction, so the mixing with the complex ester with 0AX terminal is It is good, and at this time, it can suppress the increase in viscosity. Therefore, the diol ester to ester alcohol ratio of adipic acid used is 1: 1, and it can also be 9: 1 to 1: 9. At this time, the reaction amount of 〇ΡΗ is using different stoichiometry, and the product The composition (PG) polymerization degree 1 to 2 is a factor for obtaining a low viscosity product useful in the present invention. On the other hand, a product having a degree of polymerization of (PX) η of 1 or less cannot selectively form a single unit of a linear monobasic acid, and diacetic acid is formed as a by-product, and it is necessary to remove the step. OPH can partially replace straight-chain fatty acids, but it can also be used in the form of monoesters using anhydrous substances. The purpose of this method is to produce diol diol diester and ester alcohol 1: 9 to produce 0.1 Η0 × Αχ0Η and 0.9 ΑΑχ0Η, and the reaction with 1 mole is 0.1 ΟΡχΑχΡΟ + 0.8 ΟΡχΑΟ + 0.1 0Αχ0Η — 0.1 〇ΡχΑχΡ + 0.7 〇ΡχΑΟ + Ο · 1 0ΡΧΑχΑ0 or 0.1 OPXAXOH + 0.9 OPXAO-Ol ΟΡχΑχΑχΡ0 + 0.80 PPXΑ0 The product of this reaction is a mixture of 4 to 6 products, and the product with a composition close to (κΡχχ.οΑ0. In the actual reaction, in the production of Diesterase

588043 V. Description of the invention (15) It can be carried out closely, and it cannot prevent D 0 A from being partially formed, and it is not necessary to remove it. The reaction Molar number of the product is less than the theoretical amount. The result 11 value is greater than The reaction volume of 1 and OP must also be reduced. The necessity of removing doa is a manufacturing condition for a product containing a volatile portion. The second method is a method in which the amount of OP is used, and a corresponding excess of diol (0 × 0) is added and a dehydration esterification reaction is performed. If the foregoing reaction is exemplified, 1.6 mol parts of phthalic acid S, OPOH, are produced using 1.6 mol (2.77 g) of phthalic anhydride and 2-ethylhexanol (208 g). The adipate produced by the same treatment, and the glycol ester 0.424110 ^ /: ^ 18 × ρ〇Η and 0.5 acetol 0 Α χρ 0 0 1 to 1 mixed reaction solution (the degree of polymerization is expressed by weight method) 'And start the dehydration reaction in a 2 liter reactor, add 0.16 mol (12 · 2 g) of 12-propanediol corresponding to the excess amount of OPH, and use an additional 0.1 mol when activating the catalyst 7.6 grams of propylene glycol and reacted. That is, to 7.6 g, dissolve 1.7 g (5 mmol) of titanium tetrabutoxide, and add 1 g of water and 1 g of a mixture of ethyl alcohol and 1 g of water, and activate the catalyst. Dehydration and esterification at ~ 2 1 0 ° C, and finally with an increase in acid value of 6.1 g of propylene glycol and g conversion, the reaction is performed at a half-life rate of 15 to 25 minutes, and after 2 to 3 hours You can make the acid value below 0 · 1. Next, the reactor was depressurized and finally 2 to 0.2 mm Hg, the volatile components were removed, and the cyanolytic enzymes produced by the transesterification reaction were removed together. It was confirmed that no d0a was present and the reaction was terminated. The product was cooled to 100. (3) Add a small amount of water and dilution solvent and stir to add activated clay, adsorb the residual catalyst, filter to remove the clay and catalyst, and then remove the volatile components by heating under reduced pressure to obtain 675 g of the product. Viscosity of the obtained hybrid composite ester It is a low viscosity product of 5 2 0 centipoise at 20 ° C.

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After previous experiments, it has excellent water resistance and weather resistance, and has almost no reduction in volatility. It can also be used as a non-volatile plasticizer. This can also be based on the results reported previously. Kaiping 7-3 3 0 684) to judge. This reaction is based on 1.6 〇ΡΗ + 0.42 ΗＯΧ (ΧΑ) 1] 8〇Η + 0.5 〇ΑΧΟΗ + 0.26 Η0Χ0Η Esterification to 0.42 ΟΡχ (Αχ) 118P〇 + 〇5 ΟΡΧΑΟ + 0.26 ΟΡχΟΗ — the next exchange reaction It is 〇42 ΟΡΧ (Αχ) 118PO + 〇24 ΟΡΧΑΟ + 0.26 0ΡΧΑχΡ0 or esterified to 〇32 ΟΡχ (Αχ) 118ΡΟ + 0.5 〇ΡχΑΟ + 0.16 〇ΡΧΟΗ + 〇. 1 〇Ρ (ΑΧ) 1 1δΟΗ + 0. 1 ΟΡΧΡΟ- The exchange reaction in the next stage is 0.32 ΟΡχ (ΑΧ) Κ18ΑχΡΟ + 0.24 ΟΡχΑΟ + 0.16 ΟΡχΑχΡΟ + 0.1 OP (AX) L18AXPO + 〇. 1 ΟΡχΡΟ The product in the next stage is supposed to be a product of (ρχρ) structure, which cannot be ignored. React here and over-examine the limits of the amount of OPP or Z0X0. The product of the theoretical reaction is a reaction of 1.6 mol and 1 mol and its composition is (KPXh 5Α0), which can be calculated by correcting the polymerization degree of the diol (KPX: ^ 73 (axp) u8a〇 molecular weight) 740 0.92 moles. The amount of ΟΡΗ used is different from the amount of alcohol added during the production of adipic acid alcohol. In the case where there is a large amount of 0AX, the use of 〇ΡΗ and Η0χ0Η corresponding to the excess of 〇Ρχ is of course less than 0.1 mol. The amount has increased significantly. But

C: \ 2D-CODE \ 9l-09 \ 91116007.ptd Page 20 588043 V. Description of the invention (17) Yes, the product of the PXPX structure is increased 'and must be made to such an extent that the viscosity does not increase sharply. Add the product made from 1 mole of adipic acid " one ^ one vinegar and 2 to 8 of acetol and 0.6 mole of diol corresponding to 1.8 mole of phthalic acid monoester to make a compound The ester 1 mole and the ester alcohol 0.6 mole and the dehydration esterification reaction was to completely esterify the 06 mole amount of alcohol with excess acid, followed by the transesterification (OCPXUO). The target product is OPXAXP0, and some are OPXρχΑχρο, so the viscosity of the product becomes a little high. (0.2 XAX + 0.8 0AX) + (1.2 OPH + 0.6 OPH) + 0.6 ΗΟΧΟΗ ^ 〇 · 2 ΟΡΧΑχΡΟ + 0.8 〇ΡχΑΟ + 0.6 ΟΡχ- > 〇 · 8 0ΡχΑχΡ0 + 0 · 2 0ΡχΑ0 The composition of the present invention and adipic acid must be removed Binary generation (PXP) has problems. The method of the invention is intimately carried out with adipic acid and unreacted. In the usual reaction, acid. The hetero compound ester shown by the formula RCPX ^ yAR of the byproduct of the method of the present invention, 1 ΛΓ π% j, can be prepared according to the transesterification reaction of the RPX of the ester of the formula (3). Therefore, it is necessary to use a large excess of diesters. The recovery cost of the two is characterized by the amount of two g is extremely large, using this two. The method described in T-f can also be produced, but it cannot be produced strictly. Even if the intended reaction is performed, it is a compound. Therefore, it is impossible to prevent the by-product of diacetate A: 夂! The terminal alcohol is a monool, diacetate, unreacted == the conditions for loading the specific product, according to the following formula, and the dark exchange reaction can be made into the formula R (ρ X ~ 2 AR Compound ester 588043 V. Description of the invention (18) About the first paragraph adipic acid

3 HOCO (CH2) 4COOH + 3 ROH—H0C0AC00H (abbreviated as AHRAH + RAR) About the second-stage phthalic acid P (C0) 20 + R0H-> rph RPH + H0X0H-RPX0H (or RPX) The method according to formula (3) In order to prevent R (pxpx) 0H from being produced by the removal of ROH from RPXOH, if a phthalate alcohol made by removing excess alcohol under reduced pressure (0.3 mmHg) is used for dehydration esterification reaction with 1 excess ratio

3 · 3RPX + A + RAH + RAR—RPXAXPR 10 RPXAR + RAR + O · 3RPX

RPXAXPR + 0.7 RPXAR + 0.3 RPXAXPR + RAR The above reaction is a mixed composition of 1.3RPXAXPR and 0.7RPXAR IUPXVmAR 2 Molar and 1 Molar RAR mixture. However, in this reaction, a diol reaction is performed first, and Rpx can be produced by using an excessive amount of alcohol. Any method can generate PXPX in a trace amount, so the viscosity of the product becomes a little high. On the other hand, even if the temperature of the first-stage reaction is changed to suppress the by-products of RAR diesters, the by-products of RAR diesters cannot be completely prevented, but the by-products of RAR diesters can be reduced.

This month is about the manufacturing method of adipic acid and phthalic acid heterocomplex vinegar, and its composition is mainly ^ ^ — According to the upper and lower limits, it is particularly difficult to carry out glycol two with adipic acid gt Tobacco system ^ You du, head office said the first day and the second day of the clothing, and the second condition of the reaction conditions, depending on the reaction, and the composition of the JV product is not bad, which greatly affects the manufacturing employment.

588043 Description of the invention (19) Volatility of alcohol component. 1 2-Propanediol is the cheapest and most useful in azeotropic distillation and difficult to control the product system, but hexylene glycol and U-hexanediol are volatile two. . : Propylene glycol and 2-ethyl] 3-alcohol must be considered for volatility, ethylene glycol ~, 13_, and butane are used. The diol component is an alcohol which is excessively large in dilactone depending on the purpose of use. The use of terminally burned alcohol is not particularly limited: two mixed use of various alcohols produced by the ethoxy method ~ and ethyl-hexanoate, can be effectively used phthalic anhydride dibasic acid gt ^ ;. This reaction method is to make acid, succinic acid, and hydrogenic acid also possible: right, the possibility of other maleic use. It is easy to use D0A when it is mixed with fatty acids to make fatty acids. In addition, D0P is at 70 ~ 80t: it is a thin plasticizer that is added outside in a low-viscosity type to make the film volatilize nearly half in one year. It can also be used as a poly 8 thinner for processing, which is useful for high plasticity and can be used as a non-volatile plasticizer. When it is used internationally, the volatility reduction is to increase the mixing and use of the solid volatile plastic j, & even if the remaining knife: exist and can be used as a non-no problem, so the manufacturing method "., E and tender in practical The reaction is based on a molar ratio that is not limited to HOH and is closely controlled. • It has a large molecular weight. ^: When it is in a biological environment, it has “no intrinsic polymer effect and biological activity; permeable” biological living environment hormone. Plasticizer for keeping with DQ. It can be used as a 70% non-volatile and excellent non-volatile plastic door agent with excellent weather resistance. Special plasticizer and water resistance.

588043

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Claims (1)

588043 VI. Application for patent scope 1. A method for producing a heterocomplex ester, which is the first stage of the reaction of the first dibasic acid, excess diol and monohydric alcohol at a reaction temperature below 160 ° C, A second stage in which another second dibasic acid reacts with a monohydric alcohol at a molar ratio of about 1: 1, a third stage in which the first stage reacts with the product of the second stage, and a product in the third stage The fourth stage of the transesterification reaction is carried out under reduced pressure.乂) 1 ~ 2 (person \) (] ~, 1 ^ (where, 1 ^ is a monohydric alcohol, A and P are dibasic acids, X is a diol, and the description of the ester linkage is omitted) 2. For example, the manufacturing method of the first scope of the patent application, wherein the first dibasic acid is adipic acid, and the second binary acid is the phthalic acid. 3. The manufacturing method of the first scope of the patent application, wherein the The diol is a bifunctional alcohol having 2 to 6 carbons or a polyalkylene glycol having 6 or less carbons. 4. The manufacturing method according to item 2 of the patent application scope, wherein the diol is 2 carbons ~ 6 bifunctional alcohols or polyalkylene glycols with 6 or less carbons. 5. For the manufacturing method of the first item in the scope of patent application, wherein the reaction temperature is 140-150x: 6. If the manufacturing method in the scope of the patent application item 2, the reaction temperature is from 140 to 150 ° C. 7. If the manufacturing method in the scope of the patent application item 3, the reaction temperature is 1 40 ~ 1 50 ° C. 8. The manufacturing method according to item 4 of the patent application range, wherein the reaction temperature is from 1 40 to 150 ° C. C: \ 2D-CODE \ 91-09 \ 91116007 .ptd Page 25 588043 VI. Application scope of patent 9. The manufacturing method of item 1 of the scope of patent application, wherein the second stage is under a reduced pressure of 0.2 ~ 10mmHg get on. 10. The manufacturing method according to item 2 of the scope of patent application, wherein the second stage is performed under a reduced pressure of 0.2 to 10 mmHg. 1 1. The manufacturing method according to item 3 of the scope of patent application, wherein the second stage is performed under a reduced pressure of 0.2 to 10 mmHg. 1 2. The manufacturing method according to item 4 of the scope of patent application, wherein the second stage is performed under a reduced pressure of 0.2 to 10 mmHg. 1 3. The manufacturing method according to item 5 of the scope of patent application, wherein the second stage is performed under a reduced pressure of 0.2 to 10 mmHg. 1 4. The manufacturing method according to item 6 of the scope of patent application, wherein the second stage is performed under a reduced pressure of 0.2 to 10 mmHg. 15. —Hybrid complex ester, which is a hybrid complex ester represented by the composition formula IKPXhwUX ^ yARC, where R is a monohydric alcohol, A and P are dibasic acids, X is a diol, and the description of the ester linkage is omitted) It is constructed without PXPX. C: \ 2D-CODE \ 91-09 \ 91116007.ptd Page 26 ί 1: ^ 'Λ,, Α,,: _ December 18, 1992 __ Replacement page to apply for Rises 91. 丨 f.lL8 Case number: 91116007 Farewell ... ; (The above are filled by this Office.) Invention Patent Specification 588043 Chinese Heteropolyester Production Method Invention Name English Name (Chinese) 1. Matsumoto Tetsu Inventor's Name (English) 1. Nationality 1. Japanese Residence, Residence 1. Japan 158-8, Sankai, Seya-ku, Yokohama-shi, Kanagawa Prefecture Name (Name) (Chinese 5 1. Name of independent science and technology promotion agency (English) 1. Nationality of applicant of science and technology promotion agency 1 · Japanese Residence and Residence (Office) 1. Name of Representative (Chinese), No.8, 1-Chome, 4-chome, Honmachi, Kawaguchi, Saitama, Japan. 1. Name of Representative (English), Okimura Kenki C: \ master file \ 91 \ 91116007 \ 91116007 (replace) -l.ptc Page 1