CN113105570B - Liquid two-photon initiator and preparation method and application thereof - Google Patents
Liquid two-photon initiator and preparation method and application thereof Download PDFInfo
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- CN113105570B CN113105570B CN202110398496.2A CN202110398496A CN113105570B CN 113105570 B CN113105570 B CN 113105570B CN 202110398496 A CN202110398496 A CN 202110398496A CN 113105570 B CN113105570 B CN 113105570B
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- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 239000003999 initiator Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 15
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 239000012074 organic phase Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000004440 column chromatography Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920002120 photoresistant polymer Polymers 0.000 claims description 8
- 239000007832 Na2SO4 Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 238000000746 purification Methods 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000011734 sodium Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BQWCROVNQWPSNZ-UHFFFAOYSA-N CCCC(C)CCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCC(C)CCC Chemical compound CCCC(C)CCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCC(C)CCC BQWCROVNQWPSNZ-UHFFFAOYSA-N 0.000 description 2
- KLAGFYLETXOKJL-UHFFFAOYSA-N CCCC(C)CCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCC(C)CCC Chemical compound CCCC(C)CCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCC(C)CCC KLAGFYLETXOKJL-UHFFFAOYSA-N 0.000 description 2
- HFENLGRBJDZYMG-UHFFFAOYSA-N CCCCC(C)CCCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCCC(C)CCCC Chemical compound CCCCC(C)CCCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCCC(C)CCCC HFENLGRBJDZYMG-UHFFFAOYSA-N 0.000 description 2
- INXMIGWZBMMUQJ-UHFFFAOYSA-N CCCCC(C)CCCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCCC(C)CCCC Chemical compound CCCCC(C)CCCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCCC(C)CCCC INXMIGWZBMMUQJ-UHFFFAOYSA-N 0.000 description 2
- LFFWPACEXYGYQA-UHFFFAOYSA-N CCCCC(C)CCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCC(C)CCCC Chemical compound CCCCC(C)CCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCC(C)CCCC LFFWPACEXYGYQA-UHFFFAOYSA-N 0.000 description 2
- DSUXLHMBXXBVMR-UHFFFAOYSA-N CCCCC(C)CCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCC(C)CCCC Chemical compound CCCCC(C)CCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCC(C)CCCC DSUXLHMBXXBVMR-UHFFFAOYSA-N 0.000 description 2
- GMGLYMJRHWQLBJ-UHFFFAOYSA-N CCCCCC(C)CCCCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCCCC(C)CCCCC Chemical compound CCCCCC(C)CCCCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCCCC(C)CCCCC GMGLYMJRHWQLBJ-UHFFFAOYSA-N 0.000 description 2
- ABIUKSAPMMOHHC-UHFFFAOYSA-N CCCCCC(C)CCCCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCCCC(C)CCCCC Chemical compound CCCCCC(C)CCCCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCCCC(C)CCCCC ABIUKSAPMMOHHC-UHFFFAOYSA-N 0.000 description 2
- QGKDVMOSAFDQIZ-UHFFFAOYSA-N CCCCCCC(C)CCCCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCCCC(C)CCCCCC Chemical compound CCCCCCC(C)CCCCCCCCCCCCOC(C=C1)=CC=C1OCCCCCCCCCCCCC(C)CCCCCC QGKDVMOSAFDQIZ-UHFFFAOYSA-N 0.000 description 2
- HDUOSOXVYJKYKL-UHFFFAOYSA-N CCCCCCC(C)CCCCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCCCC(C)CCCCCC Chemical compound CCCCCCC(C)CCCCCCCCCCCCOC(C=C1CBr)=C(CBr)C=C1OCCCCCCCCCCCCC(C)CCCCCC HDUOSOXVYJKYKL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000010437 gem Substances 0.000 description 2
- 229910001751 gemstone Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- RUKJCCIJLIMGEP-ONEGZZNKSA-N 4-dimethylaminocinnamaldehyde Chemical compound CN(C)C1=CC=C(\C=C\C=O)C=C1 RUKJCCIJLIMGEP-ONEGZZNKSA-N 0.000 description 1
- QRVYABWJVXXOTN-UHFFFAOYSA-N 4-methylsulfanylbenzaldehyde Chemical compound CSC1=CC=C(C=O)C=C1 QRVYABWJVXXOTN-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- RWEKWRQKAHQYNE-UHFFFAOYSA-N 7-(bromomethyl)pentadecane Chemical compound CCCCCCCCC(CBr)CCCCCC RWEKWRQKAHQYNE-UHFFFAOYSA-N 0.000 description 1
- YVKFGKLDHCVBKR-UHFFFAOYSA-N 7-(chloromethyl)hexadecane Chemical compound CCCCCCCCCC(CCl)CCCCCC YVKFGKLDHCVBKR-UHFFFAOYSA-N 0.000 description 1
- XSQSDBVMLJNZKU-UHFFFAOYSA-N 9-(bromomethyl)nonadecane Chemical compound CCCCCCCCCCC(CBr)CCCCCCCC XSQSDBVMLJNZKU-UHFFFAOYSA-N 0.000 description 1
- JHRPXHNGLBQPLD-UHFFFAOYSA-N CCCCCCCCCCC(CCCCCCC)CBr Chemical compound CCCCCCCCCCC(CCCCCCC)CBr JHRPXHNGLBQPLD-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 239000005457 ice water Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention discloses a liquid two-photon initiator and a preparation method and application thereof, comprising the steps of dispersing hydroquinone in a solvent under the action of an acid binding agent and a phase transfer catalyst, and reacting under the protection of inert gas; step two, adding the product obtained in the step one into paraformaldehyde and hydrobromic acid, and dissolving in a solvent for reaction; step three, adding the product of the step two into triphenylphosphine, dissolving the triphenylphosphine in a solvent, and reacting under the protection of inert gas; step four, introducing the product of the step three into a substituent group for reaction. The liquid two-photon initiator prepared by the invention has good stability and solubility, the scanning rate of two-photon polymerization processing is high, the microstructure precision is good, the preparation method is simple and convenient, the purification is simple, the required time is short, and the purity of the obtained product is high.
Description
Technical Field
The invention relates to the technical field of laser micro-nano processing and photosensitive materials, in particular to a liquid two-photon initiator and a preparation method and application thereof.
Background
Two-photon absorption refers to that under the excitation of strong laser, a molecule or an atom can simultaneously absorb two photons with the same frequency or different frequencies, and the two photons are transited from a ground state to an excited state through a virtual state. Two photons of the same energy are referred to as degenerate two-photon absorption and two photons of different energies are referred to as non-degenerate two-photon absorption. Photopolymerization refers to a process that the molecular weight of a polymer is increased due to light absorption, and two-photon polymerization processing is different from traditional ultraviolet single-photon polymerization, and a photoinitiator with a large two-photon absorption section is used for initiating polymerization reaction, so that the polymerization can be limited in a cubic tiny volume of incident light wavelength, the absorption intensity is in direct proportion to the square of the incident light intensity, and the processing resolution is greatly improved. And the light source of two-photon polymerization is generally near-infrared laser, the linear absorption and Rayleigh scattering of the near-infrared laser are small, and the penetration in a medium is good. The laser direct writing technology based on the two-photon polymerization has wide application prospect in communication engineering, nanotechnology and micro-electromechanical engineering.
The two-photon initiator is the core and research focus of two-photon polymerization, determines the initiation efficiency of the two-photon polymerization, and has decisive influence on reducing the polymerization threshold of two-photon micro-nano processing and improving the processing precision and speed. However, the current two-photon initiator is basically a large conjugated rigid compound with a symmetrical structure, shows solid state behavior, has poor solubility in photoresist resin and needs to be dissolved by a solvent. On one hand, the residual solvent limits the application safety of the two-photon micro-nano processing in the field of biological medical treatment and the like; on the other hand, although the content of the two-photon initiator dissolved in the photoresist is still low by the aid of solvent dissolution, the two-photon initiator is precipitated even along with the prolonging of the standing time, and the requirements of further reducing the threshold value of the polymerization laser and improving the processing precision are difficult to meet. Therefore, it is of great importance to study liquid two-photon initiators that are infinitely miscible with monomers.
Disclosure of Invention
The invention aims to provide a liquid two-photon initiator, a preparation method and application thereof, and solves the problem of poor solubility of a solid two-photon initiator in a monomer in the prior art.
The technical scheme adopted by the invention is as follows:
a liquid two-photon initiator, the molecular structural formula of which is:
R1is-CH2CH(CmH2m+1)CnH2n+1Wherein m + n is any one of 7 to 30, and m and n are non-zero natural numbers;
R2is-NO2，-CN，-OCnH2n+1，-SCnH2n+1，
Wherein n is a natural number of 1 to 10;
R3is any one of- (CH ═ CH) x-, wherein x is a natural number of 1 to 10.
The invention also provides a preparation method of the liquid two-photon initiator, which comprises the following steps:
step one, dispersing hydroquinone in a solvent under the action of an acid binding agent and a phase transfer catalyst, dropwise adding a compound A under the protection of inert gas, and reacting for 2-30 hours at 25-120 ℃; cooling to room temperature after the reaction is finished, adding water for dilution, adding an organic phase for extraction, washing the organic phase with water, and adding anhydrous Na2SO4Drying, desolventizing under reduced pressure to obtain a crude product, and purifying by column chromatography; the compound A is halogenated alkane with long chain branch, ClCH2CH(CmH2m+1)CnH2n+1Or BrCH2CH(CmH2m+1)CnH2n+1Or ICH2CH(CmH2m+1)CnH2n+1Wherein m + n is any one of 7 to 30, and m and n are non-zero natural numbers;
step two, adding the product obtained in the step one into paraformaldehyde and hydrobromic acid to be dissolved in a solvent, heating to 25-120 ℃ to react for 2-30 hours, cooling to room temperature after the reaction is finished, slowly dripping water, extracting the obtained solution, washing an organic phase with water, and adding anhydrous Na2SO4Drying, desolventizing under reduced pressure, and purifying a crude product by column chromatography to obtain a colorless liquid;
step three, adding triphenylphosphine into the product obtained in the step two, dissolving the product in a solvent, heating to 25-130 ℃ under the protection of inert gas, reacting for 2-30 hours, performing suction filtration after the reaction is finished, adding the solvent into a filter cake, leaching, and drying under reduced pressure;
dissolving the product obtained in the step three and a compound B in a solvent, adding strong base in a dark, oxygen-free and inert gas environment, reacting for 2-30h at 0-130 ℃, slowly adding water for quenching after the reaction is finished, adding an organic phase for extraction, washing the organic phase with water, and adding anhydrous Na2SO4Drying, desolventizing under reduced pressure, and purifying a crude product by column chromatography to obtain a liquid two-photon initiator which is red liquid; the compound B is 4-substituent-phenyl (alkenyl)0～1Formaldehyde, the substituent in compound B being-NO2，-CN，-OCnH2n+1，-SCnH2n+1,
N is a natural number of 1 to 10.
Further, the molar ratio of the hydroquinone to the compound A in the first step is 1: 2-1: 8.
Further, the molar ratio of the product of the first step in the second step, the paraformaldehyde and the hydrobromic acid is 1:4: 4-1: 6: 8.
Further, the molar ratio of the product of the second step in the third step to the triphenylphosphine is 1: 3-1: 20.
Further, the molar ratio of the product of the step three to the compound B in the step four is 1: 2-1: 6.
Further: the solvent respectively comprises any one or more than two of the following components: methanol, ethanol, dichloromethane, chloroform, toluene, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and acetic acid.
Further: the phase transfer catalyst in the first step comprises any one or two of the following mixtures: benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride.
Further, the third step and the fourth step are both reacted in an anhydrous environment.
The invention also provides application of the liquid two-photon initiator in the fields of photocuring, photoresist and micro-nano manufacturing and processing.
The invention at least comprises the following beneficial effects:
(1) the liquid two-photon initiator prepared by the invention has good stability and solubility, and the solubility of the initiator in monomers is greatly improved by extending the length of the alkoxy chain on the 2 and 4 positions of the central benzene ring.
(2) The liquid two-photon initiator prepared by the invention can be mixed with a monomer, can greatly reduce the polymerization threshold, shows good stability and two-photon polymerization activity, and has high scanning rate and good microstructure precision in two-photon polymerization reaction processing.
(3) The preparation method of the liquid two-photon initiator is simple and convenient, simple in purification, short in required time and high in purity of the obtained product.
Drawings
FIG. 1 is a graph showing the results of the Z-Scan test on the product of example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a microstructure formed in example 1 of the present invention;
fig. 3 is a scanning electron microscope image of the formed microstructure in embodiment 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
preparation of liquid two-photon initiator:
the method comprises the following steps: adding hydroquinone (3.3g, 30mmol), acid-binding agent potassium hydroxide (4.2g, 75mmol) and phase transfer catalyst tetrabutylammonium bromide (0.5g, 0.65mmol) into a reaction bottle, adding N, N-dimethylformamide for dissolving, dropwise adding 1-bromo-2-hexyldecane (22.9g, 75mmol) under the protection of nitrogen, and heating to 65 ℃ for reaction for 15 h. After the reaction is finished, a large amount of water is added for dilution, the obtained solution is extracted for three times, organic phases are combined, and the organic phases are washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude column chromatography to obtain 9.4g of 1, 4-bis ((2-hexyl) decyloxy) benzene as a colorless liquid with a yield of 56%.1H NMR(400MHz,CDCl3)δ6.81(s,4H,Ar-H),3.77(d,J＝5.8Hz,4H,-CH2O-),1.77–1.71(m,2H,-CH-),1.51–1.14(m,48H,-CH2-),0.90–0.86(m,12H,-CH3).
The chemical reaction formula is as follows:
step two: 1, 4-bis ((2-hexyl) decyloxy) benzene (8.4g, 15mmol), paraformaldehyde (1.8g, 60mmol), hydrobromic acid (30%, 16.2g, 60mmol) and acetic acid (20ml) were added to a reaction flask, and the temperature was raised to 70 ℃ for reaction for 30 hours. After the reaction is finished, the temperature is reduced to room temperature, 300mL of water is slowly dropped, n-hexane is used for extraction for three times, organic phases are combined, and the organic phases are washed twice by water.Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude column chromatography to obtain 7.1g of 1, 4-bis ((2-hexyl) decyloxy) -2, 5-dibromomethylbenzene as a colorless liquid in 64% yield.1H NMR(400MHz,CDCl3)δ6.84(s,2H,Ar-H),4.52(s,4H,-CH2Br),3.86(d,J＝5.4Hz,4H,-CH2O-),1.83-1.77(m,2H,-CH-),1.55–1.16(m,48H,-CH2-),0.90–0.86(m,12H,-CH3).
The chemical reaction formula is as follows:
step three: 1, 4-bis ((2-hexyl) decyloxy) -2, 5-dibromomethylbenzene (1.5g,2mmol) and triphenylphosphine (5.4g,20mmol) were added to anhydrous toluene and the mixture was heated to 100 ℃ under nitrogen for 20 h. After the reaction, the reaction solution is filtered, the filter cake is leached by adding anhydrous toluene, and the filtrate is dried under reduced pressure to obtain 1.9g of white solid phosphonium bromide salt with the yield of 77 percent.1H NMR(400MHz,CDCl3)δ7.78–7.72(m,6H,-P-Ar-H),7.69–7.55(m,24H,-P-Ar-H),6.63(s,2H,Ar-H),5.37(d,J＝12.8Hz,4H,-Ar-CH2-P),2.82(d,J＝5.7Hz,4H,-CH2O-),1.41–1.01(m,50H,-CHCH2-),0.97–0.83(m,12H,-CH3).
The chemical reaction formula is as follows:
step four: adding phosphine bromide (1.9g,1.5mmol) and p-nitrobenzaldehyde (0.68g,4.5mmol) into a reaction bottle, adding anhydrous tetrahydrofuran, adding NaH (60%, 0.72g,18mmol) under a dark and oxygen-free environment, and heating to reflux for 15 h. After the reaction was complete, the reaction was cooled to room temperature and quenched by the slow addition of 20mL of water. The dichloromethane extraction is carried out three times, and the organic phases are combined and washed twice with water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude column chromatography to obtain 0.47g of red liquid with a yield of 37%.1H NMR(400MHz,CDCl3)δ8.02(d,J＝8.8Hz,4H,Ar-H),7.37(d,J＝8.7Hz,4H,Ar-H),6.80(d,J＝12.2Hz,2H,-CH＝CH-),6.56(d,J＝12.3Hz,2H,-CH＝CH-),6.52(s,2H,Ar-H),3.31(d,J＝5.6Hz,4H,-CH2O-),1.48-1.38(m,2H,-CH-),1.25-1.02(m,48H,-CH2-),0.85–0.73(m,12H,-CH3).
The chemical reaction formula is as follows:
the liquid two-photon initiator obtained in example 1 was subjected to a performance test, and the two-photon absorption cross section of the initiator was 60GM as measured by a Z-Scan apparatus. The test results are shown in fig. 1.
The liquid two-photon initiator of example 1 was used for the processing application of the microstructures:
under the condition of keeping out of the sun, 20mg of the liquid two-photon initiator and 800mg of pentaerythritol triacrylate in the example 1 are added into a 10mL glass bottle, and the mixture is shaken for 10min and mixed uniformly to obtain the two-photon photoresist. Coating the prepared photoresist on a glass slide, and utilizing 780nm titanium gem femtosecond laser to process a micro-nano structure, wherein the femtosecond laser pulse is 100fs, and the laser frequency is 80 MHz. Different laser powers and scanning rates are adjusted to obtain a line matrix, as shown in fig. 2. Fixing a scanning rate in each row, and sequentially increasing laser power from left to right; and another line is arranged, the scanning speed is changed, and the line structure is processed. By analogy, the scanning speed is gradually increased from bottom to top, and the laser power is gradually increased from left to right. The threshold value of the initiator is measured to be low and is 4.5mW, so that a good line structure can be obtained, and the minimum line width is below 100 nm.
Example 2:
preparation of liquid two-photon initiator
The method comprises the following steps:
adding hydroquinone (1.1g, 10mmol), acid-binding agent potassium carbonate (11.06g, 80mmol) and phase transfer catalyst benzyltriethylammonium chloride (0.1g, 0.22mmol) into a reaction bottle, adding N, N-dimethylacetamide for dissolving, and dropwise adding 1-iodine-2-amyl alcohol under the protection of nitrogenNonane (9.7g, 80mmol) reacts at 25 ℃ for 5h, and after the reaction is finished, the temperature is raised to 65 ℃ for further reaction for 20 h. After the reaction is finished, a large amount of water is added for dilution, the obtained solution is extracted for three times, organic phases are combined, and the organic phases are washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying the crude product by column chromatography to obtain 2.1g of 1, 4-bis ((2-pentyl) nonanyloxy) benzene as a colorless liquid in 43% yield.1H NMR(400MHz，CDCl3)δ6.81(s，4H，Ar-H)，3.78(d，J＝5.8Hz，4H，-CH2O-)，1.79–1.73(m，2H，-CH-)，1.50–1.14(m，40H，-CH2-)，0.91–0.86(m，12H，-CH3).
Step two:
1, 4-bis ((2-pentyl) nonanyloxy) benzene (2.8g, 5mmol), paraformaldehyde (0.9g, 30mol), hydrobromic acid (30%, 10.8g, 40mol) and acetic acid (15ml) were added to a reaction flask, and the temperature was raised to 120 ℃ for reaction for 2 hours. After the reaction is finished, the temperature is reduced to room temperature, 100mL of water is slowly dropped, n-hexane is used for extraction for three times, organic phases are combined, and the organic phases are washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude column chromatography to give 1.9g of 1, 4-bis ((2-pentyl) nonanyloxy) -2, 5-dibromomethylbenzene as a colorless liquid in 56% yield.1H NMR(400MHz，CDCl3)δ6.84(s，2H，Ar-H)，4.53(s，4H，-CH2Br)，3.88(d，J＝5.4Hz，4H，-CH2O-)，1.82-1.75(m，2H，-CH-)，1.56–1.13(m，40H，-CH2-)，0.90–0.86(m，12H，-CH3).
Step three:
1, 4-bis ((2-pentyl) nonanyloxy) -2, 5-dibromomethylbenzene (1.5g, 2.2mmol) and triphenylphosphine (11.9g, 44mmol) were added to N, N-dimethylformamide and the temperature was raised to 50 ℃ under nitrogen protection and the reaction was carried outAnd the time is 30 hours. After the reaction is finished, cooling to room temperature, adding a large amount of petroleum ether, and separating out a solid from the reaction liquid. And (4) carrying out suction filtration, and adding anhydrous toluene to a filter cake for leaching. Drying under reduced pressure to obtain 2.1g of white solid phosphonium bromide salt with the yield of 79 percent.1HNMR(400MHz，CDCl3)δ7.78–7.72(m，6H，-P-Ar-H)，7.69–7.54(m，24H，-P-Ar-H)，6.62(s，2H，Ar-H)，5.37(d，J＝12.8Hz，4H，-Ar-CH2-P)，2.82(d，J＝5.7Hz，4H，-CH2O-)，1.40–1.01(m，42H，-CHCH2-)，0.97–0.81(m，12H，-CH3).
Step four:
the phosphine bromide (1.9g, 1.6mmol) and p-cyanobenzaldehyde (1.3g, 9.6mmol) were added into a reaction flask, methanol was added, potassium tert-butoxide (1.68g, 15mmol) was added under dark and oxygen-free conditions, and the temperature was raised to reflux reaction for 15 h. After the reaction was complete, the reaction was cooled to room temperature and quenched by the slow addition of 20mL of water. Extraction with dichloromethane is carried out three times, and the organic phases are combined and washed twice with water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude product column chromatography to obtain red liquid 0.39g with yield of 32%.1H NMR(400MHz，CDCl3)δ8.23(d，J＝8.8Hz，4H，Ar-H)，7.70–7.61(m，6H，Ar-H and-CH＝CH-)，7.23(d，J＝16.5Hz，2H，-CH＝CH-)，7.13(s，2H，Ar-H)，3.97(d，J＝5.5Hz，4H，-CH2O-)，1.92-1.87(m，2H，-CH-)，1.58–1.42(m，6H，-CH2-)，1.39–1.20(m，32H，-CH2-)，0.92–0.77(m，12H，-CH3).
Example 3:
preparation of liquid two-photon initiator
The method comprises the following steps:
hydroquinone (1.1g, 10mmol) and binder are added into a reaction bottleAdding potassium hydroxide (2.2g, 40mmol) as an acid agent and trioctylmethylammonium chloride (0.12g, 0.3mmol) as a phase transfer catalyst, adding N, N-dimethylformamide for dissolving, dropwise adding 1-chloro-2-hexylundecane (10.9g, 40mmol) under the protection of nitrogen, and heating to 120 ℃ for reaction for 30 hours. After the reaction is finished, a large amount of water is added for dilution, the obtained solution is extracted for three times, organic phases are combined, and the organic phases are washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude column chromatography to give 2.75g of 1, 4-bis ((2-hexyl) undecyloxy) benzene as a colorless liquid in 47% yield.1H NMR(400MHz，CDCl3)δ6.82(s，4H，Ar-H)，3.74(d，J＝5.8Hz，4H，-CH2O-)，1.75–1.71(m，2H，-CH-)，1.53–1.14(m，52H，-CH2-)，0.92–0.88(m，12H，-CH3).
Step two:
1, 4-bis ((2-hexyl) undecyloxy) benzene (5.87g, 10mmol), paraformaldehyde (1.5g, 50mol), hydrobromic acid (30%, 16.2g, 60mol) and acetic acid (20ml) were added to a reaction flask, reacted at room temperature for 2h, and then heated to 80 ℃ for 20 h. After the temperature is reduced to room temperature, 250mL of water is slowly dropped, n-hexane is used for extraction for three times, organic phases are combined, and the organic phases are washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, desolvation under reduced pressure, and purification by crude column chromatography gave 4.7g of 1, 4-bis ((2-hexyl) undecyloxy) -2, 5-dibromomethylbenzene as a colorless liquid in 61% yield.1H NMR(400MHz，CDCl3)δ6.89(s，2H，Ar-H)，4.56(s，4H，-CH2Br)，3.87(d，J＝5.4Hz，4H，-CH2O-)，1.88-1.79(m，2H，-CH-)，1.61–1.23(m，52H，-CH2-)，0.94–0.85(m，12H，-CH3).
Step three:
1，4-bis ((2-hexyl) undecyloxy) -2, 5-dibromomethylbenzene (3.9g, 5mmol) and triphenylphosphine (3.9g, 15mmol) were added to N, N-dimethylacetamide and allowed to warm to 130 ℃ under nitrogen for 2 h. After the reaction is finished, cooling to room temperature, adding a large amount of petroleum ether to separate out a solid, performing suction filtration, and adding anhydrous toluene to a filter cake for leaching. Drying under reduced pressure to obtain 3g of white solid phosphonium bromide salt with the yield of 47 percent.1H NMR(400MHz，CDCl3)δ7.73–7.64(m，6H，-P-Ar-H)，7.61–7.52(m，24H，-P-Ar-H)，6.60(s，2H，Ar-H)，5.33(d，J＝12.8Hz，4H，-Ar-CH2-P)，2.85(d，J＝5.7Hz，4H，-CH2O-)，1.47–1.02(m，54H，-CHCH2-)，0.94–0.81(m，12H，-CH3).
Step four:
the phosphine bromide salt (2.2g, 2mmol) and p-dimethylamino cinnamaldehyde (0.7g, 4mmol) are added into a reaction bottle, anhydrous tetrahydrofuran is added, potassium tert-butoxide (1.68g, 15mmol) is added under the dark and oxygen-free environment, and the reaction is carried out for 15h at room temperature. After the reaction is finished, 20mL of water is slowly added for quenching. Extraction with dichloromethane is carried out three times, and the organic phases are combined and washed twice with water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude product column chromatography to obtain red liquid 0.65g with yield of 35%.1H NMR(400MHz，CDCl3)δ7.35(d，J＝8.4Hz，4H，Ar-H)，7.02–6.66(m，12H，Ar-H and-CH＝CH-)，6.60(d，J＝15.3Hz，2H，-CH＝CH-)，3.88(d，J＝5.5Hz，4H，-CH2O-)，2.98(s，12H，-N(CH3)2)，1.90-1.81(m，2H，-CH-)，1.56–1.23(m，52H，-CH2-)，0.93–0.83(m，12H，-CH3).
The liquid two-photon initiator of example 3 was used for the processing application of the microstructures:
under the condition of keeping out of the sun, 20mg of the liquid two-photon initiator and 800mg of pentaerythritol triacrylate in the example 3 are added into a 10mL glass bottle, and the mixture is shaken for 10min and mixed uniformly to obtain the two-photon photoresist. And dropping the prepared photoresist on a glass slide, and processing the micro-nano structure by using a 780nm titanium gemstone femtosecond laser 3D printer, wherein the femtosecond laser pulse is 100fs, and the laser frequency is 80 MHz. A 3D pattern with smooth edges is obtained as shown in fig. 3.
Example 4:
preparation of liquid two-photon initiator
The method comprises the following steps:
adding hydroquinone (1.1g, 10mmol), acid-binding agent potassium hydroxide (3.4g, 60mmol) and phase transfer catalyst tetrabutylammonium bromide (0.2g, 0.26mmol) into a reaction bottle, adding N, N-dimethylformamide for dissolving, dropwise adding 1-bromo-2-octyldodecane (7.2g, 20mmol) under the protection of nitrogen, and heating to 85 ℃ for reaction for 15 hours. After the reaction is finished, a large amount of water is added for dilution, the obtained solution is extracted for three times, organic phases are combined, and the organic phases are washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by column chromatography to obtain 3.2g of 1, 4-bis ((2-octyl) dodecyloxy) benzene as a colorless liquid in 49% yield.1H NMR(400MHz，CDCl3)δ6.85(s，4H，Ar-H)，3.73(d，J＝5.8Hz，4H，-CH2O-)，1.76–1.71(m，2H，-CH-)，1.57–1.10(m，64H，-CH2-)，0.90–0.86(m，12H，-CH3).
Step two:
1, 4-di ((2-octyl) dodecyloxy) benzene (6.7g, 10mmol), paraformaldehyde (1.5g, 50mmol), hydrobromic acid (30%, 21.6g, 80mmol) and acetic acid (25mL) are added into a reaction bottle, then the temperature is increased to 80 ℃ for reaction for 30h, after the temperature is reduced to room temperature, 250mL of water is slowly dropped, n-hexane is extracted for three times, organic phases are combined and washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, vacuum desolventizing, and purifying by column chromatographyThus, 5.8g of 1, 4-bis ((2-octyl) dodecyloxy) -2, 5-dibromomethylbenzene was obtained as a colorless liquid in a yield of 68%.1H NMR(400MHz，CDCl3)δ6.89(s，2H，Ar-H)，4.53(s，4H，-CH2Br)，3.89(d，J＝5.4Hz，4H，-CH2O-)，1.89-1.76(m，2H，-CH-)，1.67–1.24(m，64H，-CH2-)，0.93–0.85(m，12H，-CH3).
Step three:
1, 4-bis ((2-octyl) dodecyloxy) -2, 5-dibromomethylbenzene (1.7g, 2mmol) and triphenylphosphine (4.3g, 16mmol) were added to anhydrous toluene and the temperature was raised to 110v under nitrogen for 20 h. After the reaction is finished, suction filtration is carried out, and anhydrous toluene is added into a filter cake for leaching. Drying under reduced pressure to obtain 2.2g of white solid phosphonium bromide salt with the yield of 79 percent.1H NMR(400MHz，CDCl3)δ7.82–7.76(m，6H，-P-Ar-H)，7.69–7.53(m，24H，-P-Ar-H)，6.68(s，2H，Ar-H)，5.43(d，J＝12.8Hz，4H，-Ar-CH2-P)，2.86(d，J＝5.7Hz，4H，-CH2O-)，1.46–1.01(m，66H，-CHCH2-)，0.95–0.81(m，12H，-CH3).
Step four:
the phosphine bromide salt (2.1g, 1.5mmol) and p-methoxybenzaldehyde (0.82g, 6mmol) are added into a reaction bottle, anhydrous tetrahydrofuran is added, NaH (60%, 0.4g, 10mmol) is added under the dark and oxygen-free environment, and the reaction is carried out for 18h under the ice-water bath. After the reaction is finished, 20mL of water is slowly added for quenching. The resulting solution was extracted three times, the organic phases were combined and washed twice with water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude product column chromatography to obtain red liquid 0.6g with yield of 43%.1H NMR(400MHz，CDCl3)δ7.51(d，J＝8.8Hz，4H，Ar-H)，7.38(d，J＝12.2Hz，2H，-CH＝CH-)，7.12(s，2H，Ar-H)，7.08(d，J＝12.3Hz，2H，-CH＝CH-)，6.92(d，J＝8.7Hz，4H，Ar-H)，3.94(s，6H，O-CH3)，3.26(d，J＝5.6Hz，4H，-CH2O-)，1.38-1.31(m，2H，-CH-)，1.22-1.02(m，64H，-CH2-)，0.82–0.71(m，12H，-CH3).
Example 5:
preparation of liquid two-photon initiator
The method comprises the following steps:
adding hydroquinone (1.1g, 10mmol), acid-binding agent sodium hydroxide (2g, 50mmol) and phase transfer catalyst tetrabutylammonium bromide (0.2g, 0.26mmol) into a reaction bottle, adding N, N-dimethylformamide for dissolving, dropwise adding 1-bromo-2-heptyldodecane (17.4g, 50mmol) under the protection of nitrogen, and heating to 90 ℃ for reaction for 15 hours. After the reaction is finished, a large amount of water is added for dilution, the obtained solution is extracted for three times, organic phases are combined, and the organic phases are washed twice by water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying the crude product by column chromatography to obtain 3.7g of 1, 4-bis ((2-heptyl) dodecyloxy) benzene as a colorless liquid in 58% yield.1H NMR(400MHz，CDCl3)δ6.86(s，4H，Ar-H)，3.72(d，J＝5.8Hz，4H，-CH2O-)，1.75–1.71(m，2H，-CH-)，1.56–1.10(m，60H，-CH2-)，0.90–0.86(m，12H，-CH3).
Step two:
a reaction flask was charged with 1, 4-bis ((2-heptyl) dodecyloxy) benzene (6.4g, 10mmol), paraformaldehyde (1.2g, 40mmol), hydrobromic acid (30%, 21.6g, 80mmol) and acetic acid (25ml), and then heated to 80 ℃ for reaction for 30h. After the temperature is reduced to the room temperature, 250mL of water is slowly dropped, n-hexane is used for extraction for three times, organic phases are combined, and water washing is carried out twice. Organic additionAdding anhydrous Na2SO4Drying, desolventizing under reduced pressure, and purifying by crude column chromatography to obtain 5g of 1, 4-bis ((2-heptyl) dodecyloxy) -2, 5-dibromomethylbenzene as a colorless liquid, with a yield of 61%.1H NMR(400MHz，CDCl3)δ6.83(s，2H，Ar-H)，4.55(s，4H，-CH2Br)，3.86(d，J＝5.4Hz，4H，-CH2O-)，1.86-1.75(m，2H，-CH-)，1.64–1.24(m，60H，-CH2-)，0.94–0.85(m，12H，-CH3).
Step three:
1, 4-bis ((2-heptyl) dodecyloxy) -2, 5-dibromomethylbenzene (1.65g, 2mmol) and triphenylphosphine (3.2g, 12mmol) were added to anhydrous toluene and the mixture was heated to 100 ℃ under nitrogen for 20 h. After the reaction is finished, carrying out suction filtration, and adding anhydrous toluene to a filter cake for leaching. Drying under reduced pressure to obtain 1.8g of white solid phosphonium bromide salt with the yield of 68 percent.1H NMR(400MHz，CDCl3)δ7.81–7.77(m，6H，-P-Ar-H)，7.66–7.53(m，24H，-P-Ar-H)，6.65(s，2H，Ar-H)，5.44(d，J＝12.8Hz，4H，-Ar-CH2-P)，2.87(d，J＝5.7Hz，4H，-CH2O-)，1.45–1.01(m，62H，-CHCH2-)，0.98–0.81(m，12H，-CH3).
Step four:
the phosphine bromide salt (2g, 1.5mmol) and the p-methylthiobenzaldehyde (0.61g, 4mmol) are added into a reaction bottle, anhydrous tetrahydrofuran is added, NaH (60%, 0.36g, 9mmol) is added under the dark and oxygen-free environment, and the reaction is carried out for 18h at room temperature. After the reaction is finished, 20mL of water is slowly added for quenching. The resulting solution was extracted three times, the organic phases were combined and washed twice with water. Adding anhydrous Na into the organic phase2SO4Drying, desolventizing under reduced pressure, and purifying by crude product column chromatography to obtain red liquid 0.55g with yield of 39%.1H NMR(400MHz，CDCl3)δ7.48(d，J＝8.8Hz，4H，Ar-H)，7.42(d，J＝12.2Hz，2H，-CH＝CH-)，7.19(d，J＝8.7Hz，4H，Ar-H)，7.10(s，2H，Ar-H)，6.97(d，J＝12.3Hz，2H，-CH＝CH-)，3.26(d，J＝5.6Hz，4H，-CH2O-)，2.47(s，6H，S-CH3)，1.37-1.31(m，2H，-CH-)，1.18-1.02(m，60H，-CH2-)，0.82–0.72(m，12H，-CH3).
Therefore, the liquid two-photon initiator prepared by the invention has good stability and solubility, greatly reduces the polymerization threshold value by mixing with the monomer, has good stability and two-photon polymerization activity, and has high scanning rate and good microstructure precision in two-photon polymerization processing. The preparation method is simple and convenient, the purification is simple, the required time is short, and the purity of the obtained product is high.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method of preparing a liquid two-photon initiator comprising the steps of:
step one, dispersing hydroquinone in a solvent under the action of an acid binding agent and a phase transfer catalyst, dropwise adding a compound A under the protection of inert gas, and reacting for 2-30 hours at 25-120 ℃; cooling to room temperature after the reaction is finished, adding water for dilution, adding an organic phase for extraction, washing the organic phase with water, and adding anhydrous Na2SO4Drying, desolventizing under reduced pressure to obtain a crude product, and purifying by column chromatography; the compound A is halogenated alkane with long chain branch, ClCH2CH(CmH2m+1)CnH2n+1Or BrCH2CH(CmH2m+1)CnH2n+1Or ICH2CH(CmH2m+1) CnH2n+1Wherein m + n = any one of 7-30, and m and n are non-zero natural numbers;
step two: adding paraformaldehyde and hydrobromic acid into the product obtained in the step one, dissolving in a solvent, heating to 25-120 ℃, reacting for 2-30 hours, cooling to room temperature after the reaction is finished, slowly dripping water, extracting the obtained solution, washing an organic phase with water, and adding anhydrous Na2SO4Drying, desolventizing under reduced pressure, and purifying a crude product by column chromatography to obtain a colorless liquid;
step three: adding triphenylphosphine into the product obtained in the second step, dissolving the product in a solvent, heating to 25-130 ℃ under the protection of inert gas, reacting for 2-30 hours, performing suction filtration after the reaction is finished, adding the solvent into a filter cake, leaching, and drying under reduced pressure;
step four: dissolving the product obtained in the third step and a compound B in a solvent, adding strong base under the conditions of light protection, oxygen free and inert gas, reacting for 2-30h at the temperature of 0-130 ℃, slowly adding water for quenching after the reaction is finished, adding an organic phase for extraction, washing the organic phase with water, and adding anhydrous Na2SO4Drying, desolventizing under reduced pressure, and purifying a crude product by column chromatography to obtain a liquid two-photon initiator which is red liquid; the compound B is 4-substituent-phenyl (alkenyl)0~1Formaldehyde, the substituent in compound B being-NO2，-CN，-OCnH2n+1，-SCnH2n+1，
N is a natural number of 1 to 10.
2. The method of claim 1 for preparing a liquid two-photon initiator, wherein: the molar ratio of the hydroquinone to the compound A in the first step is 1: 2-1: 8.
3. The method of claim 1 for preparing a liquid two-photon initiator, wherein: the molar ratio of the product of the step one in the step two, the paraformaldehyde and the hydrobromic acid is 1:4: 4-1: 6: 8.
4. The method of claim 1 for preparing a liquid two-photon initiator, wherein: the molar ratio of the product of the second step to the triphenylphosphine in the third step is 1: 3-1: 20.
5. The method of claim 1 for preparing a liquid two-photon initiator, wherein: the molar ratio of the product obtained in the third step to the compound B in the fourth step is 1: 2-1: 6.
6. A process for the preparation of a liquid two-photon initiator according to any one of claims 1 to 5, wherein: the solvent respectively comprises any one or more than two of the following components: methanol, ethanol, dichloromethane, chloroform, toluene, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and acetic acid.
7. The method of claim 1 for preparing a liquid two-photon initiator, wherein: the phase transfer catalyst in the first step comprises any one or two of the following mixtures: benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride.
8. The method of claim 1 for preparing a liquid two-photon initiator, wherein: and the third step and the fourth step are both reacted in an anhydrous environment.
9. The application of the liquid two-photon initiator prepared by the preparation method of any one of claims 1 to 8 in the fields of photocuring, photoresist and micro-nano manufacturing and processing.
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