WO2018078961A1 - Procédé de production de trans-bis(2-hydroxyalkyl) cyclohéxanedicarboxylate, et bis(2-hydroxyalkyl) cyclohéxanedicarboxylate - Google Patents

Procédé de production de trans-bis(2-hydroxyalkyl) cyclohéxanedicarboxylate, et bis(2-hydroxyalkyl) cyclohéxanedicarboxylate Download PDF

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WO2018078961A1
WO2018078961A1 PCT/JP2017/025540 JP2017025540W WO2018078961A1 WO 2018078961 A1 WO2018078961 A1 WO 2018078961A1 JP 2017025540 W JP2017025540 W JP 2017025540W WO 2018078961 A1 WO2018078961 A1 WO 2018078961A1
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bis
cyclohexanedicarboxylate
hydroxyalkyl
trans
cis
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PCT/JP2017/025540
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English (en)
Japanese (ja)
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伊藤　博
弘 今中
稲田　修司
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株式会社シンテック
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Priority claimed from JP2017115590A external-priority patent/JP6372771B2/ja
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Priority to EP17865839.9A priority Critical patent/EP3533779B1/fr
Priority to ES17865839T priority patent/ES2943583T3/es
Publication of WO2018078961A1 publication Critical patent/WO2018078961A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a process for producing trans-cyclohexanedicarboxylate bis (2-hydroxyalkyl) and bis (2-hydroxyalkyl) cyclohexanedicarboxylate.
  • PET polyethylene terephthalate
  • BHET bis (2-hydroxyethyl) terephthalate
  • BHEC bis (2-hydroxyethyl) 1,4-cyclohexanedicarboxylate
  • BHEC can be produced, for example, by reacting BHET with hydrogen (hydrogen gas) and hydrogenating (nuclear hydrogenation) the benzene ring of BHET.
  • hydrogen hydrogen gas
  • Patent Document 1 BHEC is produced by reacting BHET with hydrogen gas in the presence of a palladium-supported catalyst to perform nuclear hydrogenation of BHET.
  • BHEC includes bis-1,2-cyclohexanedicarboxylic acid bis (2-hydroxyethyl) (hereinafter referred to as “cis-BHEC”) and bis-1,4-cyclohexanedicarboxylic acid bis (2- There are two stereoisomers of (hydroxyethyl) (hereinafter referred to as “trans-BHEC”).
  • trans-BHEC bis-1,2-cyclohexanedicarboxylic acid bis
  • trans-BHEC bis-1,4-cyclohexanedicarboxylic acid bis
  • Cis-BHEC is known as a raw material for polyester resins, polyurethane resins, acrylic resins and epoxy resins.
  • trans-BHEC since trans-BHEC has high linearity, it is expected to be an excellent raw material, for example, as a chain extender (diol component) of polyurethane resin. Therefore, development of a method for obtaining trans-BHEC is desired.
  • the weight ratio of the cis-cyclohexanedicarboxylate bis (2-hydroxyalkyl) to the basic oxide is 100: 0.1 to 100: 10 as described in (1) or (2) above
  • the above liquid medium contains at least one of ethylene glycol, propylene glycol, butanediol, N, N-dimethylformamide, dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone (5)
  • trans-cyclohexanedicarboxylic acid according to any one of (1) to (6), wherein the basic oxide includes at least one of an alkali metal oxide and an alkaline earth metal oxide.
  • the cis-cyclohexanedicarboxylate bis (2-hydroxyalkyl) is cis-1,4-cyclohexanedicarboxylate bis (2-hydroxyethyl) according to any one of (1) to (8) above.
  • the cis-1,4-cyclohexanedicarboxylic acid bis (2-hydroxyethyl) is obtained by depolymerizing a raw material containing polyethylene terephthalate to obtain bis (2-hydroxyethyl) terephthalate.
  • the nuclear hydrogenation is carried out by reacting the bis (2-hydroxyethyl) terephthalate with hydrogen gas in the presence of a ruthenium catalyst. 2-hydroxyalkyl).
  • bis (2-hydroxyalkyl) trans-cyclohexanedicarboxylate can be obtained easily and in high yield from bis (2-hydroxyalkyl) cis-cyclohexanedicarboxylate. Further, bis (2-hydroxyalkyl) cyclohexanedicarboxylate containing bis (2-hydroxyalkyl) trans-cyclohexanedicarboxylate in a high ratio can be provided.
  • FIG. 2 is a gas chromatogram of the reaction mixture obtained in Example 1.
  • FIG. 4 is a gas chromatogram of the reaction mixture obtained in Example 3.
  • FIG. 4 is a gas chromatogram of the reaction mixture obtained in Example 4.
  • trans-cyclohexanedicarboxylate bis (2-hydroxyalkyl) of the present invention and preferred embodiments of bis (2-hydroxyalkyl) cyclohexanedicarboxylate will be described in detail.
  • trans-BHAC bis (2-hydroxyalkyl) trans-cyclohexanedicarboxylate
  • cis-cyclohexane dicarboxylate bis (2-hydroxyalkyl) cis-cyclohexanedicarboxylate
  • -BHAC is contacted with a basic oxide to isomerize cis-BHAC to obtain trans-BHAC.
  • a step of preparing a raw material containing cis-BHAC (raw material preparation step), the above raw material and a basic oxide are charged into an autoclave, A step of obtaining trans-BHAC by isomerizing cis-BHAC by bringing a basic oxide into contact with cis-BHAC (isomerization step).
  • raw material preparation step the above raw material and a basic oxide are charged into an autoclave
  • a raw material containing cis-BHAC is prepared.
  • cis-BHAC include compounds represented by the following general formula (1).
  • n represents an integer of 2 or more.
  • ester groups are bonded to the 1-position and 4-position of the cyclohexane ring, but the present invention is not limited to this.
  • the cis-BHAC used in the present invention include bis-1,2-cyclohexanedicarboxylic acid bis (2-hydroxyalkyl) and bis-1,3-cyclohexanedicarboxylic acid bis (2) represented by the general formula (1).
  • -Hydroxyalkyl cis-1,2-cyclohexanedicarboxylic acid bis (2-hydroxyalkyl) and the like.
  • cis-1,4-cyclohexanedicarboxylic acid bis (2-hydroxyalkyl) has a high linearity, and is therefore an excellent raw material as a chain extender (diol component) of a polyurethane resin, for example.
  • the value of n is not particularly limited as long as it is an integer of 2 or more.
  • the value of n is preferably 2 to 12, and more preferably 2 to 6.
  • Cis-BHAC having a value of n within the above range is easy to handle and has excellent productivity. Further, by using such cis-BHAC as a raw material, side reactions other than the isomerization reaction can be more reliably suppressed, so that highly pure trans-BHAC can be obtained in a higher yield.
  • BHEC cis-1,4-cyclohexanedicarboxylate bis (2-hydroxyethyl)
  • BHET bis (2-hydroxyethyl) terephthalate
  • waste PET products include waste PET bottles, waste PET films, waste PET fibers, waste PET industrial materials, and the like.
  • a method for obtaining a raw material containing cis-BHEC from waste PET products includes a step of obtaining a reaction product containing BHET by depolymerizing the waste PET product (depolymerization step), The step of obtaining cis-BHEC (nuclear hydrogenation step) is carried out by charging the reactants and catalyst with the above, and reacting BHET with hydrogen gas in the presence of the catalyst to perform nuclear hydrogenation of BHET. Have.
  • BHET is obtained from waste PET products.
  • a method for obtaining BHET from waste PET products for example, a method in which PET is depolymerized in ethylene glycol (hereinafter referred to as “EG”) is known (for example, JP-A-2000-53802, JP 2008-88096 A).
  • EG ethylene glycol
  • JP-A-2000-53802, JP 2008-88096 A high-purity BHET can be obtained in high yield from inexpensive waste PET products.
  • this method is chemical recycling that effectively uses resources, it is also a technology that greatly contributes to the protection of the global environment.
  • the BHET content (BHET purity) in the reaction product obtained by depolymerization of PET is preferably 90 wt% or more, more preferably 92 wt% or more, and even more preferably 95 wt% or more.
  • Nuclear hydrogenation process Next, the reactant and the catalyst are charged (supplied) into a container (reactor). Then, the reaction gas containing hydrogen gas is filled in the reactor, and BHET and hydrogen gas are reacted in the presence of the catalyst. Thereby, the benzene ring of BHET is hydrogenated (also referred to as nuclear hydrogenation or nuclear hydrogenation), and a raw material containing cis-BHEC is obtained.
  • a reactor an autoclave with a stirrer etc. can be used, for example.
  • the catalyst acts to efficiently hydrogenate the benzene ring of BHET.
  • a catalyst is not particularly limited, but preferably contains at least one of a noble metal and a noble metal alloy.
  • Such catalysts include simple noble metals such as Ru, Rh, Pd, Os, Ir, and Pt, alloys of two or more noble metals, noble metals and Ni, Co, Fe, Zn, Cu, Mn, Pd, Metal elements such as Cd, Cr, Ag, Au, Hg, Ga, In, Ge, Sn, Ti, Al, Si, alkaline earth metal elements such as Ca, Mg, Gr, Ba, and Li, Na, K, Rb , An alloy with at least one metal element of Cs alkali metal, and the like.
  • the catalyst preferably contains Ru (ruthenium).
  • the ruthenium catalyst can selectively hydrogenate the benzene ring of BHET.
  • the ruthenium catalyst can suppress hydrogenation of the ester group of BHET (—COOCH 2 CH 2 OH), 1,4-cyclohexanedibenzene in which both the benzene ring and the ester group are hydrogenated from BHET.
  • Generation of methanol hereinafter referred to as “CHDM”) can be suppressed. Therefore, by using a ruthenium catalyst, generation of a by-product (for example, CHDM) can be suppressed and cis-BHEC with high purity can be obtained with high yield.
  • BHEC produced by nuclear hydrogenation of BHET in the presence of a ruthenium catalyst contains trans-BHEC in addition to cis-BHEC. That is, in the presence of a ruthenium catalyst, high-purity BHEC can be obtained in a high yield by the reaction of BHET and hydrogen gas, and the obtained BHEC contains cis-BHEC and trans-BHEC. I found it.
  • a noble metal or a noble metal alloy (hereinafter simply referred to as “noble metal”) can be used as it is, but it is preferably used as a noble metal-supported carrier catalyst in which a noble metal is supported on a carrier.
  • the support adsorbs the noble metal and disperses the points acting as a catalyst (catalytic active points) on the surface of the support.
  • the contact area of a catalyst active point and BHET can be enlarged, the efficiency of the nuclear hydrogenation of BHET can be improved more.
  • durability as a catalyst can also be improved by carrying
  • the carrier for supporting the noble metal is preferably a carrier containing at least one of carbon (activated carbon), alumina, silica, titania, magnesia, zirconia, silica alumina, zeolite, clay, kaolin, talc and bentonite.
  • a carrier containing at least one of carbon, alumina, silica, titania, magnesia and zirconia is more preferred, and a carrier containing carbon is particularly preferred.
  • the amount (content) of noble metal supported on the noble metal-supported carrier is not particularly limited, but is preferably about 0.1 to 10 wt%, and more preferably about 0.5 to 10 wt%.
  • a noble metal-supported carrier catalyst in which catalytic active sites are uniformly dispersed on the surface of the carrier can be obtained while suppressing the amount of expensive noble metal used.
  • BHET can be efficiently nuclear hydrogenated at a low cost, and high purity BHEC can be obtained in a high yield.
  • such a ruthenium-supported carrier catalyst has high durability as described above, it can be reused as a catalyst by separating and recovering.
  • an activation treatment may be performed in which the noble metal is heated in advance in various gas streams such as hydrogen, nitrogen, argon, and carbon dioxide.
  • the treatment temperature is preferably about 50 to 700 ° C., more preferably about 80 to 600 ° C.
  • the activation treatment time can be appropriately adjusted depending on the amount of noble metal supported on the carrier and the treatment temperature, and can be, for example, about 0.1 to 100 hours.
  • the charging ratio of BHET and catalyst charged into the autoclave (reactor) is not particularly limited, but is preferably 100: 0.1 to 100: 10 by weight ratio of BHET and catalyst, and is preferably 100: 1 to 100 : 5 is more preferable.
  • BHET can be efficiently nuclear hydrogenated in a shorter time, and side reactions other than the BHET nuclear hydrogenation reaction (for example, hydrogenation reaction of the ester group of BHET) can be more reliably suppressed. it can.
  • BHEC with higher purity can be obtained with good yield.
  • the melting point of BHET is relatively high (about 110 ° C.)
  • a large amount of heat is required to increase the fluidity of BHET by heating. Therefore, in order to improve the fluidity of BHET, it is effective to dissolve or disperse BHET in a liquid medium. Further, by using a liquid medium, the heat of reaction is reduced, and side reactions can be more reliably suppressed.
  • the reactant, catalyst and liquid medium are charged into the autoclave and stirred with an autoclave agitator to dissolve or disperse the reactant and catalyst in the liquid medium. In this state, it is preferable to carry out nuclear hydrogenation of BHET.
  • the liquid medium that can be used in this step is not particularly limited as long as it does not adversely affect the nuclear hydrogenation reaction of BHET, but preferably contains at least one of a diol and an aprotic polar solvent. Since these liquid media have high solubility in BHET, the fluidity of BHET can be improved. In addition, side reactions such as polymerization can be suppressed during the BHET nuclear hydrogenation reaction. Therefore, by using such a liquid medium, BHEC with higher purity can be obtained with high yield.
  • the diol is not particularly limited, but preferably contains at least one of ethylene glycol, propylene glycol, butanediol and the like.
  • the aprotic polar solvent is not particularly limited, but preferably contains at least one of N, N-dimethylformamide, dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone.
  • ethylene glycol is particularly preferable from the viewpoint that it is a diol constituting BHET and has a high solubility of BHET and a high effect of suppressing side reactions such as polymerization.
  • the amount (amount of use) of the liquid medium charged into the autoclave is not particularly limited, but is preferably 5:95 to 90:10 by weight ratio of BHET to the liquid medium, and 10:90 to 70:30. More preferably. If the usage-amount of a liquid medium is in the said range, while the nuclear hydrogenation reaction of BHET advances efficiently, a side reaction can be suppressed more. As a result, the productivity of BHEC can be improved and the yield of BHEC can be further increased.
  • the inside of the autoclave is vacuum degassed (degassed under reduced pressure) and then filled with a reaction gas containing hydrogen gas, or the air inside the autoclave contains hydrogen gas Replace with reaction gas.
  • a reaction gas containing hydrogen gas or the air inside the autoclave contains hydrogen gas Replace with reaction gas.
  • reaction gas filled in the autoclave may be hydrogen gas alone or a mixed gas of nitrogen, argon, carbon dioxide gas and hydrogen gas.
  • the partial pressure of hydrogen gas (when hydrogen gas alone is used, the total pressure) is not particularly limited, but is preferably about 1 to 10 MPa, more preferably about 2 to 8 MPa, More preferably, it is about 3 to 6 MPa. If the partial pressure of the hydrogen gas is within the above range, the hydrogen gas reacts more selectively with the benzene ring of BHET, and the nuclear hydrogenation of BHET proceeds more rapidly. As a result, BHEC can be obtained efficiently. Further, with such a partial pressure, the burden on the autoclave can be suppressed, so that BHEC can be repeatedly manufactured with the same equipment over a long period of time, and the running cost can be suppressed. In addition, it is preferable to supply hydrogen gas continuously or intermittently in the autoclave so that the partial pressure of hydrogen gas in the autoclave becomes constant during the nuclear hydrogenation of BHET.
  • the reaction temperature (temperature in the autoclave) when reacting BHET with hydrogen gas is preferably about 80 to 200 ° C., more preferably about 85 to 180 ° C., and about 80 to 170 ° C. More preferably.
  • hydrogen gas reacts more selectively with the benzene ring of BHET, and the nuclear hydrogenation of BHET proceeds rapidly.
  • reaction temperature is in the said range, side reactions (BHET ester group hydrogenation reaction etc.) other than the BHET nuclear hydrogenation reaction can be more reliably suppressed.
  • high purity BHEC can be obtained in a higher yield.
  • the burden on the autoclave can be suppressed, so that the running cost can be suppressed.
  • reaction time of BHET and hydrogen gas is appropriately adjusted depending on the type of catalyst used, the charging ratio of the raw material and the catalyst, the pressure of the reaction gas (partial pressure of hydrogen gas), the reaction temperature, etc., and is not particularly limited. For example, it can be about 2 to 20 hours.
  • reaction format for obtaining BHEC can be performed batchwise (batch), continuous, or a combination of batch and continuous.
  • a reactor autoclave
  • a cooler such as a total reflux cooler
  • a known continuous fixed bed reactor can be used as the continuous hydrogenation apparatus.
  • the crude BHEC After performing the hydrogenation reaction as described above, it is cooled to room temperature (about 20 ° C.) as necessary. Thereafter, the crude BHEC can be obtained by separating the catalyst from the reaction system in the autoclave.
  • the content of BHEC in the crude BHEC is preferably 80 wt% or more. According to the above method, the production of by-products can be suppressed, and BHEC with high purity can be obtained.
  • the obtained crude BHEC contains cis-BHEC and trans-BHEC.
  • the weight ratio of cis-BHEC to trans-BHEC in the crude BHEC is preferably 99: 1 to 35:65.
  • a raw material containing cis-BHEC can be obtained.
  • cis-BHAC can be obtained by nuclear hydrogenation of bis (2-hydroxyalkyl) terephthalate (BHAT) in the same manner as cis-BHEC.
  • n represents an integer of 2 or more.
  • an autoclave with a stirrer etc. can be used, for example.
  • the method for producing trans-BHAC of the present invention is characterized in that a basic oxide is used as a catalyst (isomerization catalyst) for isomerizing cis-BHAC. That is, cis-BHAC can be rapidly isomerized to trans-BHAC by contacting the basic oxide with cis-BHAC.
  • a basic oxide by using a basic oxide, side reactions other than the isomerization reaction of cis-BHAC (for example, ester hydrolysis reaction, hydroxyl group dehydration condensation reaction, etc.) can be suppressed.
  • trans-BHAC with high purity can be obtained with good yield.
  • the basic oxide does not corrode the production apparatus (reactor) like the acidic catalyst. Therefore, in the trans-BHAC production method of the present invention, the burden on the reactor can be suppressed, so that the trans-BHAC can be repeatedly produced with the same equipment over a long period of time, and the running cost can be suppressed.
  • the basic oxide acts as a catalyst for efficiently isomerizing cis-BHAC.
  • the basic oxide is an oxide of a metal element.
  • a metal element is not particularly limited, but preferably contains at least one of an alkali metal and an alkaline earth metal.
  • cis-BHAC can be efficiently isomerized, and side reactions (eg, ester hydrolysis) can be more reliably performed. Can be suppressed.
  • side reactions eg, ester hydrolysis
  • an alkaline earth metal oxide preferably contains at least one of barium oxide, calcium oxide, and magnesium oxide.
  • examples of the method of bringing the basic oxide into contact with cis-BHAC include a suspension bed method and a fixed bed method.
  • a suspension bed system it is preferable to use a powder of a basic oxide.
  • a fixed bed system it is preferable to use a molded product obtained by molding a basic oxide.
  • the basic oxide powder a powder having an arbitrary particle size distribution can be used.
  • the shape of the molded product is not particularly limited, but is preferably a columnar shape from the viewpoint of easy molding.
  • the charging ratio of cis-BHAC and basic oxide charged into the autoclave (reactor) is not particularly limited, but is 100: 0.1 to 100: 10 in terms of the weight ratio of cis-BHAC to basic oxide. It is preferable that the ratio is 100: 0.5 to 100: 5.
  • cis-BHAC can be efficiently isomerized in a shorter time, and side reactions other than the isomerization reaction of cis-BHAC (for example, ester hydrolysis reaction, etc.) can be more reliably suppressed. Can do.
  • trans-BHAC with higher purity can be obtained with good yield.
  • the raw materials, the basic oxide and the liquid medium are put into an autoclave and stirred by an autoclave stirrer to dissolve the raw materials and cis-BHAC in the liquid medium. It is preferable to isomerize cis-BHAC in a dispersed state.
  • the liquid medium usable in this step is not particularly limited as long as it does not adversely affect the isomerization reaction of cis-BHAC, but diols such as ethylene glycol, propylene glycol and butanediol, N, N-dimethylformamide, dimethyl
  • diols such as ethylene glycol, propylene glycol and butanediol, N, N-dimethylformamide, dimethyl
  • a liquid medium containing at least one of aprotic polar solvents such as sulfoxide and 1,3-dimethyl-2-imidazolidinone is preferred.
  • ethylene glycol is particularly preferable from the viewpoint of high compatibility with cis-BHAC and a high effect of suppressing the occurrence of side reactions.
  • the amount (amount of use) of the liquid medium charged into the autoclave is not particularly limited, but is preferably 20:80 to 99: 1 as a weight ratio of cis-BHAC to the liquid medium, and 20:80 to 90: 10 is preferable. If the amount of the liquid medium used is within the above range, the isomerization reaction of cis-BHAC proceeds efficiently and side reactions can be further suppressed. As a result, the productivity of trans-BHAC can be improved and the yield of trans-BHAC can be further increased.
  • the isomerization reaction of cis-BHAC is preferably performed in an inert gas atmosphere.
  • an inert gas is preferably a gas containing at least one of nitrogen gas and argon gas.
  • this process can be performed in the state which made the pressure in an autoclave normal pressure (atmospheric pressure), when the liquid medium to be used is a low boiling point liquid, it can also be pressurized and performed.
  • the pressure inside the autoclave is preferably about 1 to 10 MPa.
  • the reaction temperature (temperature in the autoclave) when isomerizing cis-BHAC is not particularly limited, but is preferably about 160 to 300 ° C, more preferably about 180 to 280 ° C, and more preferably 180 to 240. More preferably, the temperature is about ° C. If the reaction temperature is within the above range, isomerization of cis-BHAC proceeds rapidly. In addition, if the reaction temperature is within the above range, the lower temperature more reliably suppresses side reactions (ester hydrolysis reaction, dehydration condensation reaction, etc.) other than cis-BHAC isomerization reaction, and the reaction mixture The coloring of can also be suppressed. As a result, high-purity trans-BHAC can be obtained in a higher yield.
  • the burden on the autoclave can be suppressed, so that the running cost can be suppressed.
  • the reaction temperature is about 160 to 200 ° C.
  • a low-boiling solvent can be used as the liquid medium, and further, the reaction can be performed at normal pressure (atmospheric pressure). Therefore, it is not necessary to use a high-pressure apparatus, and a relatively inexpensive reactor can be used, which is industrially advantageous.
  • the reaction time for isomerizing cis-BHAC is appropriately adjusted depending on the type of basic oxide to be used, the ratio of raw materials to basic oxide, the pressure in the autoclave, the reaction temperature, etc. Although not, for example, it may be about 2 to 20 hours.
  • reaction mode for obtaining trans-BHAC can be carried out in a batch mode (batch mode), a continuous mode, or a combination of a batch mode and a continuous mode, as in the above-described nuclear hydrogenation reaction of BHET. Also,
  • crude trans-BHAC can be obtained by fractionating the basic oxide from the reaction system in the autoclave.
  • the content of trans-BHAC in the crude trans-BHAC is preferably 60 wt% or more. That is, a BHAC having a trans-BHAC content of 60 wt% or more (the BHAC of this embodiment) can be obtained.
  • the method for producing trans-BHAC of this embodiment the production of by-products can be suppressed, and high-purity trans-BHAC can be obtained.
  • the obtained crude trans-BHAC can be purified using a known separation and purification method such as distillation or recrystallization.
  • the basic oxide separated from the above reaction system can be reused repeatedly. That is, a new raw material and a basic oxide separated and recovered from the reaction system are charged into an autoclave, and cis-BHAC is isomerized in the same manner as above to obtain trans-BHAC. Thus, even when the used basic oxide is reused, cis-BHAC can be isomerized to obtain high-purity trans-BHAC in high yield.
  • trans- cyclohexane dicarboxylate bis (2-hydroxyalkyl) of this invention was demonstrated, this invention is not limited to this, One or two or more processes for arbitrary objectives are added. You may make it do.
  • Example 1 a raw material containing cis-1,4-cyclohexanedicarboxylate bis (2-hydroxyethyl) (cis-BHEC) was obtained from a polyethylene terephthalate (PET) bottle by the method shown below.
  • cis-BHEC cis-1,4-cyclohexanedicarboxylate bis (2-hydroxyethyl)
  • the above mixed solution is supplied to a jacket type vertical thin film evaporator (UIC, “RF-6”) with a stirrer, and mixed under the conditions of a jacket temperature of 150 ° C. and an internal pressure of the evaporator body of 533 Pa.
  • the low boiling point component was evaporated from the liquid to obtain a first-stage concentrated liquid.
  • the concentrated solution in the first stage is supplied again to the jacket type vertical thin film evaporator with a stirrer (manufactured by UIC, “RF-6 type”), jacket temperature 150 ° C., internal pressure of the evaporator main body.
  • the remaining low-boiling component in the concentrate was evaporated under the condition of 133 Pa to obtain a second-stage concentrated solution (high-boiling component).
  • the second stage concentrated liquid (high boiling point component) is supplied to a jacket type vertical thin film evaporator (UIC, “RF-6 type”) equipped with a stirrer, and the BHET evaporation fraction and evaporation residue (bottle)
  • the conditions were set so that the weight ratio of the remaining) was 8: 2.
  • the setting conditions at this time were a jacket temperature of 202 ° C. and an internal pressure of the evaporator body of 13 Pa.
  • the temperature in the autoclave is set to 130 ° C. while continuing to supply hydrogen gas into the autoclave so that the partial pressure of hydrogen gas in the autoclave is maintained at 3 MPa.
  • BHET nuclear hydrogenation was carried out for 1 hour.
  • the obtained crude BHEC (raw material) contained 1,4-cyclohexanedicarboxylate bis (2-hydroxyethyl) (BHEC) having a purity of 89.3 wt% and a trans isomer ratio of 19.6%.
  • reaction rate (%) of cis-BHEC was calculated from the following formula from the cis-isomer ratio (%) of the raw material and product obtained by the previous formula.
  • Response rate of cis-BHEC (%) (Cis isomer ratio of raw material-cis isomer ratio of product) / cis isomer ratio of raw material x 100
  • Example 2 As a catalyst, isomerization was performed in the same manner as in Example 1 except that 1 g of calcium oxide powder (commercial special grade) was used instead of barium oxide powder to obtain a reaction mixture. Thereafter, the same post-treatment as in Example 1 was performed to obtain a crude trans-BHEC.
  • the crude trans-BHEC obtained in this example was 38.2 g.
  • the BHEC purity of crude trans-BHEC was 77.7 wt%
  • the trans isomer ratio was 68.8%
  • the reaction rate of cis-BHEC was 61.2%.
  • Example 3 Example 1 except that the amount of barium oxide powder was 2 g (weight ratio to cis-BHEC: about 7 wt%), the reaction temperature in the autoclave was 200 ° C., and the stirring time (reaction time) was 10 hours. Then, isomerization was performed to obtain a reaction mixture. Thereafter, the same post-treatment as in Example 1 was performed to obtain a crude trans-BHEC.
  • the crude trans-BHEC obtained in this example was 38.8 g.
  • the BHEC purity of crude trans-BHEC was 85.8 wt%
  • the trans isomer ratio was 66.9%
  • the reaction rate of cis-BHEC was 58.8%.
  • Example 4 Isomerization is performed in the same manner as in Example 3 except that the amount of EG as a solvent is 30 g (weight ratio with respect to cis-BHEC: about 105 wt%), and the reaction temperature in the autoclave is 180 ° C. A mixture was obtained. The hue of this reaction mixture was the least colored compared to the reaction mixture obtained in Example 1 (reaction temperature 260 ° C.) and Example 3 (reaction temperature 200 ° C.). Thereafter, the same post-treatment as in Example 1 was performed to obtain a crude trans-BHEC. The crude trans-BHEC obtained in this example was 39.0 g. As a result of gas chromatography analysis, the BHEC purity of crude trans-BHEC was 88.8 wt%, the trans isomer ratio was 66.5%, and the reaction rate of cis-BHEC was 58.3%.
  • Example 1 Isomerization was performed in the same manner as in Example 1 except that 1 g of aluminum oxide powder (commercial special grade) was used in place of barium oxide powder as a catalyst, to obtain a reaction mixture. Thereafter, the same post-treatment as in Example 1 was performed to obtain a crude trans-BHEC.
  • the crude trans-BHEC obtained in this comparative example was 33.5 g.
  • the BHEC purity of crude trans-BHEC was 83.0 wt%
  • the trans isomer ratio was 51.7%
  • the reaction rate of cis-BHEC was 39.9%.
  • Example 2 As a catalyst, isomerization was performed in the same manner as in Example 1 except that 1 g of zinc oxide powder (commercial special grade) was used instead of barium oxide powder to obtain a reaction mixture. Thereafter, the same post-treatment as in Example 1 was performed to obtain crude trans-BHEC.
  • the crude trans-BHEC obtained in this comparative example was 34.2 g.
  • the BHEC purity of the crude trans-BHEC was 82.0 wt%
  • the trans isomer ratio was 35.7%
  • the reaction rate of cis-BHEC was 20.0%.
  • Table 1 shows the results of analyzing the composition of the crude trans-BHEC obtained in each Example and each Comparative Example using gas chromatography. Moreover, the color of the reaction liquid mixture of each Example and each comparative example was confirmed visually, and the coloring level was evaluated in accordance with the following criteria. The results are shown in Table 1.
  • Example 1 gas chromatograms of the reaction mixture obtained in Example 1, Example 3 and Example 4 are shown in FIG. 1, FIG. 2 and FIG. 3, respectively.
  • the trans isomer ratio in the crude trans-BHEC obtained in Examples 1 to 4 is 60% or more, and high-purity trans-BHEC can be obtained from the raw material containing cis-BHEC. did it.
  • the yield of trans-BHEC is sufficiently high. it was high.
  • Example 3 was less colored than Example 1, and Example 4 was even less colored than Example 3.
  • FIGS. 1 to 3 from the gas chromatogram of each reaction mixture obtained in Example 1, Example 3 and Example 4, the hydrolyzate of ester and other by-products in the reaction mixture are obtained.
  • the amount of the product was small in the order of Example 1, Example 3, and Example 4. Therefore, even in the preferable reaction temperature range, by carrying out the reaction at a temperature as low as possible, the obtained reaction mixture solution was small in color and obtained side reactions. Furthermore, if the reaction temperature is a relatively low temperature of about 160 to 200 ° C., the reaction can be carried out at normal pressure. Therefore, it is not necessary to use a high-pressure apparatus, and a relatively inexpensive reactor can be used, which is industrially advantageous.

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Abstract

Le problème décrit par la présente invention est de fournir un procédé de production de trans-bis(2-hydroxyalkyl) cyclohéxanedicarboxylate (trans-BHAC) permettant d'obtenir du trans-BHAC de manière simple avec un rendement élevé. La solution selon l'invention porte sur un procédé de production de trans -BHAC caractérisé en ce que du trans -BHAC est obtenu par isomérisation de cis-bis(2-hydroxyalkyl) cyclohéxanedicarboxylate (cis-BHAC) par la mise en contact avec un oxyde basique. L'isomérisation est de préférence effectuée à une température de 160 °C à 300° C. Le rapport massique du cis-BHAC et de l'oxyde basique est de préférence 100:0,1 – 100:10.
PCT/JP2017/025540 2016-10-28 2017-07-13 Procédé de production de trans-bis(2-hydroxyalkyl) cyclohéxanedicarboxylate, et bis(2-hydroxyalkyl) cyclohéxanedicarboxylate WO2018078961A1 (fr)

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ES17865839T ES2943583T3 (es) 2016-10-28 2017-07-13 Método de producción para trans-ciclohexanodicarboxilato de bis(2-hidroxialquilo), y ciclohexanodicarboxilato de bis(2-hidroxialquilo)

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