CN105849074A - Method for producing hydrogenated phenolic compound and method for separating hydrogenated phenolic compound - Google Patents
Method for producing hydrogenated phenolic compound and method for separating hydrogenated phenolic compound Download PDFInfo
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- CN105849074A CN105849074A CN201480071244.7A CN201480071244A CN105849074A CN 105849074 A CN105849074 A CN 105849074A CN 201480071244 A CN201480071244 A CN 201480071244A CN 105849074 A CN105849074 A CN 105849074A
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- hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/14—Benz[f]indenes; Hydrogenated benz[f]indenes
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Abstract
Provided is an industrially easy method that makes it possible to reduce the amount of solvent used and to produce a high-purity hydrogenated phenolic compound in an easy-to-handle state. The present invention relates to a method for producing a compound represented by formula (2) by hydrogenating a compound represented by formula (1), wherein the method for producing a hydrogenated phenolic compound is characterized in that the hydrogenation reaction is conducted by using a dihydric alcohol as the reaction solvent, the hydrogenation reaction product containing a compound represented by formula (2) and dihydric alcohol obtained by the hydrogenation reaction is then distilled in the joint presence of at least one compound selected from the group comprising an aliphatic hydrocarbon having 7-18 carbon atoms, an aromatic hydrocarbon having 7-18 carbon atoms, and a hydroxyl group-free ether having 7-18 carbon atoms, and the dihydric alcohol is separated from the hydrogenation reaction product. In formula (1), X represents a single bond, alkylene group, cycloalkylene group, or cycloalkylidene group. R1 and R2 are the same or different and represent an alkyl group having 1-5 carbon atoms. m and n are the same or different and represent an integer of 0-4. In formula (2), X, R1, R2, m, and n are the same as above.
Description
Technical field
The present invention relates to be manufactured as the resin that thermostability, hydrolytic resistance, weatherability, the transparency etc. are excellent
The method of the important hydrogenation phenolic compounds of raw material or its intermediate, and separate the side of hydrogenation phenolic compounds
Method.Japanese Patent Application 2013-229959 that the application filed an application in Japan based on November 6th, 2013
Number claim priority, and its content is incorporated herein.
Background technology
At present, it is proposed that some make 4, there is the phenolic compounds of 2 hydroxy phenyls in 4'-xenol equimolecular
(phenols) hydrogenates in the presence of the solvent, generates and hydrogenates phenolic compounds accordingly (such as: employ
Be 4,4'-dicyclohexano in the case of 4,4'-xenol) method.Such as, in patent documentation 1, open
On the activated carbon in the presence of the catalyst of supported palladium, use individually as solvent or with the addition of to
The ethyl acetate of water, methyl t-butyl ether, ethanol or the hexamethylene of many 2 capacity %, makes 4,4'-biphenyl
The method that phenol carries out hydrogenating and manufactures 4,4'-dicyclohexano.
It addition, such as, Patent Document 2 discloses depositing at natrium carbonicum calcinatum and palladium-carbon catalyst
Under, using 2-propanol as solvent, making 4,4'-xenol carries out hydrogenating and manufacturing 4, the side of 4'-dicyclohexano
Method.
Further, such as, disclose ethylene glycol monoalkyl ether as molten in patent documentation 3 and 4
Agent, makes 4, and 4'-xenol carries out hydrogenating and manufacturing 4, the method for 4'-dicyclohexano.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 64-34935 publication
Patent documentation 2: Japanese Unexamined Patent Publication 1-156935 publication
Patent documentation 3: Japanese Unexamined Patent Publication 3-275637 publication
Patent documentation 4: Japanese Unexamined Patent Publication 4-279537 publication
Summary of the invention
The problem that invention is to be solved
Generally, due to the fusing point of the intramolecular phenolic compounds with 2 hydroxy phenyls higher (such as:
The fusing point of 4,4'-xenols is 280 DEG C), therefore when carrying out its hydrogenation, need to use solvent to make
Above-mentioned phenolic compounds forms solution or slurry form improves mobility, and makes it good with catalyst and hydrogen
Contact well, promote hydrogenation.Then, can be described above in patent documentation 1～4 as above-mentioned solvent
Disclosed such, use ethyl acetate, methyl t-butyl ether, ethanol, hexamethylene, 2-propanol, second two
Alcohol monoalky lether equal solvent.
But, above-mentioned phenolic compounds (such as: 4,4'-xenols) is low relative to the dissolubility of above-mentioned solvent,
In order to make above-mentioned phenolic compounds formation solution or slurry form to improve mobility, there is use substantial amounts of molten
The needs of agent.Further, since after terminating hydrogenation, by anti-to hydrogenation catalyst (solid) and hydrogenation
Answer liquid to be isolated by filtration, centrifugation, the method such as settlement separate carry out solid-liquid separation, therefore exist by
The hydrogenation phenolic compounds (such as: 4,4'-dicyclohexano) generated is dissolved completely in the needs of solvent, from the party
Face considers, there is also the needs using a large amount of solvents.
Therefore, present situation is to use above-mentioned solvent to carry out the hydrogenation of above-mentioned phenolic compounds, becoming
Need hydrogenation equipment the biggest compared with the volume of production of hydrogenation phenolic compounds, its result, obtain
Product also can become high price.Such as, in patent documentation 1, relative to 4,4'-xenol 40g, use
As ethyl acetate 500mL (445g) of solvent, 4 in the slurry obtained or solution, 4'-xenol
Concentration is only 8.2 weight %.It addition, in patent documentation 2, relative to 4,4'-xenol 100g, make
With the isopropanol 1 as solvent, 000mL (780g), 4 in the slurry obtained or solution, 4'-xenol
Concentration be only 11 weight %.Additionally, in patent documentation 3, relative to 4,4'-xenol 500g,
Employing the propylene glycol monomethyl ether 2 as solvent, 000mL (1,850g), in the slurry obtained or solution
The concentration of 4,4'-xenol is only 21 weight %.
The present inventor, previously for needing the problem of above-mentioned substantial amounts of solvent, as its solution, sends out
Show by utilizing in the hydrogenation of phenolic compounds generates the method for hydrogenation phenolic compounds, used work
The binary of both dissolubilities excellence of the phenolic compounds for raw material and the hydrogenation phenolic compounds as product
Alcohol is as reaction dissolvent, it is possible to cut down the usage amount of solvent, well can be manufactured inexpensively hydrogenation with efficiency
The method (Japanese Patent Application 2013-192052) of phenolic compounds.
But, the fusing point hydrogenating phenolic compounds owing to utilizing above-mentioned hydrogenation to obtain is high (such as: 4,4'-
The fusing point of dicyclohexano is 184 DEG C), it addition, the boiling point of the dihydroxylic alcohols of reaction dissolvent is the highest, therefore upper
State in method and be separated into dihydroxylic alcohols with maneuverable state in hydrogenation phenolic compounds operation later
Problem.Such as, by distillation from utilize that above-mentioned hydrogenation obtains containing dihydroxylic alcohols and hydrogenation phenolate
In the hydrogenation thing (hereinafter sometimes referred to simply as " hydrogenation thing ") of compound in the case of separation of glycols,
Can solidify owing to hydrogenating phenolic compounds in a reservoir, therefore after the operating difficulties of operation.Further, since
If adding solvent, then dihydroxylic alcohols and hydrogenation to the hydrogenation thing containing dihydroxylic alcohols and hydrogenation phenolic compounds
Phenolic compounds can condense and solidify, and is the most also difficult to dividing of hydrogenation phenolic compounds based on crystallization
From.
Therefore, it is an object of the invention to provide and can manufacture highly purified hydrogenation with maneuverable state
The easy method manufacturing hydrogenation phenolic compounds phenolic compounds, industrial.
It addition, other purpose of the present invention is, it is provided that can be from containing dihydroxylic alcohols and hydrogenation phenolic compounds
Mixture in maneuverable state separating high-purity hydrogenation phenolic compounds, industrial readily
The method separating hydrogenation phenolic compounds.
The method of solution problem
The present inventor conducts in-depth research to solve the problems referred to above, found that: can be by using
The hydrogenation carrying out the phenolic compounds that intramolecular has 2 hydroxy phenyls as the dihydroxylic alcohols of reaction dissolvent is anti-
Should, then, in the hydrogenation thing utilizing this hydrogenation to obtain, interpolation is molten with dihydroxylic alcohols azeotropic
Agent, and dihydroxylic alcohols is carried out azeotropic separation, and manufacture highly purified hydrogenation phenolate with maneuverable state
Compound, and then complete the present invention.
That is, the present invention provides the manufacture method of hydrogenation phenolic compounds, and it is the change utilizing following formula (1) to represent
The hydrogenation of compound manufactures the method for the compound that following formula (2) represents,
[chemical formula 1]
[in formula (1), X represents singly-bound, alkylidene, cycloalkylidene (シ Network ロ ア Le キ レ Application base) or ring
Alkylidene (シ Network ロ ア Le キ リ デ Application base).R1And R2Identical or different, represent carbon number 1～5
Alkyl.M and n is identical or different, represents the integer of 0～4.]
[chemical formula 2]
[in formula (2), X, R1、R2, m and n same as described above.]
Wherein, dihydroxylic alcohols is carried out above-mentioned hydrogenation as reaction dissolvent, then, above-mentioned hydrogen will be utilized
Change the compound represented containing formula (2) that obtains of reaction and the hydrogenation thing of dihydroxylic alcohols, and selected from carbon atom
The aliphatic hydrocarbon of several 7～18, the aromatic hydrocarbon of carbon number 7～18 and do not contain the carbon number of hydroxyl
At least one compound in the ether of 7～18 coexists and distills, and separates from above-mentioned hydrogenation thing
Dihydroxylic alcohols.
Further providing for the manufacture method of above-mentioned hydrogenation phenolic compounds, wherein, above-mentioned dihydroxylic alcohols is fat
Race's glycol or poly alkylene glycol.
Further provide for hydrogenating the separation method of phenolic compounds, wherein, the hydrogen that will represent containing following formula (2)
Change phenolic compounds and the mixture of dihydroxylic alcohols, and selected from the aliphatic hydrocarbon of carbon number 7～18, carbon atom
At least one compound in the ether of the aromatic hydrocarbon of several 7～18 and the carbon number 7～18 that do not contains hydroxyl
Coexist and distill, separation of glycols from said mixture.
[chemical formula 3]
[in formula (2), X represents singly-bound, alkylidene, cycloalkylidene or cycloalkanes fork.R1And R2Identical or
Difference, represents the alkyl of carbon number 1～5.M and n is identical or different, represents the integer of 0～4.]
The effect of invention
Owing to the manufacture method of the hydrogenation phenolic compounds of the present invention has above-mentioned composition, even if therefore by steaming
Evaporate separation of glycols from hydrogenation thing, also because container existing beyond dehydrogenation phenolic compounds and being selected from
The aliphatic hydrocarbon of carbon number 7～18, the aromatic hydrocarbon of carbon number 7～18 and do not contain the carbon of hydroxyl
At least one solvent (following, sometimes this solvent to be referred to as " azeotropic solvent ") in the ether of atomic number 7～18,
Therefore hydrogenation phenolic compounds exists with liquid or pulp-like, can manufacture high-purity with maneuverable state
Hydrogenation phenolic compounds, therefore, industrial enforcement is easy.Further, since the hydrogenation phenolate of the present invention
The separation method of compound has above-mentioned composition, can be from containing dihydroxylic alcohols and the mixture of hydrogenation phenolic compounds
In with the hydrogenation phenolic compounds of maneuverable state separating high-purity, therefore, industrial enforcement is easy.
Therefore, if using the manufacture method of hydrogenation phenolic compounds by the present invention or dividing of hydrogenation phenolic compounds
The hydrogenation phenolic compounds obtained from method, then can obtain at a low price thermostability, hydrolytic resistance, weatherability,
The resin of the excellences such as the transparency or resin raw material.
Accompanying drawing explanation
The skeleton diagram of the distilling apparatus used in [Fig. 1] embodiment 1.
Symbol description
1 heater
2 thermometeies
3 blenders
4 condensers
5 decanters
Phase liquid accepter on 6
7 times phase liquid accepters
8 reflux pumps
9 four-hole boiling flasks
Detailed description of the invention
The manufacture method of the hydrogenation phenolic compounds of the present invention, for the compound (phenol utilizing following formula (1) to represent
Compound) the hydrogenation method that manufactures the compound (hydrogenation phenolic compounds) that following formula (2) represents, for
Carry out above-mentioned hydrogenation using dihydroxylic alcohols as reaction dissolvent, then, obtain utilizing above-mentioned hydrogenation
The compound represented containing formula (2) and the hydrogenation thing of dihydroxylic alcohols, and selected from carbon number 7～18
Aliphatic hydrocarbon, the aromatic hydrocarbon of carbon number 7～18 and do not contain the ether of carbon number 7～18 of hydroxyl
In at least one compound (solvent) coexist and distill, from above-mentioned hydrogenation thing separate (azeotropic
Separate) method of dihydroxylic alcohols.
[chemical formula 4]
[chemical formula 5]
In formula (1) and formula (2), X represents singly-bound, alkylidene, cycloalkylidene or cycloalkanes fork.Make
For alkylidene, can enumerate such as: methylene, ethylidene, trimethylene, tetramethylene, pentamethylene
The straight-chain alkylidenes such as the straight-chain alkylidene Deng carbon number 1～6；Propylidene (propane-1,2-diyl),
The branched alkylene of the carbon numbers 3～6 such as propane-2,2-diyl, dimethylethylene, butane-2,2-diyl
The branched alkylidenes etc. such as base.As cycloalkylidene, can enumerate such as: 1,2-cyclopentylene, 1,3-Asia ring
Amyl group, 1,2-cyclohexylidene, 1,3-cyclohexylidene, 1,4-cyclohexylidene etc..Pitch as cycloalkanes, can enumerate
Such as: cyclopentylidene, cyclohexylidene etc..Wherein, as X, preferably singly-bound, carbon number 1～4 straight
Chain alkylidene, the branched alkylidene of carbon number 3 or 4, cycloalkanes are pitched, particularly preferred singly-bound, carbon
The straight-chain alkylidene of atomic number 1～3, the branched alkylidene of carbon number 3, cycloalkanes are pitched.
R in formula (1) and formula (2)1And R2Identical or different, represent the alkyl of carbon number 1～5.
As the alkyl of carbon number 1～5, can enumerate such as: methyl, ethyl, n-pro-pyl, isopropyl, just
Butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl etc..It should be noted that be 2 at m (or n)
In the case of above, multiple R1(or R2) can be the most identical, it is also possible to different.It addition, in formula (1)
And m and n in formula (2) is identical or different, represent the integer (integers of preferably 0～2) of 0～4.Need
Be noted that in the case of m is 0, be denoted as in formula (1) left side phenyl ring (or, formula (2)
The cyclohexane ring in middle left side) in substituent group, R1Do not exist.Similarly, in the case of n is 0,
It is denoted as in formula (1) substituent group in the phenyl ring (or, the cyclohexane ring on right side in formula (2)) on right side, R2Do not deposit
?.
For the bonding position of hydroxyl in phenyl ring (or cyclohexane ring) in formula (1) (or formula (2)), limit the most especially
Fixed, such as, if using the position of the carbon atom of X Direct Bonding in formula as 1, then can enumerate such as
It it is 4.
The compound represented as formula (1), more specifically, can enumerate such as: 4,4'-xenols, bis-phenol
[2,2-is double for A [4,4'-(propane-2,2-diyl) biphenol], Bisphenol F [double (4-hydroxy phenyl) methane], bisphenol b
(4-hydroxy phenyl) butane], bis-phenol E [1,1-double (4-hydroxy phenyl) ethane], bisphenol-c [double (the 3-methyl of 2,2-
-4-hydroxy phenyl) propane], bisphenol Z [1,1-bis(4-hydroxyphenyl)-cyclohexane] etc..
The compound represented as formula (2), more specifically, can enumerate such as: 4,4'-dicyclohexano, hydrogen
Change bisphenol-A [double (4-hydroxy-cyclohexyl) propane of 2,2'-], A Hydrogenated Bisphenol A F, A Hydrogenated Bisphenol A B, A Hydrogenated Bisphenol A
E, A Hydrogenated Bisphenol A C, A Hydrogenated Bisphenol A Z etc..
[reaction dissolvent]
The binary used as reaction dissolvent in hydrogenation as the compound represented in above-mentioned formula (1)
Alcohol, can be from such as: selects aliphatic diol, poly alkylene glycol etc..As above-mentioned aliphatic two
Alcohol, can enumerate such as: ethylene glycol, 1,2-PD, 1,3-PD, 1,2-butanediol, 1,3-fourth two
Alcohol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,5-pentanediol, 2,4-penta
The aliphatic diol etc. of the carbon numbers (total) 2～6 such as glycol, 1,2-hexanediol, 1,6-HD.It addition,
As above-mentioned poly alkylene glycol, can enumerate such as: make the oxirane of more than 2 molecules, expoxy propane,
The poly alkylene glycol etc. that the epoxyalkane such as epoxy butane carry out addition and obtain, more specifically, can arrange
Lift: HOC2H4(OC2H4)n1OC2H4Polyethylene Glycol shown in the OH integer of 0～5 [n1 be],
HOC3H6(OC3H6)n2OC3H6Polypropylene glycol shown in the OH integer of 0～5 [n2 be],
HOC4H8(OC4H8)n3OC4H8Polytetramethylene glycol etc. shown in the OH integer of 0～5 [n3 be].
As above-mentioned dihydroxylic alcohols, it is not particularly limited, under room temperature (25 DEG C), an atmospheric pressure is preferably
The dihydroxylic alcohols of liquid.Although it should be noted that can also use 25 DEG C, under an atmospheric pressure be
The dihydroxylic alcohols of solid, but the most such as by and 25 DEG C, be the dihydroxylic alcohols of liquid under an atmospheric pressure
It is combined using, and as at 25 DEG C, the mixture (reaction dissolvent) of liquid under an atmospheric pressure
Use.
Boiling point at one atm to above-mentioned dihydroxylic alcohols, is not particularly limited, from the separation of product,
From the viewpoint of the operability such as the recycling of reaction dissolvent, it is preferably such as: 180～300 DEG C, more preferably
It it is 180～250 DEG C.
Wherein, the dissolubility of compound that the compound represented from formula (1) and formula (2) represent, product
Separate, from the viewpoint of the operability such as the recycling of reaction dissolvent, be preferably carbon as above-mentioned dihydroxylic alcohols former
The dihydroxylic alcohols of subnumber (total) 2～6, the more preferably dihydroxylic alcohols of carbon number (total) 2～4.
It should be noted that the dihydroxylic alcohols as reaction dissolvent can be used alone in above-mentioned hydrogenation
1 kind, it is also possible to be applied in combination two or more.
Usage amount for dihydroxylic alcohols is not particularly limited, compound 1 weight represented relative to formula (1)
Part, preferably 0.5～10 weight portions, more preferably 0.5～5 weight portions.Such as, using as formula (1)
The 4 of the compound represented, 4'-xenol, the feelings of the dihydroxylic alcohols as reaction dissolvent are employed using aforementioned proportion
Under condition, although in room temperature 4,4'-xenol is completely insoluble in dihydroxylic alcohols, but owing to the boiling point of dihydroxylic alcohols is a height of
More than 180 DEG C, can be warming up to, at normal pressure, the temperature that comparison is high, therefore can be suitable by being heated to
Temperature prepares slurry or the solution of the high 4,4'-xenol of mobility.Such as relative to 1 weight portion
4,4'-xenols, in the case of employing the dihydroxylic alcohols of 1 weight portion, can be with the temperature system of more than 60 DEG C
The slurry of the 4,4'-xenol that standby mobility is high or solution.On the other hand, the chemical combination represented relative to formula (1)
Thing 1 weight portion, the usage amount of dihydroxylic alcohols is less than 0.5 weight portion, the then compound that possible formula (1) represents
The mobility of slurry reduce, additionally, have the compound that up-to-date style (2) represents to occur to separate out and can not be from hydrogenation
Reactant separates hydrogenation catalyst.On the other hand, if compound 1 weight represented relative to formula (1)
Part, the usage amount of dihydroxylic alcohols more than 10 weight portions, then may productivity reduce.
It addition, dihydroxylic alcohols exists owing to only showing low steam pressure in the reaction temperature of hydrogenation,
Therefore the dividing potential drop of hydrogen can be improved, the advantage accelerating the speed of hydrogenation.
It should be noted that as the reaction dissolvent in above-mentioned hydrogenation, can only use dihydroxylic alcohols,
Can also be further combined, in addition to dihydroxylic alcohols, solvent (also referred to as " other used in addition to dihydroxylic alcohols
Solvent ").As other solvent above-mentioned, can enumerate such as: water；The esters such as ethyl acetate；Methyl-tertiary fourth
The ethers such as base ether；The alcohol such as ethanol, 2-propanol；The cyclic hydrocarbons such as hexamethylene；Glycol monoethyl ether, propylene glycol list
The aklylene glycol monoether such as methyl ether, diethylene glycol monomethyl ether or polyalkylene glycol mono ether etc..Above-mentioned other
Solvent can be used alone a kind, it is also possible to is applied in combination two or more.
To dihydroxylic alcohols relative to the total amount (100 weight %) of the reaction dissolvent of use in above-mentioned hydrogenation
Ratio, be not particularly limited, such as: be preferably 50～100 weight %, more preferably 90 weight %
Above.The most above-mentioned reaction dissolvent is the most only made up of dihydroxylic alcohols (such as: the ratio of dihydroxylic alcohols is
98～100 weight %).If the ratio of dihydroxylic alcohols is less than 50 weight %, the then chemical combination that possible formula (1) represents
The mobility of the slurry of thing reduces, additionally, the compound that formula (2) represents occurs to separate out and can not carry out from hydrogen
The separation of the hydrogenation catalyst in change reactant.
The usage amount (total amount) of reaction dissolvent in above-mentioned hydrogenation is not particularly limited, but relative to formula
(1) compound 1 weight portion represented, preferably 0.5～10 weight portions, more preferably 0.5～5 weight portions.
If compound 1 weight portion represented relative to formula (1), the usage amount of reaction dissolvent is less than 0.5 weight portion,
Then the mobility of the slurry of the compound that possible formula (1) represents reduces, it addition, the compound that formula (2) represents
Occur to separate out and hydrogenation catalyst can not be separated from hydrogenation thing.On the other hand, if relative to formula
(1) compound 1 weight portion represented, the usage amount of reaction dissolvent more than 10 weight portions, then may produce
Property reduce.
[hydrogenation catalyst]
As the catalyst (hydrogenation catalyst) in above-mentioned hydrogenation, it is possible to use known or conventional hydrogen
Change catalyst, be not particularly limited, but can be from such as: nickel class catalyst, copper class catalyst, cobalt class
Catalyst, platinum-type catalyst, palladium class catalyst, ruthenium class catalyst, rhodium class catalyst etc. suitably select
And use.Wherein, preferably nickel class catalyst, more preferably Raney's nickel catalyst.
The shape of above-mentioned hydrogenation catalyst is not particularly limited, can be such as: powder, molded body
Any in Deng.It addition, above-mentioned hydrogenation catalyst can be not to be carried on carrier, it is also possible to be load
In carrier.
It should be noted that the hydrogenation catalyst in above-mentioned hydrogenation can be used alone a kind, it is possible to
Two or more to be applied in combination.
For the usage amount of above-mentioned hydrogenation catalyst, it is not particularly limited, can be according to hydrogenation catalyst
Kind, the difference such as form of reactor suitably adjust, can be according to known or conventional usage amount
Suitable selection.
[reactor]
The form of the reactor used in above-mentioned hydrogenation is not particularly limited, can be such as:
Catalyst carried out scattered suspension bed with blender, pump or hydrogen, is filled with the fixed bed of catalyst.
It addition, the running operation of above-mentioned hydrogenation can be continuous operation, it is also possible to be batch operation.
[reaction condition]
Reaction pressure, the reaction temperature of above-mentioned hydrogenation is not particularly limited, it is contemplated that productivity,
The controlling of equipment and any alternative condition.More specifically, reaction pressure can be from such as:
The scope of 0.1～30MPa (meter pressure), reaction temperature can be from such as: the scope of room temperature～250 DEG C is carried out
Suitable selection.
The response time of above-mentioned hydrogenation is not particularly limited, the journey that can carry out according to hydrogenation
Degree suitably sets.It should be noted that the degree that hydrogenation is carried out can utilize gas chromatography
Confirm Deng known or conventional analysis means.
As the result of above-mentioned hydrogenation, obtain comprising the compound that the formula (2) as product represents
Hydrogenation thing (compound represented including at least formula (2) and the mixture of dihydroxylic alcohols).Although upper
State in the case of hydrogenation thing contains catalyst, need separating catalyst from above-mentioned hydrogenation thing,
But due to can be by above-mentioned hydrogenation thing (usually slurry) be heated up to proper temperature and makes formula (2)
The compound represented is completely dissolved, therefore, it is possible to separating catalyst from hydrogenation thing.Need explanation
It is to carry to the additional dihydroxylic alcohols of hydrogenation thing (usually slurry), other solvent as required
The dissolubility of the compound that high formula (2) represents.
For the method for separating catalyst from hydrogenation thing, can fit from known or conventional method
Preferably select, be not particularly limited, can enumerate such as: filter separation, centrifugation, precipitate and separate etc..
In the manufacture method of the hydrogenation phenolic compounds of the present invention, the hydrogenation of the compound represented in formula (1) is anti-
After should, the hydrogenation thing (compound represented including at least formula (2) that this hydrogenation will be utilized to obtain
Mixture with dihydroxylic alcohols), with above-mentioned azeotropic solvent (aliphatic hydrocarbon, the carbon selected from carbon number 7～18
At least one in the ether of the aromatic hydrocarbon of atomic number 7～18 and the carbon number 7～18 that do not contains hydroxyl
Solvent) coexist and distill, azeotropic separation dihydroxylic alcohols from above-mentioned hydrogenation thing.Thus, even if
By distillation separation of glycols from hydrogenation thing, the hydrogenation phenolic compounds in container also will not solidify,
Can be easily implemented with the compound that formula (2) represents separation (compound that formula (2) represents and dihydroxylic alcohols point
From).
[azeotropic solvent]
Aliphatic hydrocarbon for the carbon number 7～18 as above-mentioned azeotropic solvent, it is possible to use constitute carbon
Known or the conventional aliphatic hydrocarbon that quantity (total) is 7～18 of atom, is not particularly limited, can arrange
Illustrate such as: heptane, octane, nonane, decane, hendecane, 12 carbon alkane, tetradecane, methyl
Hexamethylene, dimethyl cyclohexane, trimethyl-cyclohexane, tetramethyl-ring hexane, ethyl cyclohexane, diethyl
The aliphatic hydrocarbons of the carbon numbers such as butylcyclohexane, propyl cyclohexane, isopropyl cyclohexane 7～18 etc. are (special
It is not saturated aliphatic hydrocarbon).Wherein, the boiling point from an atmospheric pressure is less than 260 DEG C, can more have
From the standpoint of effect ground carries out the azeotropic separation of dihydroxylic alcohols, the sum of the carbon atom preferably comprising it is 7～12
Individual aliphatic hydrocarbon (particularly saturated aliphatic hydrocarbon).
Aromatic hydrocarbon for the carbon number 7～18 as above-mentioned azeotropic solvent, it is possible to use constitute carbon former
Known or the conventional aromatic hydrocarbon that quantity (total) is 7～18 of son, is not particularly limited, can enumerate example
As: toluene, dimethylbenzene, trimethylbenzene (such as: pseudocumene), durol, styrene, ethylbenzene,
The carbon atoms such as diethylbenzene, propyl benzene, isopropylbenzene, indenes, naphthane, Phenylcyclohexane, methyl naphthalene, biphenyl
The aromatic hydrocarbon etc. of several 7～18.Wherein, the boiling point from an atmospheric pressure be less than 260 DEG C, permissible
From the standpoint of being more effectively carried out the azeotropic separation of dihydroxylic alcohols, the sum preferably comprising carbon atom is 7～12
Individual aromatic hydrocarbon.
For not containing the ether of the carbon number 7～18 of hydroxyl as above-mentioned azeotropic solvent, it is possible to use
The quantity (total) constituting carbon atom is 7～18 and does not have the known or conventional ether of hydroxyl do not have spy
Do not limit, can enumerate such as: butyl oxide, diamyl ether, two hexyl ethers, bicyclo-hexyl ether, butyl oxide, benzene first
The carbon atoms such as ether, ethyl phenyl ether, propyl phenyl ether, methyl benzyl ether., benzyl ether, benzyl propyl ether, benzyl butyl ether
The ether etc. of several 7～18.Wherein, the boiling point from an atmospheric pressure is less than 260 DEG C, can more have
From the standpoint of effect ground carries out the azeotropic separation of dihydroxylic alcohols, preferably comprise the sum of carbon atom be 7～12 and
Not there is the ether of hydroxyl.
Boiling point under one atmospheric pressure of above-mentioned azeotropic solvent is not particularly limited, is preferably
90～260 DEG C.If the boiling point under an atmospheric pressure is less than 90 DEG C, then there is dihydroxylic alcohols and azeotropic solvent
Azeotropic mixture in the tendency that reduces of the ratio of dihydroxylic alcohols separation efficiency low, dihydroxylic alcohols.It addition,
If the boiling point under an atmospheric pressure is more than 260 DEG C, then exist hydrogenation phenolic compounds and azeotropic solvent point
From the tendency becoming difficulty.
Further, azeotropic solvent preferably carries out separatory at room temperature and dihydroxylic alcohols.By hydrogenation thing and azeotropic
Solvent coexists and distills, by carrying out the azeotropic mixture of the dihydroxylic alcohols distillated and azeotropic solvent point
Liquid and the phase of separation of glycols, and make refluxing mutually of azeotropic solvent, can imitate from hydrogenation thing
Rate separation of glycols well.Specifically, such as, as more effectively carrying out separatory at room temperature
Reaction dissolvent and the combination of azeotropic solvent, can enumerate using the dihydroxylic alcohols of carbon number 2～4 as reaction molten
Agent, with selected from carbon number 7～18 (more preferably 7～12) aliphatic hydrocarbon (particularly saturated aliphatic hydrocarbon),
The aromatic hydrocarbon of carbon number 7～18 (more preferably 7～12) and do not contain the carbon number of hydroxyl
At least one compound in the ether of 7～18 (more preferably 7～12) is as the combination of azeotropic solvent.
The usage amount of above-mentioned azeotropic solvent is not particularly limited, but relative to utilizing above-mentioned hydrogenation to obtain
To hydrogenation thing in compound 1 weight portion that represents of the formula (2) that contains, preferably 0.5～10 weight
Part, more preferably 0.5～5 weight portions.If the usage amount of azeotropic solvent is very few, then may hydrogenation
The separation of the dihydroxylic alcohols in thing requires time for, it addition, in the case of by separated dihydroxylic alcohols, hydrogen
Change phenolic compounds can solidify in a reservoir.If the usage amount of azeotropic solvent is too much, then exist equipment become big,
The tendency that productivity reduces.
[distillation procedure etc.]
The hydrogenation thing of the compound the most contained (2) represented and dihydroxylic alcohols is distilled and from
In this hydrogenation thing, the operation of separation of glycols, is not particularly limited, for example, it is possible to be to distillation dress
Put the continuous still operation putting into hydrogenation thing and azeotropic solvent continuously, it is also possible to for pre-to distilling apparatus
First put into the batch distillation operation of hydrogenation thing and azeotropic solvent.Alternatively, it is also possible to be to distilling apparatus
Put into any one in hydrogenation thing and azeotropic solvent, and the semi-batch remaining put into continuously in advance
Distillation procedure.
As condition during the above-mentioned hydrogenation thing of distillation, can suitably be chosen so that the dihydroxylic alcohols of use
With the condition of azeotropic solvent azeotropic, it is not particularly limited.Pressure when distilling above-mentioned hydrogenation thing is not had
Being particularly limited to, this distillation can be carried out at normal pressure, it is also possible under elevated pressure or carries out under decompression.It addition,
The time distilling above-mentioned hydrogenation thing is also not particularly limited, for example, it is possible to by dihydroxylic alcohols from above-mentioned hydrogen
The time distillating stopping in change reactant is set as distillation time.
In above-mentioned distillation procedure, it is also possible to reflux as required, particularly distillated by distillation
Dihydroxylic alcohols and in the case of azeotropic solvent carries out separatory, preferably make refluxing mutually of azeotropic solvent.
In above-mentioned distillation procedure, known or conventional distilling apparatus can be used as distilling apparatus, not have
It is particularly limited to.As distilling apparatus, it is, for example possible to use simple distillation device, it is possible to use many
Level distilling apparatus.
By above-mentioned distillation procedure, can be from representing including at least formula (2) obtained by above-mentioned hydrogenation
Separation of glycols in the hydrogenation thing of compound and dihydroxylic alcohols.It is said that in general, by above-mentioned distillation procedure,
Compound and the mixture of azeotropic solvent that formula (2) represents is obtained as residue.Can be by crystallization, steaming
Known or the conventional method compound that separate type (2) represents from this mixture such as evaporate, in addition it is also possible to
Said mixture is directly used in subsequent handling.Due to from the result material obtained by above-mentioned distillation procedure
(particularly said mixture) separates hydrogenation phenolic compounds and is easier to, therefore according to the hydrogenation phenolate of the present invention
The manufacture method of compound, can obtain highly purified hydrogenation phenolic compounds with maneuverable state.It addition,
Due to the method that make use of the means distilling this industrial easy enforcement, therefore, it is possible to easily expand
(scale-up), industrialization greatly.It should be noted that the dihydroxylic alcohols reclaimed by above-mentioned distillation procedure, altogether
Boil-off dose can recycle.
The separation method of the hydrogenation phenolic compounds of the present invention, for will be the most contained (2) compound of representing
With the mixture of dihydroxylic alcohols (such as: utilize the hydrogenation thing etc. that above-mentioned hydrogenation obtains), with above-mentioned
Azeotropic solvent (selected from the aliphatic hydrocarbon of carbon number 7～18, the aromatic hydrocarbon of carbon number 7～18, with
And at least one solvent in the ether of the carbon number 7～18 not containing hydroxyl) coexist and distill, from
The method that in said mixture, separation of glycols is characterized.The present invention is hydrogenated the separation side of phenolic compounds
For method, it is possible to and the distillation procedure in the manufacture method of the hydrogenation phenolic compounds of the invention described above is similarly
Carry out and implement.By the distillation procedure in the separation method of the hydrogenation phenolic compounds of the present invention, general and
Speech, obtains, as residue, compound and the mixture of azeotropic solvent that formula (2) represents.Can by crystallization,
The method compound that separate type (2) represents from this mixture that distillation etc. are known or conventional, in addition, it is possible to
So that said mixture is directly used in subsequent handling.Due to from the result thing obtained by above-mentioned distillation procedure
Matter (particularly said mixture) separates hydrogenation phenolic compounds and is easier to, therefore according to the hydrogenation phenol of the present invention
The separation method of compound, can obtain highly purified hydrogenation phenolic compounds with maneuverable state.Separately
Outward, due to the method that make use of the means distilling this industrial easy enforcement, therefore, it is possible to easily enter
Row expands (scale-up), industrialization.It should be noted that the dihydroxylic alcohols reclaimed by above-mentioned distillation procedure,
Azeotropic solvent, it is possible to recycle.
By using manufacture method (or the hydrogenation phenolate of the present invention of the hydrogenation phenolic compounds by the present invention
The separation method of compound) compound that represents of the formula (2) that obtains, thermostability, water-fast can be obtained at a low price
Resin that Xie Xing, weatherability, the transparency etc. are excellent or its raw material [such as: epoxy resin, alkyd resin,
Resin or its raw materials (epoxide etc.) such as polyester resin, polyurethane resin, polycarbonate resin].
Embodiment
Hereinafter, illustrate the present invention based on embodiment in further detail, but the present invention is not limited to these
Embodiment.
Embodiment 1
4,4'-xenol 250g, 1,2-propylene glycol (boiling point 188 DEG C) 250g and Raney's nickel catalyst (are urged
Agent) 12.5g put into 1L band blender stainless steel autoclave, after carrying out nitrogen displacement, put into hydrogen
Being 4.0MPa to meter pressure.Then, it is warming up to 160 DEG C, supplements hydrogen and make the meter pressure to be
6.0MPa is while carrying out 7 hours hydrogenations.Then, remove hydrogen and carry out nitrogen displacement, at 140 DEG C
Carry out catalyst filtering and separate.Only residual catalyst on filter paper.
Owing to above-mentioned obtained filtrate and pseudocumene 370g are put in the distilling apparatus shown in Fig. 1
1L glass four-hole boiling flask 9 (possessing condenser 4, decanter 5 and blender 3), at normal pressure, tank
Temperature 172～179 DEG C is when distilling, and it is biphase for reserving liquid separatory, will be as on decanter using reflux pump 8
The pseudocumene of phase is back to four-hole boiling flask 9 mutually, and carries out mutually accumulating about using the 1,2-PD as lower phase
250mL, to not being further added by, continues distillation 6 hours.
1,2-PD phase distillate disappearance after, stop heating, in time within 1 hour, being cooled to 40 DEG C, analysis
Go out crystallization.Being reclaimed the crystallization of precipitation by filtration, obtained 4,4'-dicyclohexano 261g, it contains
There is the 1,2-propylene glycol of 0.1%.
Comparative example 1
4,4'-xenol 250g, 1,2-propylene glycol (boiling point 188 DEG C) 250g and Raney's nickel catalyst (are urged
Agent) 12.5g put into 1L band blender stainless steel autoclave, after carrying out nitrogen displacement, put into hydrogen
Being 4.0MPa to meter pressure.Then, it is warming up to 160 DEG C, supplements hydrogen and make the meter pressure to be
6.0MPa is while carrying out 7 hours hydrogenations.Then, remove hydrogen and carry out nitrogen displacement, at 140 DEG C
Carry out catalyst filtering and separate.Only residual catalyst on filter paper.
Filtrate obtained above and pseudocumene 370g are put into the 1L glass system four mouthfuls burning possessing blender
Bottle, after being warming up to 140 DEG C, slowly cools down.
It is biphase (upper phase: pseudocumene phase, lower phase: 1,2-PD and 4,4'-bis-hexamethylene at 100 DEG C of separatory
Alcohol phase), when cooling down further, lower phase forms cake mass.When analyzing the cake mass of lower phase, contain
1,2-PD 34%, 4,4'-dicyclohexano 39%, pseudocumene 24%, the method can not separate 4,4'-bis-
Hexalin.
Industrial applicibility
For the present invention is hydrogenated the manufacture method of phenolic compounds, due to hydrogenation phenolic compounds with liquid or
Pulp-like exists, and therefore can manufacture highly purified hydrogenation phenolic compounds, industry with maneuverable state
On enforcement easy.Furthermore it is possible to easily from the mixture containing dihydroxylic alcohols and hydrogenation phenolic compounds
The hydrogenation phenolic compounds of the state separating high-purity of operation, industrial enforcement is easy.Therefore, if made
Obtain with by the manufacture method of the hydrogenation phenolic compounds of the present invention or the separation method of hydrogenation phenolic compounds
Hydrogenation phenolic compounds, then can obtain thermostability, hydrolytic resistance, weatherability, the transparency etc. at a low price
Excellent resin or resin raw material.
Claims (3)
1. hydrogenating a manufacture method for phenolic compounds, it is the compound represented by following formula (1)
Hydrogenation manufactures the method for the compound that following formula (2) represents,
In formula (1), X represents singly-bound, alkylidene, cycloalkylidene or cycloalkanes fork, R1And R2Identical or
Difference, represents the alkyl of carbon number 1～5, m and n is identical or different, represents the integer of 0～4,
In formula (2), X, R1、R2, m and n same as described above,
Wherein, dihydroxylic alcohols is carried out described hydrogenation as reaction dissolvent, then, described hydrogen will be utilized
Change the compound represented containing formula (2) that obtains of reaction and the hydrogenation thing of dihydroxylic alcohols, and selected from carbon atom
The aliphatic hydrocarbon of several 7～18, the aromatic hydrocarbon of carbon number 7～18 and do not contain the carbon number of hydroxyl
At least one compound in the ether of 7～18 coexists and distills, and separates from described hydrogenation thing
Dihydroxylic alcohols.
2. according to the manufacture method of the hydrogenation phenolic compounds described in claim 1, wherein, described two
Unit's alcohol is aliphatic diol or poly alkylene glycol.
3. hydrogenate a separation method for phenolic compounds, wherein, the hydrogenation that will represent containing following formula (2)
Phenolic compounds and the mixture of dihydroxylic alcohols, and selected from the aliphatic hydrocarbon of carbon number 7～18, carbon number
At least one compound in the ether of the aromatic hydrocarbon of 7～18 and the carbon number 7～18 that do not contains hydroxyl is altogether
Deposit and distill, separation of glycols from described mixture,
In formula (2), X represents singly-bound, alkylidene, cycloalkylidene or cycloalkanes fork, R1And R2Identical or
Difference, represents the alkyl of carbon number 1～5, m and n is identical or different, represents the integer of 0～4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-229959 | 2013-11-06 | ||
| JP2013229959 | 2013-11-06 | ||
| PCT/JP2014/079171 WO2015068677A1 (en) | 2013-11-06 | 2014-11-04 | Method for producing hydrogenated phenolic compound and method for separating hydrogenated phenolic compound |
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| CN105849074A true CN105849074A (en) | 2016-08-10 |
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| Country | Link |
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| JP (1) | JP6480867B2 (en) |
| CN (1) | CN105849074A (en) |
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| WO (1) | WO2015068677A1 (en) |
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| KR20230039949A (en) | 2021-09-15 | 2023-03-22 | 금호석유화학 주식회사 | Method for preparing hydrogenated bisphenol a |
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| JPS6058211B2 (en) * | 1980-06-30 | 1985-12-19 | 住友化学工業株式会社 | Purification method of β-phenylethyl alcohol |
| DE4003232A1 (en) * | 1990-02-03 | 1991-08-22 | Huels Chemische Werke Ag | PROCESS FOR THE PREPARATION OF TERTIAN CARBON ACIDS |
| JPH04279537A (en) * | 1991-03-05 | 1992-10-05 | New Japan Chem Co Ltd | Production of bicyclohexyldiol |
| JPH10158208A (en) * | 1996-11-25 | 1998-06-16 | Maruzen Petrochem Co Ltd | Separation and recovery of cyclohexyl vinyl ether |
| JP4182305B2 (en) * | 1998-07-28 | 2008-11-19 | 新日本理化株式会社 | Hydrogenated bisphenol A isomer composition |
| WO2013153957A1 (en) * | 2012-04-09 | 2013-10-17 | 株式会社ダイセル | Method for producing hydrogenated biphenol |
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| WO2015068677A1 (en) | 2015-05-14 |
| TW201522293A (en) | 2015-06-16 |
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Application publication date: 20160810 |