CN108026012A - The purification process of compound - Google Patents
The purification process of compound Download PDFInfo
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- CN108026012A CN108026012A CN201680051150.2A CN201680051150A CN108026012A CN 108026012 A CN108026012 A CN 108026012A CN 201680051150 A CN201680051150 A CN 201680051150A CN 108026012 A CN108026012 A CN 108026012A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings
Abstract
The purification process of the compound of the present invention includes making to include following formula (A0) and/or (B0) shown in hydroxyl substituted aromatic compound and solvent solution (A) and contacts ionic exchange resin process.(previously described formula (A0) in, n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, herein, the n0、m0And p0At least one be more than 1 integer, and then, m0For 1 when, represent previously described formula (A0) there is naphthalene skeleton or biphenyl backbone, Ra is each independently the group selected in free hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or cricoid alkyl, the optionally group of the alkenyl and combinations thereof of the aryl of the carbon number 6~40 with substituent or carbon number 2~40 composition, and the alkyl, the aryl or the alkenyl optionally include ehter bond, ketonic bond or ester bond.Previously described formula (B0) in, n1For 0~9 integer, p1For 0~9 integer, Rb is each independently the group in the group being made of hydrogen atom, hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or cricoid alkyl, the aryl of carbon number 6~40 optionally with substituent or the alkenyl and combinations thereof of carbon number 2~40, and the alkyl, the aryl or the alkenyl optionally include ehter bond, ketonic bond or ester bond.)
Description
Technical field
The present invention relates to compound (such as：Hydroxyl substituted aromatic compound) purification process.
Background technology
The hydroxyl such as dihydroxy naphthlene substituted aromatic compound is as the encapsulating material of semiconductor, smears, against corrosion
Agent with the raw material of material, the compound of semiconductor lower floor film formation material or resin be it is useful (referring for example to patent document 1~
2).In addition, the purification process as the hydroxyl substituted aromatic compound such as dihydroxy naphthlene, it is known to specific method (such as join
According to patent document 3).
Prior art literature
Patent document
Patent document 1：International Publication No. 2013/024778
Patent document 2：International Publication No. 2013/024779
Patent document 3：Chinese patent application discloses No. 103467249
The content of the invention
Problems to be solved by the invention
In such use, especially tenor is in order to which yield rate improves and becomes important performance evaluation project.That is, will
It is remaining in semiconductor hydroxyl substituted aromatic compound is as a large amount of metals are included in compound obtained from raw material or resin when
Metal and reduce the electrical characteristics of semiconductor, therefore it is required that reducing tenor as impurity.
Purifying as the tenor for reducing the compound obtained by hydroxyl substituted aromatic compound or resin
Method, considers following methods：Ion exchange water or pure is added in the mixture comprising the compound or resin and organic solvent
Water and the method that separation of solid and liquid is carried out after being recrystallized；Make the compound or resin in organic solvent arbitrarily not miscible with water
Middle dissolving, makes the solution be contacted with aqueous solution and carries out extraction process, metal ingredient is moved to water phase, then by organic phase
The method that tenor is reduced with the liquid separation of water phase.
However, in the above-mentioned methods, when the high hydroxyl substituted aromatic compound of tenor is used as raw material, then exist
The problem of insufficient such to the removal effects of specific metal species.
Therefore, it is desirable to the hydroxyl substituted aromatic compound for establishing the high-purity that tenor reduces is industrially favourable
Purification process.
In addition, when the purity of hydroxyl substituted aromatic compound is low, exists and obtained by the hydroxyl substituted aromatic compound
Compound or resin yield reduce or occur deviation it is such the problem of.
And then do not studied on reducing tenor, the reduction of tenor is not in disclosed purification process in the past
Fully.
It is an object of the present invention to provide for industrially advantageously being purified to hydroxyl substituted aromatic compound
Method.
The solution used to solve the problem
The inventors of the present invention have made intensive studies in order to solve the above problems, it turns out that by making comprising hydroxyl substitution virtue
The solution and contacts ionic exchange resin of fragrant compounds of group and solvent, the content of various metals significantly reduce, so as to complete this
Invention.
That is, the present invention is as described below.
[1]
A kind of purification process of compound, it includes making to include following formula (A0) and/or (B0) shown in hydroxyl substituted aroma
The process of the solution of compounds of group and solvent (A) and contacts ionic exchange resin.
(previously described formula (A0) in, n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, herein, the n0、m0
And p0At least one be more than 1 integer, and then, m0For 1 when, represent previously described formula (A0) there is naphthalene skeleton or biphenyl backbone,
Ra, which is each independently, to be selected free hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or cricoid alkyl, optionally has
Group in the group of the aryl of the carbon number 6~40 of substituent or alkenyl and the combinations thereof composition of carbon number 2~40, the alkane
Base, the aryl or the alkenyl optionally include ehter bond, ketonic bond or ester bond；Previously described formula (B0) in, n1For 0~9 integer, p1For 0~9
Integer, Rb is each independently selected from by hydrogen atom, hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or ring-type
Alkyl, optionally with substituent carbon number 6~40 aryl or carbon number 2~40 alkenyl and combinations thereof composition
Group in group, the alkyl, the aryl or the alkenyl optionally include ehter bond, ketonic bond or ester bond.)
[2]
The purification process of compound according to [1], wherein, foregoing hydroxy substituted aromatic compound is following formula
(A) and/or the compound shown in (B).
(in previously described formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, herein, the n0、m0
And p0At least one be more than 1 integer, and then, m0For 1 when, represent previously described formula (A0) there is naphthalene skeleton or biphenyl backbone,
R0It is each independently straight-chain, branched or the cricoid alkyl of carbon number 1~30, optionally there is the carbon number 6~15 of substituent
Aryl or carbon number 2~15 alkenyl；In above-mentioned formula (B), n1For 0~9 integer, p1For 0~9 integer, R1It is each independent
Ground is straight-chain, branched or the cricoid alkyl of carbon number 1~30, the aryl or carbon of the optional carbon number 6~15 with substituent
The alkenyl of number 2~15.)
[3]
The purification process of compound according to [1], wherein, foregoing hydroxy substituted aromatic compound is selected from following
The compound shown in compound, following formula (A-2) shown in formula (A-1), the compound shown in following formula (A-3), following formula (A-
4) more than a kind in the group of the compound composition shown in the compound and following formula (B-1) shown in.
(in previously described formula (A-1), n0For 1~5 integer, in previously described formula (A-2), n0For 0~7 integer, previously described formula (A-3)
In~(A-4), n0For 0~9 integer, in previously described formula (B-1), n1For 0~9 integer.)
[4]
The purification process of compound according to [1], wherein, foregoing hydroxy substituted aromatic compound is following formula
(1) compound shown in.
[5]
The purification process of compound according to [1], wherein, foregoing hydroxy substituted aromatic compound be selected from by 2,
More than a kind in the group of 6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene composition.
[6]
The purification process of compound according to any one of [1]~[5], wherein, in foregoing sequence, connect foregoing
After touching adsorption treatment, further the separation and recovery of solution (A) is carried out by filtering.
[7]
The purification process of compound according to any one of [1]~[6], wherein, aforementioned contact is small in oxygen concentration
Carried out in 20% atmosphere.
[8]
The purification process of compound according to any one of [1]~[7], wherein, aforementioned solvents are selected from by vinegar
Acetoacetic ester, butyl acetate, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and cyclohexanone
More than a kind in the group of composition.
The effect of invention
According to the present invention it is possible to industrially advantageously be purified to hydroxyl substituted aromatic compound, can be made
The content of various metals.
Embodiment
Hereinafter, embodiments of the present invention (are also denoted as " present embodiment " below.) be described in detail.Need to illustrate
, implementation below is the illustration for illustrating the present invention, and the present invention is not limited to these embodiments.
The purification process of the compound of present embodiment includes making to include following formula (A0) and/or (B0) shown in hydroxyl take
For the process of the solution and contacts ionic exchange resin of aromatic compound and solvent.
(previously described formula (A0) in, n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, herein, the n0、m0
And p0At least one be more than 1 integer, and then, m0For 1 when, represent previously described formula (A0) there is naphthalene skeleton or biphenyl backbone,
Ra, which is each independently, to be selected free hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or cricoid alkyl, optionally has
Group in the group of the aryl of the carbon number 6~40 of substituent or alkenyl and the combinations thereof composition of carbon number 2~40, the alkane
Base, the aryl or the alkenyl optionally include ehter bond, ketonic bond or ester bond.Previously described formula (B0) in, n1For 0~9 integer, p1For 0~9
Integer, Rb is each independently selected from by hydrogen atom, hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or ring-type
Alkyl, optionally with substituent carbon number 6~40 aryl or carbon number 2~40 alkenyl and combinations thereof composition
Group in group, the alkyl, the aryl or the alkenyl optionally include ehter bond, ketonic bond or ester bond.)
, can be industrially by the purification process of the compound of present embodiment due to forming as described above
Advantageously hydroxyl substituted aromatic compound is purified.That is, by being dissolved in above-mentioned hydroxyl substituted aromatic compound
Solvent, makes the solution and contacts ionic exchange resin and carries out adsorption treatment, can make to be included as impurity in the solution
Metal ingredient is transferred in ion exchange resin.Thereafter, which is separated with ion exchange resin, can be made and remain high-purity
Spend and reduce the hydroxyl substituted aromatic compound of metal ingredient amount.
It can be coexisted as described above, " purifying " in present embodiment is abundant reduce with hydroxyl substituted aromatic compound
Metal ingredient operation, specifically, obtain Na amounts be below 50ppb, Fe amounts are below 50ppb, Cr amounts be 50ppb with
Under and Zn amounts be below 50ppb hydroxyl substituted aromatic compound.These metal ingredient amounts can be remembered with aftermentioned embodiment
The method measure of load.
It should be noted that " contact " in present embodiment refers to, for example, making above-mentioned solution in ion exchange resin
State that surface is in contact, make above-mentioned solution be in contact on a surface on one side on one side in the exterior shifting of ion exchange resin
Dynamic mode etc., above-mentioned solution are handed over by the inside of the ion exchange resin and to ion again from the outside of ion exchange resin
Except the exterior mobile mode (that is, the mode of liquid communication) for changing resin is.
In the purification process of the compound of present embodiment, from the viewpoint of the supply of raw material, foregoing hydroxy substitution
Aromatic compound is more preferably following formula (A) and/or the hydroxyl substituted aromatic compound shown in (B).
(in previously described formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, herein, the n0、m0
And p0At least one be more than 1 integer, and then, m0For 1 when, represent previously described formula (A) there is naphthalene skeleton or biphenyl backbone, R0
It is each independently straight-chain, branched or the cricoid alkyl of carbon number 1~30, the optional carbon number 6~15 with substituent
The alkenyl of aryl or carbon number 2~15；In above-mentioned formula (B), n1For 0~9 integer, p1For 0~9 integer, R1Independently of one another
For the straight-chain of carbon number 1~30, branched or cricoid alkyl, the aryl or carbon number of the optional carbon number 6~15 with substituent
2~15 alkenyl.)
In the purification process of the compound of present embodiment, from the viewpoint of the dissolubility to organic solvent, foregoing hydroxyl
Base substituted aromatic compound is more preferably selected from as the compound shown in following formula (A-1), the chemical combination shown in following formula (A-2)
The chemical combination shown in the compound and following formula (B-1) shown in compound, following formula (A-4) shown in thing, following formula (A-3)
More than a kind in the group of thing composition.
(in previously described formula (A-1), n0For 1~5 integer, in previously described formula (A-2), n0For 0~7 integer, previously described formula (A-3)
In~(A-4), n0For 0~9 integer, in previously described formula (B-1), n1For 0~9 integer.)
In the purification process of the compound of present embodiment, the viewpoint of supply and the kettle efficiency purified from raw material is come
See, the special standby compound preferably shown in following formula (1) of foregoing hydroxy substituted aromatic compound.
Herein, to the compound shown in above-mentioned formula (1), there is no particular limitation, from the viewpoint of the supply of raw material,
Be preferably selected from by 1,2- dihydroxy naphthlenes, 1,3- dihydroxy naphthlenes, 1,4- dihydroxy naphthlenes, 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes,
In the group that 1,7- dihydroxy naphthlenes, 1,8- dihydroxy naphthlenes, 2,3- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene form
More than a kind.
In addition, to the compound shown in above-mentioned formula (1), there is no particular limitation, from using the compound shown in formula (1) as
From the viewpoint of compound obtained from raw material or the heat resistance of resin, more preferably it is selected from by 2,6- dihydroxy naphthlenes and 2,7- bis-
More than a kind in the group of hydroxyl naphthalene composition.
To the compound shown in above-mentioned formula (1), there is no particular limitation, from using the compound shown in formula (1) as raw material and
It is more preferably 2,6- dihydroxy naphthlenes from the viewpoint of obtained compound or the further heat resistance of resin.
Formula (the A used in present embodiment0), formula (B0), formula (A), formula (B), formula (A-1), formula (A-2), formula (A-3), formula
(A-4), formula (B-1) and compound shown in formula (1) respectively can be easy by means known to manufacturer and reagent business etc.
Ground obtains.Furthermore it is possible to suitably be synthesized using known gimmick, synthesizing gimmick to it is not particularly limited.
Formula (the A used in present embodiment0), formula (B0), formula (A), formula (B), formula (A-1), formula (A-2), formula (A-3), formula
(A-4), formula (B-1) and the compound shown in formula (1) can also individually mix two or more.In addition, these compounds can
To contain various surfactants, various crosslinking agents, various acid agents, various stabilizers etc..
As the solvent used in present embodiment, there is no particular limitation, preferably can be with safety applications in semiconductor system
Make the organic solvent of technique.From the viewpoint of the easy degree of solid recycling from deliquescent raising and after purification, preferably make
The amount of solvent is usually 1~100 mass times relative to the compound shown in the formula (1) used.More preferably 5~50 mass
Times, more preferably 10~50 mass are again.
As the specific example of the solvent used in present embodiment, it is not limited to following, can includes：It is ether, different
Propyl ether, n-butyl ether, hexyl ether, 2- ethylhexyls ether, ethylene oxide, 1,2 epoxy prapane, dioxolanes, 4- methyl dioxolanes,
Dioxane, dimethyl dioxane, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether second
Glycol list n-hexyl ether, ethyleneglycol monophenylether, ethylene glycol list -2- ethyls butyl ether, butyl cellosolve, diethylene glycol monomethyl ether, two
Ethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, dibutyl ethylene glycol ether, diethylene glycol list n-hexyl ether, second
Epoxide triethylene glycol, tetraethylene glycol butyl oxide, propylene glycol monomethyl ether (PGME), dipropylene glycol methyl ether, tripropylene glycol methyl ether, the third two
The ethers such as alcohol list propyl ether, tetrahydrofuran, 2- methyltetrahydrofurans, methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol,
Sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, 2- methyl butanols, sec-amyl alcohol, tert-pentyl alcohol, 3- methoxybutanols, n-hexyl alcohol, 2- first
Base amylalcohol, secondary hexyl alcohol, 2- ethyl butanols, secondary enanthol, 3- enanthol, n-octyl alcohol, 2-Ethylhexyl Alcohol, sec-octyl alcohol, nonyl alcohol, 2,6- diformazans
Base -4- enanthol, Decanol, secondary undecyl alcohol, Exxal 12, secondary tetradecyl alchohol, secondary heptadecanol, phenol, cyclohexanol, methyl cyclohexane
The unary alcohol such as alcohol, 3,3,5- cyclonols, benzylalcohol, phenyl methyl carbitol, diacetone alcohol, cresols, diethyl carbonate,
Methyl acetate, ethyl acetate, gamma-butyrolacton, gamma-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid are different
The secondary pentyl ester of butyl ester, sec-Butyl Acetate, n-Amyl acetate, acetic acid, acetic acid 3- methoxybutyls, acetic acid methyl pentyl ester, acetic acid 2- second
Base butyl ester, acetic acid 2- ethylhexyls, benzyl acetate, cyclohexyl acetate, methyl cyclohexanol acetate, acetic acid nonyl ester, acetoacetic acid first
Ester, ethyl acetoacetate, acetic acid glycol monoethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid propylene glycol monomethyl ether, acetic acid diethyl two
Alcohol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol monobutyl ether, ethylene diacetate, acetic acid methoxyl group three are sweet
Alcohol, ethyl propionate, n-butyl propionate, isoamyl propionate, methoxy methyl propionate, ethoxyl ethyl propionate, diethy-aceto oxalate, grass
Sour di-n-butyl, methyl lactate, ethyl lactate, n-butyl lactate, N_amyl lactate, diethyl malonate, phthalic acid two
The esters such as methyl esters, diethyl phthalate, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, metacetone, first
Base isobutyl ketone, Methylpentanone, ethyl butyl ketone, methyl hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methyl
The ketones such as cyclohexanone, 2,4- pentanediones, acetonyl acetone, acetophenone, 1-methyl-2-pyrrolidinone, ethylene glycol monoethyl ether acetate,
The glycol ether acetates esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), dihydroxypropane single-ether acetate
Class, N-METHYLFORMAMIDE, n,N-Dimethylformamide, N, N- diethylformamides, acetamide, N- methylacetamides, N, N- bis-
The aliphatic such as nitrogen compound series solvent, n-hexane, normal heptane such as methylacetamide, N- methyl propanamides, 1-methyl-2-pyrrolidinone
Halogenated hydrocarbons such as hydro carbons, toluene, dimethylbenzene etc. are aromatic hydrocarbon, dichloromethane, chloroform etc..
Above-mentioned solvent can be used individually, can also mix two or more use.
Among above-mentioned, from the viewpoint of operability, the management easy degree of inventory, solvent is preferably selected from by acetic acid
Ethyl ester, butyl acetate, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ring penta
More than a kind in the group of ketone and cyclohexanone composition.
To the ion exchange resin that is used in present embodiment, there is no particular limitation, such as can include with cation
The resin of exchange capacity.More specifically, such as can include in resin surface there is sulfonium base, carboxyl etc. can carry out cation
The resin of the functional group of exchange.
By using ion exchange resin, Li, Na present in the solution comprising hydroxyl substituted aromatic compound, Mg,
K, the metal ion such as Ca, Ni, Co, Fe, Cu, Al, Zn, Sn, Sr, Ti, Pb, Cr, Mo, Cd, Ba can by with resin surface
The H of functional group carries out ion exchange and removes.
The usage amount of the ion exchange resin used be take into account the amount of metal ion to be removed and ion exchange resin from
Sub- exchange capacity and determine, there is no particular limitation, and the exchange capacity of above-mentioned ion exchange resin is preferably set to higher than needing
10 times of the amount of metal ion of removal.
To the application method of ion exchange resin, there is no particular limitation, such as has：Column method, by ion exchange resin excellent
It is filled into after pulp-like is made in the solvent of choosing in column, the solution comprising hydroxyl substituted aromatic compound is flowed in the column
It is logical；Or decantation, the solution comprising hydroxyl substituted aromatic compound is mixed with ion exchange resin, when disperseing any
Between, after standing, filter off deionization exchanger resin.Particularly preferred column method among above-mentioned.
In above-mentioned column method, the usage amount of solvent during to ion exchange resin being made to pulp-like does not limit particularly
It is fixed, it is usually 1~100 mass times or so relative to hydroxyl substituted aromatic compound, is preferably 1~10 mass times, further
Preferably 5~10 mass times.
Further, the ion exchange resin that pulp-like is made is filled into column, makes to include hydroxyl substituted aromatic chemical combination
There is no particular limitation for the temperature that the solution of thing circulates in the column, is usually 0~60 DEG C, is preferably 0~40 DEG C, further excellent
Elect 10~40 DEG C as.
In above-mentioned decantation, as by solution (A) and ion exchange resin comprising hydroxyl substituted aromatic compound
The kettle of mixing, has been preferable to carry out the stainless steel of electric field grinding, has implemented the stainless steel or reality of glass lining processing
The stainless steel of fluororesin lining processing has been applied, has particularly preferably implemented the stainless steel of fluororesin lining processing.
In decantation, the solution (A) comprising hydroxyl substituted aromatic compound is mixed with ion exchange resin, as
Scattered time, more preferably at least more than 10 points, more preferably more than 30 points.It it is preferably 30 points in addition, as the time stood
More than, more preferably 1 it is small when more than.
In decantation, method that ion exchange resin is removed as filtering, there is no particular limitation, can use public affairs
The suction filtration known, pressure filtration, centrifugal separation etc..
In addition, the seal member such as the lid of each utensil, O-ring that bottom is divided, the jointing of filter, piston are included
At least one be made of perfluoroelastomer, Perfluoroelastomer, preferably these member of formation are all by selected from fluorine resin, perfluor rubber
Glue, the material of Perfluoroelastomer are formed.Further, above-mentioned seal member is particularly preferably by selected from perfluoroelastomer, perfluorinated elastomer
The material of body is formed.Sometimes cannot be by the metallic compound in hydroxyl substituted aromatic compound merely with the component beyond these
Containing ratio be reduced to ppb level.
Mixed moisture can pass through in the so obtained solution for including hydroxyl substituted aromatic compound and solvent
Implement the operation such as vacuum distillation and be readily removable.Furthermore it is possible to add solvent as needed and by hydroxyl substituted aromatic
The concentration of compound is adjusted to any concentration.
To only obtaining hydroxyl substituted aromatic compound from the solution comprising hydroxyl substituted aromatic compound and solvent
There is no particular limitation for method, such as can utilize known in decompression removal, the separation based on reprecipitation and combinations thereof etc.
Method carry out.Concentration operation, filter operation can be carried out as needed, centrifuged known to operation, drying process etc.
Processing.
In addition, contact of the solution with ion exchange resin in this embodiment party is preferably under atmosphere of the oxygen concentration less than 20%
Carry out.Oxygen concentration is more preferably less than 10%, is further preferably no larger than 5%, and particularly preferably less than 1%.By being less than oxygen concentration
20%, there is the rotten tendency for further suppressing hydroxyl substituted aromatic compound, the hydroxyl that there is to obtain higher purity takes
For the tendency of aromatic compound.
Allow oxygen concentration reduce method implemented with known method, there is no particular limitation, for example, can by
Nitrogen or decompression are blown into the column or kettle that are purified and imports nitrogen afterwards to carry out gas displacement.To the column or kettle purified
It is preferred at easy and reliable aspect that decompression imports nitrogen afterwards.
The confirmation of oxygen concentration can be implemented with known method, and there is no particular limitation, such as：It can purified
Nitrogen is blown into column or kettle, the oxygen concentration for the gas discharged with oxymeter measure by venthole.It can also purified
Oxymeter is set in column or kettle.
Embodiment
Hereinafter, enumerate embodiment and further illustrate present embodiment.But present embodiment is not limited to these realities
Apply example.
(embodiment 1) is handled using the metal reduction of column method
In the clean space of rank 1000, by ion exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins)
25g is passed through 500mL with being filled into after propylene glycol monomethyl ether (being also referred to as PGME below) 25mL swellings in Teflon (registration mark) column
PGME carry out solvent displacement.Then, 2, the 6- dihydroxy naphthlenes for making purity 99.3% (being also referred to as 2,6-DHN below) are dissolved in
Solution (2.5 mass %) 500g that PGME is formed is added in column, and then decompression removes the air inside column and imports nitrogen, by
After the oxygen concentration in portion is adjusted less than 1%, logical liquid is carried out, thus obtains 2,6- of the purity 99.3% through ion exchange resin treatment
The PGME solution of DHN.It should be noted that oxygen concentration is (following using oxymeter " OM-25MF10 " measure of ASONE manufactures
Similarly measure.).
(embodiment 2) is handled using the metal reduction of decantation
In the clean space of rank 1000, in the four-hole boiling flask (bottom detachable type) of 1000mL capacity, addition makes
2,6-DHN of purity 99.4% is dissolved in solution (2.5 mass %) 500g that PGME is formed, and then decompression removes the sky inside kettle
Gas simultaneously imports nitrogen, and internal oxygen concentration is adjusted to after less than 1%, is stirred while being heated to 30 DEG C.Then, add from
Sub-exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins) 25g, after stirring 30 minutes, when standing 1 is small.Then, from
Separation ion exchange resin is filtered in 2,6-DHN PGME solution, obtains the 2,6- of the purity 99.3% that tenor reduces
The PGME solution of DHN.
(embodiment 3) is handled using the metal reduction of decantation
In the clean space of rank 1000, in the four-hole boiling flask (bottom detachable type) of 1000mL capacity, addition makes
2,6-DHN of purity 99.4% is dissolved in solution (2.5 mass %) 500g that PGME is formed, and then decompression removes the sky inside kettle
Gas simultaneously imports nitrogen, and internal oxygen concentration is adjusted to after 5.0%, is stirred while being heated to 30 DEG C.Then, ion is added
Exchanger resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins) 25g, after stirring 30 minutes, when standing 1 is small.Then, from 2,
Separation ion exchange resin is filtered in the PGME solution of 6-DHN, obtains the 2,6-DHN of the purity 97.9% that tenor reduces
PGME solution.
(embodiment 4) is handled using the metal reduction of decantation
In the clean space of rank 1000, in the four-hole boiling flask (bottom detachable type) of 1000mL capacity, addition makes
2,6-DHN of purity 99.4% is dissolved in solution (2.5 mass %) 500g that PGME is formed, and then decompression removes the sky inside kettle
Gas simultaneously imports nitrogen, and internal oxygen concentration is adjusted to after 10.2%, is stirred while being heated to 30 DEG C.Then, add from
Sub-exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins) 25g, after stirring 30 minutes, when standing 1 is small.Then, from
Separation ion exchange resin is filtered in 2,6-DHN PGME solution, obtains the 2,6- of the purity 97.8% that tenor reduces
The PGME solution of DHN.
(embodiment 5) is handled using the metal reduction of decantation
In the clean space of rank 1000, being added in the four-hole boiling flask (removing bottom-type) of 1000mL capacity makes purity
99.4% 2,6-DHN is dissolved in solution (2.5 mass %) 500g that PGME is formed, and stirs while being heated to 30 DEG C.Connect
, add ion exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins) 25g, after stirring 30 minutes, it is small to stand 1
When.Then, separation ion exchange resin is filtered from the PGME solution of 2,6-DHN, obtains the purity that tenor reduces
The PGME solution of 97.8% 2,6-DHN.
(embodiment 6)
In the clean space of rank 1000, by ion exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins)
25g is filled into Teflon (registration mark) column after being swollen with PGME 25mL, is passed through the PGME of 500mL to carry out solvent displacement.
Then, the 4 of purity 99.2% will be made, the crude product of 4 '-xenol is dissolved in solution (2.5 mass %) 500g that PGME is formed and adds
In column, then decompression removes the air inside column and imports nitrogen, and internal oxygen concentration is adjusted to after less than 1%, is led to
Liquid, thus obtains 4 of the purity 99.2% through ion exchange resin treatment, the PGME solution of 4 '-xenol.
(embodiment 7)
In the clean space of rank 1000, by ion exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins)
25g is filled into Teflon (registration mark) column after being swollen with PGME 25mL, is passed through the PGME of 500mL to carry out solvent displacement.
Then, the crude product of the resorcinol for making purity 99.1% (1,3- dihydroxy benzenes) is dissolved in solution (2.5 matter that PGME forms
Measuring %) 500g added in column, and then decompression removes the air inside column and imports nitrogen, and internal oxygen concentration is adjusted to being less than
After 1%, logical liquid is carried out, thus obtains the resorcinol (1,3- dihydroxy benzenes) of the purity 99.0% through ion exchange resin treatment
PGME solution.
(embodiment 8)
In the clean space of rank 1000, by ion exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins)
25g is filled into Teflon (registration mark) column after being swollen with PGME 25mL, is passed through the PGME of 500mL to carry out solvent displacement.
Then, the crude product for 9, the 10- dihydroxy-anthracenes for making purity 98.8% is dissolved in solution (2.5 mass %) 500g that PGME forms to add
Enter in column, then decompression removes the air inside column and imports nitrogen, and internal oxygen concentration is adjusted to after less than 1%, is carried out
Logical liquid, thus obtains the PGME solution of 9, the 10- dihydroxy-anthracenes of the purity 98.8% through ion exchange resin treatment.
(embodiment 9)
In the clean space of rank 1000, by ion exchange resin (Mitsubishi Chemical Diaion：SMT100- hybrid resins)
25g with PGME 25mL be swollen after, be filled into Teflon (registration mark) column, the PGME for being passed through 500mL puts to carry out solvent
Change.Then, the crude product for the 1- hydroxyl pyrenes for making purity 98.9% is dissolved in solution (2.5 mass %) 500g that PGMEA forms to add
Enter in column, then decompression removes the air inside column and imports nitrogen, and internal oxygen concentration is adjusted to after less than 1%, is carried out
Logical liquid, the PGME for thus obtaining the resorcinol (1,3- dihydroxy benzenes) of the purity 98.8% through ion exchange resin treatment are molten
Liquid.
The purification process of ion exchange resin is not used in (comparative example 1)
In the four-hole boiling flask (bottom detachable type) of 1000mL capacity, addition dissolves 2,6-DHN of purity 98.7%
Solution (the 2.5 mass %) 150g formed in ethyl acetate, then decompression remove the air of flask interior and import nitrogen, on one side
Stirring obtains solution while be heated to 25 DEG C.In the process, the oxygen concentration in flask is less than 1 volume %.Then, obtaining
Solution in add oxalic acid aqueous solution (pH1.3) 37.5g stirring after five minutes, stand 30 points.Thus by oil phase and aqueous phase separation,
Therefore water removal phase is gone.After the operation is repeated 1 times, ultra-pure water 37.5g is added in obtained oil phase, stirring after five minutes, is stood
30 points, go water removal phase.The operation is repeated 3 times, thus obtains the vinegar of 2,6-DHN of the purity 98.7% that tenor reduces
Acetate solution.
For the hydroxyl substituted aromatic compound solution and the hydroxyl of before processing obtained in embodiment 1~9 and comparative example 1
Substituted aromatic compound solution, measures various tenors and organic purity.It should be noted that for embodiment 1~9,
Solution before the solution of preparation will be contacted with ion exchange resin as " before processing " for said determination, for comparing
Example 1, using the solution being about in the solution of preparation before addition oxalic acid aqueous solution as " before processing " for said determination.Measure
The results are shown in table 1.Each measure carries out under following device and determination condition.
[various tenor measure]
Using ICP-MS, the various tenors of 2,6-DHN are measured under following determination condition.
Device：ELAN DRCII (PerkinElmer Co., Ltd manufacture)
Temperature：25℃
Environment：100 toilet of rank
[organic purity testing]
Organic purity of 2,6-DHN is measured under following determination condition using high performance liquid chromatography.
Device：GL-7400 types (Hitachi's system)
Column：X-BRIDE C18
Eluent：Acetonitrile/water
Temperature：40℃
[table 1]
The application is based on Japanese patent application (Japanese Patent Application 2015-174634) filed in September in 2015 4 days, in it
Hold and be incorporated herein as reference.
Industrial applicability
According to the present invention it is possible to industrially advantageously be purified to hydroxyl substituted aromatic compound, can be made
The hydroxyl substituted aromatic compound for the high-purity that tenor reduces.
Claims (8)
1. a kind of purification process of compound, it includes making to include following formula (A0) and/or (B0) shown in hydroxyl substituted aromatic
The process of the solution of compound and solvent (A) and contacts ionic exchange resin,
Formula (the A0) in, n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, herein, the n0、m0And p0
At least one be more than 1 integer, and then, m0For 1 when, represent the formula (A0) there is naphthalene skeleton or biphenyl backbone, Ra is each
It independently is and selects free hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or cricoid alkyl, optionally there is substituent
Carbon number 6~40 aryl or carbon number 2~40 alkenyl and combinations thereof composition group in group, the alkyl, the virtue
Base or the alkenyl optionally include ehter bond, ketonic bond or ester bond；Formula (the B0) in, n1For 0~9 integer, p1For 0~9 integer,
Rb be each independently selected from by hydrogen atom, hydroxyl, halogeno-group, the straight-chain of carbon number 1~40, branched or cricoid alkyl,
Base optionally in the group of the alkenyl and combinations thereof of the aryl of the carbon number 6~40 with substituent or carbon number 2~40 composition
Group, the alkyl, the aryl or the alkenyl optionally include ehter bond, ketonic bond or ester bond.
2. the purification process of compound according to claim 1, wherein, the hydroxyl substituted aromatic compound is following
Formula (A) and/or the compound shown in (B),
In the formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, herein, the n0、m0And p0
At least one be more than 1 integer, and then, m0For 1 when, represent the formula (A0) there is naphthalene skeleton or biphenyl backbone, R0Each
Independently be carbon number 1~30 straight-chain, branched or cricoid alkyl, optionally with substituent carbon number 6~15 aryl,
Or the alkenyl of carbon number 2~15；In the formula (B), n1For 0~9 integer, p1For 0~9 integer, R1It is each independently carbon number
The aryl or carbon number 2~15 of 1~30 straight-chain, branched or cricoid alkyl, the optionally carbon number 6~15 with substituent
Alkenyl.
3. the purification process of compound according to claim 1, wherein, the hydroxyl substituted aromatic compound be selected from
As the compound shown in following formula (A-1), the compound shown in following formula (A-2), the compound shown in following formula (A-3), under
More than a kind in the group of the compound composition shown in the compound and following formula (B-1) shown in formula (A-4) is stated,
In the formula (A-1), n0For 1~5 integer, in the formula (A-2), n0For 0~7 integer, formula (A-3)~(A-
4) in, n0For 0~9 integer, in the formula (B-1), n1For 0~9 integer.
4. the purification process of compound according to claim 1, wherein, the hydroxyl substituted aromatic compound is following
Compound shown in formula (1),
5. the purification process of compound according to claim 1, wherein, the hydroxyl substituted aromatic compound be selected from
More than a kind in the group be made of 2,6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene.
6. the purification process of the compound according to any one of Claims 1 to 5, wherein, in the process, described
After Contact-sorption processing, further the separation and recovery of solution (A) is carried out by filtering.
7. the purification process of the compound according to any one of claim 1~6, wherein, the contact is in oxygen concentration
Carried out in atmosphere less than 20%.
8. the purification process of the compound according to any one of claim 1~7, wherein, the solvent be selected from by
Ethyl acetate, butyl acetate, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and hexamethylene
More than a kind in the group of ketone composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-174634 | 2015-09-04 | ||
| JP2015174634 | 2015-09-04 | ||
| PCT/JP2016/075765 WO2017038964A1 (en) | 2015-09-04 | 2016-09-02 | Compound purification method |
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| JP (1) | JP6931198B2 (en) |
| CN (1) | CN108026012A (en) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0519463A (en) * | 1991-07-17 | 1993-01-29 | Sumitomo Chem Co Ltd | Method for reducing metal in resist |
| JP2001114717A (en) * | 1999-10-19 | 2001-04-24 | Sumitomo Chem Co Ltd | Production of phenolic compound reduced with metal content |
| CN1092176C (en) * | 1995-09-28 | 2002-10-09 | 克拉里安特国际有限公司 | Low metal ion containing 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl) phenyl) ethylidene) bisphenol and photoresist compositions therefrom |
| US20120220112A1 (en) * | 2011-02-25 | 2012-08-30 | Shin-Etsu Chemical Co., Ltd. | Positive resist composition and patterning process |
| JP2014006403A (en) * | 2012-06-25 | 2014-01-16 | Shin Etsu Chem Co Ltd | Positive resist material and pattern forming method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5643228A (en) * | 1979-09-19 | 1981-04-21 | Mitsui Toatsu Chem Inc | Prevention of color development of aromatic compound having hydroxyl group |
| JPS5668634A (en) * | 1979-11-06 | 1981-06-09 | Sumitomo Chem Co Ltd | Purification of p,p'-biphenols |
| WO2010125807A1 (en) * | 2009-04-28 | 2010-11-04 | 三井化学株式会社 | Process for producing polyhydric phenol |
| JP2011042583A (en) * | 2009-08-19 | 2011-03-03 | Kawasaki Kasei Chem Ltd | Method for producing aqueous solution of naphthohydroquinone compound and radical-trapping agent aqueous solution |
-
2016
- 2016-09-02 JP JP2017538122A patent/JP6931198B2/en active Active
- 2016-09-02 WO PCT/JP2016/075765 patent/WO2017038964A1/en active Application Filing
- 2016-09-02 TW TW105128481A patent/TW201714865A/en unknown
- 2016-09-02 CN CN201680051150.2A patent/CN108026012A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0519463A (en) * | 1991-07-17 | 1993-01-29 | Sumitomo Chem Co Ltd | Method for reducing metal in resist |
| CN1092176C (en) * | 1995-09-28 | 2002-10-09 | 克拉里安特国际有限公司 | Low metal ion containing 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl) phenyl) ethylidene) bisphenol and photoresist compositions therefrom |
| JP2001114717A (en) * | 1999-10-19 | 2001-04-24 | Sumitomo Chem Co Ltd | Production of phenolic compound reduced with metal content |
| US20120220112A1 (en) * | 2011-02-25 | 2012-08-30 | Shin-Etsu Chemical Co., Ltd. | Positive resist composition and patterning process |
| JP2014006403A (en) * | 2012-06-25 | 2014-01-16 | Shin Etsu Chem Co Ltd | Positive resist material and pattern forming method |
Non-Patent Citations (1)
| Title |
|---|
| 王春艳: "《医用化学》", 31 August 2014 * |
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| Publication number | Publication date |
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| JP6931198B2 (en) | 2021-09-01 |
| TW201714865A (en) | 2017-05-01 |
| WO2017038964A1 (en) | 2017-03-09 |
| JPWO2017038964A1 (en) | 2018-06-21 |
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