CN109251285A - Conjugation microporous polymer and preparation method thereof based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine - Google Patents
Conjugation microporous polymer and preparation method thereof based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine Download PDFInfo
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Abstract
The present invention provides a kind of conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I, the present invention is 1, s-indacene -1,3 is introduced on the basis of 3,5- tri- (4- aldehyde radical pyridyl group) triazines, 5, laminated structure is presented in 7 (2H, 6H)-tetrones, the conjugation microporous polymer being prepared, for amorphous material, and has uv absorption property.The present invention provides the preparation methods of the conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I, and method is simple and easy, is advantageously implemented large-scale production.
Description
Technical field
The present invention relates to conjugation microporous polymer technical fields, and in particular to one kind is based on 1,3,5- tri- (4- aldehyde radical pyridines
Base) triazine conjugation microporous polymer and preparation method thereof.
Background technique
With the arrival of information age and the rapid development of science and technology, extensive and super large-scale integration is met the tendency of
And give birth to, application is very universal in people's lives.It is matching integrated circuit high speed development and people to high continuation of the journey demand, needs
Profession, battery material that high-performance, large capacity, portable and smart, economy and durability, charging rate are fast, and the development of lithium battery is just
In bottleneck period, because its energy density is already close to its physics limit, it is lower that continual exploitation Cost And Performance promotes ratio.
Organic porous material is in recent years because its unique texture and performance cause the close attention of scientific research personnel, many scientific research people
Member throws oneself into the developmental research of organic porous material, finds organic porous material in gas absorption, separation, heterogeneous catalysis and storage
There are huge applications values in the fields such as energy, and then in recent years, this novel-section is invested in the breach of searching superbattery by the external world
Material.
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 microporous polymers for being based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine
Object and preparation method thereof, the conjugation microporous polymer provided by the invention for being based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines are presented
Laminated structure is amorphous material, and has uv absorption property.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of conjugation microporous polymer for being based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines, with 1,3,
(the 4- aldehyde radical pyridyl group) triazine of 5- tri- and s-indacene -1,3,5,7 (2H, 6H)-tetrone are monomer, press (the 4- aldehyde of 1,3,5- tri-
Yl pyridines base) triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone molar ratios are 1:(1.3~1.7) be prepared, have
There is structure shown in Formulas I:
In Formulas I,Group both ends connection group beGroup three ends connection group be
Tri- (the 4- aldehyde radical pyridyl group) triazine of 1,3,5- has structure shown in Formula II:
The present invention provides the conjugation micropores that 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine is based on described in above-mentioned technical proposal
The preparation method of polymer, comprising the following steps:
Cyanuric Chloride, 4- pyridine aldehydes and tetrahydrofuran are mixed, substitution reaction is carried out in protective atmosphere, obtains 1,3,5-
Three (4- aldehyde radical pyridyl group) triazines；
In protective atmosphere, by described 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine, s-indacene -1,3,5,7 (2H,
6H)-tetrone, organic solvent, acidic catalyst and water mixing, carry out nucleophilic addition-elimination reaction, obtain with knot shown in Formulas I
The conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine of structure；Wherein, described 1,3,5- tri- (4- aldehyde radical pyrroles
Piperidinyl) molar ratio of triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone is 1:(1.3~1.7).
Preferably, the molar ratio of the Cyanuric Chloride and 4- pyridine aldehydes is 1:(2.5~3.5).
Preferably, the temperature of the substitution reaction is 65~75 DEG C, and the time is 70~75h.
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, mesitylene and dioxanes or several
Kind.
Preferably, the temperature of the nucleophilic addition-elimination reaction is 110~130 DEG C, and the time is 70~75h.
Preferably, after the completion of the nucleophilic addition-elimination reaction further include:
Gained system after the completion of nucleophilic addition-elimination reaction is separated by solid-liquid separation, N, N- dimethyl formyl are successively used
Amine and ethyl alcohol wash obtained solid material, dry, are successively carried out using methanol and methylene chloride to gained dried material
Soxhlet extraction, it is dry, obtain having the conjugation micropore based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine of structure shown in Formulas I poly-
Close object.
The conjugation based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I that the present invention provides a kind of
Microporous polymer, the present invention introduce s-indacene -1,3 on the basis of 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine, 5,7 (2H,
Laminated structure is presented in 6H)-tetrone, the conjugation microporous polymer being prepared, and is amorphous material, and have ultraviolet absorbability
Energy.
The present invention provides the conjugation micropores based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
The preparation method of 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 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine in embodiment 1；
Fig. 2 is the infrared spectrogram of 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine in embodiment 1；
Fig. 3 is the ultraviolet spectrogram of 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine 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 that the conjugation based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I in embodiment 1 is micro-
The infrared spectrogram of pore polymer；
Fig. 7 is that the conjugation based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I in embodiment 1 is micro-
The ultraviolet spectrogram of pore polymer；
Fig. 8 is that the conjugation based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I in embodiment 1 is micro-
The thermogravimetric analysis figure of pore polymer；
Fig. 9 is that the conjugation based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I in embodiment 1 is micro-
The XRD scanning analysis figure of pore polymer；
Figure 10 is the conjugation based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I in embodiment 1
The electron-microscope scanning figure of microporous polymer.
Specific embodiment
The present invention provides a kind of conjugation microporous polymer for being based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines, with 1,3,
(the 4- aldehyde radical pyridyl group) triazine of 5- tri- and s-indacene -1,3,5,7 (2H, 6H)-tetrone are monomer, press (the 4- aldehyde of 1,3,5- tri-
Yl pyridines base) triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone molar ratios are 1:(1.3~1.7) be prepared, have
There is structure shown in Formulas I:
In Formulas I,Group both ends connection group beGroup three ends connection group be
Tri- (the 4- aldehyde radical pyridyl group) triazine of 1,3,5- has structure shown in Formula II:
The present invention provides the conjugation micropores that 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine is based on described in above-mentioned technical proposal
The preparation method of polymer, comprising the following steps:
Cyanuric Chloride, 4- pyridine aldehydes and tetrahydrofuran are mixed, substitution reaction is carried out in protective atmosphere, obtains 1,3,5-
Three (4- aldehyde radical pyridyl group) triazines；
In protective atmosphere, by described 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine, s-indacene -1,3,5,7 (2H,
6H)-tetrone, organic solvent, acidic catalyst and water mixing, carry out nucleophilic addition-elimination reaction, obtain with knot shown in Formulas I
The conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine of structure；Wherein, described 1,3,5- tri- (4- aldehyde radical pyrroles
Piperidinyl) molar ratio of triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone is 1:(1.3~1.7).
The present invention mixes Cyanuric Chloride, 4- pyridine aldehydes and tetrahydrofuran, and substitution reaction is carried out in protective atmosphere, is obtained
1,3,5- tri- (4- aldehyde radical pyridyl group) triazine.In the present invention, the molar ratio of the Cyanuric Chloride and 4- pyridine aldehydes is preferably 1:
(2.5~3.5).The present invention mixes the Cyanuric Chloride, 4- pyridine aldehydes and tetrahydrofuran not special restriction, using this
The technical solution of the mixing of material known to the technical staff of field；In the present invention, described to mix preferably under agitation
It carries out.In the present invention, the temperature of the substitution reaction is preferably 65~75 DEG C, and more preferably 70 DEG C；Time is preferably 70~
75h, more preferably 72h.The present invention does not have special restriction for the protective gas type for providing the protective atmosphere, using this
Protective gas known to the technical staff of field, it is specific such as nitrogen.In an embodiment of the present invention, specifically by three polychlorostyrene
Cyanogen, 4- pyridine aldehydes and tetrahydrofuran mixing, stir 1.5~2.5h, so that material is sufficiently mixed and is tentatively reacted, then protecting
It protects in atmosphere, react 70~75h under the conditions of 65~75 DEG C.
After completing the substitution reaction, gained system is preferably separated by solid-liquid separation by the present invention, successively uses tetrahydrofuran
Obtained solid material is washed with ethyl alcohol, it is dry, obtain 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines.The present invention is for institute
The mode for stating separation of solid and liquid does not have special restriction, and the technical solution using separation of solid and liquid well known to those skilled in the art is
Can, it is specific as decompression filters.The present invention restriction not special for the drying, using well known to those skilled in the art dry
Dry technical solution, can be sufficiently dry by material.
After obtaining 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines, the present invention is in protective atmosphere, by described 1,3,5- tri- (4-
Aldehyde radical pyridyl group) triazine, s-indacene -1,3,5,7 (2H, 6H)-tetrones, organic solvent, acidic catalyst and water mixing, into
Row nucleophilic addition-elimination reaction obtains the conjugation based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
Microporous polymer；Wherein, described 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines and s-indacene -1,3,5,7 (2H, 6H)-four
The molar ratio of ketone is 1:(1.3~1.7).In the present invention, the acidic catalyst preferably includes in formic acid, acetic acid and propionic acid
It is one or more of.
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, mesitylene and dioxanes
Kind is several.
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
3~3.5h is reacted under the conditions of DEG C, resulting material is filtered under diminished pressure, wash obtained solid material with acetonitrile, is dried, and is obtained to citing approvingly
Up to -1,3,5,7 (2H, 6H)-tetrones of province.
In the present invention, described 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines, s-indacene -1,3,5,7 (2H, 6H) -
Tetrone, organic solvent, acidic catalyst and water mixing are preferably in protective atmosphere, by 1,3,5- tri- (4- aldehyde radical pyridyl group) three
Piperazine, s-indacene -1,3,5,7 (2H, 6H)-tetrones and organic solvent are stirred 5~15min, then to gained mixture
The aqueous solution of acidic catalyst is added in 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 nucleophilic addition-elimination reaction is preferably 110~130 DEG C, and more preferably 120 DEG C；
Time is preferably 70~75h, more preferably 72h.
After completing the nucleophilic addition-elimination reaction, the present invention is preferably proper by institute after the completion of nucleophilic addition-elimination reaction
System is separated by solid-liquid separation, and is successively washed using n,N-Dimethylformamide and ethyl alcohol to obtained solid material, dry, successively
Soxhlet extraction is carried out to gained dried material using methanol and methylene chloride, it is dry, obtain having structure shown in Formulas I based on 1,
The conjugation microporous polymer of 3,5- tri- (4- aldehyde radical pyridyl group) triazine.The present invention is not special for the mode of the separation of solid and liquid
Restriction, it is specific as decompression filters using the technical solution of separation of solid and liquid well known to those skilled in the art.The present invention couple
In the not special restriction of the washing, using the technical solution of washing well known to those skilled in the art.The present invention couple
The not special restriction of the drying carried out after washing, using the technical solution of drying well known to those skilled in the art, can
Material is sufficiently dry.The present invention does not have the Soxhlet extraction special restriction, ripe using those skilled in the art
The technical solution for the Soxhlet extraction known；The present invention carries out Soxhlet to gained dried material using methanol and methylene chloride and mentions
It takes, is to guarantee sufficiently to remove polymer surfaces and duct internal solvent and unreacted monomer.In the present invention, the rope
The drying that family name carries out after extracting preferably is dried in vacuo, and the vacuum drying temperature is preferably 40~60 DEG C, more preferably 50
℃；Time is preferably 12~for 24 hours, more preferably 15~20h.
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 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine, comprising the following steps:
1.1723g Cyanuric Chloride, 1.964g4- pyridine aldehydes and 80mL tetrahydrofuran are mixed, 2h is stirred, is then protecting
72h is reacted in atmosphere, under the conditions of 70 DEG C；Gained system is subjected to decompression suction filtration, successively using tetrahydrofuran and ethyl alcohol to gained
Solid material is washed, dry, obtains 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines.
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%.
The conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I is prepared,
The following steps are included:
Under nitrogen protection, by 0.5138g 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine, the s-indacene 0.3526g-
1,3,5,7 (2H, 6H)-tetrone, 12mL n-butanol and the mixing of 28mL o-dichlorohenzene, are then added 4mL into gained mixed material
Acetic acid aqueous solution (is formulated) by 1.4mL acetic acid and 2.6mL water, is stirred 20min, reacts 72h under the conditions of 120 DEG C,
Gained system is subjected to decompression suction filtration, successively obtained solid material is washed using n,N-Dimethylformamide and ethyl alcohol,
It is dry, Soxhlet extraction is carried out to gained dried material using methanol and methylene chloride, obtain having structure shown in Formulas I based on 1,
The conjugation microporous polymer (BHY-CMP) of 3,5- tri- (4- aldehyde radical pyridyl group) triazine.
To 1 be prepared, 3,5- tri- (4- aldehyde radical pyridyl group) triazines are characterized, specific as follows:
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines, as shown in Figure 1, the suction at δ ≈ 7.2
It receives peak and is 1 in compound, the proton peak of 6, No. 11 positions, the absorption peak at δ ≈ 1.0 is compound 2,4,7,9,12,15
The proton peak of position, the absorption peak at δ ≈ 0.1 are the proton peaks of 3,5,8,10,13, No. 14 positions of compound, remaining appearance
Peak belong to impurity peaks.Prove that gained compound is 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine really in the present embodiment.
Fig. 2 is the infrared spectrogram of 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines, as shown in Figure 2, in 3116cm-1The suction at place
It receives peak and meets the absorption frequency range that C-H is flexible in phenyl ring, in 2783cm-1The absorption peak at place meets the absorption frequency of aldehyde radical C-H
Rate range, in 1722cm-1The absorption peak at place meets the absorption frequency range of C=O stretching vibration in aldehyde radical, in 1593cm-1Place
Absorption peak meets the absorption frequency range of the C=C in phenyl ring, in 840cm-1The absorption peak at place meets the absorption for having C-C in phenyl ring
Frequency range, in 1400cm-1The absorption peak at place meets the absorption frequency range of C-N.Prove that gained compound is true in the present embodiment
Actually 1,3,5- tri- (4- aldehyde radical pyridyl group) 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
Spectral absorption in UV-visible range.
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, the infrared spectrogram of 5,7 (2H, 6H)-tetrones, as shown in Figure 5, in 1726cm-1Place
Absorption peak meet the absorption frequency range of C=O, in 1354cm-1The absorption peak at place meets the flexible absorption frequency of C=C in phenyl ring
Rate range, in 978cm-1The absorption peak at place meets the absorption frequency range of C-C absorption peak in phenyl ring.Prove institute in the present embodiment
Obtain compound is s-indacene -1,3,5,7 (2H, 6H)-tetrone really.
To the conjugation micropore based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I being prepared
Polymer (BHY-CMP) is characterized, specific as follows:
Fig. 6 is the conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
Infrared spectrogram, it will be appreciated from fig. 6 that polymer is in 2600.35cm-1The aldehyde radical characteristic peak at place disappears, in 1678.53cm-1Place has
The C=C double bond absorption peak of alkene.Prove that gained compound is with structure shown in Formulas I based on 1,3 really in the present embodiment,
The conjugation microporous polymer of 5- tri- (4- aldehyde radical pyridyl group) triazine.
Fig. 7 is the conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
Ultraviolet spectrogram compared to monomer 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine, the spectrum of subject polymer as shown in Figure 7
Absorption concentrates on 401~872nm range, shows the monomer and s-indacene -1,3, gained after the polymerization of 5,7 (2H, 6H)-tetrones
Polymer can reach full spectral absorption.
Fig. 8 is the conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
Thermogravimetric analysis figure, as shown in Figure 8, the weight-loss ratio of polymer is 55.3%；Specifically, in 17~100 DEG C of temperature-rise period,
Weight-loss ratio is 15.1%, mainly due to caused by surface adsorption water, the depigmentation of constitution water；Since 100 DEG C, sample quality
Decline rapidly, weight-loss ratio is about 40%, shows polymer architecture avalanche and structural damage in this temperature range.
Fig. 9 is the conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
XRD scanning analysis figure, as shown in Figure 9, conjugation microporous polymer provided by the invention is undefined structure without obvious strong peak,
Belong to amorphous material.
Figure 10 is the conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
Electron-microscope scanning figure, as shown in Figure 10, conjugation microporous polymer provided by the invention have laminated structure.
As seen from the above embodiment, the conjugation micropore provided by the invention for being based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines
Laminated structure is presented in polymer, is amorphous material, and have uv absorption property, can be applied to the fields such as photocatalysis.
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 the conjugation microporous polymer of 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines, with 1,3,5- tri- (4- aldehyde radical pyrrole
Piperidinyl) triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone be monomer, press 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine
With s-indacene -1,3,5,7 (2H, 6H)-tetrone molar ratios are 1:(1.3~1.7) it is prepared, there is structure shown in Formulas I:
In Formulas I,Group both ends connection group beGroup three ends connection group be
Tri- (the 4- aldehyde radical pyridyl group) triazine of 1,3,5- has structure shown in Formula II:
2. the preparation method of the conjugation microporous polymer described in claim 1 based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazines,
The following steps are included:
Cyanuric Chloride, 4- pyridine aldehydes and tetrahydrofuran are mixed, substitution reaction is carried out in protective atmosphere, obtains 1,3,5- tri-
(4- aldehyde radical pyridyl group) triazine；
In protective atmosphere, by described 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine, s-indacene -1,3,5,7 (2H, 6H) -
Tetrone, organic solvent, acidic catalyst and water mixing, carry out nucleophilic addition-elimination reaction, obtain having structure shown in Formulas I
Conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine；Wherein, described 1,3,5- tri- (4- aldehyde radical pyridines
Base) molar ratio of triazine and s-indacene -1,3,5,7 (2H, 6H)-tetrone is 1:(1.3~1.7).
3. preparation method according to claim 2, which is characterized in that the molar ratio of the Cyanuric Chloride and 4- pyridine aldehydes is
1:(2.5~3.5).
4. preparation method according to claim 2 or 3, which is characterized in that the temperature of the substitution reaction is 65~75 DEG C,
Time is 70~75h.
5. 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.
6. preparation method according to claim 2, which is characterized in that the volume ratio of the organic solvent and water be (10~
20): 1.
7. the preparation method according to claim 2 or 6, which is characterized in that the organic solvent includes n-butanol, adjacent dichloro
One or more of benzene, mesitylene and dioxanes.
8. preparation method according to claim 2, which is characterized in that the temperature of the nucleophilic addition-elimination reaction is 110
~130 DEG C, the time is 70~75h.
9. preparation method according to claim 2, which is characterized in that also wrapped after the completion of the nucleophilic addition-elimination reaction
It includes:
Gained system after the completion of nucleophilic addition-elimination reaction is separated by solid-liquid separation, successively using n,N-Dimethylformamide and
Ethyl alcohol washs obtained solid material, dry, successively carries out Soxhlet to gained dried material using methanol and methylene chloride
It extracts, it is dry, obtain the conjugation microporous polymer based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine with structure shown in Formulas I
Object.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519382A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | 2, 4, 6-tri(2, 6-dimethoxy-4-fluorene hydrazone phenoxy)-1, 3, 5-triazine and method for preparing same |
| US20150299380A1 (en) * | 2012-11-02 | 2015-10-22 | The University Of Liverpool | Soluble polymers |
| CN107814946A (en) * | 2017-11-01 | 2018-03-20 | 台州学院 | A kind of cationic covalent organic framework compound and preparation method thereof |
| CN108164549A (en) * | 2018-02-28 | 2018-06-15 | 四川大学 | COFs materials constructed based on flexible module and its preparation method and application |
-
2018
- 2018-09-21 CN CN201811106904.7A patent/CN109251285B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519382A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | 2, 4, 6-tri(2, 6-dimethoxy-4-fluorene hydrazone phenoxy)-1, 3, 5-triazine and method for preparing same |
| US20150299380A1 (en) * | 2012-11-02 | 2015-10-22 | The University Of Liverpool | Soluble polymers |
| CN107814946A (en) * | 2017-11-01 | 2018-03-20 | 台州学院 | A kind of cationic covalent organic framework compound and preparation method thereof |
| CN108164549A (en) * | 2018-02-28 | 2018-06-15 | 四川大学 | COFs materials constructed based on flexible module and its preparation method and application |
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| CN111484602B (en) * | 2019-01-28 | 2023-01-06 | 台州学院 | 1,3,6,8-tetra (p-formylphenyl) pyrene-based conjugated microporous polymer and preparation method thereof |
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| CN109942814B (en) * | 2019-03-14 | 2021-07-02 | 东华大学 | Pyridyl-containing conjugated microporous polymer and preparation method and application thereof |
| CN110204738A (en) * | 2019-07-15 | 2019-09-06 | 台州学院 | One kind be based on 1,3,5(4- aldehyde radical pyridyl group) triazine covalent organic framework material and preparation method thereof |
| CN112574370A (en) * | 2019-09-27 | 2021-03-30 | 台州学院 | Three-dimensional hydroxyl-containing covalent organic framework material and preparation method thereof |
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