CN114057576A - Method for preventing photoresist resin monomer from caking during purification, preparation method and purification method thereof - Google Patents
Method for preventing photoresist resin monomer from caking during purification, preparation method and purification method thereof Download PDFInfo
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- CN114057576A CN114057576A CN202111355888.7A CN202111355888A CN114057576A CN 114057576 A CN114057576 A CN 114057576A CN 202111355888 A CN202111355888 A CN 202111355888A CN 114057576 A CN114057576 A CN 114057576A
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- resin monomer
- organic phase
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 72
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000000178 monomer Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000746 purification Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 71
- 239000012074 organic phase Substances 0.000 claims abstract description 33
- SVURIXNDRWRAFU-OGMFBOKVSA-N cedrol Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1[C@@](O)(C)CC2 SVURIXNDRWRAFU-OGMFBOKVSA-N 0.000 claims abstract description 21
- 229940026455 cedrol Drugs 0.000 claims abstract description 21
- PCROEXHGMUJCDB-UHFFFAOYSA-N cedrol Natural products CC1CCC2C(C)(C)C3CC(C)(O)CC12C3 PCROEXHGMUJCDB-UHFFFAOYSA-N 0.000 claims abstract description 21
- SVURIXNDRWRAFU-UHFFFAOYSA-N juniperanol Natural products C1C23C(C)CCC3C(C)(C)C1C(O)(C)CC2 SVURIXNDRWRAFU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005886 esterification reaction Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 9
- 238000005191 phase separation Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
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- 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 method for preventing photoresist resin monomer from caking during purification, and a preparation method and a purification method thereof. The preparation method of the photoresist resin monomer comprises the following steps: (1) carrying out esterification reaction on cedrol and an esterification reagent; (2) phase separation is carried out on a reaction product containing a photoresist resin monomer; (3) washing the organic phase and performing chromatography by using a first solvent; (4) removing a portion of the first solvent from the mixture comprising the first solvent and the photoresist resin monomer; (5) and a second solvent are mixed and evaporated and cooled. The method prevents the photoresist resin monomer from caking during purification, is easy to filter, and further has high yield and high purity of the photoresist resin monomer.
Description
Technical Field
The invention relates to the technical field of photoresist resin monomers, in particular to a method for preventing photoresist resin monomers from caking during purification, a preparation method and a purification method thereof.
Background
The main components of the photoresist material include resin, photoacid generator, and corresponding additives and solvents, and the material has chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and changes its solubility in developer through photochemical reaction. According to the difference of photochemical reaction mechanism, the photoresist is divided into a positive photoresist and a negative photoresist: after exposure, the solubility of the photoresist in a developing solution is increased, and the photoresist with the same pattern as that of the mask is obtained and is called as a positive photoresist; after exposure, the photoresist has reduced solubility or even no solubility in a developing solution, and a negative photoresist with a pattern opposite to that of the mask is obtained. The resin component (shown below) in the photolithographic material is polymerized from resin monomers,
it is easy to agglomerate and difficult to crumble during purification.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for preventing agglomeration during purification of a photoresist resin monomer, which is easy to filter and has high yield and high purity, and a preparation method and a purification method thereof.
To achieve the above and other related objects, a first aspect of the present invention provides a method for preventing blocking during purification of a photoresist resin monomer, comprising the steps of:
a1) carrying out esterification reaction on cedrol and an esterification reagent in the presence of alkali and a fourth solvent, and purifying a product to obtain a mixture containing a first solvent and a photoresist resin monomer;
a2) removing a portion of the first solvent from a mixture comprising the first solvent and the photoresist resin monomer to obtain a first mixture;
a3) mixing the first mixture and a second solvent, and evaporating and cooling to obtain a solid containing the photoresist resin monomer;
the photoresist resin monomer has a structure shown as a formula I:
wherein R is1Is a hydrogen atom, a linear alkyl group, a branched alkyl group or a cyclic alkyl group.
Preferably, R1Is a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms, such as R1Is methyl.
Preferably, at least one of the following technical characteristics is also included:
a21) in step a2), the first solvent is selected from at least one of n-hexane, cyclohexane, n-heptane or dichloromethane;
a22) in the step a2), the removed first solvent is 88 to 92 percent of the first solvent, such as 88 to 90 percent or 90 to 92 percent;
a23) in the step a2), the temperature for removing part of the first solvent is 30-35 ℃, such as 30-33 ℃ or 33-35 ℃.
a31) In step a3), the second solvent is selected from at least one of methanol, ethanol or isopropanol;
a32) in the step a3), the mass ratio of the second solvent to the photoresist resin monomer is 1-3: 1, as 1-2: 1 or 2-3: 1;
a33) in the step a3), the evaporation temperature is 30-35 ℃, such as 30-32 ℃ or 32-35 ℃;
a34) in the step a3), the solvent volume reduction percentage of the first mixture and the second solvent after evaporation to mixing is 5-15%, such as 5-8%, 8-10% or 10-15%;
a35) in the step a3), cooling to 5-15 ℃, such as 5-8 ℃, 8-10 ℃ or 10-15 ℃;
a36) in step a3), after cooling, filtration, washing and drying are carried out. The filter cake obtained after filtration can be rinsed with a second solvent.
The second aspect of the present invention provides a method for purifying a photoresist resin monomer, comprising the steps of:
b1) carrying out esterification reaction on cedrol and an esterification reagent in the presence of alkali and a fourth solvent to obtain a reaction product containing the photoresist resin monomer;
b2) carrying out phase separation on a reaction product containing the photoresist resin monomer to obtain an organic phase and a water phase;
b3) washing the organic phase and performing chromatography by using a first solvent to obtain a mixture containing the first solvent and the photoresist resin monomer;
b4) and carrying out post-treatment on the mixture containing the first solvent and the photoresist resin monomer by adopting the method for preventing the photoresist resin monomer from caking during purification to obtain a solid containing the photoresist resin monomer.
Preferably, the method further comprises the following steps:
b5) and washing and drying the solid containing the photoresist resin monomer to obtain the photoresist resin monomer.
Preferably, step b5) further includes at least one of the following technical features:
b51) washing with a third solvent, wherein the third solvent is selected from at least one of methanol, ethanol or isopropanol;
b52) the drying temperature is 35-45 deg.C, such as 40 deg.C.
More preferably, the temperature of the third solvent is 8 to 12 ℃, such as 10 ℃.
Preferably, at least one of the following technical characteristics is also included:
b21) in step b2), adding water to the reaction product containing the photoresist resin monomer for phase separation;
b22) in the step b2), the aqueous phase is extracted to obtain an extracted organic phase, and the extracted organic phase is combined with the organic phase and then washed;
b31) in step b3), the organic phase is washed until the pH value is neutral, and can be washed by sodium hydroxide, water and/or the like;
b32) in step b3), the solvent is removed after washing and then chromatography is carried out; removing solvent by spin drying or vacuum concentrating;
b33) in step b3), the chromatography is silica gel chromatography;
b34) in the step b3), the volume ratio of the first solvent to the organic phase is 1-2: 1, such as 1-1.5: 1 or 1.5-2: 1;
b35) in step b3), washing and combining chromatographic layers after chromatography to obtain a mixture containing the first solvent and the photoresist resin monomer.
The third aspect of the present invention provides a method for preparing a photoresist resin monomer, comprising the steps of:
c1) carrying out esterification reaction on cedrol and an esterification reagent in the presence of alkali and a fourth solvent to obtain a reaction product containing the photoresist resin monomer;
c2) and purifying the reaction product containing the photoresist resin monomer by adopting the purification method of the photoresist resin monomer.
Preferably, step c1) further includes at least one of the following technical features:
c11) the esterification reagent has a structure as shown in formula II or formula III:
c12) the base is selected from at least one of triethylamine or pyridine;
c13) the fourth solvent is at least one selected from dichloromethane or methyl tert-butyl ether;
c14) the molar ratio of cedrol to the esterification reagent is 1: 1.1-1: 2.0, as 1: 1.1-1: 1.5 or 1: 1.5-1: 2.0;
c15) the molar ratio of cedrol to the base is 1: 2-1: 5, as shown in 1: 2-1: 3 or 1: 3-1: 5;
c16) the mass ratio of cedrol to the fourth solvent is 1: 5-1: 10, as shown in 1: 5-1: 8. 1: 8-1: 8.7 or 1: 8.7-1: 10;
c17) the temperature of the esterification reaction is 20-25 ℃, such as 20-23 ℃ or 23-25 ℃.
The invention provides a method for preventing photoresist resin monomer from caking during purification, a preparation method and a purification method thereof, wherein the method is capable of preventing the photoresist resin monomer from caking during purification, is easy to filter, and further is high in yield and purity of the photoresist resin monomer.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, the equipment, raw materials, etc. used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
50g of cedrol and 30.6g of acryloyl chloride, in that order, were added to 399g of dichloromethane at room temperature under nitrogen. Then, 68.3g of triethylamine was added dropwise thereto, and after completion of the addition, the reaction was allowed to warm to room temperature for 8 hours. 500ml of water was added to the reaction solution, followed by shaking and standing for 30 minutes to separate an organic phase in the lower layer, and an aqueous phase in the upper layer was extracted with methylene chloride (200 ml. times.1), followed by shaking and standing for 30 minutes to separate an organic layer, followed by combining the organic phases, washing the organic phase (lower layer) once with 200ml of a 10% sodium hydroxide solution and 200ml of water, respectively, and washing until the pH value was neutral. And (2) carrying out spin-drying on the organic phase to obtain a solvent (30 ℃), adding 500ml of n-hexane to the residue (the volume ratio of n-hexane to the organic phase obtained after spin-drying of the solvent is 1: 1), dissolving the residue, passing through silica gel (130g), washing the silica gel layer with 500ml of n-hexane once, combining the filtrates, evaporating out about 90% of the solvent (30-35 ℃), adding 100ml of methanol (2 times of the weight of the residue) when the filtrate is evaporated out, continuing to evaporate 10ml of the solvent (30-35 ℃ in a water bath, the volume reduction percentage is 5%), cooling the residual solution to 10-15 ℃ while stirring, precipitating a large amount of solid which cannot be solidified into a whole block, namely, filtering, leaching the filter cake with 60ml of 0 ℃ methanol, and drying the solid in vacuum (40 ℃) for 12 hours to obtain 39g of the product, wherein the molar yield is 62.4% and the purity is 99.6%.
Example 2
Under the protection of nitrogen, adding cedrol and acryloyl chloride which are used as raw materials into methyl tert-butyl ether at room temperature in sequence. Then, pyridine is dripped, and after dripping is finished, the temperature is raised to 23-25 ℃ for reaction for 10 hours, wherein the cedrol is 5kg, and the molar ratio of the cedrol to the acryloyl chloride is 1: 1.1, molar ratio to pyridine 1: and 5, the mass ratio of the methyl tert-butyl ether to the methyl tert-butyl ether is 1: 5. 50L of water was added to the reaction solution, followed by shaking and standing for 40 minutes to separate the lower organic phase, the upper aqueous phase was extracted with methyl t-butyl ether (20L. times.1), shaking and standing for 35 minutes to separate the organic layers, the organic phases were combined, and the organic phase (lower layer) was washed once with 20L of 10% sodium hydroxide solution and 20L of water, respectively, until the pH value was neutral. And (2) carrying out spin-drying on the organic phase to obtain a solvent (30 ℃), adding 50L of cyclohexane to the residue (the volume ratio of the cyclohexane to the organic phase obtained after spin-drying is 1.5: 1), dissolving the residue, passing through silica gel (13Kg), washing the silica gel layer with 20L of cyclohexane once, combining the filtrates, adding ethanol (methanol is 3 times of the weight of the residue) when the filtrate is distilled out to about 88% of the solvent (33-35 ℃), continuously distilling out the solvent (the volume reduction percentage is 15%) in a water bath, stirring the residual solution while cooling to 5-8 ℃, precipitating a large amount of solid which cannot be solidified into a whole block, namely, not caking, filtering, leaching the filter cake with 6L of ethanol at 0 ℃, and drying the solid in vacuum (40 ℃) for 12 hours to obtain 4Kg of the product, wherein the molar yield is 64% and the purity is 99.5%.
Example 3
Under the protection of nitrogen, 5.0kg of cedrol and 3.5kg of methacryloyl chloride as raw materials are added into 30kg of dichloromethane at room temperature in sequence and stirred until the materials are dissolved. 6.8kg of triethylamine is dripped, and after dripping is finished, the temperature is naturally raised to 20-25 ℃ for reaction for 14-16 h. 10L of deionized water was added to the reaction mixture, and the mixture was stirred for 10 minutes and allowed to stand for 30 minutes, to separate an organic phase in the lower layer, and an aqueous phase in the upper layer was extracted with methylene chloride (5L. times.2), stirred for 10 minutes and allowed to stand for 30 minutes, to separate an organic layer (lower layer). The organic phases were combined and washed once more with 2.5L of 10% sodium hydroxide in deionized water and 5L of deionized water until the pH was neutral. The organic phase was concentrated by a water pump under reduced pressure for 5 minutes without dripping (water bath 30 ℃), the residue was dissolved in 10L of n-hexane (volume ratio of n-hexane to the organic phase obtained after concentration under reduced pressure was 1: 1), and then silica gel (2.0kg) was passed through, the silica gel layer was washed with 50L of n-hexane until the filtrate spot plate was substantially free of product, and the filtrates were combined. When about 92% of the solvent is evaporated from the filtrate (33-35 ℃), adding methanol (the methanol is 1 time of the weight of the residue), continuously evaporating the solvent (the water bath is 30-32 ℃, the volume reduction percentage is 5%), transferring the solvent into a 50L reaction kettle, slowly cooling to 5-10 ℃, separating out a large amount of solids, not solidifying into a whole block, namely not caking, and stirring for 1-2 hours under heat preservation. Filtering, leaching a filter cake by using 1.5L of ice methanol at 0 ℃, drying the solid in a blast oven (40 ℃) until the reduction is less than 1g in 2 hours, and obtaining 3.9kg of a product, wherein the molar yield is 60.1%, and the purity is 98.2%.
Example 4
Under the protection of nitrogen, adding cedrol and methacrylic anhydride which are used as raw materials into dichloromethane at room temperature in sequence, and stirring until the materials are dissolved. And triethylamine is added dropwise, and after the triethylamine is added dropwise, the temperature naturally rises to 25 ℃ for reaction for 16h, wherein the cedrol is 5kg, and the molar ratio of the cedrol to methacrylic anhydride is 1: 2, the molar ratio of triethylamine to triethylamine is 1: 2, the mass ratio of the monomer to the methacrylic anhydride is 1: 10. 10L of deionized water was added to the reaction mixture, and the mixture was stirred for 15 minutes and allowed to stand for 35 minutes, to separate an organic phase in the lower layer, and an aqueous phase in the upper layer was extracted with methylene chloride (5L. times.2), stirred for 15 minutes and allowed to stand for 35 minutes, to separate an organic layer (lower layer). The organic phases were combined and washed once more with 2.5L of 10% sodium hydroxide in deionized water and 5L of deionized water until the pH was neutral. Concentrating the organic phase by a water pump under reduced pressure until no liquid drops after 5 minutes (water bath 30 ℃), adding 10L of dichloromethane (the volume ratio of the dichloromethane to the organic phase obtained after the concentration under reduced pressure is 1: 1) into the residue, dissolving the residue, passing through silica gel (2.0kg), washing a silica gel layer by 50L of dichloromethane until no product is basically produced on a filtrate point plate, combining the filtrates, adding isopropanol (2 times of the weight of the residue) when the filtrate is distilled out of about 88% of the solvent (33-35 ℃), continuously distilling out the solvent (water bath 30-32 ℃) until the volume reduction percentage is 8%), slowly cooling to 5-10 ℃ in a 50L reaction kettle, separating out a large amount of solids, not solidifying into a whole block, keeping the temperature and stirring for 1-2 hours. Filtering, leaching a filter cake by using 1.5L of ice methanol, and drying the solid in a forced air oven (40 ℃) until the reduction is less than 1g in 2 hours, so that 3.5kg of a product is obtained, the molar yield is 56%, and the purity is 98.1%.
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 preventing agglomeration during purification of a photoresist resin monomer, comprising the steps of:
a1) carrying out esterification reaction on cedrol and an esterification reagent in the presence of alkali and a fourth solvent, and purifying a product to obtain a mixture containing a first solvent and a photoresist resin monomer;
a2) removing a portion of the first solvent from a mixture comprising the first solvent and the photoresist resin monomer to obtain a first mixture;
a3) mixing the first mixture and a second solvent, and evaporating and cooling to obtain a solid containing the photoresist resin monomer;
the photoresist resin monomer has a structure shown as a formula I:
wherein R is1Is a hydrogen atom, a linear alkyl group, a branched alkyl group or a cyclic alkyl group.
2. The method for preventing agglomeration during purification of photoresist resin monomer as claimed in claim 1, wherein R is1Is a linear alkyl group, a branched alkyl group or a cyclic alkyl group having 1 to 3 carbon atoms.
3. The method for preventing agglomeration during the purification of photoresist resin monomer according to claim 1, further comprising at least one of the following technical features:
a21) in step a2), the first solvent is selected from at least one of n-hexane, cyclohexane, n-heptane or dichloromethane;
a22) in the step a2), the removed first solvent is 88-92% of the first solvent;
a23) in the step a2), the temperature for removing part of the first solvent is 30-35 ℃;
a31) in step a3), the second solvent is selected from at least one of methanol, ethanol or isopropanol;
a32) in the step a3), the mass ratio of the second solvent to the photoresist resin monomer is 1-3: 1;
a33) in the step a3), the evaporation temperature is 30-35 ℃;
a34) in the step a3), the solvent volume reduction percentage of the first mixture and the second solvent after the evaporation until the mixture is mixed is 5-15%;
a35) in the step a3), cooling to 5-15 ℃;
a36) in step a3), after cooling, filtration, washing and drying are carried out.
4. A method for purifying a photoresist resin monomer is characterized by comprising the following steps:
b1) carrying out esterification reaction on cedrol and an esterification reagent in the presence of alkali and a fourth solvent to obtain a reaction product containing the photoresist resin monomer;
b2) carrying out phase separation on a reaction product containing the photoresist resin monomer to obtain an organic phase and a water phase;
b3) washing the organic phase and performing chromatography by using a first solvent to obtain a mixture containing the first solvent and the photoresist resin monomer;
b4) subjecting the mixture containing the first solvent and the photoresist resin monomer to post-treatment by the method for preventing agglomeration during purification of the photoresist resin monomer according to any one of claims 1 to 4 to obtain a solid containing the photoresist resin monomer.
5. The method for purifying a monomer for a photoresist resin according to claim 5, further comprising the steps of:
b5) and washing and drying the solid containing the photoresist resin monomer to obtain the photoresist resin monomer.
6. The method for purifying a photoresist resin monomer according to claim 5, wherein the step b5) further comprises at least one of the following technical features:
b51) washing with a third solvent, wherein the third solvent is selected from at least one of methanol, ethanol or isopropanol;
b52) the drying temperature is 35-45 ℃.
7. The method for purifying the photoresist resin monomer according to claim 6, wherein the temperature of the third solvent is 8 to 12 ℃.
8. The method for purifying a monomer for a photoresist resin according to claim 5, further comprising at least one of the following technical features:
b21) in step b2), adding water to the reaction product containing the photoresist resin monomer for phase separation;
b22) in the step b2), the aqueous phase is extracted to obtain an extracted organic phase, and the extracted organic phase is combined with the organic phase and then washed;
b31) in step b3), the organic phase is washed to neutral pH;
b32) in step b3), the solvent is removed after washing and then chromatography is carried out;
b33) in step b3), the chromatography is silica gel chromatography;
b34) in the step b3), the volume ratio of the first solvent to the organic phase is 1-2: 1;
b35) in step b3), washing and combining chromatographic layers after chromatography to obtain a mixture containing the first solvent and the photoresist resin monomer.
9. A preparation method of a photoresist resin monomer is characterized by comprising the following steps:
c1) carrying out esterification reaction on cedrol and an esterification reagent in the presence of alkali and a fourth solvent to obtain a reaction product containing the photoresist resin monomer;
c2) purifying the reaction product containing the photoresist resin monomer by using the method for purifying the photoresist resin monomer as claimed in any one of claims 4 to 8.
10. The method for preparing a photoresist resin monomer according to claim 9, wherein the step c1) further comprises at least one of the following technical features:
c11) the esterification reagent has a structure as shown in formula II or formula III:
c12) the base is selected from at least one of triethylamine or pyridine;
c13) the fourth solvent is at least one selected from dichloromethane or methyl tert-butyl ether;
c14) the molar ratio of cedrol to the esterification reagent is 1: 1.1-1: 2.0;
c15) the molar ratio of cedrol to the base is 1: 2-1: 5;
c16) the mass ratio of cedrol to the fourth solvent is 1: 5-1: 10;
c17) the temperature of the esterification reaction is 20-25 ℃.
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| CN111056947A (en) * | 2019-12-28 | 2020-04-24 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from α -cedrene and synthesis method thereof |
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| 袁训等: "大位阻叔醇醋化合成的研究", 《浙江大学学报〔自然科学版）》, vol. 24, no. 1, pages 59 - 66 * |
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