CN116063599A - Synthesis method of PHS resin with narrow molecular weight distribution - Google Patents
Synthesis method of PHS resin with narrow molecular weight distribution Download PDFInfo
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- 238000009826 distribution Methods 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 title claims abstract description 25
- 229920005989 resin Polymers 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims abstract description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 29
- 238000005070 sampling Methods 0.000 claims description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 23
- 150000007524 organic acids Chemical class 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 150000007530 organic bases Chemical class 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 238000011010 flushing procedure Methods 0.000 claims description 7
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- -1 (2-ethylhexyl peroxy) ethane Chemical compound 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- GRFNSWBVXHLTCI-UHFFFAOYSA-N 1-ethenyl-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=C(C=C)C=C1 GRFNSWBVXHLTCI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LTGJSMARDKHZOY-UHFFFAOYSA-N 1-ethenyl-3-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=CC(C=C)=C1 LTGJSMARDKHZOY-UHFFFAOYSA-N 0.000 claims description 2
- DTNCNFLLRLHPNJ-UHFFFAOYSA-N 1-ethenyl-4-(1-ethoxyethoxy)benzene Chemical compound CCOC(C)OC1=CC=C(C=C)C=C1 DTNCNFLLRLHPNJ-UHFFFAOYSA-N 0.000 claims description 2
- KVWLLOIEGKLBPA-UHFFFAOYSA-N 3,6,9-triethyl-3,6,9-trimethyl-1,2,4,5,7,8-hexaoxonane Chemical compound CCC1(C)OOC(C)(CC)OOC(C)(CC)OO1 KVWLLOIEGKLBPA-UHFFFAOYSA-N 0.000 claims description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- GJWMYLFHBXEWNZ-UHFFFAOYSA-N tert-butyl (4-ethenylphenyl) carbonate Chemical compound CC(C)(C)OC(=O)OC1=CC=C(C=C)C=C1 GJWMYLFHBXEWNZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 19
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 230000000977 initiatory effect Effects 0.000 abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 16
- 239000010931 gold Substances 0.000 description 16
- 229910052737 gold Inorganic materials 0.000 description 16
- 239000007787 solid Substances 0.000 description 12
- 238000012546 transfer Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F112/22—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Emergency Medicine (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The application belongs to the field of functional polymer materials, in particular to a synthesis method of PHS resin with narrow molecular weight distribution, which is beneficial in that: 1. continuous flow chemical synthesis of PHS-based resins was performed using a microchannel reaction system. 2. Initiation is carried out by using a composite initiator of azo and a polyfunctional peroxy initiator. Solves the problems of poor production safety, unstable product quality and the like caused by the problem of heat instability in the polymerization process. Meanwhile, the PDI of the PHS resin is less than or equal to 1.2, and the metal impurity is less than or equal to 0.5ppb, so that the PHS resin can be suitable for preparing KrF photoresist thin rubber.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and in particular relates to a synthesis method of PHS resin with narrow molecular weight distribution
Background
KrF photoresists are one of the key materials in the field of integrated circuit fabrication and consist of resins, photosensitizers, solvents, additives, and the like. The PHS resin with molecular weight distribution (PDI) less than or equal to 1.2 is called PHS resin with narrow molecular weight distribution, can be used for preparing thin rubber of KrF photoresist, has high resolution after development and can meet 130 nm-180 nm process nodes.
In the prior art, the method for obtaining PHS resin with narrow molecular weight distribution comprises the following steps: anionic polymerization, RAFT living radical polymerization, ATRP living radical polymerization. While these methods can give PHS resins with narrow molecular weight distribution, anionic polymerization processes face the problem of metal ion removal, and RAFT and ATRP living radical polymerization processes face the problem of chain transfer agent removal. All the methods are traditional kettle polymerization methods, and the problems of low heat transfer and mass transfer, difficult temperature precise control, difficulty in efficient removal of oxygen, unstable products among batches, poor control of process, obvious amplification effect and the like caused by the characteristics of easy volatilization of solvents, easy volatilization of monomers and the like are faced.
Disclosure of Invention
In order to solve the problems, the invention provides a synthesis method of PHS resin with narrow molecular weight distribution.
The specific technical scheme provided by the invention is as follows: a synthesis method of PHS resin with narrow molecular weight distribution is characterized by comprising the following steps:
1) Cleaning a micro-channel reaction system, and respectively mixing a monomer and an azo initiator into a solvent to prepare liquid for later use; mixing organic base or organic acid with solvent for use;
2) Setting the reaction temperature of a micro-channel, wherein the first temperature zone is 60-70 ℃, the second temperature zone is 70-95 ℃, and the third temperature zone is 50-55 ℃; starting a monomer feed pump, an azo initiator feed pump, a multifunctional peroxy initiator feed pump and an organic base and/or organic acid feed pump;
3) The monomer, azo initiator, multifunctional peroxy initiator, organic base or organic acid enter a microchannel reactor through a feed pump, and the reaction pressure in the microchannel is regulated to be 1.5-10bar;
4) Receiving a reaction liquid sample at a sampling port for online analysis, and switching a terminal valve to a product tank after the detection result is qualified, wherein the product tank is stirred pure water, and a product is separated out in the water; and after the reaction is finished, closing the valve, carrying out filter pressing on the product, and carrying out sample feeding detection on the product.
The application also provides a reaction system for operating the synthesis method, which is characterized in that: the micro-channel reaction system comprises a sample injection pump, a micro-mixer, a micro-reactor, a back pressure valve, a sampling port, a waste liquid pipe and a product tank; wherein the number of micromixers and microreactors is a plurality; the micro-mixer 1, the micro-reactor 1, the micro-mixer 2, the micro-reactor 2, the micro-mixer 3 and the micro-reactor 3 are connected in sequence;
pure water, a monomer, an azo initiator and a solvent respectively enter the micro-mixer 1 through a sample injection pump, and flow into the micro-reactor 1 after being mixed;
the multifunctional peroxy initiator enters the micro-mixer 2 through a feed pump, and enters the micro-reactor 2 after being mixed;
the organic acid/alkali enters the micro-mixer 3 through a feed pump, and enters the micro-reactor 3 after being mixed; the back pressure valve can be switched and connected to the waste liquid tank, the product tank and the sampling port; wherein the back pressure valve is used to define the pressure of the system and to switch the piping connections.
The beneficial effects of the invention are as follows:
1. the PHS resin obtained by the invention has PDI less than or equal to 1.2, belongs to PHS resin with narrow molecular weight distribution, and has metal ion impurity less than or equal to 0.5ppb. Can be applied to the preparation of KrF photoresist thin films.
2. The invention uses the micro-channel reactor to carry out the flow chemical reaction, thereby avoiding the problems of unstable batch-to-batch, difficult control of the process and obvious amplification effect caused by the traditional kettle-type reactor. The preparation process of the invention can be used for industrialization, can be used for large-scale production, and has reliable product quality.
3. Generally, azo-type initiators have a longer reaction time, but the molecular weight distribution of the product is broader. The peroxy initiator initiates a reaction faster, but the reaction speed is too fast to be controlled. The use of a composite initiator allows for more effective regulation of the polymerization reaction than a single component initiator.
4. In general, composite initiators suffer from uneven initiation caused by too high local concentrations of a certain type of initiator due to uneven initiator distribution. The invention utilizes the strong mass transfer capability of the microchannel reactor, and more effectively mixes the two initiators through the mixer, thereby avoiding the problem of uneven initiation.
5. The present application uses general free radical polymerization, avoiding the difficulty of chain transfer agent removal. Meanwhile, the composite initiator is used and the micro-channel reactor is used for reaction, so that the mass transfer mixing effect of the initiator is enhanced, and the concentration stability of free radicals in a system is ensured by adding different initiators at different degrees of reaction. The multifunctional peroxy initiator has the characteristics of easy control of polymerization reaction and high product conversion rate, so that the PDI of the product is further reduced. Meanwhile, the microchannel reactor has the advantages of enhancing heat transfer, enhancing mass transfer, controlling temperature accurately, controlling polymerization rate and time accurately, removing oxygen easily, avoiding volatilization of monomer solvent, and the like, and the flow chemical production is used for solving the problems of unstable reaction batch to batch, difficult control of process and obvious amplification effect, and the PDI of the product is further reduced due to the characteristics of high-efficiency mass transfer, heat transfer and small liquid holdup.
Drawings
Fig. 1 is a schematic diagram of a detection system according to an embodiment of the present application.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
An embodiment of the present application provides a synthesis method of a PHS resin with narrow molecular weight distribution, which is characterized by comprising the following steps:
1) Cleaning a micro-channel reaction system, and respectively mixing a monomer and an azo initiator into a solvent to prepare liquid for later use; mixing organic base or organic acid with solvent for use;
2) Setting the reaction temperature of a micro-channel, wherein the first temperature zone is 60-70 ℃, the second temperature zone is 70-95 ℃, and the third temperature zone is 50-55 ℃; starting a monomer feed pump, an azo initiator feed pump, a multifunctional peroxy initiator feed pump and an organic base and/or organic acid feed pump;
3) The monomer, azo initiator, multifunctional peroxy initiator, organic base or organic acid enter a microchannel reactor through a feed pump, and the reaction pressure in the microchannel is regulated to be 1.5-10bar;
4) Receiving a reaction liquid sample at a sampling port for online analysis, and switching a terminal valve to a product tank after the detection result is qualified, wherein the product tank is stirred pure water, and a product is separated out in the water; and after the reaction is finished, closing the valve, carrying out filter pressing on the product, and carrying out sample feeding detection on the product.
In an embodiment, the solvent is a water-soluble organic solvent, and the water-soluble solvent is one or more of ethanol, isopropanol, n-butanol, 1, 4-dioxane, DMSO, DMF, NMP, PGMEA.
In one embodiment, the monomer is one or more of styrene, p-t-butoxystyrene, p-acetoxystyrene, p- (1-ethoxyethoxy) styrene, p-vinylphenylcarbonate, t-butyl acrylate, m-t-butoxystyrene.
In one embodiment, the azo initiator is one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisobutyrimidine hydrochloride or azobisisobutyronitrile Ding Mi hydrochloride;
the multifunctional peroxy initiator is one of 1, 1-bis (tert-butylperoxy) cyclohexane, diperoxyl ester 2, 5-dimethyl-2, 5-di (2-ethylhexyl peroxy) ethane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane and tetra-tert-butyl peroxydicarbonate.
In one embodiment, the organic acid comprises: one or more of p-toluene sulfonic acid, acetic acid, methanesulfonic acid, trifluoroacetic acid, benzoic acid, oxalic acid, sulfamic acid; the organic base includes: ammonia, ethylenediamine, hydrazine hydrate, diethylamine, triethylamine, DMAP.
In one embodiment, the synthetic process material molar ratio is monomer: azo initiator: peroxy-based initiator: organic acid/base = 1:2% -4%: 1-4 percent and 20-40 percent.
In one embodiment, the step of cleaning the microchannel reaction system comprises the steps of starting a feed pump, introducing pure water into the microchannel reaction system, detecting effluent at the tail joint to be less than 0.1ppb, then flushing the microchannel reaction system with electronic grade isopropanol, and detecting isopropanol at the tail joint to be less than 0.1ppb; nitrogen is blown to the micro-channel reaction system for 5-8h.
An embodiment of the present application further provides a reaction system for operating the synthesis method, which is characterized in that: the micro-channel reaction system comprises a sample injection pump, a micro-mixer, a micro-reactor, a back pressure valve, a sampling port, a waste liquid pipe and a product tank; wherein the number of micromixers and microreactors is a plurality; the micro-mixer 1, the micro-reactor 1, the micro-mixer 2, the micro-reactor 2, the micro-mixer 3 and the micro-reactor 3 are connected in sequence;
pure water, a monomer, an azo initiator and a solvent respectively enter the micro-mixer 1 through a sample injection pump, and flow into the micro-reactor 1 after being mixed;
the multifunctional peroxy initiator enters the micro-mixer 2 through a feed pump, and enters the micro-reactor 2 after being mixed;
the organic acid/alkali enters the micro-mixer 3 through a feed pump, and enters the micro-reactor 3 after being mixed; the back pressure valve can be switched and connected to the waste liquid tank, the product tank and the sampling port; wherein the back pressure valve is used to define the pressure of the system and to switch the piping connections. See fig. 1 for a specific structure.
Example 1
1. And cleaning the micro-channel system. The equipment is installed in place, a pure water feeding pump is started, a pure water flushing pipeline is flushed into the pipeline, after the pure water gold impurity concentration of a sampling port is less than or equal to 0.1ppb, the pure water feeding pump is closed, the pipeline is started to be cleaned after the pure water gold impurity concentration of the sampling port is less than or equal to 0.1ppb, a high-purity nitrogen purging pipeline is switched for 5-8 hours after the isopropyl alcohol concentration of the sampling port is less than or equal to 0.1ppb, and a valve is closed for standby.
2. And (5) proportioning before reaction. 12.5kg of p-acetoxystyrene was dissolved in 25kg of DMSO and the solution was connected to a monomer feed pump. 0.35kg of dimethyl azodiisobutyrate was dissolved in 25kg of DMSO and the solution was connected to an azo initiator feed pump. 0.8kg of tetraterbutamol peroxydicarbonate was dissolved in 25kg of DMSO and the solution was connected to a multi-functional peroxygen initiator feed pump. 1.5kg of triethylamine was dissolved in 25kg of DMSO and the solution was connected to an organic acid/base feed pump.
The heater is started, the first temperature zone is set to be 70 ℃, the second temperature zone is set to be 90 ℃, and the third temperature zone is set to be 50 ℃.
3. Starting each feeding pump, wherein the flow rate is 0.2mL/min:0.2mL/min:0.2mL/min:0.2mL/min. The reaction system pressure was regulated to 5bar by means of a back pressure valve. And (3) receiving a reaction liquid sample at a sampling port for online analysis, testing the content of single gold impurity and the molecular weight distribution, and switching a terminal valve to a product tank after the detection result is qualified. The product tank is continuously stirred pure water. The product drips out and is separated out in the product tank. And (3) carrying out reduced pressure suction filtration on the solid in the product tank, and placing filter residues in a vacuum oven to be dried at 80 ℃ for 18 hours to obtain white off-yellow solid. And detecting the product. The results are shown in Table I.
Example two
1. And cleaning the micro-channel system. The equipment is installed in place, a pure water feeding pump is started, a pure water flushing pipeline is flushed into the pipeline, after the pure water gold impurity concentration of a sampling port is less than or equal to 0.1ppb, the pure water feeding pump is closed, the pipeline is started to be cleaned after the pure water gold impurity concentration of the sampling port is less than or equal to 0.1ppb, a high-purity nitrogen purging pipeline is switched for 5-8 hours after the isopropyl alcohol concentration of the sampling port is less than or equal to 0.1ppb, and a valve is closed for standby.
2. Prepared before reaction. 12.5kg of p-acetoxystyrene was dissolved in 25kg of DMF and the solution was connected to a monomer feed pump. 0.25kg of azobisisobutyronitrile was dissolved in 25kg of DMF and the solution was connected to an azo initiator feed pump. 0.2kg of tetraterbutamol peroxydicarbonate was dissolved in 25kg of DMF and the solution was connected to a multi-functional peroxy initiator feed pump. 1.5kg of triethylamine was dissolved in 25kg of DMF and the solution was connected to an organic acid/base feed pump.
The heater is started, the first temperature zone is set to be 70 ℃, the second temperature zone is set to be 90 ℃, and the third temperature zone is set to be 50 ℃.
3. Starting each feeding pump, wherein the flow rate is 0.2mL/min:0.2mL/min:0.2mL/min:0.2mL/min. The reaction system pressure was regulated to 5bar by means of a back pressure valve. And (3) receiving a reaction liquid sample at a sampling port for online analysis, testing the content of single gold impurity and the molecular weight distribution, and switching a terminal valve to a product tank after the detection result is qualified. The product tank is continuously stirred pure water. The product drips out and is separated out in the product tank. And (3) carrying out reduced pressure suction filtration on the solid in the product tank, and placing filter residues in a vacuum oven to be dried at 80 ℃ for 18 hours to obtain white off-yellow solid. And detecting the product. The results are shown in Table I.
Example III
1. And cleaning the micro-channel system. The equipment is installed in place, a pure water feeding pump is started, a pure water flushing pipeline is flushed into the pipeline, after the pure water gold impurity concentration of a sampling port is less than or equal to 0.1ppb, the pure water feeding pump is closed, the pipeline is started to be cleaned after the pure water gold impurity concentration of the sampling port is less than or equal to 0.1ppb, a high-purity nitrogen purging pipeline is switched for 5-8 hours after the isopropyl alcohol concentration of the sampling port is less than or equal to 0.1ppb, and a valve is closed for standby.
2. And (5) proportioning before reaction. 5.1kg of p-tert-butoxystyrene, 3.3kg of styrene and 4kg of tert-butyl acrylate were dissolved in 25kg of DMSO and the solution was connected to a monomer feed pump. 0.35kg of dimethyl azodiisobutyrate was dissolved in 25kg of DMSO and the solution was connected to an azo initiator feed pump. 0.8kg of tetraterbutamol peroxydicarbonate was dissolved in 25kg of DMSO and the solution was connected to a multi-functional peroxygen initiator feed pump. 1.5kg of triethylamine was dissolved in 25kg of DMSO and the solution was connected to an organic acid/base feed pump.
The heater is started, the first temperature zone is set to be 70 ℃, the second temperature zone is set to be 90 ℃, and the third temperature zone is set to be 50 ℃.
3. Starting each feeding pump, wherein the flow rate is 0.2mL/min:0.2mL/min:0.2mL/min:0.2mL/min. The reaction system pressure was regulated to 5bar by means of a back pressure valve. And (3) receiving a reaction liquid sample at a sampling port for online analysis, testing the content of single gold impurity and the molecular weight distribution, and switching a terminal valve to a product tank after the detection result is qualified. The product tank is continuously stirred pure water. The product drips out and is separated out in the product tank. And (3) carrying out reduced pressure suction filtration on the solid in the product tank, and placing filter residues in a vacuum oven to be dried at 80 ℃ for 18 hours to obtain white off-yellow solid. And detecting the product. The results are shown in Table I.
Comparative example one
1. And cleaning the micro-channel system. The equipment is installed in place, a pure water feeding pump is started, a pure water flushing pipeline is flushed into the pipeline, after the pure water gold impurity concentration of a sampling port is less than or equal to 0.1ppb, the pure water feeding pump is closed, the pipeline is started to be cleaned after the pure water gold impurity concentration of the sampling port is less than or equal to 0.1ppb, a high-purity nitrogen purging pipeline is switched for 5-8 hours after the isopropyl alcohol concentration of the sampling port is less than or equal to 0.1ppb, and a valve is closed for standby.
2. And (5) proportioning before reaction. 12.5kg of p-acetoxystyrene was dissolved in 25kg of DMSO and the solution was connected to a monomer feed pump. 0.35kg of dimethyl azodiisobutyrate was dissolved in 25kg of DMSO and the solution was connected to an azo initiator feed pump. 0.37kg of dibenzoyl peroxide was dissolved in 25kg of DMSO and the solution was connected to a multi-functional peroxygen initiator feed pump. 1.5kg of triethylamine was dissolved in 25kg of DMSO and the solution was connected to an organic acid/base feed pump.
The heater is started, the first temperature zone is set to be 70 ℃, the second temperature zone is set to be 90 ℃, and the third temperature zone is set to be 50 ℃.
3. Starting each feeding pump, wherein the flow rate is 0.2mL/min:0.2mL/min:0.2mL/min:0.2mL/min. The reaction system pressure was regulated to 5bar by means of a back pressure valve. And (3) receiving a reaction liquid sample at a sampling port for online analysis, testing the content of single gold impurity and the molecular weight distribution, and switching a terminal valve to a product tank after the detection result is qualified. The product tank is continuously stirred pure water. The product drips out and is separated out in the product tank. And (3) carrying out reduced pressure suction filtration on the solid in the product tank, and placing filter residues in a vacuum oven to be dried at 80 ℃ for 18 hours to obtain white off-yellow solid. And detecting the product. The results are shown in Table I.
Comparative example two
1. And cleaning the micro-channel system. The equipment is installed in place, a pure water feeding pump is started, a pure water flushing pipeline is flushed into the pipeline, after the pure water gold impurity concentration of a sampling port is less than or equal to 0.1ppb, the pure water feeding pump is closed, the pipeline is started to be cleaned after the pure water gold impurity concentration of the sampling port is less than or equal to 0.1ppb, a high-purity nitrogen purging pipeline is switched for 5-8 hours after the isopropyl alcohol concentration of the sampling port is less than or equal to 0.1ppb, and a valve is closed for standby.
2. And (5) proportioning before reaction. 12.5kg of p-acetoxystyrene was dissolved in 25kg of DMSO and the solution was connected to a monomer feed pump. 0.35kg of dimethyl azodiisobutyrate was dissolved in 25kg of DMSO and the solution was connected to an azo initiator feed pump. 0.8kg of tetraterbutamol peroxydicarbonate was dissolved in 25kg of DMSO and the solution was connected to a multi-functional peroxygen initiator feed pump. 1.5kg of triethylamine was dissolved in 25kg of DMSO and the solution was connected to an organic acid/base feed pump.
The heater is started, the first temperature zone is set to 90 ℃, the second temperature zone is set to 90 ℃, and the third temperature zone is set to 50 ℃.
3. Starting each feeding pump, wherein the flow rate is 0.2mL/min:0.2mL/min:0.2mL/min:0.2mL/min. The reaction system pressure was regulated to 5bar by means of a back pressure valve. And (3) receiving a reaction liquid sample at a sampling port for online analysis, testing the content of single gold impurity and the molecular weight distribution, and switching a terminal valve to a product tank after the detection result is qualified. The product tank is continuously stirred pure water. The product drips out and is separated out in the product tank. And (3) carrying out reduced pressure suction filtration on the solid in the product tank, and placing filter residues in a vacuum oven to be dried at 80 ℃ for 18 hours to obtain white off-yellow solid. And detecting the product. The results are shown in Table I.
Comparative example three
A tank reactor was used. The kettle type reactor is cleaned by pure water and isopropanol for a plurality of times. And (5) drying with nitrogen for later use. The reaction vessel was purged with nitrogen, and 12.5kg of p-acetoxystyrene, 0.35kg of dimethyl azodiisobutyrate and 50kg of DMSO were charged into the vessel. Stirring and heating to 70 ℃, reacting for a period of time, adding 0.8kg of tetra-tert-butyl peroxydicarbonate solution into 25kg of DMSO, and heating to 90 ℃. The reaction was carried out for 10 hours. After the reaction, the temperature was lowered to 50℃and 1.5kg of triethylamine was added to the solution and dissolved in 25kg of DMSO. The reaction was carried out for 5 hours. Slowly dripping into continuously stirred pure water, carrying out reduced pressure suction filtration on precipitated solids, and placing filter residues into a vacuum oven to be dried at 80 ℃ for 18 hours to obtain white-like yellowish solids. And detecting the product. The results are shown in Table I
TABLE I, gold impurity content and molecular weight distribution detection results
| Metal ion content | Molecular weight distribution | |
| Example 1 | 0.2ppb | 1.05 |
| Example two | 0.5ppb | 1.13 |
| Example III | 0.2ppb | 1.05 |
| Comparative example one | 0.6ppb | 1.33 |
| Comparative example two | 0.2ppb | 1.42 |
| Comparative example three | 1ppb | 1.76 |
According to the detection result obtained in the embodiment, the PDI of the PHS resin prepared by the method is less than or equal to 1.2, the PHS resin belongs to PHS resin with narrow molecular weight distribution, and the metal ion impurity of the product is less than or equal to 0.5ppb. In contrast, the use of the monofunctional dibenzoyl peroxide in comparative example one resulted in a tendency of disorder of initiation upon initiation of polymerization, and a broadening of the molecular weight distribution to 1.33, which no longer satisfies the use of PHS resins having a narrow molecular weight distribution. In the second comparative example, the temperature of the first temperature zone was set to 90 degrees, and the initiation rate of the azo initiator at this temperature was too high, resulting in a broadening of the molecular weight distribution to 1.42 upon initiation of polymerization, which no longer satisfies the use of a PHS resin having a narrow molecular weight distribution. In the third comparative example, the reaction is changed from using a microchannel reactor to using a kettle-type reactor, the kettle-type reactor is accurate in heat transfer, mass transfer and temperature control, the polymerization rate and time are accurately controlled, oxygen is easy to remove, no monomer solvent volatilizes and the like, the liquid holdup is large, and the molecular weight distribution in the polymerization process is increased in all aspects, so that the PDI reaches 1.76. And the kettle type reactor is more easily influenced by the surrounding environment, so that the metal ion content reaches 1ppb. The use of PHS resins of narrow molecular weight distribution is no longer satisfactory. Therefore, the requirement that the PDI of the PHS resin is less than or equal to 1.2 can be met after the reaction by using the micro-channel reactor and using the peroxide initiator with multiple functionalities and compounding the azo initiator and the peroxide initiator with multiple functionalities through the above relation. Can be applied to the preparation of KrF photoresist thin films.
The advantages of the multi-functionality peroxy-based initiator, the temperature precision zone and the microfluidic channel reaction can be seen by comparing the first, second, and third examples with the first example.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. A synthesis method of PHS resin with narrow molecular weight distribution is characterized by comprising the following steps:
1) Cleaning a micro-channel reaction system, and respectively mixing a monomer and an azo initiator into a solvent to prepare liquid for later use; mixing organic base or organic acid with solvent for use;
2) Setting the reaction temperature of a micro-channel, wherein the first temperature zone is 60-70 ℃, the second temperature zone is 70-95 ℃, and the third temperature zone is 50-55 ℃; starting a monomer feed pump, an azo initiator feed pump, a multifunctional peroxy initiator feed pump and an organic base and/or organic acid feed pump;
3) The monomer, azo initiator, multifunctional peroxy initiator, organic base or organic acid enter a microchannel reactor through a feed pump, and the reaction pressure in the microchannel is regulated to be 1.5-10bar;
4) Receiving a reaction liquid sample at a sampling port for online analysis, and switching a terminal valve to a product tank after the detection result is qualified, wherein the product tank is stirred pure water, and a product is separated out in the water; and after the reaction is finished, closing the valve, carrying out filter pressing on the product, and carrying out sample feeding detection on the product.
2. The synthesis method according to claim 1, wherein: the solvent is one or more of ethanol, isopropanol, n-butanol, 1, 4-dioxane and DMSO, DMF, NMP, PGMEA in a water-soluble organic solvent.
3. The synthesis method according to claim 1, wherein: the monomer is one or more of styrene, p-tert-butoxystyrene, p-acetoxystyrene, p- (1-ethoxyethoxy) styrene, p-vinylphenyl tert-butyl carbonate, tert-butyl acrylate and m-tert-butoxystyrene.
4. The synthesis method according to claim 1, wherein: the azo initiator is one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisobutyrimidine hydrochloride or azobisisobutyrimidine hydrochloride;
the multifunctional peroxy initiator is one of 1, 1-bis (tert-butylperoxy) cyclohexane, diperoxyl ester 2, 5-dimethyl-2, 5-di (2-ethylhexyl peroxy) ethane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane and tetra-tert-butyl peroxydicarbonate.
5. The synthesis method according to claim 1, wherein: the organic acid includes: one or more of p-toluene sulfonic acid, acetic acid, methanesulfonic acid, trifluoroacetic acid, benzoic acid, oxalic acid, sulfamic acid; the organic base includes: ammonia, ethylenediamine, hydrazine hydrate, diethylamine, triethylamine, DMAP.
6. The synthesis method according to claim 1, wherein: the molar ratio of the materials in the synthesis method is as follows: azo initiator: peroxy-based initiator: organic acid/base = 1:2% -4%: 1-4 percent and 20-40 percent.
7. The synthesis method according to claim 1, wherein: the method comprises the steps of firstly starting a feed pump, introducing pure water into the microchannel reaction system, detecting effluent at the tail joint to be less than 0.1ppb, then flushing the microchannel reaction system by using electronic grade isopropanol, and detecting isopropanol at the tail joint to be less than 0.1ppb; nitrogen is blown to the micro-channel reaction system for 5-8h.
8. A reaction system for operating the synthesis method of claim 1, wherein: the micro-channel reaction system comprises a sample injection pump, a micro-mixer, a micro-reactor, a back pressure valve, a sampling port, a waste liquid pipe and a product tank; wherein the number of micromixers and microreactors is a plurality; the micro-mixer 1, the micro-reactor 1, the micro-mixer 2, the micro-reactor 2, the micro-mixer 3 and the micro-reactor 3 are connected in sequence;
pure water, a monomer, an azo initiator and a solvent respectively enter the micro-mixer 1 through a sample injection pump, and flow into the micro-reactor 1 after being mixed;
the multifunctional peroxy initiator enters the micro-mixer 2 through a feed pump, and enters the micro-reactor 2 after being mixed;
the organic acid/alkali enters the micro-mixer 3 through a feed pump, and enters the micro-reactor 3 after being mixed; the back pressure valve can be switched and connected to the waste liquid tank, the product tank and the sampling port; wherein the back pressure valve is used to define the pressure of the system and to switch the piping connections.
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| CN118388686A (en) * | 2024-06-25 | 2024-07-26 | 苏州润邦半导体材料科技有限公司 | Preparation method of PHS resin |
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