Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

• the present invention relates to a process for producing a heteroconjugate ester.
• R AX
• COMPLEX ESTER R AXA In contrast to R
• 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.
• 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)
• JP-A-7-330664 Japanese Patent Application No. 2 0 0 1-1 1 9 2 5
• 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
• 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.
• n 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.
• 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
• 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.
• 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).
• a manufacturing technology that reduces the amount of by-product RAR.
• 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.
• 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).
• 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.
• the composition formula of the hetero compound composite indicates the ratio of the components, not the arrangement of the components.
• 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
• 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.
• 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.
• A first dibasic acid
• X diol
• 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.
• XAX becomes de-XAXA and the degree of polymerization increases, and under normal conditions, it is formed ⁇ ⁇ ⁇ )) ⁇ 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 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
• 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.
• 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.
• 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).
• 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.
• 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.
• 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 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.
• 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.
• 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).
• 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
• 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.
• 1 AR is manufactured manufacturing method thereof.
• 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.
• AX which is the reaction product of adipic acid and a diol
• AXA or AXAX in a sequential reaction
• 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.
• 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.
• 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) ⁇ ⁇ ⁇ Is calculated.
• 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).
• 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
• 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.
• D ⁇ 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. .
• 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.
• 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.
• 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.
• 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.
• 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.
• the product of this reaction is a mixture of 4 to 6 kinds of products, and the composition is a product close to ⁇ . ⁇ ⁇ Will be obtained.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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
• phthalate adipate 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.
• 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.
• 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)
• R (PX) ⁇ 2 AR which partially contains PXP and byproducts such as DO A or DOP at the time of production
• R (PX) ⁇ 2 AR partially contains PXP and byproducts such as DO A or DOP at the time of production
• 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.
• 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.
• 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.
• 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.
• DOA When using plasticizers, DOA is easily volatilized but used as a low viscosity specification.
• 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.
• D OA and DOP 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.
• 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.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polyesters Or Polycarbonates (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Citations (4)

• 2001
  • 2001-12-25 JP JP2001391299A patent/JP3907470B2/ja not_active Expired - Fee Related
• 2002
  • 2002-06-18 KR KR1020047004380A patent/KR100619575B1/ko not_active Expired - Fee Related
  • 2002-06-18 CN CNB028261569A patent/CN1285564C/zh not_active Expired - Fee Related
  • 2002-06-18 WO PCT/JP2002/006083 patent/WO2003055842A1/ja not_active Ceased
  • 2002-07-18 TW TW091116007A patent/TW588043B/zh not_active IP Right Cessation

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