CN101348537B - Triphenyl amine-naphthalin multi-branched molecule having two-photon polymerization initiation characteristic - Google Patents
Triphenyl amine-naphthalin multi-branched molecule having two-photon polymerization initiation characteristic Download PDFInfo
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Abstract
The invention discloses a triphenylamine-naphthalene multi-branch molecule with double-photon polymerization initiation characteristics. Triphenylamine is taken as an electron donor, and naphthalene nucleus with characteristics of an electron receptor are respectively connected with the 4, 4'-bits of triphenylamine through carbon-carbon double bonds to form the topology of'Y-pn knot' with charge transferability; and then the'Y-pn knot' is taken as a connection center to be conjugately connected with a substituent to form a multi-branch molecule with a greater conjugate system. Therefore, the molecule has a great double-photon absorption cross section. The multi-branch molecule has excellent double-photon polymerization initiation capability for methacrylic acid resin with a low polymerization threshold value and a highly fine microstructure obtained from polymerization. The multi-branch molecule has great application value in the double-photon three-dimensional memory and the micro-processing and fabrication fields of photon crystal.
Description
Technical field
The present invention relates to a class triphenylamine-naphthalin multi-branched molecule, have the strong two-photon absorbent properties, methacrylic resin is had good two-photon polymerized initiation characteristic.
Background technology
Two-photon absorption is meant at high light and excites down, utilize the light source activation sample of the linear absorption wavelength that closely doubles sample, make it pass through an empty intermediate state and directly absorb the process of two photon transitions to high-energy state, it is all little than the absorption and the chromatic dispersion of long light to this wavelength to it is characterized by medium, the penetrativity of light wave is strong, and because square being directly proportional of transition probability and incident intensity, under laser was tightened focused condition, the sample scope of being excited was limited in λ
3In the volume, make to excite spatial selectivity with height.These characteristics of two-photon absorbing material make it have tempting using value in fields such as two-photon polymerized produced by micro processing, HIGH-DENSITY OPTICAL STORAGE, photonic crystal, two-photon fluorescence micro-imagings.
The double photon three dimension produced by micro processing is a kind of novel light polymerization technique that developed recently gets up.In two-photon polymerized system, adopt the strong long wavelength laser of penetrativity to cause two-photon polymerized reaction, can be the limitation of size of polyreaction in micron, submicron even nanometer scale, thereby can in polymerization system, realize three-dimensional little processing of profound level.As photonic crystal is a kind of to the regulatable periodic micro structure of light wave, has the characteristic of regulating the photon kinestate.The double photon photopolymerization technology is the easiest method of making the photonic crystal periodic micro structure at present.Therefore, the little knot manufacturing technology of two-photon polymerized reaction has caused worldwide extensive concern.Calendar year 2001, Japan scientist Kawata etc. utilizes the induced by ultrashort pulse laser photoresist material that two-photon polymerized reaction takes place, utilize wavelength to carve out the bull picture (being called " nanometer ox ") of an erythrocyte size for the near infrared femtosecond pulse of 780nm, its laser processing resolving power has reached 120nm, break through the diffraction limit of traditional optical theory, realized utilizing the two-photon processing technology to make the three-dimensional structure of sub-micrometer precision.The appearance of " nanometer ox " has caused the very big concern of people to the two-photon processing technology, and correlative study work has all extensively been carried out in countries in the world.In view of two-photon polymerized technology has high precision, density three-dimensional processing characteristic, be expected to be widely used in fields such as photonics device, MEMS (micro electro mechanical system) in the near future.
In two-photon polymerized technology, require to cause photopolymerisable active specy (being commonly referred to light trigger) and can absorb two photons simultaneously, thereby produce active substance (free radical or ion) initiated polymerization.At present, two-photon polymerized efficiently initiator is the commercial-free product still, utilize traditional ultraviolet initiator (as Benzil) though the initiated polymerization resin is having report aspect the little processing of three-dimensional, but because the two photon absorption cross section of initiator molecule is little, cause the polymerization efficiency of paradigmatic system low, luminous sensitivity is low and resolving power is low.Therefore, the exploitation of relevant efficient two-photon polymerized initiator is one of the focus in this field always.
Summary of the invention
The object of the invention provides triphenylamine-naphthalin multi-branched molecule that a class has the strong two-photon absorbent properties, methacrylic resin had good two-photon polymerized initiation characteristic.
For achieving the above object, the technical solution used in the present invention is: a kind of triphenylamine-naphthalin multi-branched molecule with two-photon polymerized initiation characteristic, be to be electron donor(ED) (D) with the triphenylamine, respectively at 4 of triphenylamine, 4 '-position connects the naphthalene nucleus with electron acceptor(EA) characteristic (A) by carbon-carbon double bond, constitutes " Y-pn knot " topological framework, is the connection center with " Y-pn knot ", conjugation connects triphenylamine-naphthalin multi-branched molecule that substituted radical forms, and its general structure is:
In the formula, R
1Be selected from H, carboxyl, bromine atoms, bromo naphthyl, 4-vinylpyridine base, 4-N, a kind of in the N-diphenylamino styryl;
R
2, R
3Be selected from H, carboxyl, bromine atoms, 4-vinylpyridine base, 4-N respectively, a kind of in the N-diphenylamino styryl.
Wherein, " Y shape-pn knot " topological framework has very strong intramolecular charge transfer ability, is the connection center with " Y-pn knot ", and conjugation connects the multi-branched molecule that different substituting groups forms big conjugated system, has strong two photon absorption characteristics.
In the technique scheme, work as R
1Be-bromo naphthyl, R
2And R
3When being bromine atoms simultaneously, described molecular structural formula is,
When a substituting group is H or carboxyl, two be during by carbon-carbon double bond connection triphen amido in addition, and molecular structural formula is respectively,
When substituting group is a 4-naphthalene bromide or when connecting the pyridine group by carbon-carbon double bond, molecular structural formula is respectively,
When substituting group is a 4-naphthalene bromide or when connecting trianilino group by two keys, molecular structural formula is respectively,
The preparation method of above-claimed cpd molecule of the present invention is referring to the explanation among the embodiment.
Because the technique scheme utilization, the present invention compared with prior art has following properties:
1. the present invention connects and composes " Y shape-pn knot " topological center with trianilino group and naphthalene nucleus, and the different substituting group of conjugation connection forms the multi-branched molecule of big conjugated system again, thereby has the strong two-photon absorption.Femtosecond ti sapphire laser 800 (300mW, repetition rate 140Hz) excites down has tangible two-photon absorption ability; Two photon absorption cross section as embodiment 2 compounds reaches 2312GM (seeing Table 1);
2. compound of the present invention has " Y shape-pn knot " topological center, has strong intramolecular charge transfer characteristics, under the exciting of light, charge separation takes place behind two photons of molecular absorption easily form free radical, has good radical polymerization initiation characteristic; The utilization laser micro-machining technology as initiator, carries out the research (seeing Table 2) of two-photon polymerized initiation characteristic with the embodiment compound to methacrylic resin.The result shows that when sweep velocity was 10 little meter per seconds, the two-photon polymerized threshold value of embodiment compound was 38kJ/cm
2, the polymerization threshold value is low, the microstructure fine degree height of processing, and (under condition, the polymerization threshold value of conventional initiator dibenzoyl then is 290kJ/cm
2), be the good two-photon polymerized initiator of a class.
Description of drawings
Fig. 1 is two-photon fluorescence spectrum (THF, 1 * 10 of embodiment 2 under the different wave length laser pumping
-4M);
Fig. 2 is embodiment 2 two photon absorption cross section (THF, 1 * 10 under the different wave length laser pumping
-4M);
Fig. 3 is two photon absorption cross section (DMF, 1 * 10 of embodiment 4-6 under the different wave length laser pumping
-4M);
Fig. 4 is to be the two-photon initiator with embodiment 4, to methacrylic resin realize after the two-photon polymerized processing the photon crystal microstructure sem photograph (vertical view, microstructure size is: 20 μ m * 20 μ m; Grid size: 0.6 μ m * 0.6 μ m);
Fig. 5 is the partial enlarged drawing of Fig. 4;
Fig. 6 is the side-view (angle of inclination: 45 °) of Fig. 4;
Fig. 7 is to be the two-photon initiator with embodiment 5, and the polymerization methacrylic resin is realized " micron ox " sem photograph (bull size: 20 μ m * 20 μ m) after the two-photon polymerized processing.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment 1:4,4 ', 4 "-three (4-bromo-1-naphthalene vinyl) triphenylamine is synthetic.
(1) 4,4 ', 4 "-triphenylamine three aldehyde preparations: under nitrogen atmosphere, earlier with 2.4g (0.62mol) 4; 4 ', 4 "-the triphenylamine tribromo places there-necked flask, after sealing is bled, inject the 30mL dry THF, inject the dry DMF of 3.5mL down, dropwise inject the 15.6mL n-Butyl Lithium under the stirring state at-78 ℃.Reaction was at room temperature reacted 3 hours after 3 hours again under dripping Bi Zaizai-78 ℃, and stopped reaction is poured reaction solution into NH
4The Cl saturated aqueous solution, CH
2Cl
2Organic layer is told in extraction, concentrates to obtain yellow solid powder, productive rate 67% behind the sherwood oil reprecipitation.MS(EI)M
+＝329，
1H?NMR(CDCl
3，300MHz)：δ9.92(s，3H)，7.84(d，6H)，7.24(d，6H).
(2) 0.4g (1.3mmol) 4-bromo-1-brooethyl naphthalene, 0.384g (1.4mmol) triphenylphosphine and 10ml dimethylbenzene are added in the 100ml there-necked flask, 120 ℃ of back flow reaction 6h, cool off the back suction filtration, get filter residue, the dehydrated alcohol recrystallization, get 4-bromo-1-brooethyl naphthalene quaternary alkylphosphonium salt (0.71g), productive rate 95%, fusing point〉280 ℃.
(3) with 4-bromo-1-brooethyl naphthalene quaternary alkylphosphonium salt (5.12g, 9.12mmol), 4,4 '; 4 "-triphenylamine three aldehyde (1.0g, 3.04mmol), 1, (0.36g 15.0mmol) adds in the 250ml there-necked flask for 4-dioxane (80ml) and sodium hydride, 110 ℃ of back flow reaction 6h, cooling off the back suction filtration, get filtrate, concentrate, is the elutriant column chromatography for separation with ethyl acetate: sherwood oil=1:3, get 1.15g embodiment 1 compound, productive rate 46%.MS (MALDI) M
+=935.0, ultimate analysis (%): Cald.69.10; H, 3.87; N, 1.49.Found.68.73; H, 3.26; N.1.98.
The compound molecule formula that obtains is,
Embodiment 2:4,4 '-two (4-triphen amido vinyl naphthalene base-1-vinyl) triphenylamine synthetic.
(1) 1-bromo-4-(1-ethene triphenylamine) naphthalene preparation: with the 4-bromo-1-brooethyl naphthalene quaternary alkylphosphonium salt (0.3g of embodiment 1 step 2 acquisition, 0.53mmol) and 4-N, N-diphenylamino phenyl aldehyde (0.08g, 0.3mmol) and sodium hydride (0.042g 1.75mmol) adds respectively in the 100ml there-necked flask, 110 ℃ of back flow reaction 6h, cool off the back suction filtration, get filtrate, concentrate, sherwood oil is the elutriant column chromatography for separation, get yellow 1-bromo-4-(1-ethene triphenylamine) naphthalene (0.064g), productive rate 40%.MS (EI) M
+=476, ultimate analysis (%): Cald.C, 75.63; H, 4.65; N, 2.94.Found.75.04; H, 4.16; N.3.28.
(2) 4,4 '-two (4-triphen amido vinyl naphthalene base-1-vinyl) triphenylamine preparation: under the anhydrous and oxygen-free condition, with 0.253g (0.53mmol) 1-bromo-4-(1-ethene triphenylamine) naphthalene, 0.08g (0.27mmol) N, N-two (4-vinylbenzene) aniline, 10ml triethylamine and 8ml acetonitrile are made solvent, 0.008g making catalyzer, adjacent methyl triphenyl phosphine and 0.0024g palladium add in the 100ml there-necked flask, 85 ℃ of back flow reaction 24h, the cooling back concentrates, with chloroform: sherwood oil=3:1 is the elutriant column chromatography for separation, gets the 0.058g target compound.Productive rate 26%, mp:134-135 ℃, MS (MALDI) M
+=1087.7. ultimate analysis (%): Cald.C, 90.49; H, 5.65; N, 3.86.Found.90.05; H.6.02; N.3.24.
The compound molecule formula that obtains is,
Embodiment 3:4,4 '-two (4-triphen amido vinyl naphthalene base-1-vinyl)-N, the N-diphenyl amino is benzoic synthetic.
Synthetic method is similar to Example 2, only need be according to the compound that obtains with the N in the step 2, and N-two (4-vinylbenzene) aniline changes N into, N-two (4-vinylbenzene)-4-benzaminic acid.Productive rate 21%, MS (MALDI) M
+=1132.30.Ultimate analysis (%): Cald.C, 88.03; H, 5.43; N, 3.71.Found.88.50; H.5.02; N.3.24.
The compound molecule formula that obtains is,
Embodiment 4:4,4 ' 4 "-three (4-vinylpyridine base-1-naphthalene vinyl) triphenylamine is synthetic.
Under the anhydrous and oxygen-free condition, with 1.0g (1.07mmol) 4,4 '; 4 "-three (4-bromo-1-naphthalene vinyl) triphenylamines (embodiment 1 compound), 0.12ml (1.07mmol) 4-vinylpridine, 10ml triethylamine and 8ml acetonitrile are made solvent, 0.0162g making catalyzer, adjacent methyl triphenyl phosphine and 0.0048g palladium add in the 100ml there-necked flask, 85 ℃ of back flow reaction 24h, the cooling back concentrates, with ethyl acetate: sherwood oil=5:1 is the elutriant column chromatography for separation, gets 0.125g embodiment 4 compounds, fusing point 88-89 ℃ .MS (MALDI)=960.16 (M
+). ultimate analysis (%): Cald.C, 76.10; H, 4.40; N, 2.91.Found.C, 76.42; H, 4.21; N, 3.22.
The compound molecule formula that obtains is,
Embodiment 5: synthetic method is similar to Example 4, only needs according to the compound that obtains with 44 ', 4 "-three (4-bromo-1-naphthalene vinyl) triphenylamine (embodiment 1 compound) and 4-vinylpridines, 1:2 reaction in molar ratio.Productive rate 46%, 115 ℃ of fusing points.MS (MALDI)=897.3 (M
+). ultimate analysis (%): Cald.C, 82.75; H, 4.90; N, 4.26.Found.C, 82.36, H, 4.28; N, 4.58.
The compound molecule formula that obtains is,
Embodiment 6: synthetic method is similar to Example 4, only needs according to the compound that obtains with 44 ', 4 "-three (4-bromo-1-naphthalene vinyl) triphenylamine (embodiment 1 compound) and 4-vinylpridines, 1:3 reaction in molar ratio.Productive rate 40%, 158 ℃ of fusing points.MS (MALDI) M
+=1010.43. ultimate analysis (%): Cald.C, 89.08; H, 5.38; N, 5.54.Found.C, 88.68; H, 4.99; N, 5.91.
The compound molecule formula that obtains is,
Embodiment 7: synthetic method is similar to Example 4, only needs to change 4-vinylpridine into the ethene triphenylamine according to the compound that obtains.Productive rate 64%.MS (MALDI) M
+=1126.26. ultimate analysis (%): Cald.C, 78.72; H, 4.64; N, 2.48.Found.C, 78.18; H, 4.16; N, 2.02.
The compound molecule formula that obtains is,
Embodiment 8: synthetic method is similar to Example 5, only needs to change 4-vinylpridine into the ethene triphenylamine according to the compound that obtains.Productive rate 56%, MS (MALDI) M
+=1320.46. ultimate analysis (%): Cald.C, 85.57; H, 5.19; N, 3.18.Found.C, 85.02; H, 4.36; N, 3.64.
The compound molecule formula that obtains is,
Embodiment 9: synthetic method is similar to Example 6, only needs to change 4-vinylpridine into the ethene triphenylamine, productive rate 41% according to the compound that obtains.MS(MALDI)M
+＝1512.06.
The compound molecule formula that obtains is,
The line spectrum of part triphenylamine-naphthalin multi-branched molecule that embodiment obtains and two-photon absorption character are shown in table 1 and Fig. 1-3.
The polymerization threshold value that the two-photon of part embodiment compound causes the methacrylic polymerization system is shown in Table 2.
The 3 D stereo microstructure (as micron ox and photonic crystal etc.) that the polymerization process of the two-photon initiation methacrylic polymerization system of part embodiment compound obtains is shown in Fig. 4-7.
The linear optics of table 1 triphenylamine-naphthalin multi-branched molecule and two-photon absorption character
Annotate:
Expression linear absorption spectrographic peak (THF, 1 * 10
-5Mol dm
-3);
Peak (THF, 1 * 10 with the single photon fluorescence spectrum
-5Mol dm
-3); Φ
f(reference is a fluorescein to the expression fluorescence quantum yield, Φ
f=0.9);
Expression two-photon fluorescence peak;
The maximum peak position of expression two-photon absorption; δ
TPAExpression two photon absorption cross section (1GM=1 * 10
-50Cm
-4Sphoton
-1Molecule
-1).Two photon absorption cross section uses two-photon fluorescence method to record (fluorescein is reference), and excitation light source is locked mode titanium jewel femto-second laser (130fs pulsewidth, output rating are 0.3W for wavelength adjustment scope 700-880nm, repetition rate 80MHz), and sample concentration is 1 * 10
-4Moldm
-3, the THF solvent.
aIn methylene dichloride, record.
bIn DMF, record.
Table 2 embodiment 4-6 compounds are as the polymerization threshold value of two-photon initiator
Annotate: with embodiment 4-6 compounds is initiator, implements two-photon polymerizedly to methacrylic resin, has investigated its two-photon initiation characteristic under same system, same concentrations.For ease of relatively, introduce commercial product light trigger dibenzoyl and make reference.Sweep velocity is: 10 μ m/s.
Claims (1)
1. triphenylamine-naphthalin multi-branched molecule with two-photon polymerized initiation characteristic, it is characterized in that: be to be electron donor(ED) with the triphenylamine, respectively at 4 of triphenylamine, 4 '-position connects the naphthalene nucleus with electron acceptor(EA) characteristic by carbon-carbon double bond, constitute " Y-pn knot " topological framework, with " Y-pn knot " is the connection center, and conjugation connects triphenylamine-naphthalin multi-branched molecule that substituted radical forms, and its structural formula is:
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| CN104861106B (en) * | 2015-04-27 | 2016-08-17 | 中国科学院理化技术研究所 | Up-conversion light-emitting polymer material based on triplet-triplet annihilation |
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