CN101417984A - A kind of initiated core and application thereof that contains triazine ring - Google Patents
A kind of initiated core and application thereof that contains triazine ring Download PDFInfo
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- CN101417984A CN101417984A CNA2008102437760A CN200810243776A CN101417984A CN 101417984 A CN101417984 A CN 101417984A CN A2008102437760 A CNA2008102437760 A CN A2008102437760A CN 200810243776 A CN200810243776 A CN 200810243776A CN 101417984 A CN101417984 A CN 101417984A
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Abstract
The invention discloses a kind of eight arm initiated cores that contain triazine ring, can be used as the macromolecular initiated core of synthesizing tree-like, its molecular formula such as the right side are represented, the described eight arm initiated cores that contain triazine ring, branch point is many: have 8 active chlorine atoms can be further and the monomer reaction that contains reactive hydrogen in the molecule, less reactions steps just can make the gained molecule have more branch, end group and molecular weight, improves the combined coefficient of dendritic macromole; Hapto is many: have 16 nitrogen-atoms and 2 hydrogen atoms in the molecule, both can with metallic ion coordination, can form hydrogen bond with heteroatomic molecule such as other hydrogen atoms or nitrogen, oxygen etc. again.
Description
Technical field
The present invention relates to a kind of compound that contains triazine ring, be specifically related to a kind of initiated core of dendrimer.
Background technology
Cyanuric chloride is because s-triazine ring heat, oxidative stability in the molecule are good, and have photolytic activity and biological activity, three chlorine atoms in the molecule have the reactive behavior of similar acyl chlorides, and can reach substep by controlled temperature replaces, therefore, cyanuric chloride is widely used in synthetic multiple derivative, is applied in a plurality of fields such as agricultural chemicals, medicine, rubber ingredients, paper process and textile auxiliary agenies.
The polyfunctionality of cyanuric chloride and the Controllable Temperature of reaction have caused dendritic macromole area research person's concern in recent years.Hassan etc. are nuclear with the polyoxyethylene glycol, utilize cyanuric chloride and thanomin alternation response, have synthesized a kind of linearity-dendroid segmented copolymer of environment sensitive; Simanek seminar contains 1 with cyanuric chloride, piperidines, piperazine, 4-aminomethyl piperazine etc. are a series of for main raw material has synthesized, 3, the dendritic macromole of 5-triazine ring, this seminar uses polyoxyethylene glycol again recently, and cyanuric chloride and taxol etc. has synthesized a kind of water miscible linearity-dendroid segmented copolymer.Usefulness cyanuric chlorides such as Takagi and p-Nitroaniline, p-NP have synthesized a class dendritic macromole; The core of these dendritic macromoles is generally two arms, three arms.
Contriver place seminar has synthesized 2 kind of four arm initiated core (referring to Lin Xiuxiu with cyanuric chloride and quadrol, hexanediamine, Liu Xiaohong, Xu Dongmei, Zhang Keda. fine chemistry industry .2007,24 (2): 194-198.[12] Zhao Zhongling, Yang Guibao, Xu Dongmei, Zhang Keda. chemical research and application .2008,20 (1): 80-83), and successfully be used for the synthetic of dendritic macromole, the molecular formula of above-mentioned two kinds of initiated cores is as follows:
Research shows that simultaneously the number of the initiation arm of initiated core is many more, and when synthesizing dendritic macromole, the branch of dendritic macromole, end group and molecular weight just increase fast more.
But report is at most that 2 cyanuric chloride molecules are replaced a chlorine by same molecule simultaneously at present, and two above cyanuric chloride molecule whiles are not appeared in the newspapers by the situation that same molecule replaces a chlorine.
Summary of the invention
The object of the invention provides a kind of eight arm initiated cores that contain triazine ring, when making it synthesize dendritic macromole as initiated core, makes branch, end group and the molecular weight of dendritic macromole increase faster; The present invention also aims to provide the preparation method and the application thereof of above-mentioned eight arm initiated cores.
For achieving the above object, the technical solution used in the present invention is: a kind of eight arm initiated cores that contain triazine ring, and the following expression of its molecular formula:
The above-mentioned preparation method who contains eight arm initiated cores of triazine ring may further comprise the steps:
(1) amount of substance (mole number) with triethylene tetramine (TETA) is 1 part, N, N-diisopropylethylamine (DIPEA): cyanuric chloride (TCT): triethylene tetramine (TETA) mol ratio=(4.3～5.0): (4.3～5.0): 1; Earlier TCT is dissolved in solvent orange 2 A, TETA and DIPEA is dissolved in simultaneously under 0～5 ℃ the solution of solvent orange 2 A, be added drop-wise to 0.5～1.0ml/min in the solution of TCT, after dropwising, in nitrogen atmosphere,, rise to room temperature reaction 36～84h again in 0～5 ℃ of reaction 3～6h down;
(2) after reaction finishes, remove solvent orange 2 A, regulate pH value to 6～7, and be washed to neutrality, suction filtration gets filter cake, and drying obtains white powder.
Above-mentioned preparation process can be expressed as follows:
In the technique scheme, it is solvent that described solvent orange 2 A is selected from anhydrous tetrahydro furan; N, N-diisopropylethylamine (DIPEA) is an alkali; Entire reaction is carried out under nitrogen protection; Use deionized water when being washed to neutrality in the step (2); Drying process is vacuum-drying under the room temperature.
The present invention also comprises the described application that contains eight arm initiated cores of triazine ring as the initiated core of dendritic macromole.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. branch point is many: have 8 active chlorine atoms can be further and the monomer reaction that contains reactive hydrogen in the molecule, less reactions steps just can make the gained molecule have more branch, end group and molecular weight, improves the combined coefficient of dendritic macromole.
2. hapto is many: have 16 nitrogen-atoms and 2 hydrogen atoms in the molecule, both can with metallic ion coordination, can form hydrogen bond with heteroatomic molecule such as other hydrogen atoms or nitrogen, oxygen etc. again.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=4.3:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=5.0:1.
Earlier TCT is dissolved in the three-necked flask with anhydrous tetrahydro furan; tetrahydrofuran solution with TETA and DIPEA under 5 ℃ is added drop-wise in the three-necked flask with 0.7ml/min, after dropwising, at 0～5 ℃ of reaction 4h; rise to room temperature reaction 48h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 6, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 62.7%.
Embodiment two:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=4.8:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=5.0:1.
Earlier TCT is dissolved in the three-necked flask with anhydrous tetrahydro furan; 0 ℃ of tetrahydrofuran solution with TETA and DIPEA is added drop-wise in the three-necked flask with 0.7ml/min, after dropwising, at 0～5 ℃ of reaction 4h; rise to room temperature reaction 48h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 6, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 67.2%.
Embodiment three:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=5.0:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=4.3:1.
Earlier TCT is dissolved in the three-necked flask with anhydrous tetrahydro furan; tetrahydrofuran solution with TETA and DIPEA under 0 ℃ is added drop-wise in the three-necked flask with 0.7ml/min, after dropwising, at 0～5 ℃ of reaction 4h; rise to room temperature reaction 48h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 7, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 63.5%.
Embodiment four:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=5.0:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=4.8:1.
Earlier TCT is dissolved in the three-necked flask with anhydrous tetrahydro furan; tetrahydrofuran solution with TETA and DIPEA under 5 ℃ is added drop-wise in the three-necked flask with 0.7ml/min, after dropwising, at 0～5 ℃ of reaction 4h; rise to room temperature reaction 48h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 6, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 67.2%.
Embodiment five:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=5.0:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=5.0:1.
Earlier TCT is dissolved in the three-necked flask with anhydrous tetrahydro furan; tetrahydrofuran solution with TETA and DIPEA under 1 ℃ is added drop-wise in the three-necked flask with 0.7ml/min, after dropwising, at 0～5 ℃ of reaction 3h; rise to room temperature reaction 48h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 6.2, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 60.9%.
Embodiment six:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=5.0:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=5.0:1.
Earlier TCT is dissolved in the three-necked flask with anhydrous tetrahydro furan; tetrahydrofuran solution with TETA and DIPEA under 2 ℃ is added drop-wise in the three-necked flask with 0.7ml/min, after dropwising, at 0～5 ℃ of reaction 5h; rise to room temperature reaction 48h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 6.5, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 73.0%.
Embodiment seven:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=5.0:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=5.0:1.
Earlier TCT is dissolved in the three-necked flask with anhydrous tetrahydro furan; tetrahydrofuran solution with TETA and DIPEA under 0 ℃ is added drop-wise in the three-necked flask with 0.7ml/min, after dropwising, at 0～5 ℃ of reaction 5h; rise to room temperature reaction 36h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 6, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 64.2%.
Embodiment eight:
With the anhydrous tetrahydro furan is solvent, N, and N-diisopropylethylamine (DIPEA) is an alkali, cyanuric chloride (TCT) and triethylene tetramine (TETA) mol ratio, n (TCT): n (TETA)=5.0:1, DIPEA and triethylene tetramine (TETA) mol ratio, n (DIPEA): n (TETA) :=5.0:1.
Earlier TCT is added drop-wise in the three-necked flask with 0.7ml/min with the tetrahydrofuran solution that anhydrous tetrahydro furan is dissolved in the three-necked flask under 5 ℃ TETA and DIPEA; after dropwising; at 0～5 ℃ of reaction 5h, rise to room temperature reaction 72h again, entire reaction is carried out under nitrogen protection.Reaction is removed tetrahydrofuran (THF) after finishing, and regulates pH value to 7, and is washed till neutrality with deionized water, and suction filtration gets filter cake, and room temperature vacuum-drying obtains white powder, and productive rate is 71.3%.
Embodiment nine:
The product test data:
Infrared spectra: can see the characteristic peak of functional group the target product structure, 3172.0cm from the infrared spectrogram of product
-1And 3272.3cm
-1The place is the stretching vibration of-NH-; 2801.5cm
-1And 2963.5cm
-1The place is
Stretching vibration; 1404.6cm
-1, 1443.2cm
-1, 1559.0cm
-1, 1613.0cm
-1The place is the skeletal vibration peak of s-triazine ring; 1242.6cm
-1Be-NH-and-C-N stretching vibration that CH-is connected; 1327.5cm
-1The C-N stretching vibration that links to each other with carbon on the triazine ring for-NH-.
Nuclear-magnetism: the proton magnetic of product (
1H-NMR) three groups of peak: δ=9.09ppm (a, 2H, triplet) are arranged in the spectrogram; δ=3.82ppm (d, 4H, triplet), 3.73 (c, 4H, triplets), 3.54 (b, 4H, multiplets), its integration a:b:c:d=1.99:4.03:4.02:3.96, more approaching with theory than 1:2:2:2, conform to the target product structure.
Mass spectrum: in the FAB-MS of product mass spectrum, can see target product (C
18H
14N
16C
18) molecular ion peak m/z=738.
In conjunction with nuclear-magnetism, infrared spectra and mass spectrometry results, can determine that products therefrom is a target product.
Target product fusing point: greater than 300 ℃.
Claims (3)
1. initiated core that contains triazine ring, it is characterized in that: the described initiated core that contains triazine ring is eight arm initiated cores, the following expression of its molecular formula:
2. the described application that contains the initiated core of triazine ring as the synthetic dendritic macromole of initiated core of claim 1.
3. prepare the described method that contains the initiated core of triazine ring of claim 1, it is characterized in that may further comprise the steps:
(1) amount of substance with triethylene tetramine is 1 part, N, N-diisopropylethylamine: cyanuric chloride: triethylene tetramine mol ratio=4.3～5.0:4.3～5.0:1; Earlier cyanuric chloride is dissolved in solvent orange 2 A, with triethylene tetramine and N, the N-diisopropylethylamine is dissolved in the solution of solvent orange 2 A simultaneously under 0～5 ℃, slowly be added drop-wise in the solution of cyanuric chloride, after dropwising, in nitrogen atmosphere, reaction 3～6h rises to room temperature reaction 36～84h again under 0～5 ℃;
(2) after reaction finishes, remove solvent orange 2 A, regulate pH value to 6～7, and be washed to neutrality, suction filtration gets filter cake, and drying obtains white powder, and white powder is the described initiated core compound that contains triazine ring;
Described solvent orange 2 A is an anhydrous tetrahydro furan.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013455A (en) * | 2015-07-02 | 2015-11-04 | 陕西科技大学 | Carboxyl terminated dendritic polymer adsorption material and preparation method thereof |
| CN110922389A (en) * | 2019-10-14 | 2020-03-27 | 天津利安隆新材料股份有限公司 | Preparation method of hindered amine light stabilizer |
| CN111363864A (en) * | 2018-12-26 | 2020-07-03 | 温州大学 | Nonmetal cation tanning agent and preparation method thereof |
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| US7399841B1 (en) * | 2005-09-15 | 2008-07-15 | The United States Of America As Represented By The Secretary Of The Navy | High-energy 1,3,5-triazinyl diazenes, and process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013455A (en) * | 2015-07-02 | 2015-11-04 | 陕西科技大学 | Carboxyl terminated dendritic polymer adsorption material and preparation method thereof |
| CN111363864A (en) * | 2018-12-26 | 2020-07-03 | 温州大学 | Nonmetal cation tanning agent and preparation method thereof |
| CN110922389A (en) * | 2019-10-14 | 2020-03-27 | 天津利安隆新材料股份有限公司 | Preparation method of hindered amine light stabilizer |
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Granted publication date: 20101229 Termination date: 20131215 |