CN101293866B - Bisphenol monomer containing pyridine group and preparation method thereof - Google Patents
Bisphenol monomer containing pyridine group and preparation method thereof Download PDFInfo
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- CN101293866B CN101293866B CN2008100508511A CN200810050851A CN101293866B CN 101293866 B CN101293866 B CN 101293866B CN 2008100508511 A CN2008100508511 A CN 2008100508511A CN 200810050851 A CN200810050851 A CN 200810050851A CN 101293866 B CN101293866 B CN 101293866B
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Abstract
The invention belongs to the field of organic compound materials and a preparation method thereof, particularly relates to a monophenol monomer containing pyridyl group, a bisphenol monomer containing pyridyl group and a preparation method of the two monomers. The monophenol monomer and the bisphenol monomer are respectively synthesized from 2-hydroxy benzaldehyde and 3-aminopyridine and 3,4-dihydroxy benzaldehyde and 3-aminopyridine as raw materials, with cyano sodium borohydride as reducing agent and anhydrous acetic acid as catalyst. The two monomers both contain functional pyridyl group, and can be assembled with other polymers containing special groups via non-covalent bond interaction. The functional polyetheretherketone can be used for producing polymer microspheres with stable structure and containing functional groups by preparing spherical micelles and fixing the structure thereof via crosslinking reaction.
Description
Technical field
The invention belongs to organic compound material and preparation field thereof, be specifically related to a kind of biphenol monomer and such monomeric preparation method who contains the pyridine group.
Background technology
Polyether-ether-ketone is the high performance special engineering plastics of a class, is celebrated with favorable mechanical performance, radiation resistance, corrosion resistance nature and electrical property etc. under its excellent thermostability, the high temperature.Obtained good application in high-tech sectors such as Aeronautics and Astronautics, nuclear energy, information, communication, electronic information, petrochemical complex, machinofacture, communications and transportation.Along with the develop rapidly of Materials science, traditional special engineering plastics is had higher requirement.It is functional more widely to need it to have, and satisfies various demand.And will being had functional group exactly, topmost means of material functional are incorporated in the middle of the polymkeric substance.In addition, polymeric microball material has special size and structure, thereby, make it be widely used, can be used as microreactor, microstructure unit, microstorage etc.Along with the development of Materials science, the demand of polymeric microball material is also progressively being improved.So we start with from the body material of constructing polymeric microball material, designed and synthesized out a kind of single phenol monomer and a kind of biphenol monomer that contains the pyridine group that contains the pyridine group, the polyether-ether-ketone that utilizes these two kinds pyridine terminated polyether ether ketone that monomer synthesized and side chain to contain the pyridine group.And can utilize the method for self-assembly that the novel polyether ether ketone that is synthesized is prepared into polymeric microball material, thereby obtain to have the high-performance polymer microballoon of polyether-ether-ketone excellent properties, simultaneously by the pyridine group had functional, can make this high performance polymer micro-sphere material that the application prospect of potential application is arranged at fluorescence, magnetic, aspect such as luminous.
Summary of the invention
Purpose of the present invention just provides a kind of biphenol monomer and monomeric preparation method of this class who contains the pyridine group.
Wherein single phenol monomer is to be that raw material, biphenol monomer are with 3 with 2-hydroxy benzaldehyde and 3-aminopyridine, and 4-Dihydroxy benzaldehyde and 3-aminopyridine are raw material, and be reductive agent all with the sodium cyanoborohydride, be that catalyzer is synthesized with the anhydrous acetic acid.These two kinds of monomers all contain functional pyridine group, can form assembly with the interaction that some other polymkeric substance that contains specific groups passes through non covalent bond, utilize this functional polyether-ether-ketone to prepare spherical micelle and its structure is carried out crosslinked fixing, can obtain constitutionally stable and contain the polymeric microball material of functional groups.
This patent synthetic list phenol monomer and biphenol monomer structural formula as follows:
Single phenol monomer biphenol monomer
The monomeric preparation method of single phenol who contains the pyridine group is:
2-hydroxy benzaldehyde, 3-aminopyridine, sodium cyanoborohydride, anhydrous methanol solvent are joined in the container that whipping appts is housed, the question response thing dissolves the back fully and adds the anhydrous acetic acid catalyzer, stirred under the room temperature 2～10 hours, reactant dissolves fully, and solution is light yellow;
After reaction finishes, earlier steam solvent with Rotary Evaporators, NaOH solution with 0.2～1.0mol/L joins in the product then, obtain white precipitate, this white precipitate is leached and can obtain the single phenol monomer that contains the pyridine group shown in the structural formula 3 with the distilled water repetitive scrubbing, productive rate is 92～96%;
In this reaction, the mol ratio of 3-aminopyridine, 2-hydroxy benzaldehyde, sodium cyanoborohydride is 1.0: 1.2～1.6: 1.5～2.0, the 3-aminopyridine of every 1mol adds 50～200ml anhydrous acetic acid, and the consumption of NaOH is identical with the consumption mole number of sodium cyanoborohydride.Its reaction formula is as follows:
The preparation method who contains the biphenol monomer of pyridine group is:
With 3,4-Dihydroxy benzaldehyde, 3-aminopyridine, sodium cyanoborohydride, solvent anhydrous methanol join in the container that whipping appts is housed, and the question response thing dissolves the back fully and adds the catalyzer anhydrous acetic acid, stirs under the room temperature 2～10 hours, reactant dissolves fully, and solution is light yellow;
After reaction finishes, steam solvent with Rotary Evaporators earlier, the NaOH solution with 0.2～1.0mol/L joins in the product then, obtain orange-red solution, with ethyl acetate product is extracted from the aqueous solution, and a large amount of ethyl acetate is steamed, the concentrated liquid that obtains is stand-by;
With the mixed solution of anhydrous methanol and methylene dichloride as moving phase, utilize the method for column chromatography that concentrated solution is separated, use a dry method on a sample during separation, separate to finish that the back evaporates solvent with Rotary Evaporators and in vacuum drying oven drying obtain the light yellow solid product, be the biphenol monomer that contains the pyridine group shown in the structural formula 5, productive rate is 90～95%.
In this reaction, 3-aminopyridine, 3, the mol ratio of 4-Dihydroxy benzaldehyde, sodium cyanoborohydride is 1.0: 1.2～1.8: 1.5～2.0, and the 3-aminopyridine of every 1mol adds 50～200ml anhydrous acetic acid, and the consumption of NaOH is identical with the consumption mole number of sodium cyanoborohydride.
Its reaction formula is as follows:
NMR (Nuclear Magnetic Resonance) spectrum, mass spectrum and results of IR show that two kinds of compounds of our institute's synthetic are respectively the biphenol monomer compound shown in single phenol monomeric compound shown in the formula 3 and the formula 5.
Description of drawings
Fig. 1: the nuclear magnetic spectrogram that contains single phenol of pyridine group;
Fig. 2: the nuclear magnetic spectrogram that contains the bis-phenol of pyridine group;
Fig. 3: the infrared spectrum that contains single phenol of pyridine group;
Fig. 4: the infrared spectrum that contains the bis-phenol of pyridine group.
As shown in Figure 1, this figure is corresponding to the single phenol monomer that contains the pyridine group that is synthesized among the embodiment 1, its structural formula as shown in Equation 3, can see each hydrogen among the figure all corresponding the particular location that is marked in the chemical formula, and concrete nuclear magnetic data is analyzed as follows:
1H NMR (DMSO-d6, δ, ppm): δ=9.536 (s, 1H), δ=7.969 (s, 1H), and δ=7.718 (dd, J=4.5Hz, 1H), δ=7.176 (d, J=7.0Hz, 1H), δ=7.062-7.009 (m, 2H), δ=6.828 (d, J=8.0Hz, 1H), δ=6.743 (t, J=7.5Hz, 1H), δ=6.254 (t, J=6.0Hz, 1H), and δ=4.203 (d, J=6.0Hz, 2H).
As shown in Figure 2, this figure is corresponding to the biphenol monomer that contains the pyridine side group that is synthesized among the embodiment 8, co-structured formula as shown in Equation 5, can see each hydrogen all corresponding the particular location that is marked in the chemical formula, and concrete nuclear magnetic data is analyzed as follows:
1H NMR (DMSO-d, δ, ppm): δ=7.970 (s, 1H), δ=7.819 (d, J=4.5Hz, 1H), δ=7.250 (dd, J=8.5Hz, 1H), δ=7.141 (d, J=8.0Hz, 1H), and δ=6.741 (s, 1H). δ=6.677 (d, J=8.0Hz, 1H), and δ=6.607 (d, J=8.0Hz, 1H), δ=4.140 (d, J=6.5Hz, 2H).
As shown in Figure 3, this figure is corresponding to the single phenol monomer that contains the pyridine group that is synthesized among the embodiment 1.Make a concrete analysis of as follows: IR (KBr): 3365cm
-1(vs, Ar-NH-R), 2855cm
-1(vs, CH
2), 3031cm
-1, 1500cm
-1And 759cm
-1(vs, pyridine ring).
As shown in Figure 4, this figure is corresponding to the biphenol monomer that contains the pyridine side group that is synthesized among the embodiment 8.Make a concrete analysis of as follows: IR (KBr): 3348cm
-1(vs, Ar-NH-R), 2854cm
-1(vs, CH
2), 3050cm
-1, 1499cm
-1And 741cm
-1(vs, pyridine ring).
Embodiment
In being housed, churned mechanically beaker, Erlenmeyer flask or round-bottomed flask add 3-aminopyridine 47g (0.5mol), 2-hydroxy benzaldehyde 73.2g (0.6mol), sodium cyanoborohydride 46.5g (0.75mol) and 1500ml anhydrous methanol add the 50ml anhydrous acetic acid then and make catalyzer.Stirred 4 hours under the room temperature, reactant dissolves fully, and solution is light yellow.After reaction finishes, earlier steam solvent with Rotary Evaporators, NaOH solution with 1500ml, 0.5mol/L joins in the product then, fully stir and obtain white precipitate, this white precipitate leached and with distilled water repetitive scrubbing after drying, thereby obtain single phenol monomeric compound shown in the 95g structural formula 3, productive rate reaches 95%.
Embodiment 2:
The reactant consumption just will be adjusted into 6 hours the reaction times with embodiment 1, and other steps obtain the single phenol monomer white solid compound shown in the 95g structural formula 3 with embodiment 1, and productive rate reaches 95%.
Embodiment 3:
The reactant consumption is with embodiment 1, just change order of addition(of ingredients), add 3-aminopyridine, 2-hydroxy benzaldehyde and solvent earlier, wait to dissolve the back and add the catalyzer anhydrous acetic acid, stirred 2 hours, light-yellow precipitate appears, again add after precipitation leached and add sodium cyanoborohydride again behind the solvent and stirred 4 hours, purify, obtain the single phenol monomer white solid compound shown in the 96g structural formula 3 according to embodiment 1 identical treating processes,, productive rate is 96%.
Embodiment 4:
Change the ratio of components of embodiment 1, in being housed, churned mechanically beaker or other containers add 3-aminopyridine 47g (0.5mol), 2-hydroxy benzaldehyde 97.8g (0.8mol), sodium cyanoborohydride 46.5g (0.75mol) and 1500ml anhydrous methanol add anhydrous acetic acid 50ml then and make catalyzer.Stirred 4 hours under the room temperature, reactant dissolves fully, and solution is light yellow.After reaction finishes, earlier steam solvent with Rotary Evaporators, NaOH solution with 1500ml, 0.5mol/L joins in the product then, fully stir and obtain white precipitate, this white precipitate leached and with distilled water repetitive scrubbing after drying, thereby obtain the single phenol monomer white solid compound shown in the 95g structural formula 3, productive rate reaches 95%.
Embodiment 5:
The reactant consumption just will be adjusted into 6 hours with embodiment 4 in the reaction times, and other steps obtain the single phenol monomer white solid compound shown in the structural formula 3 with embodiment 4, and productive rate reaches 95%.
Embodiment 6:
Change the ratio of components of embodiment 1, in being housed, churned mechanically beaker or other containers add 3-aminopyridine 47g (0.5mol), 2-hydroxy benzaldehyde 97.8g (0.8mol), sodium cyanoborohydride 55.8g (0.9mol) and 1500ml anhydrous methanol add anhydrous acetic acid 50ml then and make catalyzer.Stirred 4 hours under the room temperature, reactant dissolves fully, and solution is light yellow.After reaction finishes, earlier steam solvent with Rotary Evaporators, NaOH solution with 1500ml, 0.5mol/L joins in the product then, fully stir and obtain white precipitate, this white precipitate leached and with distilled water repetitive scrubbing after drying, thereby obtain the single phenol monomer white solid compound shown in the 96g structural formula 3, productive rate reaches 96%.
Embodiment 7:
The reactant consumption just will be adjusted into 6 hours with embodiment 6 in the reaction times, and other steps obtain the single phenol monomer white solid compound shown in the 96g structural formula 3 with embodiment 6, and productive rate reaches 96%.
Embodiment 8:
In being housed, churned mechanically beaker, Erlenmeyer flask or round-bottomed flask add 3-aminopyridine 47g (0.5mol), 3,4-Dihydroxy benzaldehyde 82.8g (0.6mol), sodium cyanoborohydride 46.5g (0.75mol) and anhydrous methanol 1500ml add anhydrous acetic acid 50ml then and make catalyzer.Stirred 4 hours under the room temperature, reactant dissolves fully, and solution is light yellow.After reaction finishes, steam solvent with Rotary Evaporators earlier, the NaOH solution with 1500ml, 0.5mol/L joins in the product then, obtains orange-red solution, and (500ml) extracts product from the aqueous solution with ethyl acetate.And a large amount of ethyl acetate steamed, the concentrated liquid that obtains is stand-by, with the mixed solution of anhydrous methanol and methylene dichloride as moving phase, utilize the method for column chromatography that concentrated solution is separated, use a dry method on a sample during separation, and in separating process, utilize the method for thin-layer chromatography to monitor at any time, with the polarity of definite moving phase and the kind of isolate.Separate to finish that the back evaporates solvent with Rotary Evaporators and in vacuum drying oven (40 ℃) drying, obtain light yellow solid product 97g, be the biphenol monomer shown in the structural formula 5, productive rate is 90%.
Embodiment 9:
Reactant consumption and reaction process just will change 6 hours into embodiment 8 in the reaction times, and other treating processess obtain the biphenol monomer compound 97g shown in the structural formula 5 with embodiment 8, and productive rate is 90%.
Embodiment 10:
The reactant consumption is with embodiment 8, just change order of addition(of ingredients), add 3-aminopyridine, 3 earlier, 4-Dihydroxy benzaldehyde and solvent are waited to dissolve the back and are added the catalyzer anhydrous acetic acid, stir 2 hours, light-yellow precipitate occurs, again add after precipitation leached and add sodium cyanoborohydride again behind the solvent and stirred 4 hours, purify according to embodiment 8 identical treating processess, obtain the biphenol monomer compound 97g shown in the structural formula 5, productive rate is 90%.
Embodiment 11:
With embodiment 8, just change 3, the 4-Dihydroxy benzaldehyde is 110.4g (0.8mol), and other amount of reagent are constant, and the building-up reactions step is identical, obtains the biphenol monomer compound 97g shown in the structural formula 5, and productive rate is 90%.
Embodiment 12:
With embodiment 11, just will the reaction times change 6 hours into, other treating processess obtain the biphenol monomer compound 97g shown in the structural formula 5 with embodiment 11, and productive rate is 90%.
Embodiment 13:
With embodiment 8, the amount that just changes sodium cyanoborohydride is 49.6g (0.8mol), and other amount of reagent are constant, and the building-up reactions step is identical, obtains the biphenol monomer compound 97g shown in the structural formula 5, and productive rate is 90%.
Claims (4)
1. the biphenol monomer that contains the pyridine group, its structural formula is as follows,
2. the described preparation method who contains the biphenol monomer of pyridine group of claim 1, its step is as follows:
With 3,4-Dihydroxy benzaldehyde, 3-aminopyridine, sodium cyanoborohydride, solvent anhydrous methanol join in the container that whipping appts is housed, and the question response thing dissolves the back fully and adds the catalyzer anhydrous acetic acid, stirs under the room temperature 2～10 hours, reactant dissolves fully, and solution is light yellow;
After reaction finishes, steam solvent with Rotary Evaporators earlier, the NaOH solution with 0.2～1.0mol/L joins in the product then, obtains orange-red solution, and it is stand-by to obtain concentrated liquid after the extraction;
Utilize the method for column chromatography that concentrated solution is separated, separate to finish that the back evaporates solvent with Rotary Evaporators and in vacuum drying oven drying obtain the light yellow solid product, be the biphenol monomer that contains the pyridine group;
Wherein, 3-aminopyridine, 3, the mol ratio of 4-Dihydroxy benzaldehyde, sodium cyanoborohydride is 1.0: 1.2～1.8: 1.5～2.0, and the 3-aminopyridine of every 1mol adds 50～200ml anhydrous acetic acid, and the consumption of NaOH is identical with the consumption mole number of sodium cyanoborohydride.
3. the preparation method who contains the biphenol monomer of pyridine group as claimed in claim 2 is characterized in that: be with ethyl acetate product to be extracted from the aqueous solution, and ethyl acetate is steamed.
4. the preparation method who contains the biphenol monomer of pyridine group as claimed in claim 2 is characterized in that: the method for utilizing column chromatography to concentrated solution separate be mixed solution with anhydrous methanol and methylene dichloride as moving phase, use a dry method on a sample during separation.
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Non-Patent Citations (3)
| Title |
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| Bahattin Yalcin, et al.Cu(Ⅱ) and Pd(Ⅱ) complexes of N-(2-hydroxybenzyl)aminopyridines.《Polyhedron》.2007,第26卷(第13期),3301-3309. * |
| 姜振玉等.聚芳醚酮的改性研究.《中国塑料》.2005,第19卷(第5期),9-16. * |
| 蹇锡高等.杂环聚芳醚砜、聚芳醚酮及其共聚物合成与性能研究.《大连理工大学学报》.2001,第41卷(第5期),538-541. * |
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