CN109265657A - Conjugation microporous polymer and preparation method thereof based on s-indacene -1,3,5,7 (2H, 6H)-tetrone - Google Patents
Conjugation microporous polymer and preparation method thereof based on s-indacene -1,3,5,7 (2H, 6H)-tetrone Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/132—Morphological aspects branched or hyperbranched
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/592—Stability against heat
Abstract
The present invention provides a kind of with structure shown in Formulas I based on s-indacene -1,3, and 5; the conjugation microporous polymer of 7 (2H, 6H)-tetrones, the present invention is 2; 4,6- tri- (4- formvlphenoxvs) -1,3; introducing s-indacene -1,3 on the basis of 5- triazine, 5; 7 (2H, 6H)-tetrones, the conjugation microporous polymer being prepared are laminated structure and crystal characteristic are presented; have uv absorption property, full spectral absorption may be implemented, thermal stability is good.The present invention provides with structure shown in Formulas I, based on s-indacene -1,3, the preparation method of the conjugation microporous polymer of 5,7 (2H, 6H)-tetrones, method is simple and easy, is advantageously implemented large-scale production.
Description
Technical field
The present invention relates to conjugation microporous polymer technical field, and in particular to one kind be based on s-indacene -1,3,5,7
Conjugation microporous polymer of (2H, 6H)-tetrone and preparation method thereof.
Background technique
Organic porous material (MOPs) is divided into four seed types according to its design feature: from tool microporous polymer (polymers
Of intrinsic microporosity, PIMs), super cross-linked polymer (Hyper-cross-linked polymers,
HCPs), covalent organic network (covalent organic frameworks, COFs) and conjugation microporous polymer
(conjugated microporous polymers, CMPs).Microporous polymer (CMPs) is conjugated as organic porous material
One branch successfully synthesizes 3DCMPs using 2D aryl acetylide, aryl bromide/iodide as monomer for the first time from Cooper seminar
(PAEs) after, more and more researchers are dedicated to the research of CMPs.CMPs has lot of advantages, such as large specific surface area, skeleton
Density is low, and intramolecule contains the molecular dimension duct of open communication, has stable physical property and chemical property.
Structural unit is constructed according to different chemical reactions, and then develops the CMPs of different structure and special nature, is become
Current research hotspot.
Summary of the invention
The purpose of the present invention is to provide a kind of conjugation micropores for being based on s-indacene -1,3,5,7 (2H, 6H)-tetrone
Polymer and preparation method thereof, provided by the invention to be based on s-indacene -1,3, the conjugation micropore of 5,7 (2H, 6H)-tetrones is poly-
It closes object and is laminated structure and crystal characteristic is presented have uv absorption property, thermal stability is good.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides one kind be based on s-indacene -1,3, the conjugation microporous polymer of 5,7 (2H, 6H)-tetrones, with
(4- the formvlphenoxv) -1,3,5- triazine of 2,4,6- tri- and s-indacene -1,3,5,7 (2H, 6H)-tetrone are monomer, press
(4- the formvlphenoxv) -1,3,5- triazine of 2,4,6- tri- and s-indacene -1,3,5,7 (2H, 6H)-tetrone molar ratio are 1:
(1.0~1.4) are prepared, and have structure shown in Formulas I:
In Formulas I,Group both ends connection group be Group three ends connection group be
The present invention provides the conjugation that s-indacene -1,3,5,7 (2H, 6H)-tetrone is based on described in above-mentioned technical proposal
The preparation method of microporous polymer, comprising the following steps:
In protective atmosphere, by 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, s-indacene -1,3,5,7
(2H, 6H)-tetrone, organic solvent, acidic catalyst and water mixing, carry out substitution reaction, obtain the base with structure shown in Formulas I
In the conjugation microporous polymer of s-indacene -1,3,5,7 (2H, 6H)-tetrone；Wherein, described 2,4,6- tri- (4- formoxyl benzene
Oxygroup) molar ratio of -1,3,5- triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone is 1:(1.0~1.4).
Preferably, the acidic catalyst includes one or more of formic acid, acetic acid and propionic acid.
Preferably, the volume ratio of the organic solvent and water is (10~20): 1.
Preferably, the organic solvent includes one of n-butanol, o-dichlorohenzene, dioxanes and mesitylene or several
Kind.
Preferably, the temperature of the substitution reaction is 110~130 DEG C, and the time is 70~75h.
Preferably, after the completion of the substitution reaction further include:
Gained system after the completion of substitution reaction is separated by solid-liquid separation, successively using dehydrated alcohol and ether to obtained solid
Material is washed, dry, obtain having structure shown in Formulas I based on s-indacene -1,3,5,7 (2H, 6H)-tetrones are total to
Yoke microporous polymer.
Preferably, the preparation method of described 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, including following step
It is rapid:
Parahydroxyben-zaldehyde, dioxane and amine reagent are mixed, are separated by solid-liquid separation after deprotonation reaction occurs,
Gained liquid material is deprotonation reaction product system；
Deprotonation reaction product system is mixed with Cyanuric Chloride and dioxane by described, substitution reaction is carried out, obtains
To 2,4,6- tri- (4- formvlphenoxv) -1,3,5- triazine.
Preferably, after the completion of the substitution reaction further include:
It will be washed, filtered, in removal gained filtrate with dioxane after gained system cooling after the completion of substitution reaction
Solvent purifies gained residue using dehydrated alcohol, obtains 2,4,6- tri- (4- formvlphenoxv) -1,3,5- tri-
Piperazine.
The present invention provides a kind of with structure shown in Formulas I based on s-indacene -1,3,5,7 (2H, 6H)-tetrone
It is conjugated microporous polymer, the present invention introduces on the basis of 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines to be reached to citing approvingly
- 1,3,5,7 (2H, 6H)-tetrones are saved, the conjugation microporous polymer being prepared is laminated structure and crystal characteristic is presented, and is had
Uv absorption property, may be implemented full spectral absorption, and thermal stability is good.
The present invention provides the conjugation based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I
The preparation method of microporous polymer, method is simple and easy, is advantageously implemented large-scale production.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 2,4,6- tri- (4- formvlphenoxv) -1,3,5- triazine in embodiment 1；
Fig. 2 is the infrared spectrogram of 2,4,6- tri- (4- formvlphenoxv) -1,3,5 triazines in embodiment 1；
Fig. 3 is the ultraviolet spectrogram of 2,4,6- tri- (4- formvlphenoxv) -1,3,5 triazines in embodiment 1；
Fig. 4 is s-indacene -1,3,5,7 (2H, 6H)-tetrone nucleus magnetic hydrogen spectrum figure in embodiment 1；
Fig. 5 is s-indacene -1,3,5,7 (2H, 6H)-tetrone infrared spectrogram in embodiment 1；
Fig. 6 is being total to based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I in embodiment 1
The infrared spectrogram of yoke microporous polymer；
Fig. 7 is being total to based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I in embodiment 1
The ultraviolet spectrogram of yoke microporous polymer；
Fig. 8 is being total to based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I in embodiment 1
The thermogravimetric analysis figure of yoke microporous polymer；
Fig. 9 is being total to based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I in embodiment 1
The XRD scanning analysis figure of yoke microporous polymer；
Figure 10 be in embodiment 1 with structure shown in Formulas I based on s-indacene -1,3,5,7 (2H, 6H)-tetrone
It is conjugated the electron-microscope scanning figure of microporous polymer.
Specific embodiment
The present invention provides one kind be based on s-indacene -1,3, the conjugation microporous polymer of 5,7 (2H, 6H)-tetrones, with
(4- the formvlphenoxv) -1,3,5- triazine of 2,4,6- tri- and s-indacene -1,3,5,7 (2H, 6H)-tetrone are monomer, press
(4- the formvlphenoxv) -1,3,5- triazine of 2,4,6- tri- and s-indacene -1,3,5,7 (2H, 6H)-tetrone molar ratio are 1:
(1.0~1.4) are prepared, and have structure shown in Formulas I:
In Formulas I,Group both ends connection group be Group three ends connection group be
The present invention provides the conjugation that s-indacene -1,3,5,7 (2H, 6H)-tetrone is based on described in above-mentioned technical proposal
The preparation method of microporous polymer, comprising the following steps:
In protective atmosphere, by 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, s-indacene -1,3,5,7
(2H, 6H)-tetrone, organic solvent, acidic catalyst and water mixing, carry out substitution reaction, obtain the base with structure shown in Formulas I
In the conjugation microporous polymer of s-indacene -1,3,5,7 (2H, 6H)-tetrone；Wherein, described 2,4,6- tri- (4- formoxyl benzene
Oxygroup) molar ratio of -1,3,5- triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone is 1:(1.0~1.4).
In the present invention, the acidic catalyst preferably includes one or more of formic acid, acetic acid and propionic acid.
In the present invention, the volume ratio of the organic solvent and water is preferably (10~20): 1, more preferably (13~17):
1.In the present invention, the organic solvent can increase the solubility of reaction raw materials, and the water energy enough adjusts the pole of reaction system
Property, guarantee that reaction is gone on smoothly.
In the present invention, the organic solvent preferably includes one in n-butanol, o-dichlorohenzene, dioxanes and mesitylene
Kind is several.
In the present invention, described 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, s-indacene -1,3,5,7
(2H, 6H)-tetrone, organic solvent, acidic catalyst and water mixing are preferably in protective atmosphere, by 2,4,6- tri- (4- formyls
Phenoxyl) -1,3,5- triazine, s-indacene -1,3,5,7 (2H, 6H)-tetrone and organic solvent be stirred 5~
Then the aqueous solution of acidic catalyst is added in 15min into gained mixed material.
The present invention does not have special restriction for the protective gas type for providing the protective atmosphere, using art technology
Protective gas known to personnel, it is specific such as nitrogen.
In the present invention, the temperature of the substitution reaction is preferably 110~130 DEG C, and more preferably 120 DEG C；Time is preferred
For 70~75h, more preferably 72h.
After completing the substitution reaction, gained system after the completion of substitution reaction is preferably separated by solid-liquid separation by the present invention, according to
It is secondary that obtained solid material is washed using dehydrated alcohol and ether, it is dry, obtain having structure shown in Formulas I based on symmetrical
Indacene -1,3,5,7 (2H, 6H)-tetrone conjugation microporous polymer.Present invention spy no for the mode of the separation of solid and liquid
Different restriction, it is specific as filtered using solid-liquid separation method well known to those skilled in the art.The present invention is washed for described
Not special restriction is washed, using the technical solution of washing well known to those skilled in the art.The present invention is for described dry
Dry not special restriction, can be sufficiently dry by resulting material after suction filtration.
In the present invention, the preparation method of described 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, preferably includes
Following steps:
Parahydroxyben-zaldehyde, dioxane and amine reagent are mixed, are separated by solid-liquid separation after deprotonation reaction occurs,
Gained liquid material is deprotonation reaction product system；
Deprotonation reaction product system is mixed with Cyanuric Chloride and dioxane by described, substitution reaction is carried out, obtains
To 2,4,6- tri- (4- formvlphenoxv) -1,3,5- triazine.
The present invention preferably mixes parahydroxyben-zaldehyde, dioxane and amine reagent, and it is laggard that deprotonation reaction occurs
Row is separated by solid-liquid separation, and gained liquid material is deprotonation reaction product system.In the present invention, the parahydroxyben-zaldehyde and two
The volume ratio of six ring of oxygen and amine reagent is preferably (9~10) g:(75~85) mL:(13~14) mL.In the present invention, described
Amine reagent preferably includes triethylamine, tripropyl amine (TPA) or isopropylamine.In the present invention, the dioxane is reaction dissolvent, described
Amine reagent is deprotonation reagent, and parahydroxyben-zaldehyde is made turn in deprotonation reaction the process of deprotonation.In this hair
In bright, the time of the deprotonation reaction is preferably 5~10min；Deprotonation reaction preferably at room temperature into
Row.The present invention does not have the mode of the separation of solid and liquid special restriction, using solid-liquid well known to those skilled in the art point
From technical solution, it is specific as filtered.In an embodiment of the present invention, specifically by parahydroxyben-zaldehyde, dioxane
After being sufficiently mixed with amine reagent, 5~10min is stood at room temperature, deprotonation reaction occurs, gained system is carried out
Filtering, gained filtrate are deprotonation reaction product system, without carrying out other post-processings, are directly used in and carry out subsequent replace instead
It answers.
After obtaining deprotonation reaction product system, the present invention is by the deprotonation reaction product system and Cyanuric Chloride
It is mixed with dioxane, carries out substitution reaction, obtain 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines.In the present invention
In, the molar ratio of the Cyanuric Chloride and parahydroxyben-zaldehyde is preferably 1:(3.5~4.5).In the present invention, described to go matter
Sonization reaction product system is mixed with Cyanuric Chloride and dioxane preferably mixes Cyanuric Chloride and dioxane, then exists
Under room temperature, stirring condition, the deprotonation reaction product system is added dropwise into gained mixture；The deprotonation reaction produces
The drop rate of objects system is preferably that 1~2 drop is per second.
In the present invention, the temperature of the substitution reaction is preferably 85~95 DEG C, and more preferably 90 DEG C；Time is preferably 15
~20h, more preferably 17~18h.In the present invention, the substitution reaction preferably carries out under agitation；The present invention for
The rate of the stirring does not have special restriction, using stirring rate well known to those skilled in the art.
After completing the substitution reaction, the present invention preferably will use dioxane after the cooling of gained system after the completion of substitution reaction
It is washed, is filtered, solvent in removal gained filtrate purifies gained residue using dehydrated alcohol, obtains 2,4,6-
Three (4- formvlphenoxv) -1,3,5- triazines.In the present invention, the cooling is preferably proper by institute after the completion of substitution reaction
System is cooled to room temperature.The present invention restriction not special for the washing, using washing well known to those skilled in the art
Technical solution.The present invention does not have special restriction for the method for removing solvent in the filtrate, using art technology
The technical solution of removal solvent known to personnel；In an embodiment of the present invention, specifically under the conditions of 55~60 DEG C into
Row vacuum distillation.In the present invention, it is preferably using the method that dehydrated alcohol purifies gained residue to the residue
Dehydrated alcohol is added in object, gained mixture is ultrasonically treated, then resulting material is filtered with dehydrated alcohol, it will
Obtained solid material is dried, and obtains 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines.
The present invention does not have special restriction to the s-indacene -1,3, the source of 5,7 (2H, 6H)-tetrones, using this
Method known to the technical staff of field is prepared.In an embodiment of the present invention, the s-indacene -1,3,5,7
The preparation method of (2H, 6H)-tetrone specifically includes the following steps:
Pyromellitic dianhydride, ethyl acetoacetate and triethylamine are mixed under agitation, heating water bath to 60~65
DEG C, acetic anhydride, oil bath heating to 98~102 DEG C of 2~2.5h of reflux are added into gained mixture；It is cooled to room after reaction
Temperature, then, there is brown precipitate, resulting material is depressurized and is filtered, uses second respectively in cooling 12~15h under the conditions of 0~5 DEG C
Acid anhydrides and ether washing, obtain orange sediment, dry；Distilled water dissolution is added in 1:100 ratio in products therefrom after will be dry,
Under the conditions of ice-water bath, the concentrated sulfuric acid is added dropwise into resulting material, becomes coffee-like to solution, is further continued for dropwise addition 1~2mL concentrated sulfuric acid,
Resulting material is washed with ethyl alcohol, it is dry；Products therefrom is mixed with 120mL acetonitrile after will be dry, in stirring, 90~95 DEG C
Under the conditions of react 3~3.5h, resulting material is filtered under diminished pressure, wash obtained solid material with acetonitrile, is dried, obtains reaching to citing approvingly
Save -1,3,5,7 (2H, 6H)-tetrones.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
Prepare 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, comprising the following steps:
9.7253g parahydroxyben-zaldehyde, 80.0mL dioxane and 13.8mL triethylamine are mixed, sufficiently dissolution is stirred
Afterwards, 5min is stood at room temperature, and gained system is filtered, with the speed that about 1~2 drop is per second, under agitation,
By in gained filtrate added drop-wise to the mixture of 3.6049g Cyanuric Chloride and 40.9mL dioxane, observation solution colour gradually becomes
To gradually become yellow emulsion again after white emulsion, after being added dropwise after about 1.5h, resulting material is placed on to 90 DEG C of oil
It is heated in bath and stirs 18h；It is filtered after gained system is cooled to room temperature with dioxane, depressurizes and steam in 55 DEG C of water-baths
It evaporates, when there is no distillate to distillate, stops distillation, 120mL dehydrated alcohol is added into gained residue and is ultrasonically treated, so
Resulting material is filtered with dehydrated alcohol afterwards, obtained solid material is dried, obtains 2,4,6- tri- (4- formoxyl benzene
Oxygroup) -1,3,5-triazines 2.5977g, yield 29.9%.
Prepare s-indacene -1,3,5,7 (2H, 6H)-tetrones, comprising the following steps:
4.9810g pyromellitic dianhydride, 9.0mL ethyl acetoacetate and 28.0mL triethylamine are mixed under agitation
It closes, 75.0mL acetic anhydride, oil bath heating to 100 DEG C of reflux 2h are added into gained mixture to 60 DEG C for heating water bath；Reaction knot
It is cooled to room temperature after beam, then, there is brown precipitate, resulting material is depressurized and is filtered in cooling 12h under the conditions of 0 DEG C, point
It is not washed with acetic anhydride and ether, obtains orange sediment, it is dry；Products therefrom is added in 1:100 ratio after will be dry distills
Water dissolution, under the conditions of ice-water bath, the concentrated sulfuric acid is added dropwise into resulting material, becomes coffee-like to solution, is further continued for that the dense sulphur of 1mL is added dropwise
Acid washs resulting material with ethyl alcohol, dry；Products therefrom is mixed with 120mL acetonitrile after will be dry, in stirring, 90
3h is reacted under the conditions of DEG C, resulting material is filtered under diminished pressure, and washs obtained solid material with acetonitrile, it is dry, obtain s-indacene-
1,3,5,7 (2H, 6H)-tetrone 2.3725g, yield 48.5%.
Prepare the conjugation microporous polymer based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I
Object, comprising the following steps:
Under nitrogen protection, 0.5g 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, 0.2g are reached to citing approvingly
It saves -1,3,5,7 (2H, 6H)-tetrones, 12mL n-butanol and 28mL o-dichlorohenzene and is stirred 10min, then to gained mixture
4mL acetic acid aqueous solution (being formulated by 1.4mL acetic acid and 2.6mL water) is added in material, 72h is reacted under the conditions of 120 DEG C, by institute
System is filtered with dehydrated alcohol, obtained solid material is dried, obtain having structure shown in Formulas I based on symmetrical
Indacene -1,3,5,7 (2H, 6H)-tetrone conjugation microporous polymer.
To 2 be prepared, 4,6- tri- (4- formvlphenoxv) -1,3,5-triazines are characterized, specific as follows:
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, as shown in Figure 1, compound
In proton peak at 1,6,11 show near at δ ≈ 10,2,5,7,10,12,15 in compound at proton peak show δ ≈
Near at 7.9,3,4,8,9,13,14 in compound at proton peak show near at δ ≈ 7.3, remaining occur peak belong to
Impurity peaks.Prove that gained compound is 2,4,6- tri- (4- formvlphenoxv) -1,3,5- triazine really in the present embodiment.
Fig. 2 is 2,4,6- tri- (4- formvlphenoxvs) -1, the infrared spectrogram of 3,5 triazines, as shown in Figure 2, compound
In 1570.06cm-1The absorption peak that place is shown (1600~1450cm similar to the C=C absorption peak feature in phenyl ring-1, phenyl ring
The stretching vibration of skeleton), in 839.03cm-1The absorption peak that place is shown it is similar to C-C absorption peak feature in phenyl ring (950~
650cm-1), in 1159.22cm-1The absorption peak that place is shown (1360~1020cm similar to=C-O-C absorption peak feature-1,
Stretching vibration), in 1290.37cm-1The absorption peak that place is shown (1360~1020cm similar to C=N absorption peak feature-1, stretch
Contracting vibration), in 2835.36cm-1The absorption peak that place is shown (2850~2710cm similar to C-H absorption peak feature in aldehyde radical-1, stretching vibration), in 1701.22cm-1The absorption peak that place is shown it is similar to C=O absorption peak feature in aldehyde radical (1755~
1665cm-1, stretching vibration).Prove that gained compound is 2,4,6- tri- (4- formvlphenoxv) -1,3 really in the present embodiment,
5- triazine.
Fig. 3 is 2,4,6- tri- (4- formvlphenoxvs) -1, the ultraviolet spectrogram of 3,5 triazines, from the figure 3, it may be seen that compound
Have higher absorption peak at two at 235nm and 289nm, after be gradually reduced, absorbance tends towards stability after 389nm.Illustrate 2,
The absorption of 4,6- tri- (4- formvlphenoxv) -1,3,5 triazines is only in ultra-violet (UV) band.
To the s-indacene -1,3 being prepared, 5,7 (2H, 6H)-tetrones are characterized, specific as follows:
Fig. 4 is s-indacene -1,3, the nucleus magnetic hydrogen spectrum figure of 5,7 (2H, 6H)-tetrones, as shown in Figure 4,2,4 in compound
The proton peak at place shows near at δ ≈ 7.3,1,3 in compound at proton peak show near at δ ≈ 1.6, remaining appearance
Peak belong to impurity peaks.Prove that gained compound is s-indacene -1,3,5,7 (2H, 6H)-tetrone really in the present embodiment.
Fig. 5 is s-indacene -1,3, and the infrared spectrogram of 5,7 (2H, 6H)-tetrones, as shown in Figure 5, compound exists
1361.74cm-1The absorption peak that place is shown (1600~1450cm similar to the C=C absorption peak feature in phenyl ring-1, phenyl ring bone
The stretching vibration of frame), in 873.75cm-1The absorption peak that place is shown it is similar to C-C absorption peak feature in phenyl ring (950~
650cm-1), in 1724.36cm-1The absorption peak that place is shown (1725~1705cm similar to C=O absorption peak feature-1, stretch
Vibration).Prove that gained compound is s-indacene -1,3,5,7 (2H, 6H)-tetrone really in the present embodiment.
To the conjugation based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I being prepared
Microporous polymer (TJF-CMP) is characterized, specific as follows:
Fig. 6 is poly- for the conjugation micropore based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I
The infrared spectrogram for closing object, it will be appreciated from fig. 6 that polymer is in 2835.36cm-1And 2740.85cm-1The aldehyde radical characteristic peak at place disappears,
In 1685.79cm-1There is C=C double bond absorption peak at place.Prove that gained compound is with structure shown in Formulas I really in the present embodiment
The conjugation microporous polymer based on s-indacene -1,3,5,7 (2H, 6H)-tetrone.
Fig. 7 is poly- for the conjugation micropore based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I
The ultraviolet spectrogram of object is closed, as shown in Figure 7, polymer and 2,4,6- tri- (4- formvlphenoxvs) -1, the ultraviolet light of 3,5 triazines
Spectrum (Fig. 3) shows that polymer conjugated degree enhances compared to red shift has occurred.
Fig. 8 is poly- for the conjugation micropore based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I
The thermogravimetric analysis figure of object is closed, as shown in Figure 8, the weight-loss ratio of polymer is 45.73%.In 0~100 DEG C of temperature-rise period, sample
The quality of product is slightly changed, and shows that previous drying process has had been removed most of water, but there are still a small amount of water not to be gone
It removes.In 100~381.04 DEG C of range of temperature, sample quality is stablized, and illustrates that polymer can be relatively stable at this temperature
Presence.At 381.04~789.79 DEG C, sample quality declines rapidly, and sample weight loss rate is about 36%, shows polymer knot
Structure avalanche and structural damage in this temperature range.At 789.79 DEG C, the final residue 54.21% of the quality of polymer.
Illustrate conjugation microporous polymer provided by the invention in 380 DEG C or less the relatively stable presence of energy, better heat stability.
Fig. 9 is poly- for the conjugation micropore based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I
The XRD scanning analysis figure of object is closed, as shown in Figure 9, conjugation microporous polymer provided by the invention has crystalline structure, illustrates this hair
Bright offer is conjugated the structurally ordered of microporous polymer.
Figure 10 is poly- for the conjugation micropore based on s-indacene -1,3,5,7 (2H, 6H)-tetrone with structure shown in Formulas I
The electron-microscope scanning figure of object is closed, as shown in Figure 10, sheet is presented in conjugation microporous polymer provided by the invention, and there are micropore knots
Structure.
As seen from the above embodiment, provided by the invention to be based on s-indacene -1,3, the conjugation of 5,7 (2H, 6H)-tetrones
Microporous polymer is laminated structure and crystal characteristic is presented, and has uv absorption property, full spectral absorption, thermostabilization may be implemented
Property is good, can be applied to the fields such as fluorescence sense.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. one kind is based on s-indacene -1,3, the conjugation microporous polymer of 5,7 (2H, 6H)-tetrones, with 2,4,6- tri- (4- first
Acyl group phenoxy group) -1,3,5- triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone be monomer, press (the 4- first of 2,4,6- tri-
Acyl group phenoxy group) -1,3,5- triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone molar ratio be 1:(1.0~1.4) system
It is standby to obtain, there is structure shown in Formulas I:
In Formulas I,Group both ends connection group be Group three ends connection group be
2. the preparation side of the conjugation microporous polymer described in claim 1 based on s-indacene -1,3,5,7 (2H, 6H)-tetrone
Method, comprising the following steps:
In protective atmosphere, by 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines, s-indacene -1,3,5,7 (2H,
6H)-tetrone, organic solvent, acidic catalyst and water mixing, carry out substitution reaction, obtain having structure shown in Formulas I based on right
Claim the conjugation microporous polymer of indacene -1,3,5,7 (2H, 6H)-tetrone；Wherein, described 2,4,6- tri- (4- formoxyl benzene oxygen
Base) molar ratio of -1,3,5- triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone is 1:(1.0~1.4).
3. preparation method according to claim 2, which is characterized in that the acidic catalyst includes formic acid, acetic acid and third
One or more of acid.
4. preparation method according to claim 2, which is characterized in that the volume ratio of the organic solvent and water be (10~
20): 1.
5. preparation method according to claim 2 or 4, which is characterized in that the organic solvent includes n-butanol, adjacent dichloro
One or more of benzene, dioxanes and mesitylene.
6. preparation method according to claim 2, which is characterized in that the temperature of the substitution reaction is 110~130 DEG C,
Time is 70~75h.
7. preparation method according to claim 2, which is characterized in that after the completion of the substitution reaction further include:
Gained system after the completion of substitution reaction is separated by solid-liquid separation, successively using dehydrated alcohol and ether to obtained solid material
Washed, it is dry, obtain having structure shown in Formulas I based on s-indacene -1,3, the conjugation of 5,7 (2H, 6H)-tetrones is micro-
Pore polymer.
8. preparation method according to claim 2, which is characterized in that described 2,4,6- tri- (4- formvlphenoxvs) -1,
The preparation method of 3,5- triazines, comprising the following steps:
Parahydroxyben-zaldehyde, dioxane and amine reagent are mixed, are separated by solid-liquid separation after deprotonation reaction occurs, gained
Liquid material is deprotonation reaction product system；
Deprotonation reaction product system is mixed with Cyanuric Chloride and dioxane by described, substitution reaction is carried out, obtains 2,
4,6- tri- (4- formvlphenoxv) -1,3,5- triazine.
9. preparation method according to claim 8, which is characterized in that after the completion of the substitution reaction further include:
It will be washed, filtered, solvent in removal gained filtrate with dioxane after gained system cooling after the completion of substitution reaction,
Gained residue is purified using dehydrated alcohol, obtains 2,4,6- tri- (4- formvlphenoxv) -1,3,5-triazines.
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