CN114573425A - Purification method and application of 1, 1, 1-tri (4-hydroxyphenyl) compound - Google Patents
Purification method and application of 1, 1, 1-tri (4-hydroxyphenyl) compound Download PDFInfo
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- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000000746 purification Methods 0.000 title claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 20
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 claims description 32
- 239000007983 Tris buffer Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- 229920005990 polystyrene resin Polymers 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 2
- 229940075931 sodium dithionate Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a purification method and application of a 1, 1, 1-tri (4-hydroxyphenyl) compound, wherein the purification method comprises the following steps: dissolving the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound in an organic solvent, adding an adsorbent, carrying out solid-liquid separation, washing a liquid phase obtained after the solid-liquid separation with water, removing the organic solvent, and carrying out concentration crystallization to obtain the 1, 1, 1-tri (4-hydroxyphenyl) compound; the organic solvent is immiscible with water. The purification method is simple and easy to industrialize, and the content of metal ions in the purified 1, 1, 1-tri (4-hydroxyphenyl) compound is lower than 100ppb, so that the method can meet the use requirements of the semiconductor electronic industry and is expected to be applied to the related fields of the semiconductor industry.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a purification method and application of a 1, 1, 1-tri (4-hydroxyphenyl) compound.
Background
1, 1, 1-tris (4-hydroxyphenyl) compounds, particularly 1, 1, 1-tris (4-hydroxyphenyl) ethane (hereinafter THPE), are trifunctional phenolic compounds useful as crosslinkers or branching agents for a variety of polymers, such as polycarbonates, epoxy resins, polyarylates, adhesives, coatings, and the like, and as intermediates for the preparation of antioxidants. THPE having a metal ion content of < 100ppb can also be used in the semiconductor field, for example, as a raw material for semiconductor photoresists. However, the content of metal ions such as sodium ions of THPE products commercially produced in the current market generally exceeds 1-5ppm, so that the THPE with low metal ion content always depends on foreign import, which always restricts the development of related fields of the semiconductor industry in China for a long time. How to remove trace metal ions in the product and obtain a product with higher purity so as to meet the use requirement of the semiconductor electronic industry becomes a key technical problem to be solved urgently in China at present.
According to the prior art, the purification method of the 1, 1, 1-tris (4-hydroxyphenyl) compound is complex, and the content of metal ions is seriously exceeded. As reported in CN1163257A, an alkali metal sodium borohydride was added during the purification of 1, 1, 1-tris (4-hydroxyphenyl) ethane; in DE69107150T2, THPE is washed with an aqueous solution of sodium dithionate; EP646613 a 1 uses an aqueous solution of sodium hydroxide to treat THPE, and so on. The addition of sodium borohydride, sodium dithionate, sodium hydroxide and the like can cause the content of sodium ions in the final product to exceed the standard, so that the use requirement of the semiconductor industry is difficult to meet.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a method for purifying 1, 1, 1-tris (4-hydroxyphenyl) compound and its use, which are used to solve the problem that the 1, 1, 1-tris (4-hydroxyphenyl) compound in the prior art has a high content of metal ions and cannot meet the use requirements of the semiconductor industry.
To achieve the above objects and other related objects, the present invention includes the following technical solutions.
The invention provides a method for purifying a 1, 1, 1-tri (4-hydroxyphenyl) compound, which comprises the following steps: dissolving the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound in an organic solvent, adding an adsorbent, carrying out solid-liquid separation, washing a liquid phase obtained after the solid-liquid separation with water, removing the organic solvent, and concentrating and crystallizing to obtain the 1, 1, 1-tri (4-hydroxyphenyl) compound; the organic solvent is immiscible with water.
Preferably, the organic solvent is selected from one or more of nitromethane, methyl ethyl ketone, ethyl acetate, methyl isobutyl ketone, chloroform, dichloromethane, benzene, diethyl ether, propyl ether, toluene, carbon tetrachloride and carbon disulfide.
Preferably, the mass ratio of the organic solvent to the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound is (5-10): 1.
Preferably, the adsorbent is selected from one or more of activated carbon, silica gel and resin; more preferably, the resin is a polystyrene resin or a polyacrylate resin.
Preferably, the adsorbent is added in an amount of 1.5-5.0 wt% based on the total weight of the crude 1, 1, 1-tris (4-hydroxyphenyl) compound.
Preferably, the amount of water added is 5-10 times based on the total weight of the crude 1, 1, 1-tris (4-hydroxyphenyl) compound.
Preferably, the purification method is a method for removing metal ions in the crude product of the 1, 1, 1-tris (4-hydroxyphenyl) compound; the content of metal ions in the purified 1, 1, 1-tris (4-hydroxyphenyl) compound is less than 100ppb, more preferably less than 50 ppb.
Preferably, the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound is a crude product of 1, 1, 1-tri (4-hydroxyphenyl) ethane.
Preferably, the purity of the 1, 1, 1-tris (4-hydroxyphenyl) compound obtained after purification is not less than 99.5%.
The invention also provides application of the 1, 1, 1-tri (4-hydroxyphenyl) compound obtained by the purification method as a raw material component of photoresist in the field of semiconductors.
As described above, the purification method and use of the 1, 1, 1-tris (4-hydroxyphenyl) compound of the present invention have the following advantageous effects: the purification method is simple and easy to industrialize, the content of metal ions in the purified 1, 1, 1-tri (4-hydroxyphenyl) compound is lower than 100ppb, the use requirement of the semiconductor electronic industry can be met, and the method is expected to be applied to the related field of the semiconductor industry.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The embodiment of the invention provides a method for purifying a 1, 1, 1-tri (4-hydroxyphenyl) compound, which comprises the following steps: dissolving the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound in an organic solvent, adding an adsorbent, carrying out solid-liquid separation, washing a liquid phase obtained after the solid-liquid separation with water, removing the organic solvent, and concentrating and crystallizing to obtain the 1, 1, 1-tri (4-hydroxyphenyl) compound; the organic solvent is immiscible with water.
In the technical scheme of the application, the adsorbent can decolorize a 1, 1, 1-tri (4-hydroxyphenyl) compound crude product dissolved in an organic solvent and primarily remove metal ions; and (3) solid-liquid separation, wherein the liquid phase after the solid-liquid separation is washed by water, metal ions can be dissolved in water, the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound and an organic solvent are not mutually soluble with water, the metal ions are further removed, then the organic solvent is removed, and the 1, 1, 1-tri (4-hydroxyphenyl) compound is obtained by concentration and crystallization.
In a particular embodiment, the organic solvent is selected from one or more of nitromethane, methyl ethyl ketone, ethyl acetate, methyl isobutyl ketone, chloroform, dichloromethane, benzene, diethyl ether, propyl ether, toluene, carbon tetrachloride and carbon disulfide.
In a specific embodiment, the mass ratio of the organic solvent to the crude 1, 1, 1-tris (4-hydroxyphenyl) compound is (5-10): 1.
In a particular embodiment, the adsorbent is selected from one or more of activated carbon, silica gel and resin. The resin is polystyrene resin or polyacrylate resin.
In a specific embodiment, the adsorbent is added in an amount of 1.5 to 5.0 wt%, such as 1.5 to 2 wt%, 2 to 2.5 wt%, 2.5 to 5 wt%, based on the total weight of the crude 1, 1, 1-tris (4-hydroxyphenyl) compound.
In a specific embodiment, the amount of water added is 5 to 10 times based on the total weight of the crude 1, 1, 1-tris (4-hydroxyphenyl) compound.
In one embodiment, the water washing step uses ultrapure water having a resistivity of > 15 M.OMEGA.cm (25 ℃).
In a more specific embodiment, the removal of the organic solvent is carried out by distillation under reduced pressure; the reduced pressure distillation pressure is-0.08 MPa, and the temperature is 40-70 deg.C, such as 40 deg.C, 45 deg.C, 50 deg.C, and 65 deg.C.
In a more specific embodiment, after the concentration and crystallization, the method further comprises a vacuum drying process, wherein the temperature of the vacuum drying process is 60-90 ℃, such as 60 ℃, 65 ℃, 70 ℃, 85 ℃, and the vacuum degree is-0.1 kPa.
In a specific embodiment, the crude 1, 1, 1-tris (4-hydroxyphenyl) compound is obtained by chemical synthesis.
In a more specific embodiment, the crude 1, 1, 1-tris (4-hydroxyphenyl) compound is crude 1, 1, 1-tris (4-hydroxyphenyl) ethane, and the process for preparing the crude 1, 1, 1-tris (4-hydroxyphenyl) ethane comprises the steps of: phenol and p-hydroxyacetophenone are used as raw materials, polystyrene sulfonic acid resin is used as an ion exchanger, 3-mercaptopropionic acid is used as a cocatalyst, and a crude product of the 1, 1, 1-tris (4-hydroxyphenyl) ethane is prepared by reaction under the protection of inert gas.
In a specific embodiment, the purification method is a method for removing metal ions from a crude 1, 1, 1-tris (4-hydroxyphenyl) compound; the content of metal ions in the purified 1, 1, 1-tris (4-hydroxyphenyl) compound is less than 100ppb, more preferably less than 50 ppb.
In a specific embodiment, the crude 1, 1, 1-tris (4-hydroxyphenyl) compound is crude 1, 1, 1-tris (4-hydroxyphenyl) ethane.
In a specific embodiment, the purity of the purified 1, 1, 1-tris (4-hydroxyphenyl) compound is not less than 99.5%.
The invention also provides application of the 1, 1, 1-tri (4-hydroxyphenyl) compound obtained by the purification method as a raw material component of photoresist in the field of semiconductors.
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
In the following examples, the preparation method of the crude 1, 1, 1-tris (4-hydroxyphenyl) ethane comprises the following steps: a mixture of 1500g of phenol, 2.7g of 3-mercaptopropionic acid, and 398g of polystyrene sulfonic acid resin was placed in a round bottom flask equipped with a condenser, thermometer, and mechanical stirrer in a N-flask2Heating to 65 ℃ under protection, and adding 180g of p-hydroxyacetophenone to the mixture; the mixture was stirred and heated, after about 4 hours, the reaction product precipitated into a dichloromethane solution (about 4mL of dichloromethane per gram of reaction product), and 1, 1, 1-tris (4-hydroxyphenyl) ethane was isolated by filtration, washed with additional dichloromethane solution, and then dried in a vacuum oven at 90 ℃ overnight to give crude 1, 1, 1-tris (4-hydroxyphenyl) ethane.
Example 1
This example provides a method for purifying a 1, 1, 1-tris (4-hydroxyphenyl) compound, comprising the steps of:
100g of 1, 1, 1-tris (4-hydroxyphenyl) ethane crude product (THPE crude product) is taken, 900g of methyl isobutyl ketone (MIBK for short) solvent is added for dissolution, 2.47g of activated carbon is added, stirring is continuously carried out for 60 minutes at room temperature, the activated carbon is filtered after standing, 800g of ultrapure water (the resistivity is more than 15M omega cm (25 ℃)) is added for washing, the mixture is stirred for 60 minutes, standing and liquid separation are carried out, the MIBK solvent is evaporated under the conditions of-0.08 MPa and 65 ℃ through a reduced pressure distillation device, concentration and crystallization are carried out, a crystallized product is obtained, and a dried sample of 1, 1, 1-tris (4-hydroxyphenyl) ethane is obtained after vacuum drying is carried out for 12 hours at the temperature of 60 ℃.
HPLC analysis showed THPE purity of 99.74%.
The contents of metal ions in the 1, 1, 1-tris (4-hydroxyphenyl) ethane before and after purification were measured by the ICP-MS method, and the results are shown in Table 1. Wherein the content of sodium ions in the 1, 1, 1-tris (4-hydroxyphenyl) ethane before purification is as follows: 3342ppb, sodium ion content in purified 1, 1, 1-tris (4-hydroxyphenyl) ethane: 38 ppb.
Example 2
This example provides a method for purifying a 1, 1, 1-tris (4-hydroxyphenyl) compound, comprising the steps of:
100.02g of crude 1, 1, 1-tris (4-hydroxyphenyl) ethane is taken, 900g of butanone solvent is added for dissolution, 2g of polyacrylate resin is added, stirring is continuously carried out for 60 minutes at 20 ℃, the polyacrylate resin is filtered after standing, then 800g of ultrapure water (the resistivity is more than 15M omega cm (25 ℃) is added for washing, after stirring for 60 minutes, standing and liquid separation are carried out, butanone is evaporated under the conditions of-0.08 MPa and 50 ℃ through a reduced pressure distillation device, and concentrated and crystallized products are obtained, and dried samples of the 1, 1, 1-tris (4-hydroxyphenyl) ethane are obtained after vacuum drying is carried out for 12 hours at 60 ℃.
HPLC analysis showed THPE purity of 99.69%.
The contents of metal ions in the 1, 1, 1-tris (4-hydroxyphenyl) ethane before and after purification were measured by the ICP-MS method, and the results are shown in Table 1. The results showed that the sodium ion content in the 1, 1, 1-tris (4-hydroxyphenyl) ethane obtained after purification: 41 ppb.
Example 3
This example provides a method for purifying a 1, 1, 1-tris (4-hydroxyphenyl) compound, comprising the steps of:
taking 200g of crude 1, 1, 1-tris (4-hydroxyphenyl) ethane, adding 1600g of mixed solvent of benzene and ethyl acetate for dissolving, wherein the mixing ratio of the two is 6: and 4, adding 5g of activated carbon, continuously stirring for 60 minutes at 25 ℃, standing, filtering the activated carbon, adding 1000g of ultrapure water (the resistivity is more than 15M omega cm (25 ℃)) for washing, stirring for 60 minutes, standing, separating liquid, evaporating the mixed solvent at 45 ℃ under-0.08 MPa by using a reduced pressure distillation device, concentrating and crystallizing to obtain a crystallized product, and performing vacuum drying at 80 ℃ for 12 hours to obtain a dried sample of the 1, 1, 1-tris (4-hydroxyphenyl) ethane.
HPLC analysis showed THPE purity of 99.50%.
The metal ion content of 1, 1, 1-tris (4-hydroxyphenyl) ethane before and after purification was measured by the ICP-MS method, and the results are shown in table 1. Wherein, the content of sodium ions in the purified 1, 1, 1-tri (4-hydroxyphenyl) ethane is as follows: 46 ppb.
Example 4
This example provides a method for purifying a 1, 1, 1-tris (4-hydroxyphenyl) compound, comprising the steps of:
100g of 1, 1, 1-tris (4-hydroxyphenyl) ethane crude product is taken, 900g of mixed solvent of ethyl acetate and butanone is added for dissolution, and the mixing ratio of the ethyl acetate and the butanone is 8: 2, adding 2.5g of activated carbon, continuously stirring for 60 minutes at room temperature, standing, filtering the activated carbon, adding 800g of ultrapure water (the resistivity is more than 15M omega cm (25 ℃) for washing, stirring for 60 minutes, standing, separating liquid, evaporating the mixed solvent by a reduced pressure distillation device under the conditions of-0.08 Mpa and 40 ℃, concentrating and crystallizing to obtain a crystallized product, and performing vacuum drying for 12 hours at 80 ℃ to obtain a dried sample of the 1, 1, 1-tris (4-hydroxyphenyl) ethane.
HPLC analysis showed THPE purity of 99.63%.
The contents of metal ions in the 1, 1, 1-tris (4-hydroxyphenyl) ethane before and after purification were measured by the ICP-MS method, and the results are shown in Table 1. Wherein, the content of sodium ions in the purified 1, 1, 1-tri (4-hydroxyphenyl) ethane is as follows: 50 ppb.
Comparative example 1
Comparative example 1 is different from example 1 in that the solvent for dissolving the crude 1, 1, 1-tris (4-hydroxyphenyl) ethane is different, 1% hydrochloric acid is used for dissolving the product, and the rest of the process is completely the same.
Comparative example 2
Comparative example 2 is different from example 1 in that the solvent for dissolving the crude 1, 1, 1-tris (4-hydroxyphenyl) ethane is different, the product is dissolved with ethanol, and the rest of the process is identical.
Comparative example 3
Comparative example 3 is different from example 2 in that the solvent for dissolving the crude 1, 1, 1-tris (4-hydroxyphenyl) ethane is different, methanol is used for dissolving the product, and the rest of the process is completely the same.
The metal ion content was measured using an inductively coupled plasma mass spectrometer (ICP-MS). The contents of metal ions in purified 1, 1, 1-tris (4-hydroxyphenyl) ethane of examples 1 to 4 and comparative examples 1 to 3 are shown in table 1:
TABLE 1 test results
As can be seen from Table 1, the THPE product obtained by the purification method of the present application has greatly reduced content of metal ions, can realize content lower than 100ppb, and part of the preferred embodiments are lower than 50ppb, and the purified 1, 1, 1-tris (4-hydroxyphenyl) compound can be used as a raw material component of a photoresist in the semiconductor field. As can be seen by comparing the data of examples 1 and 2 with those of comparative examples 1 to 3, it is necessary to use an organic solvent immiscible with water to effectively remove the metal ions from the crude THPE.
In conclusion, the purification method is simple and easy to industrialize, the content of metal ions in the purified 1, 1, 1-tris (4-hydroxyphenyl) compound is lower than 100ppb, the use requirement of the semiconductor electronic industry can be met, and the method is expected to be applied to the related field of the semiconductor industry. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for purifying a 1, 1, 1-tris (4-hydroxyphenyl) compound, comprising the steps of: dissolving the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound in an organic solvent, adding an adsorbent, carrying out solid-liquid separation, washing a liquid phase obtained after the solid-liquid separation with water, removing the organic solvent, and concentrating and crystallizing to obtain the 1, 1, 1-tri (4-hydroxyphenyl) compound; the organic solvent is immiscible with water.
2. The purification method according to claim 1, wherein: the organic solvent is selected from one or more of nitromethane, methyl ethyl ketone, ethyl acetate, methyl isobutyl ketone, chloroform, dichloromethane, benzene, diethyl ether, propyl ether, toluene, carbon tetrachloride and carbon disulfide.
3. The purification method according to claim 1, wherein: the mass ratio of the organic solvent to the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound is (5-10): 1.
4. The purification method according to claim 1, wherein: the adsorbent is selected from one or more of activated carbon, silica gel and resin.
5. The purification method according to claim 4, wherein: the resin is polystyrene resin or polyacrylate resin.
6. The purification method according to claim 1, wherein: based on the total weight of the crude product of the 1, 1, 1-tris (4-hydroxyphenyl) compound, the addition amount of the adsorbent is 1.5-5.0 wt%.
7. The purification method according to claim 1, wherein: taking the total weight of the crude product of the 1, 1, 1-tris (4-hydroxyphenyl) compound as a reference, and adding 5-10 times of water;
and/or the washing step adopts ultrapure water, and the resistivity of the ultrapure water is more than 15M omega cm.
8. The purification method according to claim 1, wherein: the purification method is a method for removing metal ions in the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound; the content of metal ions in the purified 1, 1, 1-tri (4-hydroxyphenyl) compound is less than 100 ppb.
9. The purification method according to claim 1, wherein: the crude product of the 1, 1, 1-tri (4-hydroxyphenyl) compound is a crude product of 1, 1, 1-tri (4-hydroxyphenyl) ethane;
and/or the purity of the 1, 1, 1-tri (4-hydroxyphenyl) compound obtained after purification is not less than 99.5 percent.
10. Use of a 1, 1, 1-tris (4-hydroxyphenyl) compound obtained by the purification method according to any one of claims 1 to 9 as a raw material component for a photoresist in the field of semiconductors.
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Denomination of invention: Purification method and application of a 1,1,1-tris (4-hydroxyphenyl) compound Effective date of registration: 20231110 Granted publication date: 20221209 Pledgee: Bank of China Limited Fuyang Branch Pledgor: Anhui Mituo Material Technology Co.,Ltd.|Shanghai Mituo Material Technology Co.,Ltd. Registration number: Y2023980064856 |