CN117623918A - Preparation method of acrylic resin monomer for 193nm photoresist - Google Patents
Preparation method of acrylic resin monomer for 193nm photoresist Download PDFInfo
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- CN117623918A CN117623918A CN202311365317.0A CN202311365317A CN117623918A CN 117623918 A CN117623918 A CN 117623918A CN 202311365317 A CN202311365317 A CN 202311365317A CN 117623918 A CN117623918 A CN 117623918A
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- 239000000178 monomer Substances 0.000 title claims abstract description 34
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 title description 7
- 229920000178 Acrylic resin Polymers 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 66
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 acrylic ester Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 19
- 238000001953 recrystallisation Methods 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 230000008878 coupling Effects 0.000 claims abstract description 3
- 238000010168 coupling process Methods 0.000 claims abstract description 3
- 238000005859 coupling reaction Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims abstract 3
- 229920005989 resin Polymers 0.000 claims abstract 3
- 230000001737 promoting effect Effects 0.000 claims abstract 2
- 230000001502 supplementing effect Effects 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- FOWDOWQYRZXQDP-UHFFFAOYSA-N adamantan-2-ol Chemical compound C1C(C2)CC3CC1C(O)C2C3 FOWDOWQYRZXQDP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- YUBKBLFRGDNIDR-UHFFFAOYSA-N 2-ethyladamantan-2-ol Chemical compound C1C(C2)CC3CC1C(CC)(O)C2C3 YUBKBLFRGDNIDR-UHFFFAOYSA-N 0.000 claims description 4
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 4
- JKOZWMQUOWYZAB-UHFFFAOYSA-N 2-methyladamantan-2-ol Chemical compound C1C(C2)CC3CC1C(C)(O)C2C3 JKOZWMQUOWYZAB-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000010808 liquid waste Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 67
- 238000011084 recovery Methods 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 10
- NLNVUFXLNHSIQH-UHFFFAOYSA-N (2-ethyl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C=C)C2C3 NLNVUFXLNHSIQH-UHFFFAOYSA-N 0.000 description 7
- YRPLSAWATHBYFB-UHFFFAOYSA-N (2-methyl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)(OC(=O)C=C)C2C3 YRPLSAWATHBYFB-UHFFFAOYSA-N 0.000 description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- LRFKWQGGENFBFO-UHFFFAOYSA-N fingolimod phosphate Chemical group CCCCCCCCC1=CC=C(CCC(N)(CO)COP(O)(O)=O)C=C1 LRFKWQGGENFBFO-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- MWMWRSCIFDZZGW-UHFFFAOYSA-N (2-oxooxolan-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CCOC1=O MWMWRSCIFDZZGW-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- OXHVCLNCFNQWON-UHFFFAOYSA-N 2-methyladamantan-1-ol Chemical compound C1C(C2)CC3CC1C(C)C2(O)C3 OXHVCLNCFNQWON-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WIJGTIIKQPGTSQ-UHFFFAOYSA-N adamantane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1C(C2)CC3CC1CC2C3 WIJGTIIKQPGTSQ-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DMMOZSFQHREDHM-UHFFFAOYSA-N 2-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)C2C3 DMMOZSFQHREDHM-UHFFFAOYSA-N 0.000 description 1
- UEBUOANSKOYYKC-UHFFFAOYSA-N 2-ethyladamantan-1-ol Chemical compound C1C(C2)CC3CC1C(CC)C2(O)C3 UEBUOANSKOYYKC-UHFFFAOYSA-N 0.000 description 1
- LFJJGHGXHXXDFT-UHFFFAOYSA-N 3-bromooxolan-2-one Chemical compound BrC1CCOC1=O LFJJGHGXHXXDFT-UHFFFAOYSA-N 0.000 description 1
- FWIBCWKHNZBDLS-UHFFFAOYSA-N 3-hydroxyoxolan-2-one Chemical compound OC1CCOC1=O FWIBCWKHNZBDLS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 239000012265 solid product Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of an acrylic ester resin monomer for 193nm photoresist, which comprises the steps of taking acrylic anhydride and corresponding alcohol as reaction raw materials, taking acrylic acid as a reaction solvent, adding a polymerization inhibitor, condensing the acrylic acid of the reaction solvent with the alcohol to generate acrylic ester, esterifying the acrylic anhydride to generate acrylic ester and acrylic acid, supplementing the consumption of the acrylic acid by the generated acrylic acid, improving the concentration of reaction materials, and continuously promoting the synthesis reaction of the acrylic ester to proceed towards the positive reaction direction; after the reaction is finished, the acrylic ester product is obtained by purification through a method of coupling two-phase solvent recrystallization. The preparation method of the acrylic ester resin monomer for 193nm photoresist, which is provided by the invention, has the advantages of simple operation of the reaction process, safety, environmental protection, no liquid waste, easy purification after the reaction, and the purity of the prepared acrylic ester monomer product is more than or equal to 99.9%, and the total yield is more than or equal to 94%, and is a process route suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a preparation method of an acrylic resin monomer for 193nm photoresist.
Background
193nm photoresist is a big hot spot in recent years, with the continuous updating of high-end mobile phones and electronic products, the demand for 193nm photoresist in chip manufacturing is increasing, and the synthesis and improvement of 193nm photoresist and the realization of mass production are unprecedented difficult tasks. The acrylate series is widely used in 193nm photoresists due to its good light transmission and photosensitivity. However, as the double bond in the acrylic monomer is easy to polymerize, the acid sensitive group in the monomer is easy to decompose, and the esterification reaction is generally reversible, the preparation process of the acrylic resin monomer has very strict purification requirements, the conversion rate of the product is low, and the product has almost no mass products with ultra-clean high-purity quality requirements in the market of China at present. The defect of upstream key raw materials greatly improves the development cost of the photoresist, and the development and application of photoresist components are urgent.
Current reports on the synthesis of 2-oxo-tetrahydrofuran-3-yl acrylate include: in 2010 patent JP 2010242101, the America may propose that acrylic acid and alpha-hydroxy-gamma-butyrolactone are used as raw materials, toluene is used as a solvent, and p-toluenesulfonic acid is used as a catalyst for reaction to prepare 2-oxo-tetrahydrofuran-3-yl acrylate, and the product yield is 50%; takahashi et al in 2007 indicated that acrylic acid and α -bromo- γ -butyrolactone were used as raw materials, and DMF having a high boiling point was used as a solvent for the reaction, with a product yield of 70%; at present, no relevant report on the product exists in China.
Relevant reports on adamantane acrylate synthesis include: 2016, li Wei et al propose that adamantanol and acryloyl chloride are used as raw materials, THF is used as a solvent, triethylamine is used as a catalyst, and the final product is obtained by reaction at 0 ℃, the product yield is 59%, but the product of the synthetic route is not used for photoresist monomers; in 2017 Matsumoto et al, it is proposed that adamantanol and acryloyl chloride are used as raw materials, dichloroethane is used as a solvent, the reaction is carried out for 12 hours, the product yield is 44%, and no report on the purity of the product is seen; in 2016 Averina et al, adamantanol and acryloyl chloride are taken as raw materials, triethylamine is taken as a catalyst, dichloromethane is taken as a solvent, and the reaction is carried out for 27 hours to obtain 84% of product yield; the same reaction conditions were proposed by Nakano et al in 2014 with a reaction yield of 50%. The existing problems of the reaction are long reaction time, low yield and undefined purity, and no document report on high-yield synthesis of ultra-clean high-purity adamantane acrylate is found.
Relevant reports about the synthesis of 2-methyl-2-adamantane acrylate include that concentrated sulfuric acid is adopted as a reaction reagent in patent JP2001354619 and JP2001106650, so that the dosage is very large, the environment is greatly harmed, the reaction progress is difficult to control, a plurality of impurities which are difficult to separate are formed, the purity of the product is greatly reduced, and the cost of the product and the quality of the final photoresist are directly influenced. In the patent JP 2000119220, the acryloyl chloride is used, and belongs to a highly toxic product, the operation is complicated, the use is dangerous, a large amount of hydrogen chloride is discharged in the production, the environment is seriously polluted, and the requirements on production equipment are more severe; in addition, the use of the acryloyl chloride can form more impurities, seriously affect the quality of photoresist products and is not beneficial to industrial production.
In the prior art, the existing synthetic process of acrylic ester products is easy to carry out self-polymerization due to the existence of active double bonds in the products, thereby seriously affecting the yield of the products, so that the existing preparation method is often carried out under the low-temperature condition to limit the self-polymerization rate; the toxicity of the acrylic chloride introduced by the raw materials is high, the operation safety is low, the product is easy to damage, the purification procedure at the end of the preparation process is usually to purify by adopting a distillation method, the distillation temperature is high, and the self-polymerization rate of the product can be improved at high temperature, so that the yield and purity of the product are reduced.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and disadvantages of the prior art, the invention provides a preparation method of an acrylic resin monomer for 193nm photoresist, which has the advantages of no catalyst, simple operation, high product purity and yield, easy purification of a reaction system and the like.
(II) technical scheme
A method for preparing an acrylate resin monomer for 193nm photoresist, comprising:
acrylic anhydride and corresponding alcohol are used as reaction raw materials, acrylic acid is used as a reaction solvent, a polymerization inhibitor is added, acrylic acid and alcohol in the reaction solvent are condensed to generate acrylic ester, acrylic anhydride is changed into acrylic ester and acrylic acid through esterification, the generated acrylic acid supplements the consumption of acrylic acid, the concentration of the reaction materials is improved, and the synthesis reaction of acrylic ester is continuously promoted to be carried out towards the positive reaction direction; after the reaction is finished, purifying by a method of coupling two-phase solvent recrystallization to obtain an acrylic ester product; the acrylic acid is acrylic acid containing alkyl or not containing alkyl, and the acrylic anhydride is acrylic anhydride containing alkyl or not containing alkyl.
Preferably, the alkyl is methyl or ethyl, and the acrylic acid is acrylic acid, methacrylic acid, ethacrylic acid or the like; the acrylic anhydride is acrylic anhydride, methacrylic anhydride or ethacrylic anhydride which does not contain substituent groups, and the like. In order to improve the purity of the acrylate monomer product, the acrylic acid and the acrylic anhydride added by the reaction raw materials are simultaneously free of alkyl groups or contain the same alkyl groups.
According to a preferred embodiment of the present invention, the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methylhydroquinone and tetrachlorobenzoquinone.
According to a preferred embodiment of the present invention, the alcohol is 2-adamantanol, 2-methyl-2-adamantanol, 2-ethyl-2-adamantanol or 2-carbonyl-tetrahydrofuran-3-ol, and the resulting acrylate monomer is 2-adamantylacrylate, 2-methyl-2-adamantylacrylate, 2-ethyl-2-adamantylacrylate, 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylate in that order.
According to a preferred embodiment of the invention, the molar ratio of acrylic anhydride to alcohol is 1.2-1.5:1.
According to a preferred embodiment of the invention, the mass ratio of alcohol to acrylic acid is 1g:3-5mL.
According to a preferred embodiment of the present invention, the polymerization inhibitor is added in an amount of 0.019 to 0.03% by mass of the alcohol.
According to a preferred embodiment of the present invention, the esterification reaction temperature is controlled between 100 and 120 ℃.
According to the preferred embodiment of the invention, the reaction process is that firstly, acrylic acid is added into a reaction container as a reaction solvent, reaction raw material alcohol and acrylic anhydride are added into the reaction solvent under stirring, then polymerization inhibitor is added, the temperature is raised to 100-120 ℃, and the reaction is carried out for 5-7h at the temperature.
According to the preferred embodiment of the invention, after the reaction is finished, the solvent (acrylic acid) is recovered by reduced pressure distillation, so that the production cost is saved, and the distilled recovery is acrylic acid and can be recycled; and recrystallizing the solid obtained after the distillation is finished by using a mixed solvent of small molecular alcohols and small polar alkanes to obtain a purified acrylic ester product.
Preferably, the small molecule alcohols used for recrystallization are methanol or ethanol; the small polar alkane used for recrystallization is at least one of n-hexane, cyclohexane and n-heptane; the volume ratio of the small molecular alcohols to the small polar alkanes is 1:9-3:7.
(III) beneficial effects
According to the invention, acrylic anhydride and corresponding alcohol are used as reaction raw materials, acrylic acid is used as a reaction solvent, a small amount of polymerization inhibitor is added, a catalyst is not used in a reaction system, the reaction solvent serves as a solvent and also serves as a reaction raw material, acrylic acid and alcohol are subjected to esterification reaction to generate acrylic ester, the polymerization inhibitor prevents the acrylic ester as a product from polymerizing, each molecule of acrylic anhydride and alcohol are subjected to esterification reaction to generate acrylic ester of 1 molecule and acrylic acid of 1 molecule, the acrylic acid supplements the consumption of the reaction solvent, and the concentration of the acrylic acid is maintained so as to promote the esterification reaction to proceed towards the positive reaction direction. After the reaction is finished, acrylic anhydride is converted into acrylic acid, and the acrylic acid is recycled as a reaction solvent through reduced pressure distillation and is more suitable for industrial production.
Because the catalyst, concentrated sulfuric acid, acrylic chloride and other reagents with strong corrosiveness or high toxicity are not used in the reaction process, the acrylic acid can be recycled after the reaction, the reaction process is more environment-friendly, the post-reaction treatment is simple and easy, and the method is suitable for industrial production. The polymerization between acrylic esters can be reduced by a small amount of polymerization inhibitor, so that the esterification and dehydration reaction can be still carried out at high temperature, the reaction time is short (5-7 h), the method is not limited to the conventional method that the acrylic esters are required to react for a long time at low temperature (12-27 h) in the prior art, and the preparation period can be shortened.
The alcohol consumption degree in the reaction system is detected to judge whether the reaction is finished or not, and if the alcohol consumption is finished or the alcohol is not reduced rapidly, the reaction is finished. After the reaction is finished, the acrylic acid is recovered through reduced pressure distillation (recovery amount/input amount is more than or equal to 96%), the solid product obtained after distillation is further purified by a coupled two-phase solvent recrystallization method, the conventional distillation purification method is avoided, the high-temperature and high-vacuum distillation method is avoided, the energy consumption is reduced, the polymerization of product monomers is reduced as much as possible, the product yield is improved, the high-polarity and low-polarity impurities of the tested product are removed simultaneously through the crystallization method of the two-phase solvent, the purification difficulty of the product is reduced, and the purity of the product is more than or equal to 99.9%.
The preparation method of the acrylic resin monomer for 193nm photoresist has the advantages of simple operation of the reaction process, high efficiency and safety of the reaction, and is a process route suitable for industrial production; the purity of the prepared acrylic ester monomer product is more than or equal to 99.9%, and the total yield is more than or equal to 94%.
Drawings
FIG. 1 is a GC spectrum of the 2-ethyl-2-adamantyl acrylate product prepared in example 1-2.
FIG. 2 is a GC spectrum of 2-methyl-2-adamantyl acrylate prepared in examples 3-4.
FIG. 3 is a GC spectrum of 2-adamantyl methacrylate prepared in examples 5-6.
FIG. 4 is a GC spectrum of 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylic ester prepared in example 7.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
The method for preparing the acrylic ester monomer comprises the following steps: acrylic anhydride and corresponding alcohol are used as reaction raw materials, acrylic acid is used as reaction solvent, the reaction solvent is added into the reaction container, the reaction raw materials alcohol and acrylic anhydride are added into the reaction solvent under stirring, then polymerization inhibitor is added, the temperature is raised to 100-120 ℃, and the temperature is kept for reaction for 5-7h. And a small amount of polymerization inhibitor is used for preventing raw materials and products from polymerizing in the heat preservation process, a reaction system in which acrylic anhydride and acrylic acid coexist is used in the reaction process, and the acrylic anhydride continuously generates new acrylic acid and acrylic ester, so that the conversion rate of the products is improved, and the product yield is ensured. The polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methyl hydroquinone and tetrachlorobenzoquinone. The reaction raw material alcohol is 2-adamantanol, 2-methyl-2-adamantanol, 2-ethyl-2-adamantanol or 2-carbonyl-tetrahydrofuran-3-alcohol, and the products corresponding to the reaction raw material alcohol in sequence are 2-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate and 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylate in sequence. The acrylic acid is acrylic acid containing alkyl or not containing alkyl, and the acrylic anhydride is acrylic anhydride containing alkyl or not containing alkyl.
Preferably, the alkyl is methyl or ethyl, and the acrylic acid is acrylic acid, methacrylic acid, ethacrylic acid or the like; the acrylic anhydride is acrylic anhydride, methacrylic anhydride or ethacrylic anhydride which does not contain substituent groups, and the like. In order to improve the purity of the acrylate monomer product, the acrylic acid and the acrylic anhydride added by the reaction raw materials are simultaneously free of alkyl groups or contain the same alkyl groups.
In the present application, acrylic acid and acrylic anhydride are each intended to be free of any substituents, i.e. acrylic acid is intended to mean CH 2 =ch-COOH, acrylic anhydride means (CH 2 ＝CH-COOCO-C＝CH 2 )。
After the reaction, the solvent (acrylic acid) is recovered by distillation under reduced pressure, the recovery amount is more than 96% of the input amount, and the recovered solvent can be recycled. Recrystallizing the distilled substrate by adopting a mixed solvent of alcohols and small polar alkanes to obtain a purified acrylate monomer product, wherein the purity of the product is more than or equal to 99.9%, and the total yield is more than or equal to 94%.
The following description is of the preferred embodiments of the invention.
Example 1
The method for preparing the 2-ethyl-2-adamantyl acrylate monomer in this example is as follows:
291ml of acrylic acid (305.55 g) is added into a 1L four-necked flask provided with a stirring paddle, a condenser and a thermometer, stirring is started, 97g (0.538 mol) of 2-ethyl-2-adamantanol is added into the system, 0.0072g of hydroquinone inhibitor is slowly added into the reaction system, 81.5g of acrylic anhydride is added into the reaction system, the temperature is slowly raised to 100-110 ℃, the reaction is kept for 5 hours, the reaction progress is monitored, the solvent is recovered by vacuum distillation (50-55 ℃) after sampling and detecting that the reaction is complete (whether the alcohol is consumed or not), the recovery amount of the solvent is 280ml (the recovery amount is 96.22% of the input amount), and methanol is used as a distilled residual solid: n-hexane 2: the mixed solvent of 8 (volume ratio) is used for recrystallizing the product, and the obtained solid is dried to obtain 120.17g of 2-ethyl-2-adamantyl acrylate (see the GC spectrum of the product in figure 1), the yield is 95.3%, and the purity of the product is 99.93%.
Example 2
The method for preparing the 2-ethyl-2-adamantyl acrylate monomer in this example is as follows:
388ml of acrylic acid is added into a 1L four-mouth bottle provided with a stirring paddle, a condenser pipe and a thermometer, stirring is started, 97g (0.538 mol) of 2-ethyl adamantanol is added into the system, 0.019g of polymerization inhibitor p-benzoquinone is slowly added into the reaction system, 88.3g of acrylic anhydride is added into the reaction system, the temperature is slowly increased to 100-110 ℃, the reaction is kept for 5 hours, the reaction progress is monitored, after the reaction is completely detected by sampling (40-45 ℃), the solvent is distilled under reduced pressure, the recovery amount of the solvent is 375ml (the recovery amount is 96.65 percent of the input amount), and methanol is used as the obtained solid: n-hexane 3: the mixed solvent of 7 (volume ratio) is used for recrystallizing the product, and 119.92g (see the GC spectrum of the product in figure 1) of the 2-ethyl-2-adamantyl acrylate monomer product is obtained after the obtained solid is dried, so that the yield is 95.1%, and the product purity is 99.95%.
Example 3
The method for preparing the 2-methyl-2-adamantyl acrylate monomer in this example is as follows:
600ml of acrylic acid is added into a 1L four-mouth bottle provided with a stirring paddle, a condenser pipe and a thermometer, stirring is started, 120g (0.722 mol) of 2-methyladamantanol is added into the system, 0.036g of polymerization inhibitor p-benzoquinone is slowly added into the reaction system, 127.5g of acrylic anhydride is added into the reaction system, the temperature is slowly increased to 110-120 ℃, the reaction is kept for 6 hours, the reaction progress is monitored, the solvent is recovered by reduced pressure distillation (35-40 ℃) after the reaction is completely detected by sampling, the recovery amount of the solvent is 588ml (the recovery amount is 98.00 percent of the input amount), and ethanol is used as the obtained solid: cyclohexane 1: recrystallizing the product by using a mixed solvent of 9 (volume ratio) to obtain a 2-methyl-2-adamantyl acrylate monomer (C) 15 H 22 O 2 ) 160.36g (see GC spectrum for the product of FIG. 2) yield 94.8% and a purity of 99.92% was obtained.
Example 4
The method for preparing the 2-methyl-2-adamantyl acrylate monomer in this example is as follows:
480ml of acrylic acid is added into a 1L four-mouth bottle provided with a stirring paddle, a condenser pipe and a thermometer, stirring is started, 120g (0.722 mol) of 2-methyladamantanol is added into the system, 0.024g of polymerization inhibitor hydroquinone is slowly added into the reaction system, 136.6g of acrylic anhydride is added into the reaction system, the temperature is slowly increased to 110-120 ℃, the reaction is kept for 6 hours, the reaction progress is monitored, the solvent is recovered by reduced pressure distillation (35-40 ℃) after the reaction is completely detected by sampling, the recovery amount of the solvent is 468ml (the recovery amount is 97.5 percent of the input amount), and ethanol is used as the obtained solid: cyclohexane 1: recrystallizing the product by using a mixed solvent of 9 (volume ratio) to obtain a 2-methyl-2-adamantyl acrylate monomer (C) 15 H 22 O 2 ) 160.02g (see GC spectrum for the product of FIG. 2) yield 94.6% and a purity of 99.94% was obtained.
Example 5
The method for preparing the 2-adamantyl acrylate monomer in this example is as follows:
450ml of acrylic acid is added into a 1L four-mouth bottle provided with a stirring paddle, a condenser pipe and a thermometer, stirring is started, 90g (0.591 mol) of 2-adamantanol is added into the system, 0.027g of polymerization inhibitor, namely, tetrachlorobenzoquinone is slowly added into the reaction system, 89.5g of acrylic anhydride is added into the reaction system, the temperature is slowly increased to 100-110 ℃, the temperature is kept for 7 hours, the reaction progress is monitored, the solvent is recovered by reduced pressure distillation (35-40 ℃) after the reaction is completely detected by sampling, the recovery amount of the solvent is 439ml (the recovery amount is 97.56 percent of the input amount), and the obtained solid uses methanol: cyclohexane 3: the mixed solvent of 7 (volume ratio) is used for recrystallizing the product to obtain 115.99g of 2-adamantyl acrylate monomer product (see the GC spectrum of the product in figure 3), the yield is 95.1%, and the purity of the obtained product is 99.96%.
Example 6
The method for preparing the 2-adamantyl acrylate monomer in this example is as follows:
360ml of acrylic acid is added into a 1L four-mouth bottle provided with a stirring paddle, a condenser pipe and a thermometer, stirring is started, 90g (0.591 mol) of 2-adamantanol is added into the system, 0.018g of polymerization inhibitor hydroquinone is slowly added into the reaction system, 89.5g of acrylic anhydride is added into the reaction system, the temperature is slowly increased to 100-110 ℃, the reaction is kept for 7 hours, the reaction progress is monitored, the solvent is recovered by reduced pressure distillation (35-40 ℃) after the reaction is completely detected by sampling, the recovery amount of the solvent is 352ml (the recovery amount is 97.78 percent of the input amount), and ethanol is used as the obtained solid: n-heptane 2: the mixed solvent of 8 (volume ratio) is used for recrystallizing the product to obtain 115.87g of 2-adamantyl acrylate monomer product (see the GC spectrogram of the product in figure 3), the yield is 95.0%, and the purity of the obtained product is 99.95%.
Example 7
The procedure for the preparation of 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylate monomer in this example was as follows:
340ml of acrylic acid is added into a 1L four-mouth bottle provided with a stirring paddle, a condenser tube and a thermometer, stirring is started, 85g (0.833 mol) of 2-carbonyl-tetrahydrofuran-3-ol is added into the system, 0.017g of polymerization inhibitor p-benzoquinone is slowly added into the reaction system, 126g of acrylic anhydride is added into the reaction system, the temperature is slowly raised to 100-110 ℃, the reaction is kept for 7 hours, the reaction progress is monitored, the solvent is recovered by reduced pressure distillation (40-45 ℃) after the reaction is completely detected by sampling, the recovery amount of the solvent is 332ml (the recovery amount is 97.65 percent of the input amount), and ethanol is used as the obtained solid: n-hexane 1: the mixed solvent of 9 (volume ratio) is used for recrystallizing the product to obtain 123.89g of 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylic ester monomer product (see the GC spectrum of the product in figure 4), the yield is 95.3%, and the purity of the obtained product is 99.93%.
In summary, the method takes the acrylic anhydride and the corresponding alcohol as reaction raw materials, adopts the acrylic acid as reaction solvent, adds a certain amount of polymerization inhibitor to prevent acrylic acid and acrylic ester from generating byproducts in polymerization, and the acrylic anhydride reacts with the alcohol to generate ester under the acid catalysis of the acrylic acid in the reaction process, and meanwhile, the acrylic anhydride also generates the acrylic acid, so that the concentration of the reaction raw materials can be increased, the reaction is promoted to be carried out towards the positive reaction direction, and the acrylic ester is further generated by the reaction with the alcohol under the high-temperature action, thereby improving the conversion rate of the product; and then, the acrylic acid can be recovered through reduced pressure distillation to serve as a reaction solvent for recycling, liquid waste such as waste solvent and the like are not generated, the obtained crude product is recrystallized by using an alcohol and small-polarity alkane two-phase solvent, the purity of the obtained product is more than or equal to 99.9%, and the yield of the purified product obtained through recrystallization is still more than 94%. The process route has the advantages of simple and easy operation process, no liquid waste, good environmental protection, high yield, easy purification of the product and high purity of the purified product.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; while the invention has been described in detail with reference to the foregoing embodiments, it will be appreciated by those skilled in the art that variations may be made in the techniques described in the foregoing embodiments, or equivalents may be substituted for in part or in whole; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the acrylic ester resin monomer for 193nm photoresist is characterized by comprising the steps of taking acrylic anhydride and corresponding alcohol as reaction raw materials, taking acrylic acid as a reaction solvent, adding a polymerization inhibitor, condensing the acrylic acid of the reaction solvent with the alcohol to generate acrylic ester, esterifying the acrylic anhydride to generate acrylic ester and acrylic acid, supplementing the consumption of the acrylic acid by the generated acrylic acid, improving the concentration of reaction materials, and continuously promoting the synthesis reaction of the acrylic ester to proceed towards the positive reaction direction; after the reaction is finished, purifying by a method of coupling two-phase solvent recrystallization to obtain an acrylic ester product; the acrylic acid is acrylic acid containing alkyl or not containing alkyl, and the acrylic anhydride is acrylic anhydride containing alkyl or not containing alkyl.
2. The method according to claim 1, wherein the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methylhydroquinone and tetrachlorobenzoquinone.
3. The method according to claim 1, wherein the alcohol is 2-adamantanol, 2-methyl-2-adamantanol, 2-ethyl-2-adamantanol or 2-carbonyl-tetrahydrofuran-3-ol.
4. The process according to claim 1, wherein the molar ratio of acrylic anhydride to alcohol is 1.2-1.5:1.
5. The method according to claim 1, wherein the mass ratio of the alcohol to the acrylic acid is 1 g/3-5 mL.
6. The method according to claim 4 or 5, wherein the polymerization inhibitor is added in an amount of 0.019 to 0.03% by mass of the alcohol.
7. The preparation method according to claim 1, wherein the esterification reaction temperature is controlled to 100-120 ℃.
8. The preparation method according to claim 1, wherein the reaction process is that in a reaction vessel, firstly, acrylic acid is added as a reaction solvent, reaction raw material alcohol and acrylic anhydride are added into the reaction solvent under stirring, then, a polymerization inhibitor is added, the temperature is raised to 100-120 ℃, and the reaction is carried out for 5-7 hours at a temperature.
9. The method according to claim 1, wherein the reaction is performed by sampling and detecting the extent of the reaction, and the solvent is recovered by distillation under reduced pressure after the completion of the reaction; and recrystallizing the solid obtained after the distillation is finished by using a mixed solvent of small molecular alcohols and small polar alkanes to obtain a purified acrylic ester product.
10. The method according to claim 9, wherein the small molecule alcohol used for recrystallization is methanol or ethanol; the small polar alkane used for recrystallization is at least one of n-hexane, cyclohexane and n-heptane; the volume ratio of the small molecular alcohols to the small polar alkanes is 1:9-3:7.
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