CN114560768B - Synthesis method of acrylic resin monomer for 193nm photoresist - Google Patents
Synthesis method of acrylic resin monomer for 193nm photoresist Download PDFInfo
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- CN114560768B CN114560768B CN202210223736.XA CN202210223736A CN114560768B CN 114560768 B CN114560768 B CN 114560768B CN 202210223736 A CN202210223736 A CN 202210223736A CN 114560768 B CN114560768 B CN 114560768B
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- acrylate
- vinyl
- methacrylate
- photoresist
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 41
- 239000000178 monomer Substances 0.000 title claims abstract description 24
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 13
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 9
- 238000001308 synthesis method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- -1 acrylic ester Chemical class 0.000 claims abstract description 33
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 31
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000003112 inhibitor Substances 0.000 claims abstract description 26
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 claims abstract description 23
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 10
- 238000010189 synthetic method Methods 0.000 claims abstract description 7
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 33
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 8
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical group ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 8
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 claims 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 claims description 7
- 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 claims description 7
- LRFKWQGGENFBFO-UHFFFAOYSA-N fingolimod phosphate Chemical compound CCCCCCCCC1=CC=C(CCC(N)(CO)COP(O)(O)=O)C=C1 LRFKWQGGENFBFO-UHFFFAOYSA-N 0.000 claims description 7
- DCTVCFJTKSQXED-UHFFFAOYSA-N (2-ethyl-2-adamantyl) 2-methylprop-2-enoate Chemical group C1C(C2)CC3CC1C(CC)(OC(=O)C(C)=C)C2C3 DCTVCFJTKSQXED-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- UEBUOANSKOYYKC-UHFFFAOYSA-N 2-ethyladamantan-1-ol Chemical compound C1C(C2)CC3CC1C(CC)C2(O)C3 UEBUOANSKOYYKC-UHFFFAOYSA-N 0.000 claims description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 4
- OXHVCLNCFNQWON-UHFFFAOYSA-N 2-methyladamantan-1-ol Chemical compound C1C(C2)CC3CC1C(C)C2(O)C3 OXHVCLNCFNQWON-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 55
- 238000002360 preparation method Methods 0.000 description 25
- 238000004321 preservation Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- NIUHGYUFFPSEOW-UHFFFAOYSA-N (4-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=C(OC(=O)C=C)C=C1 NIUHGYUFFPSEOW-UHFFFAOYSA-N 0.000 description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000001459 lithography Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000012827 research and development Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000006227 byproduct Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000000463 material Substances 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
- PJMXUSNWBKGQEZ-UHFFFAOYSA-N (4-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(O)C=C1 PJMXUSNWBKGQEZ-UHFFFAOYSA-N 0.000 description 2
- VMODAALDMAYACB-UHFFFAOYSA-N 2-methyladamantane Chemical compound C1C(C2)CC3CC1C(C)C2C3 VMODAALDMAYACB-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-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
- 239000002313 adhesive film Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 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
- 238000012546 transfer Methods 0.000 description 2
- MQMLKROCNSLXFA-UHFFFAOYSA-N (1-ethyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2C(OC(=O)C(C)=C)C1(CC)C3 MQMLKROCNSLXFA-UHFFFAOYSA-N 0.000 description 1
- JEHVGOACJOGXNS-UHFFFAOYSA-N (1-ethyl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC2C(OC(=O)C=C)C1(CC)C3 JEHVGOACJOGXNS-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SVTBKBTZCWQLGX-UHFFFAOYSA-N 2-(4-hydroxyphenyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=C(O)C=C1 SVTBKBTZCWQLGX-UHFFFAOYSA-N 0.000 description 1
- LFJJGHGXHXXDFT-UHFFFAOYSA-N 3-bromooxolan-2-one Chemical compound BrC1CCOC1=O LFJJGHGXHXXDFT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000011172 small scale experimental method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- C07C67/62—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic method of an acrylic ester resin monomer for 193nm photoresist, which uses vinyl acrylate or vinyl methacrylate and alcohol as reaction raw materials, uses a small polar alkane solvent as a reaction solvent, adds a polymerization inhibitor, uses alkaline ion exchange resin as a catalyst, and obtains acrylic ester through transesterification under the condition of low temperature. The synthetic method of the acrylic resin monomer for 193nm photoresist provided by the invention has the advantages of simple operation of the reaction process, high reaction efficiency and safety, 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 synthetic method of an acrylic resin monomer for 193nm photoresist.
Background
Photoresist (Photoresist), which is also called Photoresist, refers to a resist etching thin film material whose solubility is changed by irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, or the like. Photoresist is a pattern transfer medium that transfers reticle patterns to a substrate using solubility differences after a photoreaction. At present, the method is widely used for processing and manufacturing micro pattern circuits in the photoelectric information industry, and is a key material in the field of electronic manufacturing.
The resolution line width is proportional to the exposure wavelength and inversely proportional to the number of lens openings of the exposure machine, so shortening the exposure wavelength is a main way to improve the resolution. Thus, with the development of integrated circuits, the photolithography process has also undergone a development history from G line (436 nm) lithography, I line (365 nm) lithography, to deep ultraviolet 248nm lithography, and now 193nm lithography.
193nm photoresist is a big hot spot studied in recent years, and is mainly used for manufacturing chips such as high-end mobile phones, personal computers/server CPUs, middle-high end mobile phone hot spots, base bands, CPUs, graphic card processors, FPGAs, mining machine ASICs, middle-low end microprocessors, bluetooth chips, power management chips, wiFi chips, display chips and the like, and the demand for 193nm photoresist in chip manufacturing is increasing along with the continuous updating of domestic high-end mobile phones and electronic products.
At present, 193nm photoresist in China mainly depends on import, and mass production is not realized yet.
The problems of cracks, surface roughness, swelling of the adhesive film caused by partial dissolution of the adhesive film in a non-exposure area and the like exist in the 193nm photoresist production process in China, the problems can be solved only by continuously improving the main resin structure of the photoresist and further changing the performance of the photoresist, the research and development progress of the 193nm photoresist can be accelerated by synthesizing the resin monomer meeting the performance requirements, and the problem of core raw materials at the front end of the photoresist is solved.
The acrylic ester series resin monomer product is an important component of 193nm photoresist main resin, is helpful for systematically developing the research of the related fields of 193nm photoresist in China, realizes the localization of photoresist materials, and enhances the international competitiveness.
Because the acrylic ester serial products have better light transmittance and photosensitivity and are widely used for 193nm photoresist, double bonds in acrylic acid monomers are extremely easy to polymerize when (methyl) acrylic ester derivatives are polymerized, and acid sensitive groups in the monomers are also easy to decompose, so the requirements on purification conditions are ten minutes and severe, and the product has almost no mass products with ultra-clean high-purity quality requirements in domestic markets at present. The defect of upstream key raw materials greatly improves the research and development cost of the photoresist in China, and aims to solve the problem that the research and development of photoresist components are urgent in the current technology of the photoresist in China. However, the problem of the supply of photoresist raw materials is still not solved, a complete photoresist industry chain is not available in China, and the development and preparation of the production process of the ultra-clean high-purity acrylic ester serial products are very necessary for the research and development of domestic photoresist.
(1) Current reports on the synthesis of 2-oxo-tetrahydrofuran-3-yl acrylate include: in 2010 patent JP 2010242101, the Aldrin May proposes that acrylic acid and alpha-hydroxy-gamma-butyl lactone are used as raw materials, toluene is used as a solvent, 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%; there is no report on the product at present.
(2) Relevant reports currently 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 ℃, and 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 one night, 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; likewise, 2014 Nakano et al proposed the same reaction conditions with a 50% reaction yield. The existing problems of the reaction are long reaction time and low yield, and the document report on the high-yield synthesis of the ultra-clean high-purity adamantane acrylate is not seen.
(3) Relevant reports currently on the synthesis of 2-methyl-2-adamantane acrylate include: the adoption of concentrated sulfuric acid as a reactant in the patents Jpn.Kokai Tokkyo Koho,2001354619 and JP 2001106650 is extremely large in dosage, causes great harm to the environment, is difficult to control the reaction progress, forms a plurality of impurities which are difficult to separate, greatly reduces the purity of the product, and directly affects the cost of the product and the quality of the final photoresist. In patent JP 2000119220, the use of the acryloyl chloride, which belongs to a highly toxic product, is complex in operation and dangerous in use, and discharges a large amount of hydrogen chloride in production, so that the environment is seriously polluted; in addition, the use of the acryloyl chloride can also form impurities, seriously affect the quality of photoresist products, and is not beneficial to industrial production.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a synthetic method of an acrylic ester resin monomer for 193nm photoresist, which is simple to operate, high in purity, high in yield and easy to purify.
The technical scheme adopted by the invention is as follows: vinyl acrylate or vinyl methacrylate and alcohol are used as reaction raw materials, a small polar alkane solvent is used as a reaction solvent, a polymerization inhibitor is added, and an alkali ion exchange resin with the same amount as the ester is used as a catalyst, so that the acrylic ester is obtained through transesterification under the low-temperature condition.
Further, the alcohol is 1-adamantanol, 2-methyladamantanol, 2-ethyladamantanol, 2-carbonyl-tetrahydrofuran-3-ol, p-hydroxyphenol or p-aminophenol; the low-polarity alkane solvent is cyclohexane, n-hexane or n-heptane; the polymerization inhibitor is tetrachlorobenzoquinone or p-benzoquinone.
Further, the basic ion exchange resin is a weak basic ion exchange resin with secondary amino groups.
Further, the pH of the basic ion exchange resin is 7-8.
Further, the acrylate resin monomer is 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-adamantyl methacrylate, 2-adamantyl acrylate, 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate, 2-methyl-2-acrylic acid-4-hydroxyphenyl ester or 4-hydroxyphenyl acrylic acid ester.
Further, the low temperature condition is-10 ℃ to-20 ℃.
Further, in the raw materials, the molar ratio of the vinyl acrylate or the vinyl methacrylate to the alcohol is 1.2-1.4:1.
further, the addition amount of the reaction solvent is as follows: the mass ratio of the vinyl acrylate or the vinyl methacrylate to the reaction solvent is 1:30-1:40, a step of performing a; the addition amount of the polymerization inhibitor is 0.01-0.03% of the mass of the vinyl acrylate or vinyl methacrylate; the addition amount of the alkaline ion exchange resin is equal to the mass of the vinyl acrylate or the vinyl methacrylate.
Further, it comprises the steps of (1) adding a reaction solvent into a container, adding a reaction raw material alcohol under stirring, then sequentially adding a polymerization inhibitor and a catalyst, and cooling to a low temperature condition; (2) Adding reaction raw material vinyl acrylate or vinyl methacrylate, and reacting for 5-7h at a constant temperature.
Further, the method also comprises a step (3), wherein the step (3) is as follows: and (3) adding water into the product obtained in the step (2), and then extracting and separating phases.
The beneficial effects of the invention are as follows:
the invention uses vinyl acrylate or vinyl methacrylate and corresponding alcohol as reaction raw materials, uses small polar saturated alkane as solvent, adds a small amount of polymerization inhibitor, uses alkaline ion exchange resin as catalyst, and adopts extremely thin solvent to react to prepare acrylic ester products. The process route disclosed by the invention takes saturated alkane with small polarity as a reaction solvent, and the solvent has small polarity, so that the transesterification is facilitated, and the reaction is promoted to be carried out in the forward reaction direction; the raw materials of the reaction are subjected to transesterification, vinyl acrylate or vinyl methacrylate is adopted to generate vinyl alcohol, the vinyl alcohol can be automatically converted into ethylene and acetaldehyde, byproducts can be recovered for other purposes, and no byproducts are generated in the reaction process.
The reaction process uses a very dilute reaction environment, so that raw materials and products can be prevented from being polymerized, and the conversion rate of the products is improved; the addition of a small amount of polymerization inhibitor in the reaction process can reduce the self polymerization of the acrylic ester product, improve the yield, ensure the alkaline environment of the reaction process by using alkaline ion exchange resin as a catalyst, recycle the resin after the reaction is completed and the resin after the filtration is regenerated, ensure the conversion rate of the product and simultaneously reduce the reaction cost.
The synthetic method of the acrylic resin monomer for 193nm photoresist provided by the invention has the advantages of simple operation of the reaction process, high reaction efficiency and safety, and is a process route suitable for industrial production.
The purity of the product obtained by the method is more than or equal to 99 percent, and the total yield is more than or equal to 90 percent.
Drawings
FIG. 1 2-GC spectrum of ethyl-2-adamantyl methacrylate product;
FIG. 2 2-GC spectrum of ethyl-2-adamantyl acrylate product;
FIG. 3 2-methyl-2-adamantyl methacrylate GC spectrum;
FIG. 4 2-methyl-2-adamantylacrylate GC spectrum;
FIG. 5 2-adamantyl methacrylate GC spectrum;
FIG. 6 2-adamantyl acrylate GC spectrum;
FIG. 7 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylate GC spectrum;
FIG. 8 2-GC spectrum of carbonyl-tetrahydrofuran-3-hydroxy-methacrylate;
FIG. 9 2-GC spectrum of 4-hydroxyphenyl-methyl-2-acrylate;
FIG. 10 GC spectrum of 4-hydroxyphenyl acrylate.
Detailed Description
The invention provides a synthetic method of an acrylic ester resin monomer for 193nm photoresist, which takes vinyl acrylate or vinyl methacrylate and corresponding alcohol as reaction raw materials, takes small-polarity straight-chain alkane solvent as reaction solvent, adds polymerization inhibitor, takes alkaline ion exchange resin as catalyst, and obtains acrylic ester through transesterification at the low temperature of-10 ℃ to-20 ℃. A small amount of polymerization inhibitor is added into the reaction liquid to prevent the polymerization of raw materials and products, improve the conversion rate of the products and ensure the yield of the products. The structural formula of the acrylic ester series products is shown as follows:
specific R 1 Is represented by the structure containing polyhydroxyphenyl orOr->Or->Or->One of the following;
R 2 is represented by the structure H atom or methyl.
The alcohol is 1-adamantanol, 2-methyladamantanol, 2-ethyladamantanol, 2-carbonyl-tetrahydrofuran-3-ol, p-hydroxy phenol or p-amino phenol.
The low-polarity alkane solvent is cyclohexane, n-hexane or n-heptane.
The polymerization inhibitor is tetrachlorobenzoquinone or p-benzoquinone.
The acrylate resin monomer is 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-adamantyl methacrylate, 2-adamantyl acrylate, 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate,
2-methyl-2-acrylic acid-4-hydroxyphenyl ester or 4-hydroxyphenyl acrylate.
Adding a reaction solvent into a container, adding reaction raw material alcohol under stirring, then sequentially adding a polymerization inhibitor and a catalyst, and cooling to a low temperature; (2) Adding reaction raw material vinyl acrylate or vinyl methacrylate, and reacting for 5-7h at a constant temperature.
Preferably, in order to improve the purification effect, the method further comprises a step (3), wherein the step (3) is as follows: and (3) adding water into the product obtained in the step (2) and then extracting and phase-separating.
Example 1: synthesis of 2-ethyl-2-adamantyl methacrylate
2175ml of normal hexane is added into a 3L four-mouth bottle provided with a stirring paddle, a condenser tube and a thermometer, stirring is started, 97g of 2-ethyl adamantanol is added into the system, 0.0072g of the polymerization inhibitor, chloranil, 72.5g of alkaline ion exchange resin are slowly added into the reaction system, pH=7-8 is regulated, the temperature is reduced to minus 10 ℃, 72.5g of vinyl methacrylate is slowly added into the reaction system in a dropwise manner, the reaction is kept for 6 hours, the reaction progress is monitored, 800ml of water is added into the reaction system after the sampling detection reaction is complete, stirring extraction phase separation is carried out, and 125g of 2-ethyl-2-adamantyl methacrylate product is obtained after the organic phase is dried, decompressed, concentrated and evaporated to dryness, and the yield is 93.45%. The gas chromatograph of the 2-ethyl-2-adamantyl methacrylate synthesized in this example is shown in FIG. 1.
In this example, the basic ion exchange resin is a weakly basic ion exchange resin with secondary amine groups.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 6 hours.
The embodiment of the invention has a high yield 93.45% which is far higher than that of the prior art, is beneficial to industrialized production and reduces cost.
In the preparation process, a large amount of hydrogen chloride is not discharged, and the environment is not polluted.
The ion exchange resin in the embodiment of the invention is used as a catalyst, and can be recycled after being regenerated after participating in the reaction, so that the conversion rate of the product can be ensured, and the reaction cost is reduced.
The embodiment of the invention abandons the traditional raw material of the acryloyl chloride, develops a new technical route, ensures that the process is more green, ensures that the impurity of the product is less and the purity is higher.
Example 2: synthesis of 2-ethyl-2-adamantyl acrylate
Adding 3513ml of cyclohexane into a 5L four-mouth bottle with a stirring paddle, a condenser tube and a thermometer, starting stirring, adding 166.5g of 2-ethyl adamantanol into the system, slowly adding 0.011g of polymerization inhibitor p-benzoquinone into the reaction system, adding 113.3g of alkaline ion exchange resin, adjusting pH to be 7-8, cooling to-12 ℃, slowly dropwise adding 113.3g of vinyl acrylate into the reaction system, carrying out heat preservation reaction for 5h, monitoring the reaction progress, adding 1000ml of water into the reaction system after sampling and detecting the reaction completion, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure and evaporating to obtain 203g of 2-ethyl-2-adamantyl acrylate product, wherein the yield is 93.78%. The gas chromatogram of the 2-ethyl-2-adamantyl acrylate synthesized in this example is shown in FIG. 2.
In this example, the basic ion exchange resin is a weakly basic ion exchange resin with secondary amine groups.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 5 hours.
The embodiment of the invention has a high yield 93.78% which is far higher than that of the prior art, is beneficial to industrialized production and reduces cost.
In the preparation process, a large amount of hydrogen chloride is not discharged, and the environment is not polluted.
The ion exchange resin in the embodiment of the invention is used as a catalyst, and can be recycled after being regenerated after participating in the reaction, so that the conversion rate of the product can be ensured, and the reaction cost is reduced.
The embodiment of the invention abandons the traditional raw material of the acryloyl chloride, develops a new technical route, ensures that the process is more green, ensures that the impurity of the product is less and the purity is higher.
Example 3: synthesis of 2-methyl-2-adamantyl methacrylate
Adding 3546ml of n-heptane into a 5L four-mouth bottle with a stirring paddle, a condenser tube and a thermometer, starting stirring, adding 126.3g of 2-methyladamantane into the system, slowly adding 0.022g of polymerization inhibitor tetrachlorobenzoquinone into the reaction system, adding 110.8g of alkaline ion exchange resin, regulating pH to be 7-8, cooling to-13 ℃, slowly dripping 110.8g of vinyl methacrylate into the reaction system, carrying out heat preservation reaction for 7h, monitoring the reaction process, adding 1000ml of water into the reaction system after the sampling detection reaction is complete, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure and evaporating to obtain 167g of 2-methyl-2-adamantyl methacrylate product, and obtaining the yield of 93.78%. The gas chromatograph of the 2-methyl-2-adamantyl methacrylate synthesized in this example is shown in FIG. 3.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 7 hours.
The embodiment of the invention has a high yield 93.78% which is far higher than that of the prior art, is beneficial to industrialized production and reduces cost.
Example 4: synthesis of 2-methyl-2-adamantyl acrylate
Adding 3538ml of normal hexane into a 5L four-mouth bottle with a stirring paddle, a condenser tube and a thermometer, starting stirring, adding 134.55g of 2-methyladamantane into the system, slowly adding 0.032g of polymerization inhibitor p-benzoquinone into the reaction system, adding 107.2g of alkaline ion exchange resin, adjusting pH to be 7-8, cooling to-14 ℃, slowly dropwise adding 107.24g of vinyl acrylate into the reaction system, carrying out heat preservation reaction for 6h, monitoring the reaction progress, adding 1000ml of water into the reaction system after sampling and detecting the reaction completion, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure and evaporating to dryness to obtain 167g of 2-methyl-2-adamantyl acrylate product, and obtaining the yield of 93.65%. The gas chromatogram of the 2-methyl-2-adamantyl acrylate synthesized in this example is shown in FIG. 4.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 6 hours.
The embodiment of the invention has the high yield of 93.65 percent higher than that of the prior art, is beneficial to industrial production and reduces the cost.
Example 5: synthesis of 2-adamantyl methacrylate
Adding 3193ml of cyclohexane into a 5L four-mouth bottle provided with a stirring paddle, a condenser tube and a thermometer, starting stirring, adding 82.85g of 1-adamantanol into the system, slowly adding 0.017g of a polymerization inhibitor, namely tetrachlorobenzoquinone into the reaction system, adding 85.47g of alkaline ion exchange resin, adjusting pH to be 7-8, cooling to-15 ℃, slowly dripping 91.25g of vinyl methacrylate into the reaction system, carrying out heat preservation reaction for 6h, monitoring the reaction process, adding 1000ml of water into the reaction system after the sampling detection reaction is complete, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure, and evaporating to obtain 112g of 2-adamantyl methacrylate product, wherein the yield is 93.39%. The gas chromatogram of the 2-adamantyl methacrylate synthesized in this example is shown in FIG. 5.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 6 hours.
The embodiment of the invention has a high yield 93.39% which is far higher than that of the prior art, is beneficial to industrialized production and reduces cost.
Example 6: synthesis of 2-adamantyl acrylate
Adding 3065ml of cyclohexane into a 5L four-mouth bottle provided with a stirring paddle, a condenser pipe and a thermometer, starting stirring, adding 97.83g of 1-adamantanol into the system, slowly adding 0.0097g of a polymerization inhibitor, namely tetrachlorobenzoquinone into the reaction system, adding 97.3g of alkaline ion exchange resin, adjusting pH to be 7-8, cooling to-16 ℃, slowly dripping 85.15g of vinyl acrylate into the reaction system, carrying out heat preservation reaction for 5h, monitoring the reaction progress, adding 1000ml of water into the reaction system after sampling and detecting the reaction completion, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure, evaporating to obtain 124g of 2-adamantyl acrylate product, and obtaining the yield of 93.52%. The gas chromatogram of the 2-adamantyl acrylate synthesized in this example is shown in FIG. 6.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 5 hours.
The embodiment of the invention has a high yield 93.52% which is far higher than that of the prior art, is beneficial to industrialized production and reduces cost.
Example 7: synthesis of 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylic ester
Adding 3845ml of normal hexane into a 5L four-mouth bottle with a stirring paddle, a condenser tube and a thermometer, starting stirring, adding 83.20g of 2-carbonyl-tetrahydrofuran-3-ol into a system, slowly adding 0.02g of polymerization inhibitor p-benzoquinone into a reaction system, adding 103.9g of alkaline ion exchange resin, regulating pH to be 7-8, cooling to-17 ℃, slowly dropwise adding 103.92g of vinyl acrylate into the reaction system, carrying out heat preservation reaction for 7h, monitoring the reaction progress, adding 1000ml of water into the reaction system after sampling and detecting the reaction completion, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure and evaporating to obtain 119g of 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylate product, and obtaining the yield of 93.52%. The gas chromatogram of 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylic ester synthesized in this example is shown in FIG. 7.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 7 hours.
The embodiment of the invention has a high yield 93.52% which is far higher than that of the prior art, is beneficial to industrialized production and reduces cost.
Example 8: synthesis of 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate
4073ml of normal hexane is added into a 5L four-mouth bottle provided with a stirring paddle, a condenser tube and a thermometer, stirring is started, 78.10g of 2-carbonyl-tetrahydrofuran-3-ol is added into the system, 0.03g of polymerization inhibitor p-benzoquinone is slowly added into the reaction system, 107.2g of alkaline ion exchange resin is added, the pH value is regulated to be 7-8, the temperature is reduced to minus 18 ℃, 107.2g of vinyl methacrylate is slowly dripped into the reaction system, the reaction is kept for 7 hours, the reaction progress is monitored, 1000ml of water is added into the reaction system after the sampling detection reaction is complete, the stirring extraction phase separation is carried out, the organic phase is dried, the reduced pressure concentration and the evaporation are carried out, and 122g of 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate product is obtained, and the yield is 93.72%. The gas chromatogram of 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate synthesized in this example is shown in FIG. 8.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 7 hours.
The embodiment of the invention has the high yield of 93.72 percent higher than the prior art, is beneficial to industrial production and reduces the cost.
Example 9: synthesis of 2-methyl-2-propenoic acid-4-hydroxyphenyl ester
Adding 3992ml of normal hexane into a 5L four-mouth bottle with a stirring paddle, a condenser pipe and a thermometer, starting stirring, adding 83.78g of p-hydroxyphenol into the system, slowly adding 0.02g of p-benzoquinone as a polymerization inhibitor into the reaction system, adding 102.36g of alkaline ion exchange resin, adjusting pH to be 7-8, cooling to-19 ℃, slowly dripping 102.36g of vinyl methacrylate into the reaction system, carrying out heat preservation reaction for 6h, monitoring the reaction progress, adding 1000ml of water into the reaction system after sampling and detecting the reaction completion, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure, and evaporating to obtain 127g of 2-methyl-2-acrylic acid-4-hydroxyphenyl ester product, wherein the yield is 93.68%. The gas chromatogram of the 2-methyl-2-propenoic acid-4-hydroxyphenyl ester synthesized in this example is shown in FIG. 9.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 7 hours.
The embodiment of the invention has a high yield 93.68% which is far higher than that of the prior art, is beneficial to industrialized production and reduces cost.
Example 10: synthesis of 4-hydroxyphenyl acrylate
Adding 4043ml of cyclohexane into a 5L four-mouth bottle provided with a stirring paddle, a condenser tube and a thermometer, starting stirring, adding 94.55g of p-hydroxyphenol into the system, slowly adding 0.02g of a polymerization inhibitor, namely tetrachlorobenzoquinone into the reaction system, adding 101.08g of alkaline ion exchange resin, adjusting pH to be 7-8, cooling to-20 ℃, slowly dropwise adding 101.08g of vinyl acrylate into the reaction system, carrying out heat preservation reaction for 7h, monitoring the reaction progress, adding 1000ml of water into the reaction system after sampling and detecting the reaction completion, stirring, extracting and phase-splitting, drying an organic phase, concentrating under reduced pressure, and evaporating to obtain 132g of a 4-hydroxyphenyl acrylic ester product with the yield of 93.64%. The gas chromatogram of the 4-hydroxyphenyl acrylate synthesized in this example is shown in FIG. 10.
Compared with the prior art, the preparation method of the embodiment of the invention can greatly shorten the reaction time, and in the preparation process of the invention, the heat preservation time is only 7 hours.
The embodiment of the invention has the high yield of 93.64 percent higher than that of the prior art, is beneficial to industrial production and reduces the cost.
In summary, in examples 3-10, a large amount of hydrogen chloride was not discharged during the preparation process, and the environment was not polluted.
The ion exchange resin of each embodiment is used as a catalyst, and can be recycled after being regenerated after participating in the reaction, so that the conversion rate of the product can be ensured, and the reaction cost is reduced.
The traditional acrylic chloride raw material is abandoned in each embodiment, a new technical route is developed, the process is greener, the impurities of the product are fewer, and the purity is higher.
According to the invention, vinyl acrylate or vinyl methacrylate and corresponding alcohol are used as reaction raw materials, small-polarity alkane is used as a solvent, a certain amount of polymerization inhibitor is added to prevent raw materials and products from polymerizing to generate byproducts, transesterification is carried out under the action of a catalyst in an extremely dilute solution to prepare corresponding photoresist resin monomer acrylic ester products, the purity of the obtained products is more than or equal to 99%, and the total yield of the products is more than or equal to 90% after recrystallization. The technological route disclosed by the invention is simple and feasible in operation process and high in product yield in the reaction process.
At present, the technical scheme of the invention has been subjected to pilot-scale experiments, namely small-scale experiments of products before large-scale mass production; after the pilot test is finished, the use investigation of the user is performed in a small range, and the investigation result shows that the user satisfaction is higher; now, the preparation of the formal production of the product for industrialization (including intellectual property risk early warning investigation) is started.
The above described embodiments are preferred examples of the invention and are not intended to be exhaustive of the practical implementations of the invention. Various modifications of the invention, which are apparent to those skilled in the art, should be deemed to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. A synthetic method of an acrylic ester resin monomer for 193nm photoresist is characterized in that vinyl acrylate or vinyl methacrylate and alcohol are used as reaction raw materials, a small polar alkane solvent is used as a reaction solvent, a polymerization inhibitor is added, and an alkaline ion exchange resin is used as a catalyst, so that the acrylic ester resin monomer is obtained through transesterification under the low-temperature condition;
the alcohol is 1-adamantanol, 2-methyladamantanol, 2-ethyladamantanol or 2-carbonyl-tetrahydrofuran-3-ol; the low-polarity alkane solvent is cyclohexane, n-hexane or n-heptane; the polymerization inhibitor is tetrachlorobenzoquinone or p-benzoquinone;
the alkaline ion exchange resin is weak alkaline ion exchange resin with secondary amino groups;
the low temperature condition is-10 ℃ to-20 ℃.
2. The method for synthesizing an acrylic resin monomer for 193nm photoresist according to claim 1, wherein the basic ion exchange resin has a pH of 7 to 8.
3. The method for synthesizing an acrylate resin monomer for 193nm photoresist according to claim 1, wherein the acrylate resin monomer is 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-adamantyl methacrylate, 2-adamantyl acrylate, 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylate or 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate.
4. The method for synthesizing an acrylic resin monomer for 193nm photoresist according to claim 1, wherein the molar ratio of vinyl acrylate or vinyl methacrylate to alcohol in the raw material is 1.2-1.4:1.
5. the method for synthesizing an acrylic resin monomer for 193nm photoresist according to claim 1, wherein the reaction solvent is added in an amount of: the mass ratio of the vinyl acrylate or vinyl methacrylate to the reaction solvent is 1:30-1:40, a step of performing a; the addition amount of the polymerization inhibitor is 0.01-0.03% of the mass of the vinyl acrylate or vinyl methacrylate; the addition amount of the alkaline ion exchange resin is equal to the mass of the vinyl acrylate or the vinyl methacrylate.
6. The method for synthesizing an acrylic resin monomer for 193nm photoresist according to claim 1, comprising the steps of (1) adding a reaction solvent in a container, adding a reaction raw material alcohol under stirring, then sequentially adding a polymerization inhibitor and a catalyst, and cooling to a low temperature condition; (2) Adding reaction raw material vinyl acrylate or vinyl methacrylate, and reacting for 5-7h at a constant temperature.
7. The method of claim 6, further comprising a step (3), wherein the step (3) is: and (3) adding water into the product obtained in the step (2) and then extracting and phase-separating.
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