CN109705344A - A kind of method that nickel complex as catalyst prepares 1,5- stereoregular polytriazoles - Google Patents
A kind of method that nickel complex as catalyst prepares 1,5- stereoregular polytriazoles Download PDFInfo
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Abstract
The invention belongs to the technical fields of polymer chemistry, disclose a kind of method of nickel complex as catalyst preparation 1,5- stereoregular polytriazoles.Method includes the following steps: under the conditions of existing for the alkaline environment and organophosphorus ligand, the catalytic action that binary alkynyl compounds and binary azido cpd pass through nickel complex in organic solvent is subjected to click polymerization, subsequent processing, obtain 1,5- stereoregular polytriazoles, structure are formula (I).Method mild condition of the invention, reaction efficiently, Atom economy it is good and with very high regioselectivity.Polytriazoles obtained by the present invention is 1,5- stereoregular polytriazoles, and degree of regioregularity is high, and yield is high, and has outstanding processability and extraordinary thermal stability.
Description
Technical field
The present invention relates to polymer chemistry and materialogy field, and in particular to a kind of nitrine of nickel complex as catalyst-alkynes point
Hit the method that polymerization prepares 1,5- stereoregular polytriazoles.
Background technique
In polymer science field, develop efficient and selective polymerization reaction have for preparation determine structure and
The functional polymer of peculiar property is most important.It clicks polymerization and reacts efficient, mild condition, Atom economy and region by it
Good selective has obtained extensive concern, and obtains extensively in fields such as biomaterial, photoelectric material and self-repair materials
General application.It is clicked in polymerization however, current research hotspot is concentrated mainly on copper (I) catalysis nitrine-alkynes, other metals is urged
The research that the nitrine of change-alkynes clicks polymerization is also considerably less.In addition, it is contemplated that copper (I) catalysis nitrine-alkynes is clicked polymerization and can only be made
Isosorbide-5-Nitrae-stereoregular polytriazoles develops nitrine that is new, being capable of providing 1,5- stereoregular polytriazoles-alkynes click polymerization and not only may be used
With offer prepare the new method of polytriazoles and also can enrich click polymerization type, for click polymerization it is further development with
More extensive application is of great significance.
Preparation for 1,5- stereoregular polytriazoles, a small amount of report existing at present.2008, Tang Benzhong seminar disclosed
A kind of catalyzed by ruthenium complexes nitrine-alkynes clicks the method (Hyperbranched that polymerization prepares 1,5- stereoregular polytriazoles
polytriazoles:Click polymerization,regioisomeric structure,light emission,and
fluorescent patterning.Macromolecules 2008,41,3808-3822)；2015, which reported again
Road organic base tetramethyl oxyammonia catalysis nitrine-alkynes clicks polymerization and is used to prepare 1,5- stereoregular polytriazoles
(Synthesis of 1,5-regioregular polytriazoles by efficient NMe4OH-mediated
azide-alkyne click polymerization.Polym.Chem.2015,6,5545-5549).However, both sides
Method has certain limitation, the former needs to react at 60 DEG C of heating, and the latter is only applicable to fragrant acetylenic monomer and fragrance is folded
Nitrogen class monomer.Therefore, exploit condition milder, substrate spectrum are wider and are capable of providing the nitrine-of 1,5- stereoregular polytriazoles
Alkynes clicks polymerization and is necessary.
Summary of the invention
In order to overcome the disadvantages and deficiencies of the prior art, the purpose of the present invention is to provide a kind of preparations of nickel complex as catalyst
The method of 1,5- stereoregular polytriazoles, this method mild condition, reaction efficiently, can synthesize the polymer of high molecular weight.
The purpose of the present invention is achieved through the following technical solutions:
A kind of method of nickel complex as catalyst preparation 1,5- stereoregular polytriazoles, comprising the following steps:
Under the conditions of existing for the alkaline environment and organophosphorus ligand, by binary alkynyl compounds and binary azido cpd
Click polymerization is carried out by the catalytic action of nickel complex in organic solvent, subsequent processing obtains 1,5- stereoregular poly- three
Azoles；
The structure of the 1,5- stereoregular polytriazoles is formula (I):
The structural formula of the binary alkynyl compounds is formula (II):
The structural formula of the binary azido cpd is formula (III):
In formula (I)~(III), the integer that n is 2~200, R1、R2For identical or different organic group.
R in the formula (I) and (II)1For any one in following chemical structural formula 1~17:
Wherein, the positive integer that m, k, h are 1~20；X is selected from N, O, P, S or Si；* the position of substitution is indicated.
R in the formula (I) and (III)2For any one in following chemical structural formula 1~18:
Wherein, the positive integer that m, k, h are 1~20；X is selected from N, O, P, S or Si；* the position of substitution is indicated.
The alkaline environment is by cesium carbonate, trimethylace tonitric caesium, sodium hydroxide, sodium ascorbate, potassium phosphate, hydroxide
At least one of potassium, sodium carbonate, sodium phosphate, potassium carbonate provide.
The nickel complex is in dicyclopentadienyl nickel, two (methyl cyclopentadienyl) nickel and two (tetramethyl-ring pentadienyl) nickel
It is at least one；The organophosphorus ligand is the bis- diphenylphosphine -9,9- xanthphos of 4,5- or bis- (2- diphenylphosphine phenyl)
Ether.
The reaction temperature of the click polymerization is 15~35 DEG C.
The reaction time of the click polymerization is 0.1~12 hour.
The molar ratio of the binary alkynyl compounds and binary azido cpd is 1:(1~1.1), binary alkynyl chemical combination
The concentration of object in organic solvent is 0.05~1mol/L；
The organic solvent be toluene, tetrahydrofuran, methylene chloride, chloroform, 1,4- dioxane, dimethyl sulfoxide and N,
At least one of dinethylformamide.
The nickel complex dosage is 5mol%~30mol% (binary alkynyl compounds mole of binary alkynyl compounds
The 5%~30% of dosage)；The organophosphorus ligand dosage is 5mol%~30mol% (binary alkynyl of binary alkynyl compounds
The 5%~30% of compound mole dosage).
Click of the invention, which is aggregated in inert atmosphere and air, can all carry out.
The subsequent processing refers to after completion of the reaction, in organic solvent by product dissolution, is then added drop-wise in precipitating reagent
It is precipitated, collects sediment, it is dry to constant weight, obtain 1,5- stereoregular polytriazoles.
The precipitating reagent is methanol or n-hexane.
The organic solvent be toluene, tetrahydrofuran, methylene chloride, chloroform, 1,4- dioxane, dimethyl sulfoxide and N,
At least one of dinethylformamide.
The 1,5- stereoregular polytriazoles is prepared by the above method.
Compared with prior art, the present invention has the following advantages and beneficial effects:
1. method of the invention is capable of providing 1,5- stereoregular polytriazoles, and degree of regioregularity is high.
2. method mild condition of the invention, simple process, polymerization efficiency is high, such as: room temperature reaction can be obtained for 30 minutes
The polymer of high molecular weight.
3. polymerization process no coupling product of the invention generates, meet Atom economy.
4. method reaction raw materials of the invention are easy to get, can directly buy or by simply reaction preparation.
Detailed description of the invention
Fig. 1 is 1,5- stereoregular polytriazoles P1 prepared by embodiment 1 and its corresponding monomer and Model Molecule in CD2Cl2/
DMSO-d6Nuclear magnetic resonance spectroscopy comparison diagram in (volume ratio 1:2)；C is the disubstituted triazole of Isosorbide-5-Nitrae-(Model Molecule), and D is 1,5-
Disubstituted triazole (Model Molecule), E are 1,5- stereoregular polytriazoles P1；
Fig. 2 is 1,5- stereoregular polytriazoles P1 prepared by embodiment 1 and its corresponding monomer and Model Molecule in CDCl3In
Carbon-13 nmr spectra comparison diagram；C is the disubstituted triazole of Isosorbide-5-Nitrae-(Model Molecule), and D is the disubstituted triazole of 1,5- (Model Molecule),
E is 1,5- stereoregular polytriazoles P1；
Fig. 3 is the thermogravimetric curve figure that polytriazoles P1-P9 is made in Examples 1 to 9；
Fig. 4 is circular dichroism spectra (the tetrahydro furan of embodiment 5~6,8~9 obtained polytriazoles P5, P6, P8, P9 and monomer M6, M7
It mutters solution, concentration: 10-5M)。
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
Nickel complex as catalyst M1 and M2 prepare polytriazoles P1:
Wherein, monomer M1 is according to (Catalyst-free thiol-yne click in published document
polymerization:A powerful and facile tool for preparation of functional poly
(vinylene sulfide) s.Macromolecules 2014,47,1325-1333) synthetic method synthesis；Monomer M2 is pressed
According in published document (Hyperbranched polytriazoles:Click polymerization,
regioisomeric structure,light emission,and fluorescent
Patterning.Macromolecules 2008,41,3808-3822) synthetic method synthesis.
91.2mg (0.2mmol) monomer M1,72mg (0.2mmol) monomer M2,7.6mg are added in the polymerization pipe of 10mL
(0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P1.
It analyzes after measured, the yield of final product polytriazoles P1 is 96.7%, weight average molecular weight 60100, molecular weight point
Cloth is that 1.69 (molecular weight and molecualr weight distribution is the ultra high efficiency polymer chromatography system by being configured with diode array detector
(APC) it measures.Using THF as mobile phase, flow velocity 0.5mL/min, with the linear polystyrene (PS) that is singly distributed be reference substance into
Row correction).
Fig. 1 is 1,5- stereoregular polytriazoles P1 prepared by embodiment 1 and its corresponding monomer and Model Molecule in CD2Cl2/
DMSO-d6Nuclear magnetic resonance spectroscopy comparison diagram in (volume ratio 1:2)；C is the disubstituted triazole of Isosorbide-5-Nitrae-(Model Molecule), and D is 1,5-
Disubstituted triazole (Model Molecule), E are 1,5- stereoregular polytriazoles P1；Fig. 2 is that 1,5- stereoregular prepared by embodiment 1 is poly-
Triazole P1 and its corresponding monomer and Model Molecule are in CDCl3In carbon-13 nmr spectra comparison diagram；C is the disubstituted triazole of 1,4-
(Model Molecule), D are the disubstituted triazoles of 1,5- (Model Molecule), and E is 1,5- stereoregular polytriazoles P1.Embodiment 1 is made poly-
The thermogravimetric curve figure of triazole P1 is as shown in Figure 3.
The nuclear magnetic resoance spectrum of polytriazoles P1 and its corresponding monomer and Model Molecule is shown in Fig. 1, Fig. 2 (* represents solvent peak), such as schemes
Shown in 1, the nuclear magnetic resonance spectroscopy of polymer P 1 has not observed alkynes hydrogen peak substantially at chemical shift 3.98ppm, in chemical potential
It moves at 7.73ppm and the corresponding characteristic peak of the disubstituted triazole hydrogen of obviously 1,5- occurs, and at chemical shift 8.42ppm
Observe the corresponding characteristic peak of the disubstituted triazole hydrogen of very weak 1,4-；Simultaneously as shown in Fig. 2, polymer P 1 nuclear magnetic resonance
In carbon spectrum, the corresponding characteristic peak of alkynes carbon has not been observed at chemical shift 83.53ppm and 77.52ppm, and in chemical shift
Occur the corresponding characteristic peak of the disubstituted triazole carbon of obviously 1,5- at 138.84ppm and 133.25ppm, and in chemical potential
It moves at 147.88ppm and 119.60ppm and characteristic peak corresponding with the disubstituted triazole carbon of 1,4- is not observed.These characterization results
Show monomer fully reacting and obtained the stereoregulated polytriazoles product of 1,5-, can be calculated by nuclear magnetic resonance spectroscopy
The 1,5- steric regularity for obtaining P1 is 95%.The polytriazoles dissolves in methylene chloride, chloroform, tetrahydrofuran and N, N- at room temperature
In the common organic solvent such as dimethylformamide, show it with excellent machinability；From Fig. 3 (test condition: nitrogen atmosphere
Under, heating rate is 10 DEG C/min) as can be seen that 5% thermal weight loss temperature of the polytriazoles is 366.8 DEG C, show it with non-
Often good thermal stability.
The structure of the disubstituted triazole of 1,4- (Model Molecule) is
The structure of the disubstituted triazole of 1,5- (Model Molecule) is
When the reaction in embodiment 1 carries out in air, 1,5- stereoregular with similar structure can equally be made
Polytriazoles is analyzed after measured, yield 94.9%, weight average molecular weight 21250, molecular weight distribution 1.55,1, and 5- founds structure
Regularity is 93.6%.
Embodiment 2
Nickel complex as catalyst M1 and M3 prepare polytriazoles P2:
Wherein, monomer M1 is according to (Catalyst-free thiol-yne click in published document
polymerization:A powerful and facile tool for preparation of functional poly
(vinylene sulfide) s.Macromolecules 2014,47,1325-1333) synthetic method synthesis；Monomer M3 is pressed
According to (A recyclable and reusable supported Cu (I) catalyzed azide- in published document
Alkyne click polymerization.Sci.Rep.2014,4,5107) synthetic method synthesis.
91.2mg (0.2mmol) monomer M1,95.6mg (0.2mmol) monomer M3,7.6mg are added in the polymerization pipe of 10mL
(0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P2.
It analyzes after measured, the yield of final product polytriazoles P2 is 94.3%, weight average molecular weight 60000, molecular weight point
Cloth is 1.78.It is 96% by the 1,5- steric regularity that P2 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles at room temperature may be used
It is dissolved in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.
The thermogravimetric curve figure that polytriazoles P2 is made in embodiment 2 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature is 372.3 DEG C, shows it with extraordinary thermal stability.
Embodiment 3
Nickel complex as catalyst M1 and M4 prepare polytriazoles P3:
Wherein, monomer M1 is according to (Catalyst-free thiol-yne click in published document
polymerization:A powerful and facile tool for preparation of functional poly
(vinylene sulfide) s.Macromolecules 2014,47,1325-1333) synthetic method synthesis；Monomer M4 is pressed
According to (A recyclable and reusable supported Cu (I) catalyzed azide- in published document
Alkyne click polymerization.Sci.Rep.2014,4,5107) synthetic method synthesis.
In the polymerization pipe of 10mL be added 91.2mg (0.2mmol) monomer M1,122.8mg (0.2mmol) monomer M4,
7.6mg (0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P3.
It analyzes after measured, the yield of final product polytriazoles P3 is 96.4%, weight average molecular weight 67900, molecular weight point
Cloth is 1.92.It is 95% by the 1,5- steric regularity that P3 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles at room temperature may be used
It is dissolved in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.The thermogravimetric curve figure that polytriazoles P3 is made in embodiment 3 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature is 368.7 DEG C, shows it with extraordinary thermal stability.
Embodiment 4
Nickel complex as catalyst M1 and M5 prepare polytriazoles P4:
Wherein, monomer M1 is according to (Catalyst-free thiol-yne click in published document
polymerization:A powerful and facile tool for preparation of functional poly
(vinylene sulfide) s.Macromolecules 2014,47,1325-1333) synthetic method synthesis；Monomer M5 is pressed
According to (Polytriazoles with aggregation-induced emission in published document
characteristics:Synthesis by click polymerization and application as
Explosive chemosensors.Macromolecules 2009,42,1421-1424) synthetic method synthesis.
91.2mg (0.2mmol) monomer M1,88.4mg (0.2mmol) monomer M5,7.6mg are added in the polymerization pipe of 10mL
(0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P4.
It analyzes after measured, the yield of final product polytriazoles P4 is 93.3%, weight average molecular weight 29800, molecular weight point
Cloth is 1.68.It is 92.5% by the 1,5- steric regularity that P4 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles is at room temperature
It dissolves in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.The thermogravimetric curve figure that polytriazoles P4 is made in embodiment 4 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature be 368.6 DEG C, show it with extraordinary thermal stability.
Embodiment 5
Nickel complex as catalyst M1 and M6 prepare polytriazoles P5:
Wherein, monomer M1 is according to (Catalyst-free thiol-yne click in published document
polymerization:A powerful and facile tool for preparation of functional poly
(vinylene sulfide) s.Macromolecules 2014,47,1325-1333) synthetic method synthesis；Monomer M6 ginseng
Examine the synthetic method synthesis of monomer M1.
In the polymerization pipe of 10mL be added 91.2mg (0.2mmol) monomer M1,107.2mg (0.2mmol) monomer M6,
7.6mg (0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P5.
It analyzes after measured, the yield of final product polytriazoles P5 is 89.8%, weight average molecular weight 47000, molecular weight point
Cloth is 1.73.It is 94% by the 1,5- steric regularity that P5 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles at room temperature may be used
It is dissolved in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.The thermogravimetric curve figure that polytriazoles P5 is made in embodiment 5 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature is 369.8 DEG C, shows it with extraordinary thermal stability.Further, since introducing with chiral axis
Binaphthalene primitive, polytriazoles P5 are shown and monomer M6 consistent chiral (Fig. 4).Polytriazoles P5 and monomer is made in embodiment 5
Circular dichroism spectra (tetrahydrofuran solution, the concentration: 10 of M6-5M) as shown in Figure 4.
Embodiment 6
Nickel complex as catalyst M1 and M7 prepare polytriazoles P6:
Wherein, monomer M1 is according to (Catalyst-free thiol-yne click in published document
polymerization:A powerful and facile tool for preparation of functional poly
(vinylene sulfide) s.Macromolecules 2014,47,1325-1333) synthetic method synthesis；Monomer M7 ginseng
Examine the synthetic method synthesis of monomer M1.
In the polymerization pipe of 10mL be added 91.2mg (0.2mmol) monomer M1,107.2mg (0.2mmol) monomer M7,
7.6mg (0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P6.
It analyzes after measured, the yield of final product polytriazoles P6 is 90.4%, weight average molecular weight 53800, molecular weight point
Cloth is 1.72.It is 95.5% by the 1,5- steric regularity that P6 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles is at room temperature
It dissolves in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.The thermogravimetric curve figure that polytriazoles P6 is made in embodiment 6 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature be 371.3 DEG C, show it with extraordinary thermal stability；Further, since introducing with chiral axis
Binaphthalene primitive, polytriazoles P6 is shown and monomer M7 consistent chiral (Fig. 4).Polytriazoles P6 and list is made in embodiment 6
Circular dichroism spectra (tetrahydrofuran solution, the concentration: 10 of body M7-5M) as shown in Figure 4.
Embodiment 7
Nickel complex as catalyst M8 and M2 prepare polytriazoles P7:
Wherein, monomer M8 is according to (Indium-catalyzed polycyclotrimerization in published document
of diynes:a facile route to prepare regioregular hyperbranched
Polyarylenes.Polym.Chem.2014,5,5890-5894 synthetic method synthesis)；Monomer M2 is according to published text
(Hyperbranched polytriazoles:Click polymerization, regioisomeric in offering
structure,light emission,and fluorescent patterning.Macromolecules 2008,41,
Synthetic method synthesis 3808-3822).
63.6mg (0.2mmol) monomer M8,72mg (0.2mmol) monomer M2,7.6mg are added in the polymerization pipe of 10mL
(0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P7.
It analyzes after measured, the yield of final product polytriazoles P7 is 91.3%, weight average molecular weight 46900, molecular weight point
Cloth is 1.70.It is 97% by the 1,5- steric regularity that P7 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles at room temperature may be used
It is dissolved in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.The thermogravimetric curve figure that polytriazoles P7 is made in embodiment 7 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature is 388.1 DEG C, shows it with extraordinary thermal stability.
Embodiment 8
Nickel complex as catalyst M9 and M6 prepare polytriazoles P8:
Wherein, monomer M9 is according to (Hyperbranched polytriazoles with high in published document
molecular compressibility:aggregation-induced emission and superamplified
Explosive detection.J.Mater.Chem.2011,21,4056-4059) synthetic method synthesis；Monomer M6 reference
The synthetic method of monomer M1 synthesizes.
76mg (0.2mmol) monomer M9,107.2mg (0.2mmol) monomer M6,7.6mg are added in the polymerization pipe of 10mL
(0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(0.2mmol) cesium carbonate vacuum and exchange nitrogen 3 times, injects the super dry n,N-Dimethylformamide of 0.5mL with syringe, in room temperature
Lower reaction 30 minutes.After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, the polymer solution that will be obtained
It is added drop-wise in the methanol that 80mL is vigorously stirred and is precipitated after cotton is filtered, is then allowed to stand, collect sediment, obtained after dry
Polytriazoles P8.
It analyzes after measured, the yield of final product polytriazoles P8 is 85.9%, weight average molecular weight 47500, molecular weight point
Cloth is 1.86.It is 94.5% by the 1,5- steric regularity that P8 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles is at room temperature
It dissolves in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.The thermogravimetric curve figure that polytriazoles P8 is made in embodiment 8 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature be 385.6 DEG C, show it with extraordinary thermal stability；Further, since introducing with chiral axis
Binaphthalene primitive, polytriazoles P8 is shown and monomer M6 consistent chiral (Fig. 4).Polytriazoles P8 and list is made in embodiment 8
Circular dichroism spectra (tetrahydrofuran solution, the concentration: 10 of body M6-5M) as shown in Figure 4.
Embodiment 9
Nickel complex as catalyst M9 and M7 prepare polytriazoles P9:
Wherein, monomer M9 is according to (Hyperbranched polytriazoles with high in published document
molecular compressibility:aggregation-induced emission and superamplified
Explosive detection.J.Mater.Chem.2011,21,4056-4059) synthetic method synthesis；Monomer M7 reference
The synthetic method of monomer M1 synthesizes.
76mg (0.2mmol) monomer M9,107.2mg (0.2mmol) monomer M7,7.6mg are added in the polymerization pipe of 10mL
(0.04mmol) dicyclopentadienyl nickel, the bis- diphenylphosphine -9,9- xanthphos of 23.1mg (0.04mmol) 4,5- and 65.2mg
(dosage for providing the substance of alkaline environment is the 0.01~10 of binary alkynyl compounds mole dosage to (0.2mmol) cesium carbonate
Times), vacuum and exchange nitrogen 3 times, the super dry n,N-Dimethylformamide of 0.5mL is injected with syringe, is reacted 30 minutes at room temperature.
After reaction, 4mL methylene chloride is added into polymerization pipe to be diluted, obtained polymer solution is dripped after cotton is filtered
It is added in the methanol that 80mL is vigorously stirred and is precipitated, is then allowed to stand, collect sediment, obtain polytriazoles P9 after dry.
It analyzes after measured, the yield of final product polytriazoles P9 is 81.6%, weight average molecular weight 32000, molecular weight point
Cloth is 1.75.It is 93.5% by the 1,5- steric regularity that P9 can be calculated in nuclear magnetic resonance spectroscopy.The polytriazoles is at room temperature
It dissolves in the common organic solvent such as methylene chloride, chloroform, tetrahydrofuran and n,N-Dimethylformamide, shows it with excellent
Machinability.The thermogravimetric curve figure that polytriazoles P9 is made in embodiment 9 is as shown in Figure 3.From figure 3, it can be seen that the polytriazoles
5% thermal weight loss temperature be 388 DEG C, show it with extraordinary thermal stability；Further, since introducing with chiral axis
Binaphthalene primitive, polytriazoles P9 are shown and monomer M7 consistent chiral (Fig. 4).Polytriazoles P9 and monomer is made in embodiment 9
Circular dichroism spectra (tetrahydrofuran solution, the concentration: 10 of M7-5M) as shown in Figure 4.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method of nickel complex as catalyst preparation 1,5- stereoregular polytriazoles, it is characterised in that: the following steps are included:
Under the conditions of alkaline environment and organophosphorus ligand are existing, by binary alkynyl compounds and binary azido cpd in organic solvent
In click polymerization carried out by the catalytic action of nickel complex, subsequent processing obtains 1,5- stereoregular polytriazoles；
The structure of the 1,5- stereoregular polytriazoles is formula (I):
The structural formula of the binary alkynyl compounds is formula (II):
The structural formula of the binary azido cpd is formula (III):
N3-R2-N3 (III)
In formula (I)~(III), the integer that n is 2~200, R1、R2For identical or different organic group；The nickel complex
For at least one of dicyclopentadienyl nickel, two (methyl cyclopentadienyl) nickel and two (tetramethyl-ring pentadienyl) nickel.
2. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 1, it is characterised in that: institute
State R in formula (I) and (II)1For any one in following chemical structural formula 1~17:
Wherein, the positive integer that m, k, h are 1~20；X is selected from N, O, P, S or Si；* the position of substitution is indicated.
3. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 1, it is characterised in that: institute
State R in formula (I) and (III)2For any one in following chemical structural formula 1~18:
Wherein, the positive integer that m, k, h are 1~20；X is selected from N, O, P, S or Si；* the position of substitution is indicated.
4. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 1, it is characterised in that: institute
Stating organophosphorus ligand is the bis- diphenylphosphine -9,9- xanthphos of 4,5- or bis- (2- diphenylphosphine phenyl) ethers.
5. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 1, it is characterised in that: institute
Alkaline environment is stated by cesium carbonate, trimethylace tonitric caesium, sodium hydroxide, sodium ascorbate, potassium phosphate, potassium hydroxide, sodium carbonate, phosphorus
At least one of sour sodium, potassium carbonate provide.
6. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 1, it is characterised in that: institute
Stating and clicking the reaction temperature of polymerization is 15~35 DEG C；
The reaction time for clicking polymerization is 0.1~12 hour；
The molar ratio of binary alkynyl compounds and binary azido cpd is 1:(1~1.1)；
The nickel complex dosage is 5mol%~30mol% of binary alkynyl compounds；The organophosphorus ligand dosage is two
5mol%~30mol% of first alkynyl compounds.
7. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 1, it is characterised in that: two
The concentration of first alkynyl compounds in organic solvent is 0.05~1mol/L；
The organic solvent is toluene, tetrahydrofuran, methylene chloride, chloroform, 1,4- dioxane, dimethyl sulfoxide and N, N- bis-
At least one of methylformamide.
8. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 1, it is characterised in that: institute
It states subsequent processing to refer to after completion of the reaction, in organic solvent by product dissolution, is then added drop-wise in precipitating reagent and is precipitated, receive
Collect sediment, it is dry to constant weight, obtain 1,5- stereoregular polytriazoles.
9. the method for nickel complex as catalyst preparation 1,5- stereoregular polytriazoles according to claim 8, it is characterised in that: institute
Stating precipitating reagent is methanol or n-hexane；
The organic solvent is toluene, tetrahydrofuran, methylene chloride, chloroform, 1,4- dioxane, dimethyl sulfoxide and N, N- bis-
At least one of methylformamide.
10. a kind of 1,5- stereoregular polytriazoles being prepared by any one of claim 1~9 the method.
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| CN105906807A (en) * | 2016-06-16 | 2016-08-31 | 华南理工大学 | Polytriazole with intrinsic flame retardance and preparing method and application thereof |
| CN106866963A (en) * | 2017-02-28 | 2017-06-20 | 华南理工大学 | A kind of method that phosphine nitrile alkali mediation prepares 1,5 stereoregular polytriazoles |
| CN106916303A (en) * | 2017-02-28 | 2017-07-04 | 华南理工大学 | A kind of method of dodecyl imidazole part monovalence copper catalyst catalyzed preparation of poly triazole |
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| WO2011098851A1 (en) * | 2010-02-11 | 2011-08-18 | King Abdullah University Of Science And Technology | Self-assembled block copolymer membrane |
| CN105906807A (en) * | 2016-06-16 | 2016-08-31 | 华南理工大学 | Polytriazole with intrinsic flame retardance and preparing method and application thereof |
| CN106866963A (en) * | 2017-02-28 | 2017-06-20 | 华南理工大学 | A kind of method that phosphine nitrile alkali mediation prepares 1,5 stereoregular polytriazoles |
| CN106916303A (en) * | 2017-02-28 | 2017-07-04 | 华南理工大学 | A kind of method of dodecyl imidazole part monovalence copper catalyst catalyzed preparation of poly triazole |
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