CN106967217A - Polyimidazole class compound and its in-situ preparation method and application - Google Patents
Polyimidazole class compound and its in-situ preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of polyimidazole class compound and its in-situ preparation method and application.It is that binary isonitrile based compound is carried out into cyclopolymerization reaction in the presence of cyclopolymerization catalyst in organic solvent, obtains polyimidazole class compound.Imidazole unit is the blank that prior art is compensate for by the monomer in situ polymerization without imidazole unit in polyimidazole class compound prepared by the present invention；Cyclopolymerization reaction is one-component polymerisation, without considering monomer ratio, and its technique is simple, and reaction raw materials and catalyst are easy to get, and polymeric reaction condition is gentle, can just be polymerize at room temperature, saves the energy.In addition, the polymerisation polymerization efficiency is high, reaction only needs very short time with regard to that can obtain the polymer of higher molecular weight, and there is the polymerisation no coupling product in excellent regional choice type and three-dimensional selection type, polymerization process to generate, and meet Atom economy.
Description
Technical field
The present invention relates to macromolecule preparing technical field, in particular to a kind of polyimidazole class compound and its original position
Preparation method and application.
Background technology
Imidazole ring is five yuan of heteroaromatics containing two meta nitrogen-atoms in molecular structure, contains the organic of imidazole ring structure
Compound is widely used in the field such as catalysis, biology, photoelectricity.In addition to imidazoles micromolecular compound, contain
The macromolecule of imidazole group has also been reported, and is also widely used in the field such as catalysis and photoelectricity.
At present, the larger high molecular method containing imidazole group of synthetic molecular weight is relatively simple, mainly contains imidazole radicals
Vinyl monomer (D.Mecerreyes.Progress in Polymer Science are achieved by radical living polymerization
36(2011)1629–1648；J.Yuan,M.Antonietti.Polymer 52(2011)1469-1482；J.Yuan et
al.Progress in Polymer Science 38(2013)1009–1036).In the polymer that this polymerisation is obtained
Imidazole group is predominantly located at side chain, and seldom for the polymer report containing imidazole group on main chain.Document 1
(Hiroyuki Ohno et al.Macromolecules 2006,39,6924-6927) although in disclose on a kind of main chain
Polymer containing imidazole group, but can be used for the kind that this kind of method prepares the monomer of the polymer containing imidazole ring on main chain
Seldom, polymerization is also very limited, greatly limit the development of polyimidazole class compound for class.
The content of the invention
In order to make up the blank and deficiency of prior art, the present invention is intended to provide a kind of polyimidazole class compound and its original position
Preparation method and application.This method is a kind of one pack system polymerization system in situ using binary isonitrile based compound (double isonitrile monomers)
The highly effective reaction of standby polyimidazole, the preparation method is catalyst using silver ion, only needs one pack system monomer to polymerize, it is possible to poly-
In-situ preparation imidazole group on compound main chain.
To achieve these goals, the invention provides a kind of polyimidazole class compound, described polyimidazole class compound
For the polymer with the repeat unit B shown in the repeat unit A shown in following formula (I)s and formula (II)：
Formula (I) is identical with R in formula (II), selected from-alkyl-,-alkyl-aryl-alkyl-,-alkyl-R1- aryl-R1- alkane
Base-, the R1Selected from-O-；
Wherein, the number of repeat unit shown in formula (I) be 40~200, the number of repeat unit shown in formula (II) be 40~
200。
According to the present invention, the alkyl is C1-20Straight or branched alkyl, preferably C1-12Straight or branched alkyl, more
It is preferred that C1-12Straight chained alkyl.
According to the present invention, the aryl is the monocyclic or polycyclic aromatic group with 6-20 carbon atom, representational virtue
Base includes：The aromatic rings such as phenyl, naphthyl, anthryl, pyrenyl, fluorenyl and pyrrole radicals, pyridine radicals, pyrimidine radicals, imidazole radicals, thiazolyl,
The aromatic heterocycles such as indyl, azepine naphthyl, azepine anthryl, azepine pyrenyl, diazosulfide base.
According to the present invention, the R is any of formula (V-1)~(V-5)：
Wherein, * represents the position of substitution.
Further, preferably, described polyimidazole class compound is with such as following formula (PI)~(PV)
The polymer of shown structure：
Wherein, n, m span are 40~200.
Present invention also offers a kind of method that original position prepares above-mentioned polyimidazole class compound, comprise the following steps：
Will as shown in formula (III) structure binary isonitrile based compound in the presence of cyclopolymerization catalyst in organic molten
Cyclopolymerization reaction is carried out in agent, so as to obtain the polyimidazole class compound；
Wherein, R is defined as above.
In the present invention, monomer is used as by the binary isonitrile based compound from said structure, it is easy to operate.
Further, the step of cyclopolymerization is reacted specifically includes：
1) the binary isonitrile based compound and the cyclopolymerization catalyst are added in polymer reactor, and lazy
Organic solvent is added under property atmosphere, reaction mixture is configured to；
2) after monomer fully dissolves, stir at the polymerization temperature, polymer solution is obtained through cyclopolymerization reaction；
3) post processing obtains the polyimidazole class compound.
Further, in step 1) reaction mixture in, the concentration of the binary isonitrile based compound for 0.25~
1mol/L；Preferably 0.5~1mol/L.
The cyclopolymerization catalyst is silver salt solution, preferably for example can be silver acetate solution.Preferably, the silver salt
The concentration of solution is 0.01~0.04mol/L.
Alternatively, the mol ratio of the binary isonitrile based compound and the cyclopolymerization catalyst is 1:0.04~1:
0.1；The cyclopolymerization reaction is carried out under atmosphere of inert gases.
Further, step 1) described in organic solvent be intensive polar solvent, such as acetonitrile.
Further, the step 2) in cyclopolymerization reaction polymerization temperature be 0~60 DEG C, preferably 20~40
℃；The temperature of such as polymerisation can be 25 DEG C.The time of polymerisation be 0.5~12 hour, preferably 2~4 hours, for example
It can be 2 hours.
Further, the step 3) be specifically：The polymer solution is diluted, by the polymerization after dilution
Thing solution is filtered, and the mixed solvent (V of appropriate n-hexane and chloroform is added drop-wise to afterwardsN-hexane/VChloroform=30:1~15:1, for example
20:1) in, polymer precipitation is obtained, filtering obtains the polyimidazole class compound after being dried under conditions of room temperature in vacuo.
Further, above-mentioned steps 3) in dilution use organic solvent, such as acetonitrile or DMF.
According to the present invention, the step of cyclopolymerization is reacted specifically includes：
By the binary isonitrile based compound and the cyclopolymerization catalyst with (1:0.04)~(1:0.1) (such as 1:
0.04) mol ratio is added in polymerization pipe, and organic solvent acetonitrile is added under atmosphere of inert gases, is configured to reaction mixing
Liquid, wherein, the molar concentration of the binary isonitrile based compound is 0.25~1mol/L (such as 0.5mol/L), and the cyclisation is poly-
Conjunction catalyst is silver salt solution (for example can be silver acetate solution), and the concentration of the silver salt solution is 0.01~0.04mol/L；
(it is preferably 20~40 DEG C at 0~60 DEG C fully after dissolving；For example, 25 DEG C) under stirring reaction 0.5~12 hour
(preferably 2~4 hours, such as, can be 2 hours), polymer solution be obtained after the completion of reaction.
To a small amount of dilution in acetonitrile of the polymer solution, the polymer solution after dilution is filtered by cotton
Device, is added drop-wise to the mixed solvent (V of appropriate n-hexane and chloroform afterwardsN-hexane/VChloroform=20:1) in, polymer precipitation is obtained, it is quiet
Put overnight, filtering, the polyimidazole class compound is obtained after being dried under conditions of room temperature in vacuo.
Present invention also offers the purposes of above-mentioned polyimidazole class compound, it is used for biological antibiotic or polyelectrolyte.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
1. the present invention polyimidazole class compound in imidazole unit be by the monomer in situ polymerization without imidazole unit,
It compensate for the blank of prior art.
2. the present invention carries out one-component cyclopolymerization reaction using binary isonitrile based compound under catalyst action, this is anti-
Should meet from organic reaction to polymerisation it is necessary efficiently, catalyst is easy to get, substrate is simple, simple operation etc. is required, is one
Preferable, efficient polymerisation process is planted, obtained molecular backbone contains the polymer of imidazole group in biological antibiotic and poly- electricity
Solving matter field has potential application.
3. cyclopolymerization reaction is one-component polymerisation, without considering monomer ratio, its technique is simple, reaction raw materials
It is easy to get with catalyst, monomer can directly be bought or by simply reacting preparation.Polymeric reaction condition is gentle, can just gather at room temperature
Close, save the energy.Polymerization efficiency is high, and reaction only needs very short time with regard to that can obtain the polymer of higher molecular weight.And the polymerization
There is no coupling product in excellent regional choice type and three-dimensional selection type, polymerization process to generate for reaction, meet Atom economy.
Brief description of the drawings
Fig. 1 is the infrared absorption spectra of polymer P I monomers corresponding to its.
Fig. 2 is polymer P I monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent peak
And water peak).
Fig. 3 is polymer P I monomers corresponding to its in DMSO-d6In carbon-13 nmr spectra comparison diagram.
Fig. 4 is the infrared absorption spectra of polymer P II monomers corresponding to its.
Fig. 5 is polymer P II monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent peak
And water peak).
Fig. 6 is polymer P II monomers corresponding to its in DMSO-d6In carbon-13 nmr spectra comparison diagram.
Fig. 7 is the infrared absorption spectra of polymer P III monomers corresponding to its.
Fig. 8 is polymer P III monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent
Peak and water peak).
Fig. 9 is polymer P III monomers corresponding to its in DMSO-d6In carbon-13 nmr spectra comparison diagram.
Figure 10 is the infrared absorption spectra of polymer P IV monomers corresponding to its.
Figure 11 is polymer P IV monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent
Peak and water peak).
Figure 12 is polymer P IV monomers corresponding to its in DMSO-d6In carbon-13 nmr spectra comparison diagram.
Figure 13 is the infrared absorption spectra of polymer P V monomers corresponding to its.
Figure 14 is polymer P V monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent peak
And water peak).
Figure 15 is polymer P V monomers corresponding to its in DMSO-d6In carbon-13 nmr spectra comparison diagram.
Embodiment
As described above, the invention discloses a kind of with the repeat unit A shown in formula (I) and the repetition list shown in formula (II)
First B polyimidazole is birdsed of the same feather flock together compound, causes the polymer to have many uniquenesses containing imidazole group and other special groups on main chain
Performance, such as modifiability, hydrophily, enhanced photoelectric properties and biocompatibility.
The exploitation source of polymerisation process is small molecule reaction.Document (Ronald Grigg et
Al.Tetrahedron 55 (1999) 2025-2044) middle report：Isonitrile guanidine-acetic acid ester type compound be a class reactivity compared with
High compound, efficiently can obtain imidazole derivative under the catalysis of silver ion.But the reaction is only small molecule reaction, nothing
Method obtains the polymer containing imidazole group on main chain.
The present invention proposes a kind of method of in-situ preparation of poly glyoxaline compound based on this first, comprises the following steps：
The binary isonitrile based compound of structure shown in formula (III) is carried out into one-component cyclisation in organic solvent under catalyst action to gather
Reaction is closed, polyimidazole class compound is obtained.
The repeat unit A and repeat unit B of the polyimidazole class compound span are 40~200.The present invention
Span is limited within the above range, the dissolubility of molecular size range and polymer mainly in view of polymer compared with
It is good.
As described above, the step of cyclopolymerization is reacted includes：
1) the binary isonitrile based compound and the cyclopolymerization catalyst are added in polymer reactor, and lazy
Organic solvent is added under property atmosphere, reaction mixture is configured to；
2) after monomer fully dissolves, stir at the polymerization temperature, polymer solution is obtained through cyclopolymerization reaction；
3) post processing obtains the polyimidazole class compound.
The present invention is in the presence of catalyst, by the molecule in adjacent double isonitrile base monomer moleculesBase
In group and another moleculeThe reaction of 2+3 cycloaddition occurs for group, so that having obtained main chain contains the poly- of imidazole group
Compound.
In the step 1) in, using organic solvent and polymerisation is added under inert atmosphere, mainly exclude in air
The influence to polymerisation of moisture and oxygen.It is by the mol ratio control of binary isonitrile based compound and cyclopolymerization catalyst
(1:0.04)~(1:0.1), if mainly can excessively reduce polymerisation production in view of the consumption of binary isonitrile based compound
Rate；On the contrary, if the consumption of catalyst is excessive, occurs and the problem of silver content is excessive is remained in polymer, and catalyst
In itself also costly, it is uneconomical.It is preferred that the molar ratio of binary isonitrile based compound and cyclopolymerization catalyst such as can be
1:0.04。
Concentration in view of polymerization reaction monomer can produce influence to the yield of reaction, it is preferable that in reaction mixture,
The concentration control of binary isonitrile based compound is 0.25~1mol/L by the present invention.If concentration is too high polymerization system can be caused to glue
Degree rise, polymer solubility is deteriorated, on the contrary, polymer molecular weight is less than normal if concentration is too low.It is preferred that binary isonitrile base
The concentration of compound is 0.5~1mol/L.
In the cyclopolymerization reaction of the present invention, the cyclopolymerization catalyst used is preferably silver salt solution, that is, is contained
The solution of silver ion, for example, can be silver acetate solution.It is mainly using the solution for containing silver ion as catalyst and is considered
Silver can activate isonitrile group.Preferably, the concentration of the silver salt solution is 0.01~0.04mol/L.
According to the present invention, the organic solvent is intensive polar solvent acetonitrile.It is preferred that cyclopolymerization reaction is carried out in acetonitrile,
It can obtain that molecular weight is higher and the preferable polyimidazole class compound of solubility, be easy to next step application.
In the step 2) in, the polymerization temperature of cyclopolymerization reaction is 0~60 DEG C, preferably 20~30 DEG C；For example gather
The temperature for closing reaction can be 25 DEG C.Polymerization reaction time is 0.5~12 hour, preferably 2~4 hours, for example can be small for 2
When.The present invention by the polymerization temperature and time control of polymerisation within the above range, mainly in view of polymer molecular weight
The problem of with polymer solubility.If polymerization temperature is too high or the time oversize dissolubility that can cause polymer is deteriorated；Phase
Instead, if polymerization temperature is too low or the time it is too short polymer molecular weight can be caused less than normal, be unfavorable for cyclopolymerization reaction
Carry out, also cannot get the polyimidazole class compound of excellent performance.
In one particular embodiment of the present invention, what cyclopolymerization was reacted concretely comprises the following steps：By binary isonitrile base chemical combination
Thing and cyclopolymerization catalyst are with 1:0.04 mol ratio is added in polymerization pipe, and organic solvent is added under atmosphere of inert gases
Acetonitrile, is configured to the reaction mixture that binary isonitrile based compound molar concentration is 0.5mol/L.After monomer fully dissolves,
Stirring reaction 2 hours under normal temperature.Polymer solution is obtained after the completion of reaction, through a small amount of dilution in acetonitrile, passes through cotton filter
Polymer solution is added drop-wise to the mixed solvent (V/V 20 of appropriate n-hexane and chloroform:1) in, polymer precipitation is obtained, it is quiet
Put overnight, filtering, polyimidazole class compound is obtained after being dried under conditions of room temperature in vacuo.
In addition, present invention also offers a kind of preparation method of above-mentioned binary isonitrile based compound monomer, the monomer
Preparation process is as follows：
(1) under inert gas shielding, compound 1 (for example can be isonitrile guanidine-acetic acid potassium) and compound 2 (for example can be with
It is 1,6- dibromo-hexanes) fully reacted at 50 DEG C in DMF (dimethylformamide) solvent；
(2) after reaction terminates, reaction dissolvent is removed, is 1 with petroleum ether and ethyl acetate volume ratio:1 mixed solvent is made
Eluant, eluent column chromatography for separation final product, obtains binary isonitrile based compound monomer.
The present invention is specifically described below in conjunction with embodiment, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
Polyimidazole compound of the preparation structure formula as shown in PII：
1) monomer 3, i.e., above-mentioned monomer have been synthesized by reaction equation (one) firstIts
Middle R is (V-2).
Formula (one)
The specific preparation process of the monomer 3 is as follows：
(1) under inert gas shielding, compound 1 (isonitrile guanidine-acetic acid potassium) and compound 2 (1,6- dibromo-hexane) are with 1:
0.45 ratio is mixed, and is fully reacted 8 hours at 50 DEG C in DMF solvent.
(2) after reaction terminates, reaction dissolvent DMF is removed, with volume ratio 1:1 petroleum ether and the mixed solvent of ethyl acetate
Make eluant, eluent column chromatography for separation final product, obtain monomer 3.
Polymer P II is prepared by reaction equation (two) using monomer 3, comprised the following steps that：
1) under inert gas shielding, by monomer 3 and catalyst acetic acid silver according to mol ratio 1:0.04 is added to polymerization instead
Answer in device, and add organic solvent acetonitrile, it is substantially dissolved in acetonitrile, obtain reaction mixture.In reaction mixture,
The concentration of the monomer 3 is 0.25mol/L, and the concentration of the silver acetate solution is 0.01mol/L.
2) cyclopolymerization is stirred under room temperature (25 DEG C) to react 2 hours, obtain polymer reaction mother liquor.
3) after completion of the reaction, with appropriate acetonitrile solution diluted polymer reaction mother liquor, by the polymer after dilution
Reaction mother liquor is filtered, then is added dropwise to n-hexane and chloroform (VN-hexane/VChloroform=20:1) in the mixed solvent, collects sediment, then
Dried under conditions of room temperature in vacuo to constant weight, obtain polyimidazole and birds of the same feather flock together compound.Reaction equation is as follows：
Formula (two)
Fig. 4 is the infrared comparison diagram of polymer P II and monomer 3, figure 4, it is seen that the present invention in situ generated master
Polymer containing imidazole group on chain.
The polyimidazole prepared in the present embodiment 1 is birdsed of the same feather flock together the hydrogen spectrum nuclear magnetic spectrogram such as Fig. 5 of compound in deuterated dimethyl sulfoxide
(C) shown in.It can be seen that from Fig. 5 (C), the solvent peak and water peak of deuterated dimethyl sulfoxide are located at 2.5 and 3.3ppm respectively；
It is the appearance of hydrogen atom in polymer in addition.
(A) (B) in Fig. 5 is the hydrogen spectrum nuclear magnetic spectrogram of monomer and model compound, and the nuclear-magnetism of polymer is understood by contrast
Proton nmr spectra of the hydrogen spectrum that resonates well with model compound be corresponding, and the hydrogen of imidazole ring goes out peak position significantly in spectrogram
On characterized and also there is change the peak position that goes out of feature hydrogen accordingly in monomer.
Fig. 6 is the carbon spectrum comparison diagram of monomer 3, polymer P II and model compound, as can be seen from Figure 6 polymer
Carbon spectrum of the carbon-13 nmr spectra well with model compound it is corresponding, three feature carbon on imidazole ring are clearly in spectrogram
In characterized and the peak position that goes out of isonitrile base carbon is disappeared in monomer, this shows that isonitrile take part in reaction completely.
The polymer P II finally prepared characterize data：White solid, yield：97%.Gel permeation chromatography (GPC) is tied
Fruit shows：Weight average molecular weight (Mw) it is 19400, molecular weight distribution (PDI) is 1.32.IR (film), ν (cm-1):3270,3128,
2936,2860,1747,1718,1384,1211,987,772.1H NMR(500MHz,DMSO-d6),δ(TMS,ppm):
7.893,7.737,5.031,4.172,4.103,1.636,1.579,1.394,1.355,1.299。
Embodiment 2~5
Embodiment 2~5 has investigated influence of the different reaction temperatures to reaction condition.Wherein, the preparation of polymerized monomer with
And using monomer prepare polymer the step of it is same as Example 1, difference is polymeric reaction temperature.Specific polymerization is anti-
The condition answered is shown in Table 1.
The influence that the polymeric reaction temperature of table 1. polymerize to monomer 3a
aReacted in air in acetonitrile；Reaction time 2h；[M]0=0.5M.
bT=reaction temperatures.
cDetermined by GPC, using linear polystyrene as correction thing, using DMF as mobile phase.
It is completely dissolved in conventional organic solvent such as DMF (dimethylformamide) and DMSO (dimethyl sulfoxide (DMSO)).
From table 1 it follows that the polymerization activity is very high, it is of a relatively high to generate molecular weight at 0 DEG C
Polymer, when temperature is increased to more than room temperature (25 DEG C) and room temperature (25 DEG C), the yield of polymerisation reaches more than 85%, point
Son amount reaches more than 15000.Under room temperature (25 DEG C), it has been found that its yield and molecular weight are all optimal, therefore selection room
Warm (25 DEG C) are used as the temperature conditionss optimized.
Embodiment 6~8
Embodiment 6~8 has investigated influence of the different monomer concentrations to reaction condition, the preparation and use of polymerized monomer
The step of monomer prepares polymer is same as Example 1, and difference is that the concentration of monomer in polymerizeing is different, specific reaction
Condition and it the results are shown in Table 2.
Influence of the monomer concentration of table 2. to the polymerisation of monomer 3a
aReacted in air in acetonitrile；Reaction time 2h；Temperature is room temperature (25 DEG C).
bDetermined by GPC, using linear polystyrene as correction thing, using DMF as mobile phase.
It is completely dissolved in conventional organic solvent such as DMF and DMSO.
Monomer concentration is too high as can be seen from Table 2 or the too low generation for being all unfavorable for polymerisation, and concentration is too low to be caused
Intermolecular collision probability diminishes, so that yield step-down molecular weight is less than normal.Concentration is too big, and system viscosity becomes big, equally limits
Intermolecular mutual collision, causes the relatively low molecular weight of yield less than normal.This illustrates that the optimal monomer concentration of the polymerisation is
0.5mol/L。
Embodiment 9~15
Embodiment 9~15 has investigated influence of the different times to reaction condition, and the preparation and use of polymerized monomer are single
The step of body prepares polymer is same as Example 1, difference be react time, wherein specific reaction condition and
It the results are shown in Table 1.
Influence of the time of table 3. to the polymerisation of monomer 3a
aReacted in acetonitrile；Reaction temperature is room temperature (25 DEG C)；Monomer concentration [M]0=0.5M.
bTime=reaction time.
cDetermined by GPC, using linear polystyrene as correction thing, using DMF as mobile phase.
It is completely dissolved in conventional organic solvent such as DMF and DMSO.
From table 3 it is observed that the extension time can improve the yield of polymerisation and the molecular weight of polymer, 2 is small
When with the yield and the change of molecular weight of post-polymerization all less substantially, therefore 2 hours be the optimal reaction time.
Embodiment 16
(1) binary isonitrile R is the monomer of formula (V-1)The synthetic method of (being designated as monomer 4)
Be the same as Example 1, difference is to instead of 1,6- dibromo-hexanes using Isosorbide-5-Nitrae-dibromobutane.
(2) polyimidazole class compound PI preparation be the same as Example 1, difference is that binary isonitrile monomer is monomer 4.
Polyimidazole class compound PI characterize data：White solid, yield：92%.Gel permeation chromatography (GPC) result shows
Show：Weight average molecular weight (Mw) it is 14320, molecular weight distribution (PDI) is 1.36.IR (film), ν (cm-1):3140,3120,
2960,2568,1740,1712,1555,1206,973,772。1H NMR(500MHz,DMSO-d6),δ(TMS,ppm):7.91,
7.75,5.048,4.734,4.172,1.719,1.669.13C NMR(125MHz,d6-DMSO),δ(ppm):168.9,
163.1,140.2,132.5,127.9,65.2,63.9,60.8,47.8,24.3。
Fig. 1 is the infrared absorption spectra of polymer P I monomers corresponding to its.From figure 1 it appears that different in polymer
The infrared absorption peak of nitrile group has been wholly absent, and shows that isonitrile group has completely reacted.
Fig. 2 is polymer P I monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent peak
And water peak).The hydrogen spectrum that the hydrogen spectrum contrast of polymer and monomer can be seen that in polymer from Fig. 2 occurs in that new peak,
7.75 and 7,91 position illustrates the heterocycle imidazole ring for generating new armaticity.
Fig. 3 is carbon-13 nmr spectra comparison diagram of the polymer P I monomers corresponding to its in DMSO-d6.It polymerize from Fig. 3
The carbon spectrum contrast of thing and monomer in 140.2,132.5,127.9 positions in polymer carbon spectrogram as can be seen that occur in that new virtue
The appearance of fragrance carbon atom, this three groups of peaks are that three carbon goes out peak position on imidazole ring, further illustrate and generate imidazole ring.
Embodiment 17
(1) R is the binary isonitrile monomer of formula (V-3)(being designated as monomer 5) synthetic method is same
Embodiment 1, difference is to use the bromooctanes of 1,8- bis- to instead of 1,6- dibromo-hexanes.
(2) polyimidazole class compound PIII preparation be the same as Example 1, difference is that binary isonitrile monomer is monomer 5.
Polyimidazole class compound PIII characterize data：White powder, yield：97%.Gel permeation chromatography (GPC) result
Display：Weight average molecular weight (Mw) it is 21730, molecular weight distribution (PDI) is 1.17.IR (film), ν (cm-1):3142,3120,
2933,2854,1745,1714,1555,1218,982,772。(500MHz,DMSO-d6),δ(TMS,ppm):7.882,
7.731,5.028,4.154,4.096,1.631,1.571,1.278,1.259.13C NMR(125MHz,DMSO-d6),δ
(ppm):168.7,163.1,140.2,132.4,128.0,65.7,63.8,61.0,47.9,32.9,31.9,28.8,25.7。
Fig. 7 is the infrared absorption spectra of polymer P III monomers corresponding to its, it can be seen that the isonitrile group in polymer
Infrared absorption peak be wholly absent, show that isonitrile group has completely reacted.
Fig. 8 is polymer P III monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent
Peak and water peak), from the hydrogen spectrum contrast of polymer and monomer as can be seen that the hydrogen spectrum in polymer occurs in that new peak, 7.882
Position with 7.731, illustrates the heterocycle imidazole ring for generating new armaticity.
Fig. 9 is carbon-13 nmr spectra comparison diagram of the polymer P III monomers corresponding to its in DMSO-d6, can therefrom be seen
Go out in polymer carbon spectrogram to occur in that the appearance of new armaticity carbon atom in 140.2,132.4,128.0 positions, this three groups of peaks
It is that three carbon goes out peak position on imidazole ring, further illustrates and generate imidazole ring.
Embodiment 18
(1) R is the binary isonitrile monomer of formula (V-4)The synthetic method of (being designated as monomer 6)
Be the same as Example 1, difference is to use instead of 1,6- dibromo-hexanes to bromomethyl benzyl bromide a-bromotoluene.
(2) polyimidazole class compound PIV preparation be the same as Example 1, difference is that binary isonitrile monomer is monomer 6.
Polyimidazole class compound PIV characterize data：White powder, yield：85%.Gel permeation chromatography (GPC) result
Display：Weight average molecular weight (Mw) is 25110, and molecular weight distribution (PDI) is 1.28.IR (film), ν (cm-1):3138,2989,
2951,2211,2163,1737,1710,1550,1202,972.1H NMR(500MHz,DMSO-d6),δ(TMS,ppm):
7.970,7.768,7.421,5.231,5.099,4.78.13C NMR(125MHz,DMSO-d6),δ(ppm):168.6,
165.2,162.2,140.3,137.4,136.0,132.4,128.9,67.2,65.2,47.9,44.8。
Figure 10 is the infrared absorption spectra of polymer P IV monomers corresponding to its, it can be seen that the infrared absorption of isonitrile group
Peak has been wholly absent, and shows that isonitrile group has completely reacted.
Figure 11 is polymer P IV monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent
Peak and water peak), from the hydrogen spectrum contrast of polymer and monomer as can be seen that the hydrogen spectrum in polymer occurs in that new peak, 7.970
Position with 7.768, illustrates the heterocycle imidazole ring for generating new armaticity.
Figure 12 is carbon-13 nmr spectra comparison diagram of the polymer P IV monomers corresponding to its in DMSO-d6, from polymer and
As can be seen that occurring in that new fragrance in 140.3,132.4,128.9 positions in polymer carbon spectrogram in the carbon spectrum contrast of monomer
The appearance of property carbon atom, this three groups of peaks are that three carbon goes out peak position on imidazole ring, further illustrate and generate imidazole ring.
Embodiment 19
(1) R is the binary isonitrile monomer of formula (V-5)The synthetic method of (being designated as monomer 7)
Be the same as Example 1, difference is to useIt instead of 1,6- dibromo-hexanes.
(2) polyimidazole class compound PV preparation be the same as Example 1, difference is that binary isonitrile monomer is monomer 7.
Polyimidazole class compound PV characterize data：White powder, yield：95%.Gel permeation chromatography (GPC) result shows
Show：Weight average molecular weight (Mw) is 20890, and molecular weight distribution (PDI) is 1.45.IR (film), ν (cm-1):3141,2936,
2856,1761,1717,1510,1229,1024,820,732.1H NMR(500MHz,DMSO-d),δ(TMS,ppm):7.880,
7.729,6.815,5.016,4.144,3.857,1.657,1.616,1.413,1.378,1.346.13C NMR(125MHz,
DMSO-d6),δ(ppm):168.7,162.8,153.1,140.5,132.7,128.3,115.7,68.3,66.3,65.4,
64.2,48.2,44.2,29.1,28.5,25.4.)。
Figure 13 is the infrared absorption spectra of polymer P V monomers corresponding to its, it can be seen that the infrared absorption peak of isonitrile group
It has been be wholly absent that, show that isonitrile group has completely reacted.
Figure 14 is polymer P V monomers corresponding to its in DMSO-d6In proton nmr spectra comparison diagram (* represents solvent peak
And water peak), it can be seen that the hydrogen spectrum in polymer occurs in that new peak in 7.880 and 7.729 position, illustrates there is new virtue
The heterocycle imidazole ring generation of fragrance.
Figure 15 is carbon-13 nmr spectra comparison diagram of the polymer P V monomers corresponding to its in DMSO-d6, can from contrast
To find out the appearance that new armaticity carbon atom is occurred in that in polymer carbon spectrogram in 140.5,132.7,128.3 positions, this three
Group peak is that three carbon goes out peak position on imidazole ring, has further illustrated imidazole ring generation.
Claims (10)
1. a kind of polyimidazole class compound, it is characterised in that described polyimidazole class compound is with shown in following formula (I)s
Repeat unit A and the repeat unit B shown in formula (II) polymer：
In formula (I) and formula (II), R is identical, selected from-alkyl-,-alkyl-aryl-alkyl-,-alkyl-R1- aryl-R1- alkyl-,
The R1Selected from-O-；
Wherein, the number of repeat unit shown in formula (I) is 40~200, and the number of repeat unit shown in formula (II) is 40~200.
2. polyimidazole class compound according to claim 1, it is characterised in that the alkyl is C1-20Straight or branched
Alkyl, preferably C1-12Straight or branched alkyl, more preferably C1-12Straight chained alkyl；
Preferably, the aryl is the monocyclic or polycyclic aromatic group with 6-20 carbon atom, and representational aryl includes：Benzene
The aromatic rings such as base, naphthyl, anthryl, pyrenyl, fluorenyl and pyrrole radicals, pyridine radicals, pyrimidine radicals, imidazole radicals, thiazolyl, indyl, nitrogen
The aromatic heterocycles such as miscellaneous naphthyl, azepine anthryl, azepine pyrenyl, diazosulfide base.
3. polyimidazole class compound according to claim 2, it is characterised in that the R is in formula (V-1)~(V-5)
It is any：
Wherein, * represents the position of substitution.
4. the polyimidazole class compound according to any one of claim 1-3, it is characterised in that
Described polyimidazole class compound is the polymer with the structure as shown in following formula (PI)~(PV)：
Wherein, n, m span are 40~200.
5. a kind of in-situ preparation method of the polyimidazole class compound any one of claim 1-4, it is characterised in that bag
Include following steps：
Will as shown in formula (III) structure binary isonitrile based compound in the presence of cyclopolymerization catalyst in organic solvent
Cyclopolymerization reaction is carried out, the polyimidazole class compound is obtained；
Wherein, R be selected from-alkyl-,-alkyl-aryl-alkyl-,-alkyl-R1- aryl-R1- alkyl-, the R1Selected from-O-；
Preferably, the alkyl is C1-20Straight or branched alkyl, preferably C1-12Straight or branched alkyl, more preferably C1-12
Straight chained alkyl.
Preferably, the aryl is the monocyclic or polycyclic aromatic group with 6-20 carbon atom, and representational aryl includes：Benzene
The aromatic rings such as base, naphthyl, anthryl, pyrenyl, fluorenyl and pyrrole radicals, pyridine radicals, pyrimidine radicals, imidazole radicals, thiazolyl, indyl, nitrogen
The aromatic heterocycles such as miscellaneous naphthyl, azepine anthryl, azepine pyrenyl, diazosulfide base.
6. in-situ preparation method according to claim 5, it is characterised in that the step of cyclopolymerization is reacted specifically is wrapped
Include：
1) the binary isonitrile based compound and the cyclopolymerization catalyst are added in polymer reactor, and in indifferent gas
Organic solvent is added under body atmosphere, reaction mixture is configured to；
2) after monomer fully dissolves, stir at the polymerization temperature, polymer solution is obtained through cyclopolymerization reaction；
3) post processing obtains the polyimidazole class compound.
7. in-situ preparation method according to claim 6, it is characterised in that
In step 1) reaction mixture in, the concentration of the binary isonitrile based compound is 0.25~1mol/L；Preferably 0.5
~1mol/L；
The cyclopolymerization catalyst is silver salt solution, preferably for example can be silver acetate solution.
Preferably, the concentration of the silver salt solution is 0.01~0.04mol/L；
Preferably, step 1) in, the mol ratio of the binary isonitrile based compound and the cyclopolymerization catalyst is 1:0.04
~1:0.1；It is preferred that for example can be 1:0.04；The cyclopolymerization reaction is carried out under atmosphere of inert gases；
Preferably, the organic solvent is intensive polar solvent, such as acetonitrile.
8. the in-situ preparation method according to claim 6 or 7, it is characterised in that the step 2) in cyclopolymerization it is anti-
The polymerization temperature answered is 0~60 DEG C, preferably 20~40 DEG C；The temperature of such as polymerisation can be 25 DEG C；
Polymerization reaction time is 0.5~12 hour, and preferably 2~4 hours, for example, can be 2 hours；
Preferably, the step 3) be specifically：The polymer solution is diluted, by the polymer solution after dilution
Filtering, is added drop-wise to the mixed solvent (V of appropriate n-hexane and chloroform afterwardsN-hexane/VChloroform=30:1~15:1, such as 20:1) in,
Polymer precipitation is obtained, filtering obtains the polyimidazole class compound after being dried under conditions of room temperature in vacuo.
Preferably, above-mentioned steps 3) in dilution use organic solvent, such as acetonitrile or DMF.
9. the in-situ preparation method according to claim any one of 5-8, it is characterised in that the step of the cyclopolymerization reaction
Suddenly specifically include：
By the binary isonitrile based compound and the cyclopolymerization catalyst with 1:0.04~1:0.1 (such as 1:0.04) rub
You are added in polymerization pipe ratio, are added organic solvent acetonitrile under atmosphere of inert gases, are configured to reaction mixture, wherein, institute
The molar concentration for stating binary isonitrile based compound is 0.25~1mol/L (such as 0.5mol/L), and the cyclopolymerization catalyst is
Silver salt solution (for example can be silver acetate solution), the concentration of the silver salt solution is 0.01~0.04mol/L；
(it is preferably 20~40 DEG C at 0~60 DEG C fully after dissolving；For example, 25 DEG C) under stirring reaction 0.5~12 hour (preferably
2~4 hours, for example, can be 2 hours), obtain polymer solution after the completion of reaction；
To a small amount of dilution in acetonitrile of the polymer solution, by the polymer solution after dilution by cotton filter, it
Mixed solvent (the V of appropriate n-hexane and chloroform is added drop-wise to afterwardsN-hexane/VChloroform=20:1) in, polymer precipitation is obtained, was stood
Night, filtering obtains the polyimidazole class compound after being dried under conditions of room temperature in vacuo.
10. the purposes of the polyimidazole class compound described in claim any one of 1-4, it is used for biological antibiotic or polyelectrolyte.
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