CN108929392B - A kind of silicon substrate two-photon initiator and preparation method thereof - Google Patents
A kind of silicon substrate two-photon initiator and preparation method thereof Download PDFInfo
- Publication number
- CN108929392B CN108929392B CN201810833336.4A CN201810833336A CN108929392B CN 108929392 B CN108929392 B CN 108929392B CN 201810833336 A CN201810833336 A CN 201810833336A CN 108929392 B CN108929392 B CN 108929392B
- Authority
- CN
- China
- Prior art keywords
- silicon substrate
- reaction
- photon
- compound
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003999 initiator Substances 0.000 title claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 47
- 239000010703 silicon Substances 0.000 title claims abstract description 47
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 18
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 14
- 229940126062 Compound A Drugs 0.000 claims abstract description 10
- 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 abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 4
- 239000012530 fluid Substances 0.000 claims 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 2
- FNWQKSHFBHPPGU-UHFFFAOYSA-N [Si].ClC=C Chemical compound [Si].ClC=C FNWQKSHFBHPPGU-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- -1 acyloxy phosphine oxides Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- PECAOKZHORDWAI-UHFFFAOYSA-N 3,6-diiodo-9h-carbazole Chemical compound C1=C(I)C=C2C3=CC(I)=CC=C3NC2=C1 PECAOKZHORDWAI-UHFFFAOYSA-N 0.000 description 1
- IYXVSRXFGYDNEV-UHFFFAOYSA-N 3-phenylprop-2-ynenitrile Chemical group N#CC#CC1=CC=CC=C1 IYXVSRXFGYDNEV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- LKFAPHHHWRMPGC-UHFFFAOYSA-N butan-1-ol prop-2-enoic acid Chemical compound CCCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C LKFAPHHHWRMPGC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FHQRQPAFALORSL-UHFFFAOYSA-N dimethylsilyl(trimethyl)silane Chemical compound C[SiH](C)[Si](C)(C)C FHQRQPAFALORSL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The present invention relates to a kind of silicon substrate two-photon initiators and preparation method thereof, belong to technical field of chemical synthesis, preparation method is as follows, reaction 1: by compound A and compound B disperse in the presence of a catalyst in a solvent, in be protected from light and inert gas environment under 20-150 DEG C reaction 2-30 hours, then purification obtains compound C, compound A is 3,6- dihalo carbazole, 2,7- dihalo carbazole, 2, any one in 6- dihalo carbazole, compound B are 4- substitution -1- phenylacetylene；Reaction 2: dispersed in a solvent in the presence of acid binding agent by the compound C and compound D, in -20-100 DEG C reaction 1-10 hours, then purification obtains silicon substrate two-photon initiator, compound D is one silicon hexachloride of tri-methyl-chlorosilane or pentamethyl, silicon substrate two-photon initiator prepared by the present invention, preparation step is few, purification is simple, purity is greater than 95%, and can cause two-photon polymerized reaction under 500-1200nm wavelength laser, and polymerization efficiency is high.
Description
Technical field
The present invention relates to a kind of silicon substrate two-photon initiators and preparation method thereof, belong to technical field of chemical synthesis.
Background technique
It is two-photon polymerized with spatial resolution is high, controllability is good, femtosecond laser compared with traditional UV single photon photopolymerization
Penetrability waits by force remarkable advantages.The technology adds in the storage of high density optical information, micro-nano optical device and microfluidic device
Work, biological support the high-end fields such as construct and are used widely.
Two-photon initiator (2PI) is the important component of two-photon polymerized system, it is related to formula system and is swashing
Can oligomer and reactive diluent be changed into solid-state by liquid rapidly when light irradiates.The basic characteristics of its action principle are as follows: draw
It sends out agent molecule and absorbs two photons under the laser of nearly twice sample linear absorption wavelength, to complete electronics from ground state to swashing
It sends out the transition of state and generates reactive species, finally cause the polymerization reaction of monomer or oligomer.The two-photon initiator of high activity is
It improves photoetching speed and obtains the key of high-resolution three-dimension stereochemical structure.Many researchs pass through electronics of the building containing long conjugated chain
Donor/electronic acceptor systems increase two photon absorption cross section, and efficiency of initiation is significantly improved.
Other than big two photon absorption cross section, similar to traditional Norrish I type photoinitiator, the energy under irradiation
It is also vital for enough generating the 2PI of living radical by photo-cleavage processing efficient.Currently, photo-cleavage can occur
Photoinitiator is mainly carbonyls.The UV photoinitiator of several commercializations, such as Irgacure 369, Lucirin TPO-
L18, Irgacure 819 and some modification acyloxy phosphine oxides with " push-and-pull " structure have been applied to two-photon polymerized
(2PP).But since conjugate length is short, the two photon absorption cross section of these compounds is smaller (being less than 40G), needs longer exposure
Time and biggish laser power, are easy to destroy micro-nano structure.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of silicon substrate two-photon initiator and preparation method thereof, the present invention
Initiator molecule centered on carbazole, by 2,3,6,7 of carbazole it is upper extend conjugation chain lengths, increase the suction of its two-photon
Section is received, in 9 upper bonded silane groups that photo-cleavage occurs and generates living radical, prepares a series of silicon substrate two-photons
Initiator.Initiator preparation route of the present invention is short, purity is greater than 95%, and can cause double light under 500-1200nm wavelength laser
Sub- polymerization reaction, polymerization efficiency is high, and the micro-structure precision for being carried out two-photon polymerized reacting processing is preferable.
A kind of silicon substrate two-photon initiator proposed by the present invention, chemical structure are as follows:
Wherein, R1IncludingR2Respectively include-H ,-NO2、·-CN、·-O-CnH2n+1、·-
CnH2n+1,In any one.
The invention proposes a kind of preparation methods of silicon substrate two-photon initiator, comprising the following steps:
Reaction 1: dispersed in the presence of a catalyst in a solvent by compound A and compound B, in being protected from light and inert gas ring
20-150 DEG C reaction 2-30 hours under border, then purification obtains compound C, and compound A is 3,6- dihalo carbazole, 2,7- dihalo-
For any one in carbazole, 2,6- dihalo carbazole, compound B is 4- substitution -1- phenylacetylene；
Reaction 2: dispersed in a solvent in the presence of acid binding agent by the compound C and compound D, in -20-100 DEG C
Reaction 1-10 hours, then purification obtains silicon substrate two-photon initiator, and compound D is one chlorine of tri-methyl-chlorosilane or pentamethyl
Disilane.
Further, in reaction 1, the molar ratio of the compound A and compound B are 1:2~1:6.
Further, in reaction 1, the molar ratio of the compound A and compound B are 1:2~1:3.
Further, the compound A includes In any one, wherein R3=Cl, Br or I.
Further, the structural formula of the compound B is as follows:
R2Including-H ,-NO2、·-CN、·-O-CnH2n+1、·-CnH2n+1,In any one.
Further, the structural formula of the compound C is as follows:
Wherein, R2Including-H ,-NO2、·-CN、·-O-CnH2n+1、·-CnH2n+1,In
Any one.
Further, catalyst includes any of the following or two or more mixing in the reaction 1: cuprous iodide, double
Triphenylphosphine palladium, bi triphenyl phosphine dichloride nickel.
Further, solvent includes any of the following or two or more mixing in the reaction 1: methylene chloride, chloroform,
Methanol, ethyl alcohol, toluene, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, triethylamine.
Further, the preparation method of the compound C is specific as follows:
By the catalysis of the compound B and 0.01~0.1 molar ratio of the compound A of 1 molfraction and 2~3 times of molar ratios
Agent is dissolved in solvent, inert gas and under the conditions of be protected from light in 20-150 DEG C reaction 2-30 hours, then remove solvent, silicagel column
Chromatography purity, vacuum drying, obtains compound C.
Further, the molar ratio of the compound C and compound D is 1:1~1:6.
Further, the molar ratio of the compound C and compound D is 1:1~1:3.
Further, the structural formula of the compound D is
Further, acid binding agent includes any of the following or two or more mixing in the reaction 2: triethylamine, carbon
Sour sodium, potassium carbonate, sodium hydroxide, sodium hydride.
Further, solvent includes any of the following or two or more mixing in the reaction 2: methylene chloride, chloroform,
Methanol, ethyl alcohol, toluene, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide.
Further, reaction 2 carries out in anhydrous conditions.
Further, the preparation method of the silicon substrate two-photon initiator is specific as follows:
The compound D of the compound C of 1 molfraction and 1~3 times of molfraction are dissolved in solvent, in 1~4 molar ratio
Acid binding agent existence condition under in -20-100 DEG C reaction 1-10 hours, then remove solvent, silica gel column chromatography purification, vacuum is dry
It is dry, obtain silicon substrate two-photon initiator silicon substrate two-photon initiator.
The invention proposes silicon substrate two-photon initiators to construct field, micro-nano technology field or three-dimensional light storage in biological support
Deposit the application in field.
According to the above aspect of the present invention, the present invention has at least the following advantages: initiator molecule of the invention is led to centered on carbazole
2,3,6,7 upper extend crossed in carbazole are conjugated chain length, in 9 upper bonded silane groups, prepare a series of silicon substrate two-photons
Initiator.Initiator preparation step of the present invention is few, purification is simple, purity is greater than 95%, and under 500-1200nm wavelength laser
Two-photon polymerized reaction can be caused, the micro-structure precision for being carried out two-photon polymerized reacting processing is preferable, the micro-structure of processing
Line width is less than 300nm.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of product in the embodiment of the present invention 1；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of product in the embodiment of the present invention 2；
Fig. 3 for institute's molded micro structure in the embodiment of the present invention 3 scanning electron microscope (SEM) photograph.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1:
The preparation of compound C:
3,6- diiodocarbazol (419mg, 1.0mmol) is added in the single port brown flask of 50mL, to cyano phenylacetylene
(300mg, 2.36mmol), cuprous iodide (42mg, 0.2mmol) and bis- (triphenylphosphine) palladium chlorides (45mg, 0.1mmol),
It is dispersed in 20mL tetrahydrofuran/triethylamine=1:1 in the mixed solvent, is protected from light, lower 60 DEG C of nitrogen protection are stirred to react 6h, and solution is in
Brown is purified after removing solvent using silica gel column chromatography, 40 DEG C of drying in vacuum oven.210mg brown solid is obtained, is produced
Rate 50.4%, purity (being calculated according to nucleus magnetic hydrogen spectrum) are greater than 95%.1H NMR(400MHz,DMSO-d6)δ11.64(s,1H),
8.49 (d, J=8.3Hz, 2H), 7.63 (dd, J=8.6,8.2Hz, 4H), 7.39 (d, J=8.4Hz, 4H), and 6.78 (d, J
=8.3Hz, 4H) the obtained nucleus magnetic hydrogen spectrum figure of product of is as shown in Figure 1.
Chemical equation:
Embodiment 2:
The preparation of silicon substrate two-photon initiator:
Product (50mg, 0.12mmol), trimethylsilyl chloride in embodiment 1 are added in 50mL dry single port brown flask
Silane (54mg, 0.50mmol) and sodium hydride (20mg, 0.83mmol), add 20mL anhydrous tetrahydro furan, ice bath and nitrogen
Protection is lower to stir 4h, after removing solvent, is purified using silica gel column chromatography, 40 DEG C of drying in vacuum oven.Obtain 35.6mg Huang
Color solid, yield 60.6%, purity (being calculated according to nucleus magnetic hydrogen spectrum) are greater than 95%.1H NMR(400MHz,DMSO-d6)δ8.33
(d, J=8.3Hz, 2H), 7.67 (dd, J=8.3,8.6Hz, 4H), 7.41 (d, J=8.2Hz, 4H), 7.23 (d, J=8.4Hz,
4H),and 0.81(s,9H).
The nucleus magnetic hydrogen spectrum figure of obtained product is as shown in Figure 2.
Chemical equation:
Performance measurement is carried out to the silicon substrate two-photon initiator that embodiment 2 obtains, is tested and calculated by aperture Z-scan
The initiator two photon absorption cross section is 230GM.Good two-photon polymerized active (threshold is shown in two-photon molding test
Value is only 5mW) and processing efficiency (60 μm/s).
Embodiment 3
Under the conditions of being protected from light, the resulting initiator of 2mg embodiment 2,340mg tri- are added in the glass container equipped with stirrer
Hydroxymethyl-propane triacrylate and 350mg ethoxylated trimethylolpropane triacrylate, stirring oscillation make embodiment for 24 hours
2 resulting initiator dissolutions completely, can be obtained double-photon optical photoresist, be applied on glass slide, in the femtosecond of 800nm wavelength
Laser, the femtosecond laser of 80fs pulse, 60 μm/s print speed under processing micro structure, processed structure be Y type matrix, obtain
The preferable micro-structure of precision (most narrow linewidth is about 230nm, most wide to be no more than 300nm), such as Fig. 3.The microstructure in manuscript 3
When, laser spot focuses in resin, fixes an energy, processes a row (6) Y structure, then improve laser energy, sets up another one
Row processes Y structure, and so on, from the bottom to top, energy gradually rises, and the threshold value for measuring initiator (is part Y structure in Fig. 3
Scanning electron microscope (SEM) photograph, energy is 5-9mW from the bottom to top).It was found that the threshold value of silicon substrate two-photon initiator of the invention is lower, threshold value is
5mW。
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (26)
1. a kind of silicon substrate two-photon initiator, it is characterised in that: its chemical structural formula is as follows:
R1IncludingR2Including-H ,-NO2、·-CN、·-O-CnH2n+1、·-CnH2n+1,In any one.
2. the preparation method of silicon substrate two-photon initiator described in claim 1, it is characterised in that: the following steps are included:
Reaction 1: by compound A and compound B disperse in the presence of a catalyst in a solvent, in be protected from light and inert gas environment under
20-150 DEG C reaction 2-30 hours, then purification obtains compound C, and compound A is 3,6- dihalo carbazole, 2,7- dihalo click
Any one in azoles, 2,6- dihalo carbazole, compound B are 4- substitution -1- phenylacetylene, in compound B substituent group include -
H、·-NO2、·-CN、·-O-CnH2n+1、·-CnH2n+1,In any one；
Reaction 2: disperse in a solvent, to react in -20-100 DEG C in the presence of acid binding agent by the compound C and compound D
1-10 hours, then purification obtained silicon substrate two-photon initiator, and compound D is one chloroethene silicon of tri-methyl-chlorosilane or pentamethyl
Alkane.
3. the preparation method of silicon substrate two-photon initiator according to claim 2, it is characterised in that: in reaction 1, describedization
The molar ratio for closing object A and compound B is 1:2~1:6.
4. the preparation method of silicon substrate two-photon initiator according to claim 2, it is characterised in that: in reaction 1, catalyst
It includes any of the following or two or more mixing: cuprous iodide, bis-triphenylphosphipalladium palladium dichloride, bi triphenyl phosphine dichloride
Nickel.
5. the preparation method of silicon substrate two-photon initiator according to claim 3, it is characterised in that: in reaction 1, catalyst
It includes any of the following or two or more mixing: cuprous iodide, bis-triphenylphosphipalladium palladium dichloride, bi triphenyl phosphine dichloride
Nickel.
6. the preparation method of silicon substrate two-photon initiator according to claim 2, it is characterised in that: reaction 1 and reaction 2
In, solvent respectively includes following any one or two or more mixing: methylene chloride, chloroform, methanol, ethyl alcohol, toluene, tetrahydro furan
It mutters, N,N-dimethylformamide, dimethyl sulfoxide.
7. the preparation method of silicon substrate two-photon initiator according to claim 3, it is characterised in that: reaction 1 and reaction 2
In, solvent respectively includes following any one or two or more mixing: methylene chloride, chloroform, methanol, ethyl alcohol, toluene, tetrahydro furan
It mutters, N,N-dimethylformamide, dimethyl sulfoxide.
8. the preparation method of silicon substrate two-photon initiator according to claim 4, it is characterised in that: reaction 1 and reaction 2
In, solvent respectively includes following any one or two or more mixing: methylene chloride, chloroform, methanol, ethyl alcohol, toluene, tetrahydro furan
It mutters, N,N-dimethylformamide, dimethyl sulfoxide.
9. the preparation method of silicon substrate two-photon initiator according to claim 5, it is characterised in that: reaction 1 and reaction 2
In, solvent respectively includes following any one or two or more mixing: methylene chloride, chloroform, methanol, ethyl alcohol, toluene, tetrahydro furan
It mutters, N,N-dimethylformamide, dimethyl sulfoxide.
10. according to the preparation method of the described in any item silicon substrate two-photon initiators of claim 2-9, it is characterised in that: reaction 2
In, the molar ratio of the compound C and compound D are 1:1~1:6.
11. according to the preparation method of the described in any item silicon substrate two-photon initiators of claim 2-9, it is characterised in that: reaction 2
In, acid binding agent includes any of the following or two or more mixing: triethylamine, sodium carbonate, potassium carbonate, sodium hydroxide, hydrogenation
Sodium.
12. the preparation method of silicon substrate two-photon initiator according to claim 10, it is characterised in that: in reaction 2, tie up acid
Agent includes any of the following or two or more mixing: triethylamine, sodium carbonate, potassium carbonate, sodium hydroxide, sodium hydride.
13. according to the preparation method of the described in any item silicon substrate two-photon initiators of claim 2-9, it is characterised in that: reaction 2
It carries out in anhydrous conditions.
14. the preparation method of silicon substrate two-photon initiator according to claim 10, it is characterised in that: reaction 2 is anhydrous
Under the conditions of carry out.
15. the preparation method of silicon substrate two-photon initiator according to claim 11, it is characterised in that: reaction 2 is anhydrous
Under the conditions of carry out.
16. the preparation method of silicon substrate two-photon initiator according to claim 12, it is characterised in that: reaction 2 is anhydrous
Under the conditions of carry out.
17. the silicon substrate two-photon initiator that any one of claim 2-9 the method is prepared.
18. the silicon substrate two-photon initiator that claim 10 the method is prepared.
19. the silicon substrate two-photon initiator that claim 11 the method is prepared.
20. the silicon substrate two-photon initiator that claim 12 the method is prepared.
21. the silicon substrate two-photon initiator that claim 13 the method is prepared.
22. the silicon substrate two-photon initiator that any one of claim 14-16 the method is prepared.
23. silicon substrate two-photon initiator described in claim 1 is in the storage of high density optical information, micro-nano optical device and miniflow
Body device fabrication, biological support construct the application in field.
24. silicon substrate two-photon initiator described in claim 17 is stored in high density optical information, micro-nano optical device and micro-
The application in field is constructed in fluid device processing, biological support.
25. the described in any item silicon substrate two-photon initiators of claim 18-21 are in the storage of high density optical information, micro-nano optics
Device and microfluidic device processing, biological support construct the application in field.
26. silicon substrate two-photon initiator described in claim 22 is stored in high density optical information, micro-nano optical device and micro-
The application in field is constructed in fluid device processing, biological support.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810341500X | 2018-04-17 | ||
| CN201810341500 | 2018-04-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108929392A CN108929392A (en) | 2018-12-04 |
| CN108929392B true CN108929392B (en) | 2019-09-03 |
Family
ID=64444512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810833336.4A Active CN108929392B (en) | 2018-04-17 | 2018-07-26 | A kind of silicon substrate two-photon initiator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108929392B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684134B (en) * | 2019-10-28 | 2021-09-21 | 中国工程物理研究院激光聚变研究中心 | Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof |
| CN114415471B (en) * | 2022-03-01 | 2022-09-02 | 之江实验室 | Siloxane-based two-photon photoresist and preparation method, use method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10304819A1 (en) * | 2003-02-06 | 2004-08-19 | Covion Organic Semiconductors Gmbh | Carbazole-containing conjugated polymers and blends, their preparation and use |
| KR20180014982A (en) * | 2016-08-02 | 2018-02-12 | 동우 화인켐 주식회사 | Carbazole Derivatives and Photocurable Composition Comprising the Same |
| CN108299574B (en) * | 2018-03-13 | 2020-08-25 | 中国科学院理化技术研究所 | Water-soluble two-photon initiator and preparation and application thereof |
-
2018
- 2018-07-26 CN CN201810833336.4A patent/CN108929392B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108929392A (en) | 2018-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lalevée et al. | N-Vinylcarbazole: an additive for free radical promoted cationic polymerization upon visible light | |
| CN108929392B (en) | A kind of silicon substrate two-photon initiator and preparation method thereof | |
| JP5645165B2 (en) | Polymerization initiator for living radical polymerization | |
| CN1228359C (en) | High molecular polymer of chemical amplification type light resistance agent compsn. | |
| Corakci et al. | Long wavelength photosensitizers in photoinitiated cationic polymerization: The effect of quinoxaline derivatives on photopolymerization | |
| Erdur et al. | Poly (phenylenevinylene) s as sensitizers for visible light induced cationic polymerization | |
| CN104829771B (en) | A kind of side chain contains polymer of ring-type azobenzene binaphthyl structure and its production and use | |
| Qiu et al. | Polyarylcyanation of diyne: A one-pot three-component convenient route for in situ generation of polymers with AIE characteristics | |
| JP2016538400A (en) | Polymer containing carboxyl group, production method and use thereof, supported metal catalyst and method for producing penem antibiotic intermediate | |
| CN108586299A (en) | A kind of Preparation method and use for the fragrant disulfide causing, polymerize and reduce volume contraction | |
| Mugemana et al. | Functionalized nanoporous thin films from metallo-supramolecular diblock copolymers | |
| CN1462909A (en) | Chemical amplification light resistance agent compsn. | |
| JP2010209340A (en) | Method for producing multi-branched polymer | |
| CN107129451A (en) | Novel belt cyano group diphenylethyllene sulfosalt preparation method and applications | |
| EP1734074A1 (en) | Photofunctional optical material comprising fluorinated acrylate polymer | |
| CN102127195B (en) | Photosensitive luminescent polymer and preparation method thereof | |
| CN107459505B (en) | Fluorescent functional carbonate, preparation method and application thereof, and fluorescent polycarbonate prepared from fluorescent functional carbonate | |
| CN114621159B (en) | Diazosulfide-based fluorescent material, fluorescent polymer, fluorescent nanoparticles, and preparation method and application thereof | |
| Kawa et al. | Improved antenna effect of terbium (III)-cored dendrimer complex and green-luminescent hydrogel by radical copolymerization | |
| JP2008212765A (en) | Transition metal-immobilized reactor and its manufacturing method | |
| CN116670589A (en) | Resin, resin composition, and display device using same | |
| CN109134726B (en) | Phthalocyanine dye high-molecular method | |
| CN103665053B (en) | A kind of diallyl three carbon ester ferrocene monomer and preparation method thereof | |
| Ye et al. | Alkali-promoted tandem polymerization of nucleophilic acetylide monomers and aldehydes toward luminescent polymeric materials | |
| CN106084092A (en) | A kind of carbazyl two-photon initiator and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200805 Address after: No.14, Zhujin pedestrian street, Luojia group, Mazhang village, Xinhua Road sub district office, Yanliang District, Xi'an City, Shaanxi Province Patentee after: Xi'an Jiangda micro nano material technology Co., Ltd Address before: 1800 No. 214000 Jiangsu city of Wuxi Province Li Lake Avenue Patentee before: Jiangnan University |
|
| TR01 | Transfer of patent right |